PartIIISessionAV4 PDF

Advances
in Optics, Photonics, Spectroscopy and Applications

Sept. 2008, Nhatrang, Vietnam
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NANOCRYSTALLINE TIO2 FILMS: PREPARATION AND CHARACTERIZATION

OF PHOTOCATALYTIC PROPERTIES
Nguyen Nang Dinh a, Pham Hoang Ngan a, Pham Van Nho b
a)
College of Technology, Vietnam National University, Hanoi

144, Xuan Thuy, Cau Giay, Hanoi Vietnam
E-mal: dinhnn@vnu.edu.vn
b)
College of Natural Science, Vietnam National University, Hanoi
334, Nguyen Trai, Thanh Xuan Hanoi, Vietnam
E-mail: nhopv@vnu.edu.vn
Abstract: Nanocrystalline TiO2 films on glass (TiO2/glass) were prepared by a spray pyrolysis
method. TiO2 films on quartz sand (TiO2/SiO2) were synthesized by a sol-gel method, followed
by an annealing treatment. Ag-doped TiO2 films were also synthesized to improve the efficiency
of the photocatalytic treatment. The influence of the annealing temperature on photocatalytic
properties of the films was investigated. To examine the photocatalytic activity of the TiO2 films,
the photo-decomposition of methylene blue was carried-out. The structural and morphology
analysis of the products were examined by X-ray diffraction and scanning electron microscopy,
respectively. The results have shown that the spray pyrolysis made TiO2/glass films can be used
for the photocatalytic performance. However, in comparison with the TiO2 films coated on glass
substrate, photocatalytic efficiency of TiO2 deposited on quartz sand was much larger. For the
latter, the transmittance spectra of methylene blue after 30 minutes treated under solar light
increased from initial value of 70% to 96%. This suggests an application of nanocrystalline TiO2
films in photocatalytic treatments for the polluted water and air in the environment.
Key words: Spray pyrolysis, Sol-gel, TiO2 film, Photocatalysis, Transmittance spectra.
1. Introduction
In 1972 Fujishita discovered the photocatalystic property of TiO2 [1], later, it is known that
the photocatalytic behavior of TiO2 was explained due to its absorption of UV-light, resulting to
generation of electron-hole pairs and decomposition of organic compounds adsorbing on the
TiO2 surface [2]. Moreover, under UV-light irradiation the surface of TiO2 becomes highly
hydrophilic with a water contact angle of almost zero degree [3-4]. These characteristics have
been applied to the self-cleaning glass windows, anti-fogging mirrors, etc. As shown [5], in the
market share of the photocatatytic products, the category of purification facilities increased very
fast. Numerous methods can be used for preparation of nanoporous TiO2 films, such as
hydrolysis processing [6], sol-gel [7], and magnetron sputtering [8]. It is known that, the most
type of materials used for photo-catalysts is anatase TiO2. Its band gap is ~ 3.2 eV, so mainly UV
radiation with wavelengths below 390 nm is effective. This limits the applicability for the indoor
photocatalytic purification. A second generation of visible-active materials is currently
investigated for nitrogen-doped TiO2 which is able to diminish the band gap, and films of TiO2xNx can be used for air and water purification [9-10].
In this work we present the results on the preparation and characterization of TiO2
(TiO2/glass) and silver-doped TiO2 (Ag-TiO2/glass) deposited onto glass by spray pyrolysis
method, and TiO2 coated onto quartz sand (TiO2/QS) by sol-gel processing.
To characterize nanocrystalline structure of the samples X-ray difraction patterns were done on a
SIMENS D5005 X-ray difractometer. Study of the photocatalytic properties was carried-out by
comparison of transmittance spectra of a standard methylene blue (MB) and of that which was
treated by photocatalytic performance.
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tin b trong Quang hc, Quang t, Quang ph v ng dng 9/2008, Nha Trang, Vit Nam
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Table 1. TiO2-based photocatalytic products that have appeared on the market in Japan [5]
Categories
Products
Properties
Market share of the

products
in 2002
in 2003
(%)
(%)
Exterior
Tiles, glass, tents, plastic
construction films, aluminum panels,
materials
coatings,
Self-cleaning
61
44
Interior
furnishing
materials
Self-cleaning,
antibacterial
20
13
RoadSoundproof walls, tunnel Self-cleaning,

construction walls, road-blocks,
air-cleaning
materials
coatings, traffic signs and
reflectors, lamp covers
Purification
facilities
33
Tiles, wallpaper, window

blinds,
Air cleaners, air

conditioners, purification
system for wastewater
and sewage, purification
system for pools
Air-cleaning,
water-cleaning,
Household
goods
Fibers, clothes, leathers,

lightings, sprays
Self-cleaning,
antibacterial
Others
Facilities for agricultural

uses
Air-cleaning,
antibacterial
antibacterial
2. Experimental
For depositing nanocrystalline titanium dioxide films (TiO2/glass) and silver-doped TiO2
(Ag-TiO2/glass) on glass, a pulsed spray pyrolysis method was used. In case of preparing pure
TiO2 films, titanium tetrachloride (TiCl4) was dissolved into distilled water in an appropriate
concentration (0.1M) to form spray solution. In the silver doping case, spray solution used was a
solution of TiCl4 in water embedded with AgNO3. The AgNO3/TiCl4 ratios were set to be of
weight 1.6%, 3.2%, 4.8%, 6.4%, 8% and 9.6%. Substrate temperature was kept at 4000C during
the spraying. Corning glass of 2.57.51.2 mm size was used for substrates; the pressure of
carrier gas was maintained at 73.5 kPa. Obtained TiO2 films were subjected to thermal treatment
at annealing temperature ranging form 3000C to 4500C for 30 minutes.
TiO2/QS samples were prepared by sol-gel method. For this, tetra-n-butylonthotitanate
(C16H36O4Ti) solution was mixed into butanol. The molar ratio of C16H36O4Ti / butanol was 1:2.
The clean quartz sand, after being filtered to remove dust, was dried at 1000C, and then
immersed in the solution. The process was taken place under vigorous stirring for 30 minutes.
After that, the quartz sand was filtered form the solution, dried at 600C to form powders. When
the powders were totally dried, they were subjected to annealing at 4000C for 5 hours.
The photo-oxidation experiment was carried out in a tray-shaped reactor. A volume of 2 ml
methylene blue 1% was used for each 3 grams of quartz sand in each photocatalysis experiment.
TiO2/QS samples were dispersed in 2 ml of aqueous methylene blue dye solution. It was then
photo-irradiated at room temperature under solar light. The decomposition of methylene blue dye
was monitored by measuring the transmittance of the methylene blue samples collected at 10
minutes interval for the total irradiated time of 30 minutes.
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3. Results and Discussion
0,9
cos
140
(101)
TiO2/Glass
Intensity (ab. units)
The crystalline structure of a TiO2

sample annealed at 4500C is shown in
X-ray diffraction patterns (Figure 1).
From this figure, one can see that the
high crystallinity of the sample with the
preferred crystalline orientations of
anatase phase was formed. Indeed, with
the annealing temperature around 250 to
6000C, TiO2 was usually crystallized in
anatase phase, and at higher 6000C, the
phase transformation occured and TiO2
was formed in rutile phase [11]. To
determine the size () of the crystalline
grains, the Sherrer formula was used:
110
80
50
(200)
(004)
20
(105), (211) (204)
-10
15
25
35
45
55
65
2 Theta
Fig.1. XRD patterns of a TiO2 film deposited on

galss by spaying. This proves that TiO2 clusters
were crystallized on nanograins form.
(1)
Transmittance (%)
90
450 oC
where is wavelength of the X-ray used,
400 oC
- the peak width of half height in
80
300 oC
radians and - the Bragg angle of the
MB
considered diffraction peak [12]. In this
70
work all the XRD data were made with
60
CuK radiation ( = 0.15406 nm). The
average size of nanocrystal was estimated
50
from the line broadening of X-ray
diffraction reflections using the Sherrer
40
formula (1). The value of the grain size of
300
350
400
450
500
550
TiO2 formed in TiO2/glass samples was
Wavelength (nm)
found to be of ~15 nm.
Fig. 2. Photocatalytic activity of the samples
In Fig. 2 shows the effect of annealing
annealed at different temperatures. The best phototemperature during the sample preparation
catalys treatment was observed for the sample
toward photocatalytic treatment of the
annealed at 4500C.
MB. The last exhibited the highest
saturation bleaching for the sample annealed at 4500C, for 30 min. The treatment processes were
taken place for 4 hours. We have also made comparison of the roughness of the samples with
annealing temperature of 300, 400 and 4500C, it was found that the roughness of the TiO2 with
4000C was the largest, and then decreased as the annealing temperature increased. However,
according to the result shown in Fig. 2, the higher annealing temperature taken, the stronger
photocatalysis was active. This means that the crystallinity a factor of the highest transmittance
- plays a more significant role in the photodecomposition reaction. However, one can suggest
that there could be an optimal annealing temperature that enables TiO2 be the best in both the
optical property and the roughness for the photo-catalysts. In this work, the annealing
temperatures chosen were not higher than 450C, because of the low heat-resistant ability of
glass substrates.
In case of AgNO3 doping, although the crystalline structure of the doped TiO2 was not changed in
comparison with that of a pure TiO2, it can not be attributed to the substitution doping of nitrogen or
silver atoms into the TiO2 lattice. Indeed, during spraying and annealing the thermal decomposition
of AgNO3 occurred according to the scheme [13]:
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Transmittance (%)
92
90
TiO2 : 6.4%N
88
TiO2 : 3.2%N
TiO2 : 8.0%N
86
TiO2: 9.6%N
84
82
TiO2: 1.6%N
80
78
76
50
100
150
200
250
Time (min)
Fig. 3. Photo-catalys treatment of MB solution vs. doping AgNO3 concentration.

Transmittance spectra at wavelength 425 nm.
AgNO3 Ag 2 O + N 2 Ag
(2)
To dope with nitrogen into TiO2, the last was grown by controlled oxidation of Ti metal under
vacuum conditions and doped with nitrogen by N+ bombardment [9], or by treating anatase TiO2
powder in NH3 atmosphere at 6000C [10]. However, with the AgNO3 doping the enhancement of
the visible-active photocatalytic activity was also obtained (Fig. 3). By using a visible light
source, the MB solution with Ag-TiO2 sample filled in was illuminated for 4 h, the transmittance
of the MB solution increased vs. the concentration of AgNO3. Below a concentration of 6.4%M,
photocatalysis efficiency increased with the increase of the dopants concentration. Continuously
raising the dopant concentration has caused the decrease of the visible-active photocatalysis
efficiency. This enhancement in photocatalytic activity can normally be attributed due to the
silver doping in TiO2 crystalline lattice. But, as reported in [13], the radius of Ag+ ions (0.126 nm)
is much larger than that of Ti4+ (0.068 nm) and so the Ag+ ions could not enter into the lattice of
anatase phase. During annealing, these uniformly dispersed Ag+ ions would gradually migrate
from the volume of the TiO2 to the surface by enhancing their crystallinity. Electron transfer
from conduction band of TiO2 to the metallic silver particles at the interface is possible, because
0.3
TiO2/Glass
TiO2/Quartz sand
TiO2/QS
85
Ag-TiO2/glass
TiO2/glass
75
A bsorption
Transmitance (%)
95
0.2
0.1
MB
65
0
55
0
300
350
400
450
500
550
600
Wavelength (nm)
Fig. 4. Transmittance spectra of MB before (the

first curve from bottom) and after being treated by
TiO2/glass for 4h (the second from bottom), AgTiO2 for 4h (the third from bottom) and TiO2/QS
for 30 min (top).
50
100
150
200
250
Time (nm)
Fig. 5. The comparison of photo-catalys

treatment of MB solution using TiO2/glass
(top) and TiO2/quartz-sand (bottom).
Sunshine irradiation at noon and outdoor
temperature of 40oC.
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the Fermi level of TiO2 is higher than that of silver metal [14]. This results in the formation of
Schottky barrier at the AgTiO2 contact region, which improves the photocatalytic activity [15].
Since the amount of silver atoms introduced into the TiO2 is so small that the structure of the last
is unchanged. Thus this case can be not seen as a substitution doping, however as accepted in
almost references it is also referred to Ag-doped TiO2 [13].
To compare the photocatalytic activity of nc-TiO2 coated on glass and on quartz sand, these
samples were filled by MB solution in glass trays and put under sunshine irradiation at the
outdoor temperature of 40oC. Transmittance plots of these treated MB solutions are showed in
Fig. 4. From this figure one can see that for the same irradiation time (e.g. 4h) the MB solution
treated by the Ag-TiO2 sample (6.4% of AgNO3) possessed much higher transmittance than the
one treated by pure TiO2. However the best photocatalytic treatment was obtained for TiO2/QS
powders, although the last was not doped with either silver or nitrogen.
A clearer comparison can be seen in absorption spectra plotted in Fig. 5. A much rapid
photocatalytic treatment of TiO2/QS in comparison with that of TiO2/glass can be explained by
two factors as follows: (i) the large surface area of the nc-TiO2-coated sand could be irradiated
with the MB solution and (ii) when the quartz sand was coated by TiO2, numerous
interfacesbetween TiO2 and SiO2 were formed and these interfaces acted as potential barriers for
the carriers photo-generated in the TiO2 and the photo-generated species pass through the SiO2
overlayer depending on the SiO2 film properties. The similar result was obtained for a system of
two oxides as TiO2/SnO2 reporting in [8].
4. Conclusion
By using spray pyrolysis method nc-TiO2 and AgNO3 doped films on glass substrates were
prepared. Nc-TiO2 films on quartz sand (TiO2/SiO2) were synthesized by a sol-gel method,
followed by an annealing treatment. The influence of both the annealing temperature and doping
concentration on photocatalytic activity of the films was investigated. The optimal annealing
temperature for photo-catalys performance was found to be of 450oC, and the most suitable Agconcentration for Ag-TiO2/glass was obtained in the case of 6.4% AgNO3 embedded in the initial
spay solution. Photocatalytic efficiency of TiO2 coated on quartz sand was significantly large.
This was explained due to a large surface area of the nc-TiO2 being irradiated with the MB
solution and numerous interfaces TiO2/SiO2 which acted as potential barriers for the carriers
photo-generated in the TiO2. This suggests an application of nanocrystalline TiO2 films in
photocatalytic treatments for polluted water and air in the environment.
Acknowledgments: This work was supported in part by Vietnam National Foundation for Basic
Scientific Research in Physics (2006-2008) under Projects No. 410306 and No. 405606. One of
the authors (N.N.D) expresses his sincere thanks to the AS-ICTP (Trieste, Italy) for the senior
associate financial support, permitting the completion of the manuscript for this paper during his
stay in Trieste from June 30 to August 13, 2008.
References
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4.
5.
Fujishima, K. Honda, Nature 238, 38 (1972)

Fujishima, K. Hashimoto, T. Watanabe, TiO2 Photocatalysis: Fundamentals and
Application, BKC Inc, Tokyo, 1999.
R. Wang, K. Hashimoto, A. Fujishima, M. Chikuni, E. Kojima, A. Kitamura, M.
Shimohigoshi, T. Watanabe, Nature 388, 431 (1997)
N. Sakai, A. Fujishima, T.Watanabe, K. Hashimoto, J. Phys. Chem., B 107, 1028 (2003)
Fujishima, X. Zhang, Titanium dioxide photocatalysis: present situation and future
approaches, C. R. Chimie 9, 750 (2006).
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1373089 (20021009).
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Thin Solid Films 502, 125 (2006).
H. Ohsaki, N. Kanai, Y. Fukunaga, M. Suzuki, T. Watanabe, K. Hashimoto, Thin Solid
Films 502, 138 (2006).
E.C.H. Sykes, M.S. Tikhov, R.M. Lambert, J. Phys. Chem. B, 106, 7290 (2002).
T. Morikawa, Y. Irokawa, T. Ohwaki, Applied Catalysis A: General 314, 123 (2006).
S. Sakthivel, M. Janczarek, H. Kisch, J. Phys. Chem. B 108, 19384 (2004)
D. Cullity, Elements of X-ray Difraction, 2nd ed. (Addison-Wesley Publishing Company,
Inc., Reading, MA, 1978), p. 102.
M. K. Seery, R. George, P. Floris, S. C. Pillai, J. Photochem. Photobiol A: Chemistry 189,
258 (2007).
Sclafani, J.M. Hermann, J. Photochem. Photobiol. A 113, 181 (1998).
V. Iliev, D. Tomova, L. Bilyarska, A. Eliyas, L. Petrov, Appl. Catal. B 63, 266 (2006).
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EFFECTS OF THERMAL TREATED ENVIRONMENT ON SOME PROPERTIES OF

COBALT-DOPED ZINC OXIDE FABRICATED BY SOL-GEL.
P.V.Hai, V.T. Thu, P.D. Chung, N.D.Lam, N.T.Khoi and L.H.Hoang
Faculty of Physics, Hanoi National University of Education
Abstract: We present structural, optical and magnetic properties of at x.% ZnO:Co (x max = 10)
grown on glass substrates in air, vacuum and nitrogen gas using sol-gel technique. Thin films are
polycrystalline in nature having wurtzite structure and a tendency of growth of (002) reflection
with both pure and doping. Annealed environment have no notable effect on the absorption
spectra, which show clearly replacing zinc ions of cobalt ions. In contrasly, it changes sharply
luminescence spectra, which imply oxygen vacancies absence of thin films prepared in nitrogen
gas.The magnetization curves show a strong reduction of saturate magnetization as one fabricated
thin films in nitrogen gas. This result is in agreement with theoretical predictions assumed
defects, for instance oxygen vacancies, have contributed signally to raise ferromagnetism of
diluted magnetic semiconductor.
Keyword: diluted magnetic semicondutor, ZnO, spin-coating
1. Introduction
Because of the complementary properties of semiconductor and ferromagnetic material
systems, a growing effort is directed toward studies of diluted magnetic semiconductors (DMS).
DMS are refered by randomly replacing some fraction (some or tens percents) of the host atoms
in a semiconductor with magnetic elements. Applications in sensors, memories, as well as for
computing using electron spins can be envisaged[1]. Spintronics is origined from the the
possiblity to control both charge and spin when spin is polarised in DMS[2]. The important
challenge of material science to understand the ferromagnetism in DMS and to develop multifunctional semiconductor systems[3] with the Curie temperatures exceeding comfortably
(perfectly) the room temperature(RT).
As a II-VI oxide-DMS, transition metal-doped ZnO has currently drawn considerable
attention because of some theoretical predicts of the possibility of above room temperature
ferromagnetism in ZnO-based DMS. Many works[4,5,6,11] reported ferromagnetism of ZnO:Co
thin films is origined replacing zinc ions of cobalt ions in tetrahedron field. Bao Huang etal. [7]
reported ferromagnetic features with Curie tempeature above RT in ZnO:Co thin films fabricated
by submolecule-doping technique is resulted from oxygen vacancies. The ferromagnetism was
observed in several articles actually originated from the second phases formed during the
growth[8]. These controversial results raise questions about the intrinsic nature of magnetism in
ZnO:Co. To clear the controversy around ferromagnetism in Co-doped ZnO the choice of sample
preparation procedure therefore is of crictical importance (keystone). There are many methods to
fabricate ZnO:Co such as laser pulsed deposition [4,8], solgel [5,11], submolecule-doping
technique [7], sputtering [9] The ideal preparation procedure should be: the one that can drive
the doped magnetic ions into substitutional site and have atomic scale randomly mixing with host
atoms without formation of second phases such as magnetic nanoparticles, clusters, and
precipitates. Sol-gel is an ideal technique that can meet these requirements. Since the radius of
the Co2+ ions in tetrahedral coordination (0.58A0) is very close to that of Zn2+ ions (0.6A0)[3],
the cobalt ions should preferentially occupy substitutional Zn sites.
In this report, we investigate the effect of thermal treated environment on some physical
properties of cobalt-doped zinc oxide fabricated by sol-gel.
Nhng
tin b trong Quang hc, Quang t, Quang ph v ng dng
9/2008, Nha Trang, Vit Nam
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2. Experimental details
Pure ZnO and x at.% ZnO:Co thin films were fabricated by sol-gel process. Table 1 shows list
of fabricated specimens. Zinc acetate dihydrate and cobalt acetate four-hydrate were first
dissolved in a ethanol solvent at room temperature, added diethanol amine (DEA) as stabilizer.
The molar ratio of DEA to metal salts as kept at 1.0 and the total concentration of metal salts was
0.5 mol/l. The mixture was stirred at te temperature of 65C and the velocity of 600 rpm. That
yielded a clear and homogeneous solution, which served as coating solution after stirring at room
tempeature for 10h. The gel films were realised by spin-coating this solution on Laimann glass
substrates at a rate of 3000rpm for 45s. After each coating, the films were pre-heated at 300C for
10min to evaporate the solvent and remove organic residuals. The deposition were repeated 10
times until the thickness of films reaches 500nm. Finally, all the ZnO:Co films have been treated
at 500C for 4h in air, vacuum or pure nitrogen gas.
Table. 1. List of fabricated specimens.
No.
1
2
3
4
5
6
7
8
9
Name
K0
N0
C0
K5
N5
C5
K10
N10
C10
Doping content (%)

0
0
0
5
5
5
10
10
10
Annealed environment
air
N2
vacuum
air
N2
vacuum
air
N2
vacuum
X-ray diffraction data are collectted by a D5500 Siemens diffractometer equipped with a
radiated source CuK =0.15460nm. The surface morphology of the film was evaluated by mean
of scanning electron microscopy (SEM. Ultra Violet visible spectrum and photoluminescence
spectrum were carried to investigate optical properties. The ferromagnetism of films was
quantitatiely determined by vibrating sample magnetometor (VSM).
3. Results and discussion
Fig. 1(a) shows the X-rays diffraction data of the pure film annealed at 500C in air . There
are five peaks localed at 2 =31.870 ,34.510, 36.350,46.160, 55.970 matched with standard
hexagonal wurtzite structure of ZnO. The intensity of peak (002) is very larger than that of peak
(101) means film is oriented (002). Fig. 1(b,c,d) shows the X-rays diffraction data of the cobalt
doped zinc oxide films for various contents: 5%(b), 7%(c), 10%(d). Many works [13,14]
reported that cobalt ions could substitute in zinc ions site in tetrahedron coordination until
content is under 10%. In this report, maximum content were choosen is 10. As pure film, there
are no second phase, all films crystalised well and was oriented (002). In conclusion, there are no
considerable effect on crystal structure of ZnO phase unti doping content is 10%, all patterns
show the single-phase hexagonal wurtzite structure with well-oriented (002) texture.
The average crystal diameter is evaluated from Scherer formular. Fig. 2 shows the content
reduction of the crystal diameter.
The morphology analysis of ZnO0.95Co0.05 film prepared by solgel technique was studied
using scanning electron microscopy (SEM). Fig. 4 shows the SEM photograph for the
ZnO0.95Co0.05 film. The crystallized film is composed of almost mono-dispersed superfine ZnO
nanoparticles; their average diameters are estimated to be 10-50nm, larger than X-ray data.
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400
15.5
350
15.0
14.5
Crystal diameter(nm)
300
Intensity
250
d)
200
c)
150
b)
100
50
a)
14.0
13.5
13.0
5
12.5
12.0
11.5
11.0
10
10.5
10.0
9.5
20
30
40
50
60
Fig.1. X-rays diffraction of ZnO:Co films at

various content.
Fig. 5 shows the optical absorbtion spectra of

the pure film (a) prepared in air and doped films at
5%(b), 7%(c), 10%(d). All of the film exhibited a
transmission of higher than 80% in the visible
region with a sharp fundamental absorption edge.
Optical band-gap of the samples is varying,
depending on the Co doping concentration, from
3.26eV for undoped ZnO films to 3.10eV for cobalt
doping (5%). In general, the red shift of the
absorption onset of Co doped thin films is
associated with the increase of number of impurity
energy levels in bandgap, in contrastly with the
-1
10
11
Doping content (%)
Fig.3. Doping content dependence of

crystal diameter.
Fig.4. SEM of ZnO0.95Co0.05 thin film

fabricated in air
2.0
Intensity (%)
1.5
1.0
K0
0.5
K5
0.0
K1
-0.5
400
500
600
700
800
Wavelength (nm)
Fig.5. Absorption spectra of Zn1-xCoxO with x=0(a); 0.01(b); 0.05(c).
Burstein-Moss effect[15]. The red shift of Eg with Co doping has already been observed and
explained due to sp-d exchange interactions between the band electrons in ZnO and the localized
d electrons of the Co 2+ [6].
The filled curves are assigned as typical d-d transitions of high spin states Co 2+ 3d7 (4F) in a
tetrahedral oxygen coordination. In its neutral charge state, the Co ions has an [Ar]3d 7 electron
configuration. The atomic ground state 4F splits under the influence of the tetrahedral component
of the crystal coordination into 4A2 ground state and 4T1+ 4T2 excited states.The smaller
trigonal distortion and spin orbit interaction split the ground state into E 1/2 +E3/2. The absorption
4
4
2
2
around 660, 609, and 562 nm in the visible range was derived from separately A2 ( F ) A1 ( G) ,
4
4
2
T1 ( 2G) transitions of tetrahedrally coordinated Co 2+[6]. These absorptions
A ( F)
T ( P) , A2 ( F )
4
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are ascribed to the charge-transfer transitions between donor and acceptor ionization levels
presumably located within the band gap of the host ZnO.
0.8
5%
0.6
Intensity (a.u)
The effect of cobalt doping on optical property

of ZnO:Co thin films has been studied. Fig. 6
shows the optical absorbtion spectra of
ZnO0.95Co0.05 film prepared in various
environment: air, vacumum, nitrogen. Two last
show a blue shift, about 20nm. In comparation
with the air, nitrogen and vacuum environment
restricted impurities better.
0.4
0.2
a
b
0.0
400
500
600
700
800
Wavelength (nm)
Luminescence spectra of pure (a) and at 5% (b)

thin films grown in air are shown on Fig. 7 Fig. 6. Absorption spectra of ZnO0.95Co0.05 prepared
in air(a), vacuum(b), nitrogen gas(c).
(substracted basic line). There are two peaks.
The first located at 382nm, corresponds
3.25eV, is origined from exciton of ZnO.
The second corresponds green wavelength, spreaded from 490 to 630 nm, located at 547nm. The
origin of this peak is still a argument[6,7,9,10], but the most common hypothesis is in agreement
with oxygen vacancies[7,9]. The increase of its relative intensity indicated the increase of
vacancies with doping.
6000
6000
5%
4000
b)
a)
a)
4000
Intensity (a.u)
Intensity (a.u)
5000
2000
b)
3000
2000
c)
1000
0
300
400
500
600
700
800
900
Wavelength (nm)
300
400
500
600
700
800
900
1000
Wavelength (nm)
Fig.7. Photoluminescence spectra of ZnO(a) and

ZnO0.95Co0.05 prepared in air
0.08
0.04
Mmen t M (memu/cm2)
t ha M (memu/cm2)
0.06
K10
K5
0.08
5%
0.06
0.003
K5
0.000
-0.003
0.02
-100
100
K0
T trng H (Oe)
0.00
-0.02
-0.04
Magnetization (memu/cm2)
0.10
Fig.8. Photoluminescence spectra of ZnO0.95Co0.05

prepared in air(a), vacuum(b), nitrogen gas(c).
0.04
0.02
0.00
-0.02
-0.04
-0.06
-0.08
-0.06
-0.10
-0.08
-6000
-0.10
-6000
-4000
-2000
2000
4000
6000
-4000
-2000
2000
4000
6000
Magnetic field intensity (Oe)
T trng H (Oe)
Fig.9. The M-H curve magnetic field dependence

of magnetization of Co-doped ZnO films was
measured at 300K showed hysteresis loops with
doping concentration of
0%(K0),5%(K5) and 15%(c).
Fig.10. The M-H curve magnetic field dependence

of magnetization of Co-doped ZnO films prepared
in air(a), vacuum(b), nitrogen(c) was measured at
300K showed hysteresis loops with doping
concentration 5%.
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Fig. 9 shows magnetization curves of ZnO (a), and ZnO:5%Co (b), ZnO:10%Co(c). In fact,
ZnO is paramagnetic and ZnO:Co is ferromagnetic. Saturation magnetization increases with
doping content.
4. Conclussion
ZnO:Co thin films were prepared by sol-gel method at x.% (xmax=10). X-ray diffraction
data indicated that all prepared films crystallised at wurtzite structure and cobalt ions have
replaced perfectly in zinc ions site. SEM showed that nanoparticles distributed homogeneously
and their dimension are about 10 50nm.
Absorb spectrum was denoted that at 5.% ZnO:Co, cobalt ions have replaced best in zinc
ions site. We have also observed three trasition between energy levels of cobalt ions in tetrahedra
4
4
A ( F)
2
A ( G)
4
A ( F)
4
T ( P)
4
A ( F)
2
T ( G)
1
1
1
coordination: 2
, 2
, 2
at wavelength of 562 nm, 609
nm, 660 nm, repectively. Photoluminescence has ensured that, oxygen vacancies of films that
prepared in vacuum less than air and in nitrogen gas reduced strongly.
The magnetization curves show that all prepared films have ferromagnetism. The minimum
saturation magnetization was found at 5.% ZnO:Co fabricated in nitrogen atmosphere. We have
seen that from the analysis of the magnetization data that indirect exchange interaction between
moments through intrinsic carriers, formed by oxgen vacancies, is the dominant mechanism for
the exchange coupling between Co ions in ZnO:Co thin films. This mechanism has contributed
notably to ferromagnetism of thin films. The exact value of the effective exchange integral has
not been denoted yet.
Films that fabricated in nitrogen gas have best structure, but their ferromagnetism is less than
desiderated results. Unfortunately, best structures havent been best candidates for spintronics.
References
1. Tomasz Dietl, Semicond. Sci. Technol. 17 377-392
2. S.J.Pearton, D.P.Norton, K.Ip, Y.W.Heo, T.Steuner; Superlattices and Microstructures,
Vol.32 (2001) 3-32.
3. Claudia Felser, Gerhard H.Fecher, Benjamin Balke; Angewante Chemie, 46 (2007) 688-699.
4. C.B.Fitzgerald, M.Venkatesan, J.G. Lunney, L.S.Dorlenes, J.M.D Coey, Materials Science,
247 (2005) 493 496.
5. Hyeon-Jun Lee, Se-Young Jeonga; App. Phy. Lett. 81 (2005) 21-25
6. Xue-Chao Er-Wei Shia, Zhi-Zhan Chena, Hua-Wei Zhanga, Li-Xin Songa, Huan Wangc,
Shu-De Yaoc; Solid State Communication, 296 (2006) 135140.
7. Bao Huang, Deliang Zhu, Xiaocui; Sience Direct; App. Surf. Sci, 253 (2007) 6892-6895.
8. Jung H.Park, Min G.Kim, Hyun M.Jang, Sang woo Ryu, Young M.Kim; App. Phy. Lett.;
Vol. 84 (2004) 13381441.
9. Bixia Lin and Zhuxi Fu; App. Phy. Lett.; Vol. 79, number 7 (2001).
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OPTICAL PROPERTIES OF Zn1-x-yCoxCuyO

Nguyen Thi Thuc Hien, Nguyen Chi Thanh, Ngo Thanh Dung, Ngo Xuan Dai
Faculty of Physics, Hanoi University of Science, VNU Hanoi
334 Nguyen Trai Road, Thanh Xuan, Ha Noi
E-mail: hienntt@vnu.vn
Abstract: Zn1-x-yCoxCuyO (x=0.0050.05, y=00.02) powders have been prepared by Sol-gel
method starting from Zn (NO3)2, Co (NO3)2 and Cu (NO3)2. Raman spectra showed that for y=0,
x=0.0050.05 and x=0.05, y<0.01, no new phase was formed except ZnO. When y>0.01, a new
phase appeared. Photoluminescence (PL) spectra were measured by excitation at 335 nm and 600
nm. The peak position of the 690 nm PL band for Zn1-xCoxO excited by the wavelength of 600
nm was red- shifted with the increase of x. When Cu (y=00.02) was added into Zn1-xCoxO
(x=0.05), 690 nm PL band was blue-shifted with the increase of y. The reasons of the shifts were
investigated.
Keywords: Co, Cu doped ZnO, Photoluminescence
1. Introduction
Diluted magnetic semiconductors (DMS) have attracted much interest in recent years
because of the possibility involving charge and spin degrees of freedom in a single substance.
DMS are also expected to play an important role in magnetical and magneto-optical fields by
realizing new functionality that has not separately existed in magnetic materials or
semiconductors. Among DMS, ZnO is a candidate due to suggestion of having a high Tc and
large magnetization [1].
Recently, Spandil [2] theoretically showed that doping Mn or Co could not result in
ferromagnetism (FM) in ZnO, except if adding holes to stabilize the ferromagnetic state. This is
why there were several reports announced co-dope Mn or Co with Cu in ZnO in order to bring
out some good candidates [3].
The ferromagnetic properties of our Zn1-x-yCoxCuyO samples were investigated in [4]. In
this work, we performed luminescence experiments on these samples to probe the electronic
structure of Co2+, Cu2+ in the host and the possibility of formation of a Co2+, Cu2+ related d-band
within the band gap of ZnO. Knowledge of the electronic structure of Co2+, Cu2+ in ZnO may
improve the understanding of the mechanism inducing high-temperature ferromagnetism.
It is known that the PL band at about 690 nm is typical for ZnO: Co . The red shift of the band
with the increase of cobalt concentration often occures, but to our knowledge it seems no
discussion on that. Moreover, by adding Cu into ZnO: Co we revealed that the 690 nm peak had
an opposite tendency (blue shift) with the increase of the Cu concentration. In this report we
would like to discuss these two effects.
2. Experiments
Zn1-x-yCoxCuyO (x=0.0050.05, y=00.02) powders were prepared by Sol-Gel method. The
precursors were Zn(NO3)2, Co(NO3)2, and Cu(NO3)2. The purity of the chemical was 99.5 %
(Prolabo).
For preparing ZnO:Co, Zn(NO3)2 and Co(NO3)2 were mixed with a desirable composition of
at%. The solution was magnetically stirred at 70 oC. Then, acid citric and NH4OH with pH >7
were added to the starting solution. The solution was heated at 700C for 20 h and then at 3000C
for drying. The samples were annealed at 5000C and 6000C for 30 min. to be formed ZnO:Co
powders. The atomic concentrations of Co were from 0.5 to 5 at%.
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For preparation of ZnO:Cu, an amount of 1M of Zn(NO3)2 and 0.2M of Cu(NO3)2 were chosen.
We followed the procedure similar to that of ZnO:Co.
For co-doping Co and Cu, an amount of 1M, 0.2M and 0.2M of Zn(NO3)2, Co(NO3)2 and
Cu(NO3)2, respectively, were used. Co-doping Cu was prepared for only ZnO:Co with 5at%. The
Cu concentrations were 0.2, 0.5, 1 and 2 at%.
The crystalline phase and crystal structure of ZnO and the impurity-doped ZnO powders
were determined by Brucker D5005 X-ray diffractometer using CuK radiation (=1.54 ) and
Renishaw
invia micro Raman instrument. The photoluminescence spectrum (PL) and
photoluminescence excitation spectrum (PLE) was collected by Jobin-Yvon FL3-22
spectrometer using a xenon lamp of 450 W.
(101)
(102)
(103)
1. y=0.005
2. y=0.01
3. y=0.02
(110)
(100)
(103)
(110)
(102)
Zn0.95yCo0.05Cu yO
(002)
Zn1-xCoxO
1. x=0.005
2. x=0.05
(002)
(100)
(101)
The result from DSC-TGA spectrum (not shown here) showed that, from 4500C, no reaction,
no decrease of weight of the sample occurred, so the ZnO: Co, Cu samples in this report were
annealed at 5000C and higher.
The XRD patterns for Zn1-xCoxO (x=0.0050.05) showed that the ZnO powders have a
wurtzite structure and no new phase appeared. The XRD patterns for x=0.005 and x=0.05 are
shown in Fig.1
Fig.2. XRD patterns for Zn0.95-y Co0,05CuyO

(y= 0.005;
Fig.1. XRD patterns for Zn1-xCoxO

( x=0.005 and 0.05)
0.01; 0.02)
Table 1: The lattice constants of Zn1-xCoxO and Zn1-x-yCoxCuyO
Zn1-xCoxO
Zn1-xCoxO
Zn1-xCoxO
Zn1-x-yCoxCuyO
Zn1-x-yCoxCuyO
0.00
5
0.02
5
0.05
0.05
0.05
0.00
5
0.01
2
(100)
31.758
31.749
31.754
31.749
31.744
Zn1-x-yCoxCuyO
0.05
0.02
31.750
2
(100)
34.421
34.416
34.420
34.421
34.415
a
[]
3.2508
3.2517
3.2512
3.2517
3.2522
c
[]
5.2067
5.2074
5.2068
5.2067
5.2075
34.418
3.2516
5.2071
When Cu was co-doped, it was shown by XRD patterns that for x=0.05 and y ranging from
0.005 to 0.02, the structure was also ZnO wurtzite and no new phase occurred (Fig.2). From
XRD patterns, the lattice parameters were calculated. The results are shown in table 1. The
results in the table 1 show that, for Zn1-xCoxO and Zn1-x-yCoxCuyO, the parameters a and c
changed little with x and y. Besides, by analyzing Raman scattering spectra we saw that for
y=0.005, the Raman spectrum was not different from y=0. This is shown in Fig.3.
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Fig.3. Raman spectra for Zn1-x-yCoxCuyO

(x=0.05;y=0 and 0.005)
Fig. 4. Raman spectra for Zn1-x-yCoxCuyO (x=0.05;

y=0.005, 0.01 and 0.02)
From y=0.01, the Raman spectra showed that a new phase occurred (Fig.4), though the XRD
did not revealed. This shows that in our case, the Raman analysis gives more sensitive results
than XRD one. The new phase may be spinel ZnCo2O4 because the peaks 486, 525, and 684 cm-1
in the Raman spectra are similar to ZnCo2O4 peaks [5].
Fig.5 shows room temperature photoluminescence spectra (PL) for Zn1-xCoxO (x=0.025) samples
annealed at 6000C, excited by the wavelength of 335 nm.
Fig. 5. PL spectra of Zn1-xCoxO ( x=0.025) excited by

the wavelength of 335 nm
Fig. 6. PLE spectra of Zn1-xCoxO

( x=0.025)
It is seen from Fig.5 that by the edge band excitation, there are two principal bands of
emission. The first one is UV band at 380 nm and the second band at the visible range. The first
one is well known as an exciton recombination . The second band was attributed to the emission
of charge transfer as Co2+(d7) + hCo3+(d6+)+e-cb [6]. The mechanism is that, the liberated
conduction electron could be recaptured by the photoionized Co3+ via excited Co2+ states which
then returns radiatively to the Co2+ ground state. The PLE spectrum in Fig.6 showed clearly the
charge transfer, as there is a edge absorption at 372 nm.
Zn1-xCoxO samples were also excited at 600 nm. Each emission spectrum has a wide band
localized at about 690 nm, as shown in Fig.7. The emission peak at 690 nm (it is denoted as
CoB) was interpreted as a mixed 4T1(P), 2T1(G),2E(G)4A2(F) transition between cobalt d-levels
incorporated in the ZnO host [7]. The PLE spectrum of Zn0.75Co0.25O for the 690 nm emission is
shown in Fig.8.The absorption peaks from this spectrum are attributed to the transitions from 4A2
(F) to 4T1(P), 2T1(P),2E(G) and 2A1(G) [7]. It is clearly seen from Fig.7 that, the more cobalt
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concentration is, the less emission intensity is and the peak position is red shifted. The peak
position shift versus the cobalt concentration for the Zn1-xCoxO samples is shown in Fig.9a. It is
seen from Fig.9a that the shift is monotone to the cobalt concentration. It is complicated to
clarify this red-shift. There would be three possibilities leading to the red shift. First, 690 nm
band (CoB) measured at 4.2 K [6] at an improved resolution with the transmission spectrum was
Fig.7. PL spectra for Zn1-xCoxO powders excited by

the wavelength of 600 nm
Fig.8. PLE spectrum of Zn1-xCoxO for the emission

band of 690 nm (x=0.025)
8000
a
6000
Intensity(Cps)
Peak Position (nm)
692
688
684
Zn1-xCoxO
Zn0.95-yCo0.5CuyO
C4721
a: x=0.05
y=0.002
C4321
b: x=0.05
=0.005
C4421
c: x=0.05
y=0.01
d: x=0.05
y=0.02
C4621
a
b
c
d
4000
2000
680
0
Dopant Concentration (%)
Fig. 9. Peak position and dopant concentration
640
660
680
700
720
740
Wavelength(nm)
Fig.10. PL spectra for Zn1-x-yCoxCuyO powders

excited by the wavelenght of 600 nm
an emission doublet, one of that in shorter wavelength is subject to self-absorption by Co2+

internal transitions. So only the low-energy line is displayed in the emission. This may be the
reason of the red shift as the cobalt concentration increasing. However, the splitting of the
emission doublet is only 0.7 meV, while the highest shift in our case was 13 meV, so we rule
out this case.
Secondly, as mentioned in [7], the red shift of the band gap of ZnO:Co was due to the sp-d
exchange. It would cause the shift of the 690 nm band. In our case, this reason was also ruled
out because the CoB is the internal transition in cobalt ions. Finally, according to our opinion, it
could be related to Co2+ pairs. The presence of Co2+ pairs had earlier been shown from EPR
spectra [8] and discussed in [9]. Here we would explain the red shift like the case of ZnS:Mn. In
ZnS:Mn, two zero-phonon lines appear at the PL spectrum at low temperatures. These two zerophonon lines are ascribed to the transition in a single Mn2+ ion and an Mn2+-Mn2+ pair
respectively. In this material, the luminescence band shift to longer wavelength with increasing
Mn2+ concentration. These effects are attributed to Mn2+-Mn2+ interactions. We suppose that this
pair model is also available for our ZnO:Co samples.
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The explanation of the blue shift of the CoB in Zn1-x-yCoxCuyO (Fig.9b and 10) seems to be
more complicated than the red-shift in Zn1-xCoxO. We can say that co-doping Cu into ZnO:Co
makes a reducing of the symmetry of Co2+ sites. This leads to the shift of the emission peaks
corresponding to the inner transition of Co2+ ions. The reason also may concern with the new
spinel phase ZnCo2O4. As seen in Fig 4, when the cobalt concentration increases, the new spinel
phase appears. So Co2+ ions can occupy not only tetrahedral but also octahedral sites. This means
the crystal field increases and led to the blue shift as shown by Tanabe-Sugano diagram for d7
configuration [10].
4. Conclusion
Zn1-x-yCoxCuyO (x=0.0050.05; y=00.02) powders have been successfully prepared by the
sol- gel method. The XRD patterns of the samples showed that the powders have wurtzite
structure with lattice constants little changing with the dopant concentrations and no new phase
appeared. The Raman spectra showed that for x=0.05 and y> 0.01 there a new phase appeared.
The new phase may be spinel ZnCo2O4. The red shift of the 690 nm PL band of Zn1-xCoxO was
explained as the Co2+-Co2+ pairs. The blue shift of this band when co-doped with Cu is supposed
to be with the reduce of the symmetry of Co2+sites.
Acknowledgments
Authors would like to thank the Center for Materials Science, Hanoi University of Science for
permission to use XRD and PL equipments.
This work was supported by the National Fundamental Research Program, Grant No. 4 063
06.
References
1. T. Dietl, H. Ohno, F. Matsukura, J. Cibert, D. Ferrand, Science 287 (2000) 1019
2. N. A. Spandil, Phys. Rev. B 69 (2004) 125201
3. Hung-Ta Lin, Tsung- Shune Chin, Jhy-Chau Shih, Show-Hau Lin, Tzay-Minh Hong, RongTan Hoang, Fu-Rong Chen, and Ji-Jung Kai, Appl. Phys. Lett. 85 (2004) 621
4. Ngo Thanh Dung, Nguyen Chi Thanh, and Nguyen Thi Thuc Hien, Ferromagnetic properties
of Zn1-x-yCoxCuyO powders prepared by Sol-Gel method. Proceeding of the Eleventh
Vietnamese-German Seminar on Physics and Engineering, Nha Trang, from March, 31, to
April, 5, 2008, 274
5. K. Samanta, P. Bhattacharya, R. S. Katiyar, W. Iwamoto, P. G. Pagliuso, and C. Rettori,
Phys. Rev. B 73, (2006) 245213
6. H. J. Schulz, M. Thiede, Phys. Rev. B 36 (1987) 19
7. P. Koidl, Phys. Rev. B 15 (1977) 2493
8. T. L. Estle and M. De Wit, Bull. Am. Phys. Soc. 6 (1961) 445
9. Stephan Lany, Hannes Raebiger, and Alex Zunger, Phys. Rev. B 77 (2008) 241201(R)
10. Shigeo Shionoya, William M. Yen, Phosphor handbook, CRC press, 1998
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FABRICATING AND STUDYING STRUCTURE,

OPTICAL PROPERTIES OF ZnO NANORODS
Nguyen Thuy Linha, Do Thi Sama, Nguyen Huy Danb
a)
b)

Institute of Materials Science, Vietnamese Academy of Science and Technology
Abstract: ZnO nanorods are prepared by the low temperature aqueous solution method. The
morphology of ZnO nanorods depends on the fabrication conditions such as the precursor
concentrations and the deposition temperature. Scanning electron microscopy observations reveal
that ZnO nanorods are well formed with 0.02M concentration at 80oC. The diameters of nanorods
are from 200 to 900 nm. X-ray patterns show that all the samples are ZnO single phase. The
absorption spectra show that the energy gap Eg of the samples increases from 3.2 to 3.25 eV
when the precursor concentration increases. The effects of the precursor concentration and the
deposition temperature on photoluminescence (PL) and raman scattering spectra properties are
also studied and discussed.
Keywords: ZnO nanorods, precursor concentration, deposition temperature, photoluminescence
(PL), raman scattering.
1. Introduction
The Zinc oxide is a direct band gap (~3.3 eV at room temperature), transparent
semiconductor having a high exciton binding energy about 60 meV. Therefore, they have a lot of
applications in optoelectronic and functional materials. In recent years, the semiconductor
nanostructures are studied intensively because of their interesting dimensional effects and
potential applications [1-10]. One-dimensional (1-D) structures, such as nanowires, nanorods,
nanotubes have remarkable attention due to their applications in data storage, advanced catalyst,
photoelectronic devices 1-D ZnO nanomaterials are attracted extensive interests. Especially,
UV-nanowire laser under optical excitation in ZnO was realized at room temperature by Huang
et al. in 2001 [7].
Various methods are used for fabricating (1-D) ZnO structures, they can be grouped in two
main categories: high-temperature techniques, such as chemical vapor deposition, pulsed-laser
deposition and thermal evaporation which the growth temperature is higher than 400oC, and
chemical solution methods at low temperature around 100oC [2]. The methods at low
temperature are usually simple and high effect. In this report, we fabricate ZnO nanorods by an
aqueous solution deposition method. The influence of precursor solution concentration and
deposition temperature on morphological, structure and optical properties are studied and
discussed.
2. Experimental
Zn(NO3)2.6H2O and C6H12N4 were dissolved in high-purity water with molecular ratio 1:1
and solution concentrations 0.01 M, 0.02 M, 0.04 M, 0.06 M. The cleaned Si (111) substrates
were placed in the bottom of a glass cup containing the solution. The deposition process was
carried out at 80oC for 5 hours in an oven. The products obtained on the substrates were rinsed
with high-purity water and then dried at 100 oC.
To study structure and properties, scanning electron microscopy (SEM) was employed to
examine the morphology of the product. The crystal structure of the samples was characterized
by x-ray diffraction (XRD) using copper K radiation. Photoluminescence (PL) was also used to
characterize the emission spectra of ZnO samples excited by the 350 nm wavelength from a He-
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Cd laser. The Raman scattering spectra were measured by a Labram B100 Ramanscope under
the excitation of He-Ne laser. All measurements were taken at room temperature.
Figure 1 shows the XDR patterns of the 0.01 M, 0.02 M, 0.04 M and 0.06 M samples at
80 C deposition temperature. All diffraction peaks, except the one of Si (111) substrate at 2 =
28.5o, correspond to the diffraction pattern of ZnO wurtzite structure and no impurity phase is
found. We can see that the higher solution concentration is, the stronger X-ray intensity of the
peaks are. It can be explained by the increasing in solution concentration leading to increasing
the crystal ability of samples.
o
7000
6000
Si
Intensity(a.u.)
5000
4000
0.06M
3000
0.04M
2000
0.02M
1000
0.01M
0
20
30
40
50
60
70
2 (o)
Figure 1: The XDR patterns of the 0.01 M, 0.02 M, 0.04 M and 0.06 M samples at 80oC deposition
temperature.
Figure 2: The SEM images of 0.01 M sample (a); 0.02 M sample (b); 0.04 M sample (c); 0.06 M sample
(d) at 80oC deposition temperature.
The SEM images of samples are showed in figure 2. We can see that the 0.01 M, 0.02 M,
0.04 M samples have a rod morphology. The diameter and length of the rods varied with
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different preparation conditions. 0.01 M sample crystallizes with quite large diameter (2-3 m).
It can be caused low solution concentration to lead slow crystal speed, large size. 0.06 M sample
isnt like rods with many particle sizes. 0.02 M and 0.04 M have a quite good crystal structure
with a hexagonal plane. Their diameter of rods are about 200 400 nm. The length of 0.02 M
sample is longer than 0.04 M sample while the diameter is similar.
0,8
0.01M
0.02M
0.04M
0.06M
Abs
0,6
0,4
0,2
400
450
Wavelength (nm)
Figure 3: The absorption spectra of 0.01 M, 0.02 M, 0.04 M, 0.06 M samples at 80 oC deposition
temperature.
Figure 3 shows the absorption spectra of 0.01 M, 0.02 M, 0.04 M, 0.06 M samples at 80oC
deposition temperature. All samples only have one absorption edge. It can be seen the absorption
wavelength increases with solution concentration. It means the energy gap decreases with
solution concentration but not much about 3.25 eV.
5
001
002
004
006
Intensity (a.u.)
400
450
500
550
600
wavelength (nm)
Figure 4: Photoluminescence spectra of 0.01 M, 0.02 M, 0.04 M, 0.06 M samples at room temperature.
Photoluminescence (PL) spectra of 0.01 M, 0.02 M, 0.04 M, 0.06 M samples at room

temperature are presented in figure 4. All samples have three emission peaks, a weak peak at
385 nm, a peak at 500 nm and a peak in the orange-red wavelength range. The 385 nm peak
originates from the recombination of exciton, the 500 nm peak is attributable to the electron
transfer from the singly ionized oxygen vacancy state to the photoexcited hole in the valence
band [4] and the strong peak in the orange-red wavelength range may be attributed to oxygen
interstitials [3]. When the solution concentration increases, the intensity of 500 nm and orangered wavelength is stronger. It can be explained that when the solution concentration increase crystalline speed is high so the defects are more. The more defects are, the less excitons are.
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Intensity (a.u.)
24000
16000
0.06 M
8000
0.02 M
200
400
600
800
1000
1200
1400
Raman Shift (cm-1)
Figure 5: Raman spectra of 0.02 M and 0.06 M samples
Figure 5 shows the Raman spectra for 0.02 M and 0.06 M samples. In the figure, the
vibrational peaks at about 106, 336, 440, 581, 661, 1050, and 1148 cm-1 appeared. All the peaks
(eliminate 1050 cm-1 peak) were assigned on the basis of group theoretical analysis. The peak
that appears at 106 cm-1 can be assigned to the E2 (high) mode. All peaks, which appear in 0.02
M sample, are also found in 0.06 M sample. Table 1 lists the results comparison with previous
reports. One can see that our results quite agree with those of previous references.
Table 1: Wavenumber (in cm-1) and symmetries of the modes found in Raman spectra and their
assignments.
Wave
number
(cm-1)
Symmetry
331
383
410
438
540
584
660
776
987
1101
1154
A1
A1 (TO)
E1 (LO)
E2
A1 (LO)
E1 (LO)
A1
A1, E2
A1, E2
A1, E2
A1
Process
Ref.
[8]
Acoust. Overtone
First progress
First progress
First progress
First progress
First progress
Acoust. Overtone
Acoust.opt.comp.
Opt. comp.
Acoust. comp.
Opt. overtone
331
383
438
549
484
660
Ref.
[9]
381
407
441
583
Ref.
[10]
397
426
449
559
577
Ref.
[1]
332
383
438
583
987
1101
1154
My result
0.02M
sample
335
383
0.06M
sample
334
390
439
542
581
667
440
1149
1150
580
657
4. Conclusion
ZnO nanorods are prepared by a low temperature aqueous solution method. When
Zn(NO3)2.6H2O and C6H12N4 are stirred with stoichiometric 1:1 and accumulate at 80 oC. The
ZnO nanorods were with an average diameter of 300 nm and length of 3.5 m at 0.02 0.04 M
solution concentration, particle crystallize with lager size at 0.01 M concentration and with many
sizes at 0.06 M concentration. The energy gap of samples is about 3.25 eV. All samples have a
strong photoluminescence peak at 500 nm wavelength and a strong photoluminescence in the
orange-red wavelength range. Intensity of these peaks increases when solution concentration
increases from 0.01 M to 0.06 M. Most Raman peaks were assigned on the basis of group
theoretical analysis.
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References
1. Libo Fan, Hongwei Song, Lixin Yu, Zhongxin Liu, Linmei Yang, Guohui Pan, Xue Bai,
Yanqiang Lei, Tie Wang, Zhuhong Zheng, Xianggui Kong, ScienceDirect 29 (2007) 532.
2. N. Boukos, C. Chandrinou, K. Giannakopoulos, G. Pistolis, A. Travlos, Appl. Phys. A 88
(2007) 35.
3. T Mahalingam, Kyung Moon Lee, Kyung Ho Park, Soonil Lee, Yeonghwan Ahn, Ji-Yong
Park, Ken Ha Koh, Nanotechnology 18 (2007).
4. C X Xu, X W Sun, Z L Dong, M B Yu, T D My, X H Zhang, S J Chua and T J White,
Nanotechnology 15 (2004) 839.
5. Yong-Jin Kim, Chul-Ho Lee, Young Joon Hong and Gyu-Chul Yi, Appl. Phys. Lett. 89
(2006) 163128.
6. Zijie Yan, Yanwei Ma, Dongliang Wang, Junhong Wang, Zhaoshun Gao, Lei Wang, Peng
Yu, and Tao Song, Appl. Phys. Lett. 92 (2008) 081911.
7. M Huang, S. Mao, H Feick, H. Yan, Y. Wu, H. Kind, E. Weber, R. Russo, P. Yang, Science
292 (2001) 1897.
8. G. Xu, P. Jin, Phys. Rev. B 69 (2004) 113303.
9. R. H. Callender, S.S. Sussman, M. Selders, R.K. Chang, Phys. Rev. B 7 (1973) 3788.
10. F. Decremps, J. P. Porres, A. M. Saitta, J. C. Chervin, A. Polian, Phys. Rev. B 65 (2002)
092101.
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EFFECT OF ZnS SHELL THICKNESS AND TEMPERATURE ON

PHOTOLUMINESCENCE DECAY IN CdSe/ZnS QUANTUM DOTS
Pham Thu Ngaa, Nguyen Xuan Nghiaa, Vu Duc Chinha, Pham Thuy Linha,
Vu Thi Hong Hanha, Vu Thi Bichb, Khong Cat Cuonga,c, Nguyen Van Hungc,
C. Barthoud, C. Viond, P. Bennallould, A. Maitred
a)
Institute of Materials Science, Vietnamese Academy of Science & Technology,

Hanoi, Vietnam
b)
Institute of Physics, Vietnamese Academy of Science & Technology
c)
d)
Institut des Nanosciences de Paris, UMR-CNRS 7588,
Universits Pierre et Marie Curie, F-75015 Paris, France
E-mail address: phtnga@ims.vast.ac.vn
Abstract: We report an investigation of photoluminescence (PL) decay behavior with temperature

(from 4 K to 300 K) of series of samples of CdSe/ZnS quantum dots (QDs) with different sizes and
different ZnS shell thickness. The contributions of radiative and non-radiative different processes as
of e-h intrinsic excitonic recombination, non-radiative carrier relaxation, interaction of exciton surface phonon and surface states emission to the PL decay results were different for the studied
samples confirming the decisive role of the ZnS shell in the improvement of CdSe/ZnS QDs quantum
yield. The role of lattice structure will be discussed.
Key words: CdSe/ZnS quantum dots, PL decays, lifetimes, nano-powder
1. Introduction
Colloidal nanodots and nanorods are nano-emitters consisting of a 110 nm semiconductor
core surrounded by a few-monolayer thick shell of a second semiconductor material. The most
prominent system is the CdSe/ZnS core/shell nanocrystal systems with radii around 2 to 3 nm
and emission spectra in the range from green to yellow [1]. These nanostructures are potential
candidates for advanced devices with much improved performance, e.g., blue green
semiconductor diode lasers, light-emitting diodes (LEDs), bio-luminescence markers, etc. [25].
There are some investigations to optimize the shell, for example: the thickness, the essence of the
shell, the use of multi-shell for conserving and enhance the CdSe QDs emission. The case of
over coating QDs with ZnS resulting in the saturation of the CdSe dangling bonds suggests that
surface native defects such as sulfur or cadmium vacancies can be efficiently eliminated by
epitaxial growth of the shell. Our investigation on the ZnS shell thickness by X-rays diffraction
(XRD) shows a clear contribution from the ZnS shell only for the samples with high ZnS
coverage of 2.5 monolayer (ML), similar to the previous reported in [6]. The bulk CdSe exists in
two crystalline lattice structures: wurtzite (WZ, hexagonal) and zinc blende (ZB, cubic). The traditional
synthesis of high quality spherical CdSe QDs is usually carried out at temperatures >300C, and
it always yields to dots which have WZ lattice structure, sometimes with a few ZB stacking
faults [7]. The seed particles have a ZB structure at the beginning of the growth, but a structural
phase transition to the WZ structure occurs as the particles grow in size [7-9]. In our synthesis,
we have fabricated CdSe dots having the ZB lattice structure with the quantum yield was the
order of 35%. The effect of crystal structure on the spectroscopy of CdSe QDs was previously
studied theoretically [10, 11]. These models predict that the intrinsic asymmetry of the hexagonal
lattice structure of the crystal splits the 4-fold degenerate hole state into two-fold degenerate hole
state. The changes in the band edge exciton structure, which are due to the differences between
the two structures (WZ and ZB), are expected to exhibit different optical properties and kinetics.
In the core/shell structure of the CdSe/ZnS, the holes are confined in the CdSe core due to the
passivation of the QD surface by the ZnS layer, but the electron wave function extends into the
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ZnS shell. In the measurements of ensemble CdSe/ZnS dots, the multi-exponential behavior was
observed at short time but the long time behavior was fitted with a mono - exponential, with a
radiative lifetime of ~ 1 s at low temperatures (~ 4 K) by far exceeds the value found in bulk
CdSe (~1 ns). The band edge exciton (1S3/21Se), which is eightfold degenerate in spherically
symmetric dots [12, 13], is split into five levels by the crystal shape asymmetry, the intrinsic
crystal field, and the enhanced electron-hole exchange interaction. It has been reported [14] that
the band edge states responsible for the exciton radiative recombination in CdSe QDs which are
characterized by the three-state model as following: G is the zero exciton ground state. The
bright state B and dark state D are the two lowest states of the band edge exciton with
respective lifetimes B (~10 ns) and D (~1 s). At low temperatures, these processes are much
slower than those of direct optical recombination. This leads to the formation of a long-lived
exciton state.
From the literature, we note that the exact interpretation of the different components is still a
topic of much discussion. In general, we have to pay attention on the difference in the electronic
structure of the samples different in size, shape, crystal structure or surface structure. In this
work, we present the new obtained results of the study of PL decay behaviors of the ZB CdSe
QDs with different ZnS shell thicknesses. Finally, we will compare the luminescence decay
curves of ensemble CdSe/ZnS QDs in ZB and WZ structures in the temperature range of 4 and
300 K.
2. Experiment
The CdSe cores (2.3 6.2 nm in diameter) were prepared following the method described by
Bawendi et al., Peng et al. [7, 8] and developed in our laboratory by growing the nanocrystals in
the organometallic solution in excess of Se. We have grown the ZnS shell by using the approach
described by Talapin et al. in Ref. [14]. The diameter of the core increases with the increasing
growing temperature. The thickness of the ZnS shell varies from 0.38 nm to 2.3 nm which
corresponding to the 1 monolayer (ML) to 6 ML. The QDs were re-dispersed in toluene for
measurements of UVVIS (Cary 5000), PL, transmission electron microscopy (TEM) (not show
in this report). The X-ray diffraction (XRD) was done without any size selection on
diffractometer D5005 (Siemens). The PL measurements were performed by the photonic
excitation at 400 nm which was obtained with a dye laser (Laser Photonics LN102, Coumarine
420) pumped by a pulsed nitrogen laser (Laser Photonics LN 1000, 0.14 mJ energy per pulse,
pulse width 0.6 ns). The visible emitted light from the sample, collected by an optical fiber on
the same side as the excitation, was analyzed with a Jobin-Yvon Spectrometer HR460 and a
multichannel CCD detector (2000 pixel). The decays were analyzed with a PM Hamamatsu
R5600U and a scope Tektronix TDS 784A with a time constant of the order of 1 ns. The low
temperature experiments were carried out in a Janis Supertran-VP dewar with a variable
temperature controlled between 4 to 300 K. Some samples were excited by 488 nm line from Ar+
laser. The dots solution was diluted in PMMA polymer before being drop-cast onto glass slides.
3.1. Influence of ZnS shell thickness on the PL decay of CdSe QDs
The lifetime is the inverse of the total decay rate -1 = (+ knr)-1 (1), where is the
radiative decay rate, and k nr is the non-radiative decay rate. As the fluorescence intensity is
proportional to n(t) which is the number of excited carriers at time t after excitation, therefore we
have:
I (t) = I0.exp(- t/ ) (2), where I0 is the intensity at the time zero. Lifetimes can be characterized
by many mechanisms. We use the mechanism described by O. Labeau et al. [15] who obtained
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the same type of decays in dependence on temperature. They interpreted well by the two - level
model. This model is also used to interpret well our decay behavior observation in the sample
CdSe QD (No.10a), such as present below. The decay mechanism is following: at low
temperature, after excitation the electrons relax very quickly from B level to D (relaxation
time = 0 inferior 1 ns). Because temperature is very low, the electrons have not many
possibilities to come back B level. So that we have a very fast part, it is 0 and a slow part that
grows gradually with time of relaxation of D . For the higher temperatures, in this case the
electrons can be promoted to B level (4 meV between B and D ). For certain temperature,
two levels are equally populated (nB = nD) and the fast lifetime can not be observed. For the
higher temperature, the slow decay becomes faster and faster to 300 K. We can also calculate the
integration from 0 to infinite of the equation (2) and with I0 = 1. In our case, the average time SN
1
.
is determined as following: S =
N
I o I ( t ) dt
0
It means the area under the normalized decay curve I(0) = 1.

1
CdSe 640 nm
CdSe/ZnS 1 ML 640 nm
CdSe/ZnS 1.6 ML 640 nm
CdSe/ZnS 2.5 ML 640 nm
0.1
0.01
1E-3
1E-4
0
100
200
300
400
t (ns)
Fig.1. Luminescence decay curves of CdSe QDs

powder, with ZnS different thickness shell at
different emission wavelength, exc.= 400 nm at
300K.
CdSe-ZnS-1.OPJ (G13)
CdSe/ZnS
anal
exc=400nm
Intensity (norm.)
Intensity (norm.)
exc=400 nm
11.4 544nm 5K
11-4 544nm 300K
0.1
0.01
1E-3
0
100
200
300
400
500
600
t (ns)
Fig.2. Comparison of two decay curves of

CdSe/ZnS 2.5 ML QDs at 300 K and 5 K,
analyze at 544 nm emission, exc.= 400
nm.
From Fig. 1 we can notice that the kinetics show similar general behavior in all cases, especially,
a slower decay for more shell thickness. We established the average lifetime through average
value aver. = <SN>, which are listed in the table 1. As seen in Fig.1, the PL of CdSe cores with
out shell present decay fast. With the ZnS shell of 1 monolayer, the decay is slower down than
decay of CdSe core only, but their PL intensity is increase. With 1.6 ML and 2.5 ML the decays
are longer, as seen in table 1. It is clear that with the ZnS shell, the intrinsic radiative lifetime of
CdSe increases with the shell thickness. For the CdSe/ZnS, the kinetic traces are best fitted with
two or three exponentials depending on the shell thickness. Fig. 2 is the decay curves of samples
at 5 K, the decay curves give the SN values vary from 4 and 7 ns compared to the SN values vary
from 3 and 5 ns at 300 K. The result obtained from core/shell QDs point out the contribution of
different origins on the surface states.
In all measurements, the kinetic of an ensemble of CdSe QDs in all samples shows a
consistent behavior: the curve can be described by non- exponentials fitting model. Our work
indicates that the decay curve of CdSe results from at least four processes covering a range of
lifetimes between nanosecond up to hundreds of ns, the shell seems not affect much to the decay
curves. In the literature, nanosecond kinetics of CdSe present for the relaxation decay resulting
from the e-h recombination ( ~25 ns at room temperature). At low temperature, this decay
comes from the forbidden state relaxation D with a very long lifetime (> 100 ns). Radiative
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lifetime is longer at 5 K than that at 300 K. The ZnS shell seems not affect much to the PL
decays of CdSe/ZnS.
Table 1. The parameters of the luminescence decay curves for different samples at exc. = 400 nm.
SN(1) represents for fast lifetime from B level to D , SN(2) represents for intrinsic lifetime from B
level to G level.
SN (1)
(ns)
3.6
5.4
15
19
Powder samples
CdSe (88)
CdSe/ZnS 1ML (88-1)
CdSe/ZnS 1.6ML (88-2)
CdSe (10a)
CdSe (97)
CdSe/ZnS 2.5ML (97-1a)
SN (2)
(ns)
24.7
21.0
18.6
18.9
27.0
18.0
14.4
14.6
Quantum
Yield (QY)
6.3
9.5
22.7
34.8
32.9
FWHM
(nm)
60.5
64.4
63.2
63.8
27.9
29.8
34
27
31.3
1.1
3.2. Temperature dependence of the PL decay time of CdSe with ZB lattice structure
Fig. 3 presents the luminescence decay curves of the CdSe QDs recorded in the range of
temperature from 4.5 K to 300 K, analyzed at the PL emission peak maximum for each
temperature. Fig. 4 shows the XRD pattern of this sample (10a) with the characteristic diffraction
lines for the cubic phase. Fig.5 presents luminescence decay curves picked at three lowest
temperatures to illustrate the changes of the QDs slow component: the lifetime is shorter when
the temperature increases from 4.5 K to 31 K. We measure the value of lifetime rad. using only
the data toward the end of the decay, when the signal is very small compared to the initial signal
at t = 0. At 4.5 K, rad. is long (0.736 s).
4.5K
12K
31K
54K
74K
102K
132K
158K
191K
221K
247K
280K
295K
exc=400nm
Intensity (norm.)
anal=peak
0.1
0.01
1E-3
1600
(111)
CdSe9
CdSe10a
1400
1200
Intensity (a.u.)
1000
(220)
800
(311)
600
400
200
0
1E-4
0
100
200
300
400
500
10
20
t (ns)
Fig.3. PL decays (logarithm scale) from 6.1 nm

CdSe QDs at the indicated temperature. exc. = 400
nm. Analyzed at emission peak.
40
50
60
70
Fig.4. XRD patterns of CdSe powder nanocrystals

samples (No.10a and No.9)
9-1a CdSe/ZnS
1
4.5K
12K
31K
anal=peak
0.1
0.01
1E-3
1E-4
0
500
1000
1500
2000
t (ns)
Fig.5. Luminescence decay curves at the three

lowest temperatures to illustrate the change of
CdSe slow component lifetime with temperature.
550nm
550nm
555nm
560nm
565nm
570nm
575nm
580nm
585nm
exc=400nm
T = 4.4K
Intensity (norm.)
exc=400nm
Intensity (norm.)
30
2 theta (degree)
0.1
0.01
100
200
300
400
500
600
t (ns)
Fig.6. Row PL decay (logarithmic scale) from 6.1

nm CdSe/Zns QDs at the peak indicated at 4.4 K,
exc. = 400 nm. Analyzed at emission peaks
appeared at different temperature.
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Our observation is similar to those reported in [15, 16]. The lifetime values calculated from Fig.
3.
In the next part, we will present the temperature dependent kinetic studies of the electron-hole
recombination over a broad temperature range (from 4 to 300 K) in CdSe/ZnS 2.5 ML QDs. At
first, we study PL decays behavior in low temperature. Fig. 6 presents the decay curves at 4.4 K
of CdSe/ZnS 2.5 ML QDs analyzed at different peak maximum which arise due to the emission
peak temperature shifting which is about 15 nm. The emission peak shifts from 550 nm at 4.4 K
to 580 nm (237 K) and 585 nm at 300 K. Therefore, the PL decay is analyzed for every PL
emission peak. In this measurement, the fastest decay is observed for 550 nm emission (at 4.4
K). We used a multi-exponential fit function for all of decay curves. But, first and second
component lifetimes are too fast to detected so we fit all decay curves with three-exponential.
We received in general, two values: 1 (~ 20 ns) presents for the direct e-h radiative
recombination through B state, 2 is longer that can be attributed for the recombination
through D state. The 3 is very short (~ 1 ns) and can not be resolved precisely, caused by the
electron relaxation from B state to D state. The lifetime values obtained at 4.4 K (in fig.6),
from the fit multi-exponential functions are listed in table 2.
Table 2. Lifetime values of CdSe/ZnS 2.5 ML QDs (9-1a), analyzed at different peak maximum at 4.4 K.
Analyse at peak
1 (ns)
2 (ns)
550 nm
14.8
170
555 nm
19.1
185
560 nm
20
204
570 nm
26.5
207
575 nm
24
580 nm
20
585 nm
20
255
269
290
1
4K
14K
21K
40K
0.1
0.029e
0.01
CdSe QDs 9-1a, 10a & B
50
40
-t/220
-t/88
0.075*e
Area-91a-10a-B.OPJ (G2)
10a-Sn
91a-Sn
B-Sn
exc=400nm
SN (ns)
Intensity (norm.)
exc=400nm
anal=567nm
30
20
1E-3
10
1E-4
0
100
200
300
400
500
t (ns)
Fig. 7. Decay curves picked at the four lowest

temperatures to illustrate the changes of CdSe/ZnS
slow component lifetime at low temperature.
0
0
50
100
150
200
250
300
T (K)
Fig.8. SN - temperature curves of three QDs

samples, exc. = 400 nm.
From other parts of the decay curves, we obtained the longer lifetime values. They are observed
as much longer decays, but much shorter than the time constant of our system. For 4 K and 14 K,
we can simulate this long decay with an exponential of = 220 and 88 ns, corresponding (Fig.7).
These values are in good agreement with those found by O. Labeau et al. [15]. From 60 K, the
general shape of the decay curves changes a little up to 300 K but the SN increases with
temperature. This augmentation is essential due to the shortening of lifetime caused by the
disappearance of the fast decay component.
Now we will discuss about obtained results of lifetime from decay curves. The integrated
intensity of the PL peak as a function of temperature can be used to obtain the main exciton
decay mechanism. Decay signal can occur due to the trapping of excitons in defect states and
coupling with phonons of the nanocrystals [17]. In low temperature, the main decay mechanism
is defect trapping, defect states play a dominant role below 50 K and process with phonon
assisted decay plays a major role above 50 K. Fig. 8 presents the SN values for three decays of
intrinsic radiative relaxation versus temperature in CdSe QDs (ZB) (No.10a), CdSe/ZnS 2.5 ML
(ZB-WZ) (No.9-1) and CdSe/CdS (No.B). Lifetime is longest (25 ns) at 4.5 K and decreases
with increasing temperature, about 15 - 20 ns for the sample CdSe (ZB). Lifetime is longer (~ 40
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ns) at 4 K, about 30 ns for the CdSe/ZnS 2.5 ML. We note a similar tendency of these two
curves. which is not observed in the CdSe/CdS sample. In conclusion, for CdSe QDs crystallized
in cubic lattice and CdSe in cubic lattice with a ZnS hexagonal shell, the radiative intrinsic
recombination lifetime is determined only by the nature of the CdSe core. We can point out that
in a CdSe with ZB lattice structure, the temperature dependence PL decay effect reveals a similar
behavior to CdSe/ZnS ZB-WZ structure.
4. Conclusions
We have analyzed the PL decays of CdSe and CdSe/ZnS quantum dots in temperatures in
the range from 4 K to 300 K. We observe non-exponential decays for all sample, two lifetime
values can be identified precisely by our measurement system. The PL of WZ structure CdSe
core without shell presents very fast decays. However, in the case of CdSe/ZnS, the intrinsic
radiative lifetime is longer.The tendencies of lifetimes in both two cases of CdSe and CdSe/ZnS
with CdSe core zinc blende structure are similar. We find that the long decay time component
strongly depends on temperature. At 4 K, rad. is the longest for CdSe core and CdSe/ZnS
core/shell. However, above 60 K the temperature does not affect the decay curves much.
Acknowledgments
Research supported, in part, by the bilateral VAST CNRS France Scientific Research
project 2007-2008 and by the VAST Research project 2007-2008 and the National Natural
Science Program. We thank to Prof. Nguyen Van Hieu and Prof. Nguyen Dai Hung (IoP) for his
helps in this research.
References
U. Woggon , J. Appl. Phys. 101 081727 (2007).
Suresh C. Sharma, Jay Murphree, Tonmoy Chakraborty, J. Lumin. (2008) (Article in press).
V.I. Klimov, et al., Science 290 314 (2000).
M.K. So, et al., Nature Biotechnol. 24 339 (2006).
K. Kyhm, et al., J. Lumin. 122 808 (2007).
A.V. Baranov, Yu.P. Rakovich, J.P. Donegan, T.S. Perona, R.A. Moore, D.V. Talapin, A.L.
Rogach, Y. Masumoto and I. Nabiev, Physical Review B 68, 165306 (2003).
7. Murray, C.B., D.J. Norris, and M.G. Bawendi, J. of the American Chemical Society, 115(19),
8706-8715 (1993).
8. Peng, Z.A. and X.G. Peng, Journal of the American Chemical Society, 2002. 124(13): 33433353.
9. Manna, L., E.C. Scher, and A.P. Alivisatos, Journal of the American Chemical Society,
122(51), 12700-12706 (2000).
10. Efros, A.L. and M. Rosen, Annual Review of Materials Science, 30 475-521 (2000).
11. Grnberg, H.H.v., Phys. Rev. B,. 55: p. 2293 (1997)
12. A. L. Efros et al., Phys. Rev. B 54, 4843 (1996).
13. M. Nirmal et al., Phys. Rev. Lett. 75, 3728 (1995).
14. D.V. Talapin, A.L. Rogach, A. Kornowski, M. Haase, H. Weller, Nano Lett. 1 207 (2001).
15. O. Labeau, P. Tamarat, and B. Lounis, Physical Review Letters, V.90, No.25 257404 (2003).
16. S.A. Crooker, T. Barrick, J.A. Hollingsworth and V.I Klimov, Appied Physics Letters V. 82,
No.17 2793-2795 (2003).
1.
2.
3.
4.
5.
6.
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TEMPERATURE DEPENDENCE OF THE PHOTOLUMINESCENCE

PROPERTIES OF CdSe/CdS CORE/SHELL NANOSTRUCTURES
PREPARED IN OCTADECENE
Le Ba Hai a,b, Nguyen Xuan Nghia a, Pham Thu Nga a, Nguyen Thi Thu Trang a
a)

18 Hoang Quoc Viet Rd., Cau Giay Dist., Hanoi, Vietnam.
b)
Le Qui Don upper high school, Khanh Hoa, Vietnam
E-mail: nghianx@ims.vast.ac.vn
Abstract: The CdSe/CdS core/shell nanostructures were prepared by chemical method in

octadecene. The photoluminescence spectra of cores and core/shell nanostructures with the
different shell thickness have been comparatively investigated in the temperature range from 79
to 430 K. The obtained results show that the temperature-dependent behavior of emission energy
is similar for CdSe cores and CdSe/CdS nanostructures with different shell thickness. Especially,
the luminescence temperature antiquenching was observed for both CdSe and CdSe/CdS samples.
This observation is unique as it is the opposite of the commonly observed temperature quenching
of luminescence. The effect of shell layer on the temperature dependence of the emission energy
and the origin of the luminescence temperature antiquenching in CdSe cores and CdSe/CdS
core/shell nanostructures has been discussed.
Keywords: CdSe/CdS
antiquenching.
core/shell
nanostructures,
temperature,
photoluminescence,
1. Introduction
Semiconductor nanocrystals have attracted great interest over the past years because their
properties can be tailored by a judicious control of particle composition, size, and surface [1].
These characteristics arise from several phenomena (quantum confinement of charge carriers,
surface effects, and geometrical confinement of phonons) and have turned semiconductor
nanocrystals into promising materials for many applications, such as light emitting diodes [2],
lasers [3], and biomedical tags for fluoroimmunoassays, nanosensors, and biological imaging [4].
The main strategy to increase the photoluminescence (PL) quantum yield (QY) and the
stability of nanocrystals is to grow a passivating shell on the cores surface. This removes the
surface defects acting as traps for the carries, and therefore reduces the probability for the
undesired processes of emission quenching via nonradiative decay. Moreover, the passivating
shell protects the core and reduces surface degradation. To suppress surface effects, the inorganic
passivation with wide band gap material is a well developed solution to enhance the QY and
stability of nanocrystals [5]. The PL QY is known to be very sensitive to subtle changes in the
synthetic procedure, thus indicating that the surface structure is a key factor for the occurrence of
band gap states that quench the exciton luminescence [6]. However, the role of the
semiconductor surface and its interaction with the passivation layer has not reached the complete
level of understanding.
The temperature quenching of the luminescence of quantum dots (QDs) is a commonly
observed phenomenon, both in colloidal suspension or in solvent-free systems such as QDs
embedded in polymeric matrices and QD solids, and is ascribed to the thermally activated carrier
trapping [7-9]. The thermally induced luminescence recovery is thus highly remarkable. The
luminescence temperature antiquenching (LTAQ) has been observed by Wuister et al. and shown
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that the organic passivation layer not only passivates the dangling lone pairs but also plays an
active role in surface reconstruction [10]. Furthermore, LTAQ is strongly dependent on the
surface ligands [11]. Recently, LTAQ was observed for CdTe/CdSe colloidal heteronanocrystals
in decalin, and a reversible surfactant-assisted surface relaxation (and/or reconstruction) was
proposed for explaining this interesting phenomenon.
In this work, we present the temperature dependence of the PL properties of CdSe/CdS
core/shell nanostructures. The temperature-dependent behavior of emission energy is similar for
both CdSe cores and CdSe/CdS nanostructures with different shell thicknesses, indicating that
the strain in these nanostructures is low. Especially, a recovery of the emission intensity of
CdSe/CdS nanostructures was observed in the temperature range of 180-350 K.
2. Experimental
The CdSe/CdS core/shell nanostructures were prepared by chemical method in octadecene.
The synthetic procedure is described in more detail in [12].
The optical absorption spectra of CdSe cores were recorded by Jasco V670 UV-Vis-NIR
spectrometer. The PL spectra of CdSe cores and CdSe/CdS nanostructures were colected on
LABRAM-1B spectrometer, fitted with the Argon ion laser of wavelength 488 nm. The PL
measurements in the temperature range of 79-430 K were performed using Linkam 600
microthermometric cell. The PL spectra were measured from low to high temperature and
corrected for the sensitivity of the detection system. All samples were purified and dried.
Normalized intensity
Figure 1 presents the room-temperature PL

4ML
spectra of CdSe cores with the size of 4.8 nm and
2ML
CdSe/CdS core/shell nanostructures with the shell
0ML
thicknesses of 2 and 4 ML. All spectra are
normalized in the intensity. The PL full width at
half maximum (PL FWHM) of CdSe cores and
CdSe/CdS nanostructures with the shell
thicknesses of 2 and 4 ML is 22, 23, and 25 nm,
respectively, indicating a narrow size distribution
of the obtained nanocrystals. The surface
emission band disappears due to the passivation
of CdSe core surface by the CdS shell layer. As
can see, the increase of shell thickness leads to
the redshift of emission peaks of CdSe/CdS
nanostructures, reflecting an increased leakage of
550 600 650 700 750 800
the exciton into the thicker shell [13]. Therefore,
Wavelength (nm)
the CdS shell cannot provide a potential barrier
large enough to prevent the leakage of the exciton, Fig. 1. Room temperature PL spectra of CdSe
and not only core/shell interface but also CdS
core and CdSe/CdS nanostructures with
shell surface influence on the optical properties of
different shell thicknesses. All spectra were
normalized in intensity
CdSe/CdS nanostructures.
The PL spectra of CdSe cores and CdSe/CdS core/shell nanostructures as a function of
temperature are reported in Figure 2. As the sample temperature is increased, the emission energy
redshifts and the spectra become broader. Especially, the thermally induced luminescence
recovery is observed clearly for CdSe/CdS core/shell nanostructures.
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78 K 430 K
4ML
78 K 430 K
560
580
600
Wavelength (nm)
78 K
430 K
Intensity (a. u.)
2ML
Intensity (a. u.)
Intensity (a. u.)
0ML
570
600
630
660
Wavelength (nm)
600
620 640 660

Wavelength (nm)
680
Fig. 2. The PL spectra of CdSe cores and CdSe/CdS core/shell nanostructures

at different temperatures in the range of 79-430 K.
The temperature dependence of the emission energy, which represents the energy gap of
CdSe and CdSe/CdS nanocrystals, is presented in Figure 3(a). The emission energy of CdSe
cores shows a redshift of about 85 meV as the temperature increases from 79 to 360 K. For wide
band gap materials, such as CdSe nanocrystals, where the exciton binding energy is much smaller
than the energy band gap (Eg), Eg can be approximated as the energy of the first exciton peak
observed in the optical absorption spectrum. The experimental data have been fitted to the
Varshni relation [14]:
E g (T ) = E g (0)
T2
(T + )
(1)
Here, Eg(T) and Eg(0) is the energy gap at T and 0 K, respectively; is the temperature
coefficient, and is close to the Debye D temperature of the material.
0ML
2ML
4ML
2.1
2.0
1.9
(b) 1.0
Emission energy (eV)
(a)
0ML
2ML
4ML
0.8
0.6
0.4
0.2
0.0
100
200 300 400

Temperature (K)
100
200
300
400
Temperature (K)
Fig. 3. The variation of the emission energy (a) and intensity (b)
of CdSe cores and CdSe/CdS nanostructures in dependence on temperature
The best-fit curves are shown by the solid lines in Figure 3(a), and the obtained fitting values
are presented in Table 1. The values of and are consistent with the values known in the
literature for bulk CdSe: (2.8-4.1)10-4 eV/K for and (181-315) K for D [15], thus
demonstrating that the energy shift with temperature is due to the temperature-dependent
bandgap shringkage of the CdSe, while the confinement energies for the carries are not
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dependent on the sample temperature. Moreover, assuming a linear thermal dilatation coefficient
of bulk CdSe (7.4x10-6 K-1) [8], the emission energy variation caused by the variation of the size
due to thermal expansion is negligible in comparison with the observed shift of emission energy.
Note that the value of 2.15 eV is the band gap energy of both CdSe and CdSe/CdS
nanocrystals at 0 K. The lower band gap energies obtained for CdSe/CdS nanostructures are due
to the leakage of the exciton into CdS shell, leads to the redshift of the exciton peak. Remarkably,
the different thermal expansions of CdSe core and outer CdS shell layer influence inconsiderably
on the emission properties of CdSe/CdS nanostructures.
Table I. The fitting values obtained from Varshni's relation.
Sample
CdSe core
CdSe/CdS (2ML)
CdSe/CdS (4ML)
Eg(0) (eV)
2.15
2.05
2.00
(10-4 eV/K)
(K)
4.6
4.5
4.7
250
250
250
The variation in emission intensity of CdSe cores and CdSe/CdS nanostructures in

dependence on the sample temperature is presented in detail in Figure 3(b). As the sample
temperature is increased from 79 to 180 K, the emission intensity decreases. This luminescence
temperature quenching can be ascribed to thermally activated carrier trapping and nonradiative
recombination at defects [15-16]. The exciton luminescence is recovered in the temperature
range of 180-350 K. At 180 K the emission intensity strongly increases, and then gradually
decreases. From 350 K the emission intensity decreases rapidly with temperature until it is
almost totally quenched at about 400 K. The behavior of temperature-dependent curve in Figure
3(b) is similar for CdSe/CdS nanostructures with the shell thicknesses of 2 and 4 ML. Similarly,
a small increase in the emission intensity of CdSe cores also is observed at 220 K.
In the case of CdSe QDs capped by organic molecules, the LTAQ is explained by the
influence of a phase transition in the capping layer on surface states of the QD. The surface Cd
and Se atoms shift slightly from their regular lattice position. This relaxation minimizes the
energy, and it also removes the surface states that are present in the band gap for the unrelaxed
surface. The surface states in the band gap act as the quenching centers, and to obtain high
luminescence QY, the removal of these surface states by surface relaxation is essential [11]. In
our case, the surface of CdSe cores and CdSe/CdS nanostructures were purified as presented
above. Thus, the mechanism behind LTAQ can not be explained by a phase transition in the layer
of capping organic molecules.
In our previous experiments it was found that a disorder CdSe1-xSx layer was created between
CdSe core and CdS shell of CdSe/CdS nanostructures due to the interdiffusion of Se- and
S-atoms in the shell growth process at high temperature. The presence of this alloy layer at
CdSe/CdS interface decreases strain caused by the lattice mismatch and different thermal
expansion coefficients between CdSe and CdS material, leading to the similar temperature
dependence of the emission energies of CdSe cores and CdSe/CdS nanostructures with different
shell thicknesses. Moreover, it also was found that a thin disorder CdSe layer was formed around
the high quality CdSe core from unreacted precursors when the reaction mixture was cooled to
room temperature [17].
In the solid phase the atoms strongly interacts each other, and the interface atoms can be
removed from their positions at low temperatures. As a result, the surface quenching states are
created that lower the luminescence intensity. At higher temperatures the increased mobility of
the atoms and the thermal expansion of lattice lift the strain at the interface and allow for
interface relaxation, resulting in the recovery of the emission intensity. A weak LTAQ observed
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for CdSe cores is assigned to the small difference of lattice constants and the thermal expansion
coefficients between CdSe core and outer thin disorder CdSe layer.
As mentioned above, not only the core/shell interface but also the exterior suface of CdS
shell influence on the optical properties of CdSe/CdS nanostructures due to the leakage of
exciton into the CdS shell. Figure 4(a) presents the PL spectra of CdSe/CdS/ZnS core/shell/shell
nanostructures as a function of temperature. The variation of the emission intensity in
dependence on the sample temperature is shown in Figure 4(b) for clarity. The temperature
dependence of the luminescence intensity of CdSe/CdS nanostructures with the shell thickness of
2 ML also is inserted in Figure 4(b) for comparison. The exciton luminescence of CdSe/CdS/ZnS
nanostructures also is recovered in the temperature range of 180-350 K. However, the
luminescence recovery of CdSe/CdS/ZnS nanostructures occurs strongly at higher temperatures
in comparison with its of CdSe/CdS nanostructures. It is possible that the passivation of
CdSe/CdS nanostructures by ZnS layer and the CdS/ZnS interface relaxation decreases the
carrier trappings activated at higher temperatures.
(b) 1.0
430 K
78 K
Intensity (a. u)
(a)
CdSe/CdS
CdSe/CdS/ZnS
0.8
0.6
0.4
0.2
0.0
580 600 620 640 660 680

Wavelength (nm)
100
200 300 400

Temperature (K)
Fig. 4. PL spectra (a) and the emission intensity (b) of CdSe/CdS/ZnS nanostructures
as a function of temperature. The temperature dependence of the luminescence intensity
of CdSe/CdS nanostructures is inserted in Fig. 4(b) for comparison
4. Conclusions
In summary, the CdSe/CdS core/shell nanostructures with the shell thicknesses of 2 and 4
ML were synthesized by chemical method in octadecene. The PL spectra of CdSe cores and
CdSe/CdS nanostructures have been comparatively investigated in the temperature range of
79-430 K. The temperature dependence of the emisson energy is well described by Varshni
expression and similar for both CdSe cores and CdSe/CdS nanostructures with the different shell
thicknesses. As the shell thickness increases, the luminescence peak redshifts due to the leakage
of the exciton into the thicker CdS shell. The energy shift with temperature is due to the
temperature-dependent bandgap shringkage of the CdSe, while the confinement energies for the
carries are not dependent on the sample temperature.
The LTAQ of CdSe/CdS nanostructures was observed clearly in the temperature range of
180-350 K and explained by the interface relaxation in CdSe/CdS nanostructures. The LTAQ
was also observed for CdSe/CdS/ZnS core/shell/shell nanostructures and occurs strongly at
higher temperatures in comparison with CdSe/CdS nanostructures. It is possible that the
passivation of CdSe/CdS QDs by ZnS layer and the CdS/ZnS interface relaxation decreases the
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carrier trappings activated at high temperatures. A weak recovery of the exciton luminescence of
CdSe nanocrystals was observed at about 220 K and has been assigned to the interface effect
between the CdSe core and outer thin disorder CdSe layer created from the unreacted precursors
when the reaction mixture was cooled to room temperature.
Acknowledgement
This work was financially supported by the National Fundamental Research Foundation of
Vietnam and by the Institute of Materials Science, Vietnamese Academy of Science and
Technology
References
1. A.P. Alivisatos, J. Phys. Chem. 100, 13226 (1996).
2. M. Gao, C. Lesser, S. Kristein, H. Mohwald, A.L. Rogach, and H. Weller, J. Appl. Phys. 87,
2297 (2000).
3. V.I. Klimov, A.A. Mikhailovsky, S. Xu, J.A. Hollingsworth, C.A. Leatherdale, H.J. Eisler,
and M.G. Bawendi, Science 290, 314 (2000).
4. D. Gerion, F. Pinaud, S.C. Williams, W.J. Warak, D. Zanchet, S. Weiss, and A.P. Alivisatos,
J. Phys. Chem. B 105, 8861 (2001).
5. J. Li, Y.A. Wang, W. Guo, J.C. Keay, T.D. Mishima, M.B. Johnson, and X. Peng, J. Am.
Chem. Soc. 125, 12567 (2003).
6. D.V. Talapin, A.L. Rogach, A. Kornowski, M. Haase, and H. Weller, Nano Lett. 1, 207
(2001).
7. Y-h. Wu, K. Arai, and T. Yao, Phys. Rev. B 53, R10485 (1996).
8. D. Valerini, A. Cret, M. Lomascolo, L. Manna, R. Cingolani, and M. Anni, Phys. Rev. B 71,
235409 (2005).
9. J.C. Kim, H. Rho, L.M. Smith, H.E. Jackson, S. Lee, M. Dobrowolska, and J.K. Furdyna,
Appl. Phys. Lett. 75, 214 (1999).
10. S.F. Wuister, A. van Houselt, C. de Mello Donega, D. Vanmaekelberg, and A. Meijerink,
Angew. Chem. Int. Ed. 43, 3029 (2004).
11. S.F. Wuister, C. de Mello Donega, and A. Meijerink, J. Am. Chem. Soc. 126, 10397 (2004).
12. Le Ba Hai, Nguyen Xuan Nghia, Pham Thu Nga, Vu Duc Chinh, Nguyen Thi Thu Trang, Vu
Thi Hong Hanh, Advance in Natural Sciences, 8, 295 (2007).
13. D.V. Talapin, I. Mekis, S. Goltzinger, A. Kornowski, O. Benson, and H. Weller, J. Phys.
Chem. B 108, 18826 (2004).
14 Y.P. Varshni, Physica 34, 149 (1967).
15. Y. Terai, S. Kuroda, K. Takita, T. Okuno, and Y. Masumoto, Appl. Phys. Lett. 73, 3737
(1998).
16. P.T.K. Chin, C.M. Donega, S.S. Bavel, S.C.J. Meskers, N.A.J.M. Sommerdijk, and R.A.J.
Janssen, J. Am. Chem. Soc. 129, 14880 (2007).
17. L.B. Hai, N.X. Nghia, P.T. Nga, V.D. Chinh, N.T.T. Trang, and V.T.H. Hanh, Journal of
Experimental Nanoscience (2008), In press.
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HIGH LUMINESCENCE EFFICIENCY CdTe QUANTUM DOTS

SYNTHESIZED IN AQUEOUS SOLUTION
Pham Song Toana, Trinh Duc Thiena,b, Dang Diep Minh Tana,c,
Do Xuan Thanha, and Nguyen Quang Liema
a)
Institute of Materials Science, VAST, 18 Hoang Quoc Viet, Cau Giay, Hanoi, Vietnam
Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Hanoi, Vietnam
c)
University of Tra Vinh, Tra Vinh, Vietnam
E-mail: liemnq@ims.vast.ac.vn or songtoanpham@yahoo.com
b)
Abstract. This article presents the results of the systematical study about the role of various
experimental parameters in the synthesis of CdTe quantum dots in aqueous solution: the Cd-to-Te
and Cd-to-MPA (3-mercaptopropionic acid) molar ratios, pH of the reaction solution, and the
reaction/growth temperature. With optimal parameters, the high quality CdTe quantum dots were
nucleated directly in aqueous media in the presence of MPA at room temperature and then were
grown at 100120 0C for several minutes to hours to reach desired sizes (in a few nanometers).
The synthesized CdTe quantum dots emit strongly photoluminescence in the 520650 nm range.
In addition, the CdTe/CdS core/shell structures were synthesized to have the better luminescence
quantum yield of the CdTe core and to improve the stability to irradiation and oxidation of the
QDs as well.
Keywords: Quantum dots, aqueous, photoluminescence, CdTe, core/shell structure.
1. Introduction
Nowadays, colloidal semiconductor nanocrystals (NCs), known as quantum dots (QDs), have
a lot of applications which are based on the unique size-dependent properties of the nanomaterials. Among semiconductor nanocrystals, CdTe QDs are the subject of many investigations.
One of the most expected characteristics of these QDs is the high luminescence efficiency, which
can find applications in solid-state lighting, display, optic communications, sensor, as well as
biological labeling and detection.
Many references have been proved that the hot-injection of the Cd and the Te, Se precursors
in organic solution, typically trioctylphosphine oxide (TOPO), hexadecylamine (HDA) or
octadecene (ODE), can make very good quality CdTe and CdSe QDs. These QDs have narrow
full width at half maximum (FWHM), high luminescence quantum yield (~80-85%) and are
soluble in nonpolar solvents such as n-hexane [1]... However, most of the bio-labeling
applications require hydrophilic QDs. Therefore, the exchange of the ligand of hydrophobic QDs
to hydrophilic QDs is necessary to obtain the water-soluble QDs. Unfortunately, this method
needs expensive chemicals and rigorous process, and in some cases, the luminescence efficiency
of the QDs can be reduced. Another way is preparing them directly in aqueous phase. Using
popular chemicals like cadmium bromide, 3-mecaptopropionic acid (MPA), tellurium powder
and sodium borohydride... the cost of productions can be decreased. Moreover, this method is
simpler, less toxic and more bio-compatible than hot-inject organometallic ones [3,4].
Especially, this synthesis in aqueous phase has ability to manufacture in a large quantity of high
quality QDs.
It is well-known that the emission efficiency and the stability of QDs depend strongly on
their surface due to the high surface-to-volume ratio and the presence of the surface traps,
unsaturated bond, etc [2]To improve the quality of QDs, it is necessary to passivate both
anionic and cationic dangling bonds of QDs by an inorganic shell made of materials which have
the band gap larger than that of the core. For this reason, the CdS shell is chosen to coat the
CdTe core.
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There are many factors affecting the quality of final QDs such as the pH value of media, the
molar ratios of chemical components or the annealing time In our work, we find the technical
parameters to obtain the highest quality CdTe nanocrystals and CdTe/CdS core-shell structures
by determining the optimal synthesis conditions.
2. Experiment
2.1. Chemicals
Sodium borohydride (NaBH4, 99%), tellurium powder (99.8%), cadmium bromide (CdBr2,
99+ %), thiourea (97%), and 3-mercaptopropionic acid (MPA, 99%) were purchased from
Aldrich. All chemicals were used without additional purication. Distilled water was used
throughout.
2.2. Synthesis of CdTe core and CdTe/CdS core/shell QDs
The tellurium powder and NaBH4 were loaded in a two-necked ask and air in the system
was pumped off and replaced with N2. Then, an amount of degassing water was added. The
reaction mixture was put in ultrasonic generator for 30 min at 50-60oC under the protection of N2
to get a deep red clear solution via the reaction:
2 NaBH4 + Te + 2 H20 = NaHTe + NaBO2 + 11/2 H2
The NaHTe solution obtained was cooled to room temperature for further use.
The pH level of mixture solution of CdBr 2 and MPA was adjusted by dropwise addition of
1.0 M NaOH solution with stirring. This solution was placed in a three-necked ask and was
degassing. Under stirring, freshly prepared NaHTe solution was added into the Cd precursor
solution at room temperature to obtain the CdTe nanocrystals in the presence of MPA.
In order to coat the CdS shell, the solution CdTe QDs with the excessive amount of thiourea
was annealed at 120oC for 5 minutes to stabilize their characteristic.... Due to the structural
similarities between CdTe and CdS, the excess of Cd2+ ion in solution tend to combine with the
S2- ion released from thiourea at high temperature, thus the CdS shell was formed on the surface
of CdTe nanoparticles.
The above approach is readily extended to gram-scale production and the production period
can be usually finished in few hours.
3. Optimizing the production process
(a)
(b)
After systematic experiments, we

clearly observe that samples quality
depends strongly on the pH and the
Cd:Te:MPA ratio. To determine the optimal
process by which we can synthesize the best
QDs CdTe directly in aqueous phase, only
one technical parameter was changed
during each experiment while the others
were remained unchanged. In the following,
we present the influence of each parameter
on the synthesis of the CdTe QDs.
3.1. The effect of pH value of solution
The pH value of solution is an important
factor in aqueous synthesis [5,6]. After
preparing some samples under different pH
Figure 1: Absorbance of CdTe (Cd:Te:MPA =

1:0.2:1) in different pH-level media before (a)
and after (b) annealing
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solution, the better CdTe QDs can be fabricated in pH7 environment, which show
sharper exciton peak position at 430nm with narrow FWHM (Fig. 1); that mean the higher
quality of nuclei was form in very small size (about 3-4 nm in diameter). If pH level of solution
was increase, the characters of CdTe nuclei would go to unexpected trends (Fig. 1a).
However, it is hard to stabilize the quality and characteristics of QDs for a long time at the
room temperature, which is caused by the decay of MPA. For this reason, the QDs solution was
added 1M NaOH solution to increase the pH to 8-10 to keep the QDs in colloidal phase.
(a)
(b)
Figure 2: Two types of Cd-MPA

complex
Figure 3: Absorbance and PL spectra of QDs

CdTe (Cd:Te ratio of 1:1)
3.2. The effect of MPA ratio

MPA molecules play a significant role in the synthesis of CdTe QDs, which prevent the
aggregation of these QDs and passivate their surface to protect them from the environment or
oxidation. To study the contributions of MPA to the nucleation, some samples having different
MPA-to-Cd ratio was synthesized. Base on their absorbance and PL spectra (Fig. 2), it is
obviously that proficient Cd-to-MPA ratio for synthesis is about 1:1 to 1:1.5.
We believe that this result can be explained by two types of MPA-Cd complex (Fig. 3). Type
(a) will dominate when Cd:MPA ratio is between 1:1 and 1:1.5 and type (b) will be the main CdMPA complex when this ratio is larger than 1:1.5.
Since the Cd tend to combine with S more than with O and the strong reaction between Cd
and the HS function of MPA, it is more difficult to separate S-Cd-S bonds in type (b) than O-CdS bonds in type (a) precursor for generating CdTe monomer. That is why the Cd:MPA ratio of
1:1 to 1.5 is the best for the nucleation.
3.3. The effect of Cd-to-Te ratio
The Cd-to-Te ratio is the main factor which determines the concentration of QDs in the
solution. When this ratio is changed, the sizes of QDs remain the same showed by absorbance
peak positions at about 460-480 nm after annealing (Fig. 4). Only the size distribution and the
concentration of QDs in solution were increased in direct ratio to the reacted Te molecules. If the
Cd:Te ratio is larger than 1:1, the black precipitations which is attributed to the oxide of
tellurium was formed. In addition, the excess of Cd molecules is required for further coating
CdS, thus the amount of Te is always taken less than of the Cd molecule.
Using the optimal parameters studied above, the high quality CdTe QDs and CdTe/CdS
core/shell structure can be synthesized with the design PL peak of 510 - 615 nm (Fig. 5 and Fig.
6) with narrow FWHM of 30-50 nm. The quantum yield of as-prepared QDs are about 40% by
comparing the integrated emission of QDs samples in water with that of fluorescent dye,
rhodamine
6G(in
ethanol,
QY
=
95%
with
identical
optical
density.
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Figure 4: Absorbance of QDs

CdTe (Cd:MPA =1:1) with
different ratio of Cd:Te
Figure 5: Temporal evolution of CdTe QDs at 120oC
Figure 6: Photograph of CdTe samples under the irradiation of UV lamp

4. Conclusion
Base on the obtained result, the high PL quantum yield of CdTe QDs (up to 40%) can be
produced in neutral media with molar ratio of Cd:Te:MPA of 1:1:1-1.5. After nucleation, these
QDs solution was added an excessive amount of thiourea and then annealed at 120 oC to coat the
CdS shell around CdTe NCs. Finally, 1M NaOH solution was dropwised to adjust pH value to 810 in order to keep CdTe QDs in colloidal phase.
This process is a low-cost, safe, simple method to synthesize CdTe NCs in large scale with
designed PL peak positions. We hope that this synthesis could provide a large amount and stable
source of CdTe QDs and CdTe/CdS core/shell structure for further applications and studies.
Acknowledgements
Authors thank Vietnam Academy of Science and Technology for financial supports.
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References
1. Dmitri V. Talapin, Experimental and theoretical studies on the formation of highly
luminescent II-VI, III-V and core-shell semiconductor nanocrystals. PhD thesis 2002.
2. Kortan A R, Hull R, Opila R L, Bawendi M G, Steigerwald M L, Carrol P J and Brus L E
1990 J. Am. Chem. Soc. 112 1327, Nucleation and growth of cadmium selenide on zinc
sulfide quantum crystallite seeds, and vice versa, in inverse micelle media
3. Gaponik N, Talapin D V, Rogach A L, Hoppe K, Shevchenko E V, Kornowski A,
Eychmuller A and Weller H 2002 J. Phys. Chem. B 106 7177, Thiol-Capping of CdTe
Nanocrystals: An Alternative to Organometallic Synthetic Routes
4. Zhang H, Wang L, Xiong H, Hu L, Yang B and Li W 2003 Adv. Mater 15 1712,
Hydrothermal Synthesis for High-Quality CdTe Nanocrystals
5. Zhenyu Gu, Lei Zou, Zheng Fang, Weihong Zhu and Xinhua Zhong, Nanotechnology 19
(2008) 135604 (7pp). One-pot synthesis of highly luminescent CdTe/CdS core/shell
nanocrystals in aqueous phase.
6. Yan Liu, Qihui Shen, Dongdong Yu, Weiguang Shi, Jixue Li, Jianguang Zhou, and Xiaoyang
Liu, Nanotechnology 19 (2008) 245601 (6pp). A facile and green preparation of highquality CdTe semiconductor nanocrystals at room temperature.
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STUDYING STRUCTURAL AND MAGNETIC PROPERTIES OF SnO2:Co

Duong Manh Toan, Pham Van Hai, Luc Huy Hoang, Nguyen Van Minh, Pham Anh
Duc, Nguyen The Khoi and Nguyen Van Hung
136 Xuan-Thuy Rd, Cau-Giay, Hanoi, Vietnam
Abstract. The influence of annealing temperature and Co concentration on structure and
magnetic properties of SnO2 films synthesized by sol-gel method have been investigated using Xray diffraction (XRD), scanning electron microscopy (SEM) and PPMS techniques. The XRD
results confirmed that the cassiterite phase structure of SnO2 is maintained for SnO2 doped with
Co up to 4%. The SEM images showed a good homogeneity of the prepared films with average
particles size of 30 nm. The particle size increases with increasing annealing temperature from
350 oC to 600oC, and decreases with increasing the Co contents. Sn1-xCoxO with x 1% exhibits
ferromagnetism behavior at room temperature and the saturated magnetization is found to be
dependence on the concentration of Co.
Key words: SnO2:Co, structure, Ferromagnetic.
1. Introduction
As a wide band semiconductor (Eg ~ 3.6 eV at 300 K), tin dioxide (SnO2) is a key functional
material that has been used extensively for gas sensor, transparent conductor, and nanoelectronic
device [1]. SnO2, a chemically stable transparent oxide semiconductor with a band gap of ~3.6
eV, is an attractive system for a wide variety of practical applications. It has been shown that Co
doping produces ferromagnetism in SnO2, thus making it a promising ferromagnetic
semiconductor at room temperature. This is a very important step in producing practically useful
spintronic devices [2]. The presence of oxygen vacancies is crucial in producing the
ferromagnetism in transition-metal-doped semiconductor oxides [3].
Nanoparticles of Sn1-xCoxO2 (x = 0, 0.5, 1, 1.5, 3, 4, 5, 6, 8, 10%) were prepared by the wet
chemical method from CoCl2.6H2O and SnCl2.2H2O as precursors [4]. In a typical preparation,
SnCl2.2H2O, an appropriate amount of CoC12.6H2O, and NH4OH were added and the precursors
were stirred in air in several hours, during which time the Co2+:SnO2 powder formed. The
precipitates were annealed at various temperatures (350, 450 and 6000C) The physical properties
of Co-doped SnO2 powders were investigated by using x-ray diffractometer (XRD), Scanning
electron microscope (SEM) and PPMS measurements.
The samples were prepared by the chemical method following the schema on fig. 1
CH3CH2O
SnCl2.2H2
SnCl2 1M
NH4O
CoCl2
Magnetic
CoCl2.6H2
O
HCl
Gel
Anneal
Fig 1. Schema of preparing nanoparticles of Sn1-xCoxO2
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Structural characterization was performed by means of X-ray diffraction using a

diffractometer D5005 (Siemens) with Cu K radiation. Scanning electron microscopy (SEM)
was operated using a JSM-5600 microscope. The magnetic properties of the obtained
nanoparticles were investigated by a magnetic property measurement system-check PPMS 6000
(Quantum Design).
3.1. X ray diffraction
b
C assiterite,syn-SnO 2
9 00
C obalt Oxide-Co 3 O 4
VNU-HN-SIEMENS D5005 - Mau SnO2:Co - 3% - 600C
1000
Lin(Cps)
900
700
d=2.6460
d=3.354
800
d=1.7646
Lin (Cps)
600
500
6 00
3 00
400
10 %
8%
6%
100
d=1.4369
d=1.4987
d=1.5921
d=2.3082
200
d=1.6738
d=2.3690
300
5%
0
0
15
20
30
40
50
60
20
40
60
Fig.2 X-ray diffraction pattern of Sn1-xCoxO2 powders with x=3% (a) and x = 5, 6, 8 and
10% (b)
The XRD patterns confirm that for x 4% there is only cassiterite phase of pure SnO2 (Fig. 2a.
They can be readily indexed to a pure rutile phase SnO2 with lattice constants of a = b = 4,738
and c =3,187 . At high Co content (>4%) the peaks corresponding to Co3O4 phase appear at 2
=36.70 (fig 2b).
3.2. SEM
1%
6%
10%
8%
Fig 3. SEM of Sn1-xCoxO2 powders with x = 1, 6, 8,

10%
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It can be seen from the Fig.3 that, the particle size increases with increasing the annealed
temperature, and decreases with increasing the Co contents. The average particle size of samples
annealed at 600oC with x = 6; 8; 10 % is about 15-20 nm.
3.3.The magnetic properties
Typical VSM hysteresis loop taken at room temperature from cassiterite Sn1-xCoxO2 sample is
shown in Fig. 4
M (emu/g)
0.00004
hysteristic loop
paramagnetic
ferromagnetism
0.00000
-0.00004
-4000
-2000
2000
4000
H (Oe)
Fig. 4 Hysteresis loop of sample with x = 0.5% annealed at 6000C at room
The hysteresis curve shows to be consisted of two parts related with ferromagnetism and
paramagnetism behavious, respectively.
Because of that, the ferromagnetic behavior appears in the samples annealed at 600oC with
saturation magnetization about 3.10-5 emu/g and coercivity (Hc) of 60 Oe. The
superparamagnetism dominates the magnetism of the powder samples annealed at 350oC and at
450oC.
Experiments with different annealing temperature of undoped SnO2 yielded only
diamagnetism (not shown), indicating that the ferromagnetism is indeed due to the Co2+ dopants.
We propose that, the synthesis condition and Co content have the important role in the
occurrence of room-temperature ferromagnetism. The origin of ferromagnetism is still unknown
at this time. In further work, we will investigate the magnetization dependence on temperature in
order to explain its origin.
4. Conclusion
In summary, (x = 0 - 0.1) were successfully synthesized using sol-gel method. Evidence for
both substitutional and interstitial incorporation of Co were observed in the XRD. In samples
with Co doping greater than 4%, there appear peaks corresponding to Co atoms, implying that
the solubility of Co in SnO2 is about 4%. Magnetic properties of SnO2Cox powders are strongly
dependence on the Co contents and annealing temperature.
References
1. G. Ansari et al. Thin Solid Films 295 (1997) 271; M.J. Zheng et al. Chem. Mater. 13 (2001)
3859.
2. G. A. Prinz, Science 282, (1998) 1660; J. Magn. Magn. Mater. 200, (1999)57.
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3. J. M. D. Coey, A. P. Douvalis, C. B. Fitzgerald, and M. Venkatesan, Appl.Phys. Lett. 84,

(2004) 1332.
4. J.Hays, A.Punnoose, R.Baldner, M.H.Engelhard, J.Peloquin, K.M.Reddy, Physical review
B72, (2005) 07203.
5. P.S. Peercy and B. Morosin, Phys. Rev., B7 (1973) 2779.
6. J. Hays, A. Punnoose, R. Baldner, M. H. Engelhard, J. Peloquin, K. M. Reddy, Physical
Review B 72, 2005, 075203, 1-7.
7. A. Bouaine, N. Brihi, G. Schmerber, C. Ulhaq Bouillet, S. Colis, A. Dinia, J. Phys. Chem.,
2007, 111, 2924 - 2928.
8. S. B. Ogale, R. J. Choudhary, J. P. Buban, S. E. Lofland, S. R. Shinde, S. N. Kale, V. N.
Kulkarni, J. Higgins, C. Lanci, J. R. Simpson, N. D. Browing, S. Das Sarma, H. D. Drew, R.
L. Greene, T. Venkatesan, Physical Review Letters, 2003, 077205, 1-4.
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GROWTH SINGLE CRYSTAL Li2B4O7 AND THE KINETIC PARAMETERS

OF THERMAL STIMULATION LUMINESCENCE.
Bui The Huy, Vinh Hao, Huynh Ky Hanh, Doan Phan Thao Tien,
Dinh Van Kinh, Ngo Van Tam, Vo Thi Thu Ha
Nhatrang Institute of Technology Research and Application, Vietnam
02 Hungvuong, Nhatrang, Vietnam; Email: buithehuy.nt@gmail.com
Abstract. The authors have primarily succeeded in the studying of the technology for growing
single crystal Li2B4O7 doped with Cu ions by Bridgman technique. The block single crystal have
dimension 20 mm x L35 mm. The kinetic parameters of thermal stimulation luminescence were
investigated by FGT method. This success opened out an opportunity in the radiotherapy to
manufacture scintillators for neutron detection.
Keywords: single crystal, kinetic parameter, FGT method, thermoluminescence
1. Introduction
Lithium Tetraborate (Li2B4O7, LBO) single crystals have attracted much attention of
researchers for use in surface acoustic wave (SAW), bulk acoustic wave (BAW) devices and
dosimeter in radiotherapy. LBO is considered to be a promising material for piezoelectric
materials due to its high electromechanical coupling coefficient (k2=1) and very low temperature
coefficient of delay (TCD, 0 ppm/0C) [1]. LBO materials have found application in neutron
detection and nonlinear harmonic generation [2]. Initially, Lithium Tetraborate single crystals
were grown by Czochralski method and subsequently both vertical and horizontal Bridgman
methods were applied [3,4]. The LBO single crystals of lager size were grown by Bridgman [5].
Thermoluminescence (TL) phenomenon is a result of the stimulated radiative recombination
of released electrons, initially trapped by some centers and defects in the material lattice after
being exposed to a source of ionizing radiation. The studies of TL have revealed useful
information on the properties of the various types of defects within insulator or semiconductors.
Many TL glow curve has been determined and a variety of methods for analyzing TL glow curve
has been developed. Several methods are applied to obtain the trap parameters of the glow peaks
[6-9].
LBO single crystals doped Cu were grown in a graphite crucible by the Bridgman method at
our laboratory. The FGT method has been applied for the investigation of the kinetic parameters
of thermal stimulated luminescence as the order kinetics, energy of trap etc.
2. Fractional glow technique
The fractional glow technique (FGT) is known to be the most precise method for the
investigation of the trap distribution spectrum in thermoluminescent material. This method first
applied by Gobrecht and Hofmann (1966) was improved by taking into account the difference
between the heating and cooling ratio in a cycle. The average energy of trap emptied in the i-th
cycle Ei is described by :
Ei = Eih + bc(Eic-Eih)/(bc+bh)
where Eih is the energy estimated for the heating part of TL curve in i-th cycle, Eic is the energy
obtained for the cooling part of i-th cycle; bh and bc are the heating and cooling rates,
respectively. One can present direct measurement results in the form of trap energy dependence
on the maximum temperature in the cycle (called E(T)) and the dependence on the sum under the
TL curve obtained for one cycle on the maximum temperature in this cycle (called the light sum
L(T)). The trap occupation spectrum H(E) is taken as the sum over all Hi for which E < Ei <E
+E, where:
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Hi =
Li
Ei Ei 1
Li is the sum under the TL curve obtained for i-th cycle, the so-called partial light sum. E is the
bar width of trap spectrum histogram.
3. Experimental
Single crystal of LBO:Cu was grown by the modified vertical Bridgman method. The electric
furnace has two independent heating zones. The raw material was a polycrystalline disc of
99.99% purity. The raw material was charged into the graphite crucible after being doped Cu2O
0.03 wt%. The inside diameter of the crucible is 20 mm and the length is 110 mm. The charge
was melted in a nitrogen atmosphere. A seed crystal oriented to <110> direction with a
dimension of 5 mm in diameter and 50 mm in length was placed at the bottom of the crucible.
An important parameter of the growth process is temperature gradient of the furnace system.
It requires that the gradient should be from 15 to 20 0C/cm. The furnace was heated to 930 0C in
both zone, the temperature gradient was reached to 17 0C/ cm.
The raw materials were melted for 10 hours and then the crucible was moving down with the
rate of movement of 0.4- 0.8 mm/hour in 100 hours. The furnace was cooled with the rate of 20
0
C/hour to room temperature. After the growth, the crucible was peeled off to get the crystal out
of it.
The crystal sample has cylinder shape
with about 35 mm in length. The crystal is
transparent but there are some bubbles in the
out of surface of sample. The reason is the
difference between heat transfer coefficients
of graphite and the crystal. The block crystal
is shown in Fig. 1.
The block crystal was cut perpendicular
to the growth direction and polished to mirror
finish. The crystal sample was measured by
slice surface measurement method on the Injury Lawyers system at Shonan Institute of
Technology. The measurements were carried out with the four sites 0, 90, 180 and 270 degree of
cylinder slice-sample.
The crystal Li2B4O7 belongs to tetragonal crystal system and consists of eight Li2O/2B2O3
per unit cell. The lattice constants are a0=9,479 Ao and c0=10,280 Ao. The distance spacing dhkl
between neighboring lattice plane express an equation:
dhkl =
a0
l
h2 + k 2 + ( )2
c
d110 = 6,7
Therefore, at the each site there were 3 measurements with the tilt angle 0, +7 and -7 degrees.
Fig. 2 shows X-ray pattern of crystal at site 0 degree. It proves that the sample is single crystal.
At the others sites, the results are same.
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3 5 0
T ilt a n g le
T ilt a n g le
T ilt a n g le
3 0 0
0
0
+ 7
0
-7
2 5 0
Count
2 0 0
1 5 0
1 0 0
5 0
0
- 3
- 2
- 1
(d e g .)
Fig. 2. X-ray pattern of crystal of LBO:Cu crystal
The thermoluminescence glow curve was received from Harshaw Reader 3500 with the heating
rate of 1 0C/sec as shown in Fig. 3. There are main peaks at 209 0C and a shoulder at 345 0C. The
TL intensity of LBO:Cu crystal is equal to half of TL intensity of TLD-100 chip.
2500000
800000
2000000
600000
I (a.u.)
400000
TL
TL
I (a.u.)
1500000
1000000
200000
500000
0
50
100 150 200 250 300 350 400

0
Temperature ( C)
50
100 150 200 250 300 350 400

0
Temperature ( C)
Fig. 3. TL glow curve of LBO:Cu crystal (left) and TLD-100 (right)
Copper involved into the crystal as the dopant, may exist in a form of Cu, Cu+ and Cu2+ ions.
The atomic-ionic radius for copper (1,35Ao) is less then that for lithium (1,45Ao), it is obvious
that a certain part of the copper atoms may be occupy the lithium atoms positions. The copper
ions also form the positively charge complexes with oxygen atom vacancies and other defects.
Therefore, the carrier capture cross section increases resulting in the appearance of the maximan.
The crystal samples was measured the TL- 3D and shown in Fig. 4. The spectra show that
there is a peak at around 375 nm and near 200 0C. This emission relate to the emission of Cu+
(3d94s 3d10 radiative excitation transition). The peak 345 0C did not appear in the spectra
because the measurement was performed in the long time, so the intensity of this peak was
decreased and overlaped by blackbody signal.
Fig. 4. TL-3D spectra of LBO:Cu crystal
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There are a different position of peaks between in Fig.3 and Fig.4. The reason is accuracy
of the temperature system of TL-3D home-made equipment.
Fig. 5 show the results of FGT method for LBO:Cu crystal sample.
(a)
(b)
(a)
(c)
(b)
(c)
Fig. 5. The FGT results for LBO:Cu crystalwith fast growing (left), low growing (right)
(a)-The raw FGT curver and the light sum dependence on cycle number
(b)-The energy values for heating and cooling cycles.
(c)-50 meV energy step histogram of the density spectrum of trap energy
calculated for the above results.
The average values of the depth of all traps were calculated by FGT technique. All FGT
experiments were performed with the same heating rate 0.1oC/s and temperature was repeatedly
increased by 12 0C and lowered by 10 0C (step 2 0C) starting at 70 0C, up to 180 0C. The whole
procedure consists of about 50 heating-cooling cycles. The main peak appear at around 118 0C.
This peak shifts to lower temperature in comparison with the result from Fig. 3 because the
heating rate is low.
The sample with the fast and low growing are maximal distribution of the depth of all traps
about 1.5 eV and 1.35 eV, respectively. The different of these results may be in the distribution
of defects in the crystals. Theses results are according to result from different method, which are
calculated from the formula 500/Tmax.
5. Conclusion
Single crystals of Li2B4O7:Cu have been successful grown to a size of 20 mm in diameter and
35 mm in length by the Bridgman method. The emission of single crystal Li2B4O7:Cu relate to
Cu+ (375 nm).
The FGT method can quickly estimate the distribution of all traps without initial parameters.
The FGT method is reliable and accurate in evaluation of kinetic parameters of
thermoluminescence curves.
These results open out an opportunity in the radiotherapy to manufacture single crystal
scintillators for neutron detection.
Acknowledgments. The authors wish to thank Prof. M. Ishii, Shonan Institute of TechnologyJapan for his assistance in providing our laboratory with the Bridgman furnace as a gift. This
work is supported in part by the Vietnamese Academy of Science and Technology.
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References
1. S.Trolier-McKinstry, L.E. Cross, Y. Yamashita, Piezoelectric Single crystal and Their

Application, University Park, Pennsylvania (2004).
2. R. Komatsu, T. Sugawara, K. Sassa, N. Sarukura, Z. Liu, S. Izumida, Y. Segawa, S. Uda, T.
Fukuda, K. Yamanouchi, Appl. Phys. Lett. 70 (1997)
3. J. D. Garrett, M. Natarajan Iyer, J. E. Greedan, J. Crystal growth 41 (1977) 225
4. T. Katsumataa, H. Konouraa, H. Imagawaa, A. Konnob, K. Takeib, M. Shinoharab, K.
Kanoc and K. Takahashi, J. Crystal growth 128 (1993) 924-928
5. N.Tsutsui, Y. Ino, K. Imai, N. Senguttuvan, M. Ishii, J.Crystal growth, 211 (2000) 271-275
6. M.S. Rasheedy, Physica B, 228 (1996) 342-344
7. J. Manam, S.K. Sharma, Radia. Phys. And Chem., 7 (2005) 423-427
8. F.O. Ogundare, F.A. Balogun, L.A. Hussain, Radia. Measu. 41 (2006) 892-896
9. M.S. Rasheedy, A.I.Abd-Elmageed, Jour. of Phys. and. Solids 68 (2007) 243-248
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SPECTROSCOPIC EVALUATION OF GD3+ IONS IN LITHIUM TETRABORATE

GLASS BY JUDD-OFELT THEORY.
Bui The Huya, Vu Xuan Quanga , Huynh Thi Ngoc Ngab, Be Kim Giapc
a)
Nhatrang Institute of Technology Research and Application, Vietnam

02 Hungvuong str., Nhatrang city, Vietnam
b)
University of Dalat, Vietnam
c)
Quanngbinh Training Collegue
Abstract: Evaluations of optical absorption spectra in UV-VIS band of Gd3+ions in lithium

tetraborate glasses were carried out by Judd-Ofelt (JO) theory. The JO intensity parameters (
= 2,4,6) with gadolinium oxide concentrations of 3 and 5 mol% are 14.9 x10-20 cm2, 0 , 5.47 x1020
cm2 and 17.4 x10-20 cm2, 0, 5.88 x10-20 cm2, respectively. These values were used to estimate
radiative properties such as electric and magnetic dipoles (Sed and Smd) line strengths, transition
probabilities AT, lifetime for the excited levels of Gd3+ ions.
Keywords: rare earth ions, absorption, Borate glass, Judd-Ofelt theory
1. Introduction
Glasses doped with rare earth ions are of importance for the development of optical fibre,
optical amplifier, laser. Many investigations have been carried out in order to seek and
improve new glass matrix, which contains rare earth ions. The characteristic absorption is
influenced by the ligand surrounding rare earth ions [1]. Among rare earth ions, the
spectroscopic properties of Gd3+ ions are less studied than those of other ions, although some
studies on the optical properties of Gd3+ doped aqueous ions [2,3], glasses [4-5] and crystal [6]
have been found.
In this paper, we present the absorption spectra of Gd3+ ions in Lithium Tetraborate
Li2B4O7 (LBO) glass. The Judd-Ofelt theory was used to predict radiative properties for the
levels which are located in the region from 200 nm to about 600 nm. The radiative properties of
5 Gd3+ levels (in VIS region) were predicted.
2. Experimental
Li2B4O7 powder (Merck) was used for preparation of glass samples. The powder was mixed
with Gd2O3 of 99.9% purity (Johson Matthey Chemicals Ltd.) and then melted in an electric
furnace at temperature 920 - 9400C for about 30 minutes in a platinum crucible. After melting,
the mixing was poured onto a high purity graphite mould. Finally, these glass samples were
polished by a diamond powder.
Absorption spectra were recorded at room temperature on a spectrometer UV-VIS- JASCO
Corp., V-550.
3. Theory
The f-f intensity model described in detail elsewhere [1-3] has been used. So that in this work
only the most important formulas will be presented
3.1 Oscillator strengths and Judd- Ofelt analysis
The oscillator strengths P of the absorption bands could be determined experimentally from
the area under the absorption band using following formula [1-3]:
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Pexp 4.318 109 ( )d
(1)
-1
where is molar extinction coefficient at average energy, cm .

The f-f intensity model of the JO theory gives the oscillator strength, P, of an electric dipole
transition between two multiplets. Accordingly, the calculated oscillator strength from the initial
state to an excited state is given by [7]
P 8 2mcv / 3h(2 J 1) (n2 2)2 / 9n

Pmd
3mc
2 J 1 M ,M '
2,4,6
(J U ' J ') (2)
2

JM L 2S J ' M '
(2a)
where m is a mass of the electron, c - velocity of light in vacuum, h - Planks constant, n refractive index of the medium, J - total angular momentum of the initial state, - mean energy
of the transition in cm-1 and (=2,4,6) - JO intensity parameters and U - squared doubly
reduced matrix elements of the unit tensor operator of the rank =2,4 and 6, which are calculated
from the intermediate coupling approximation for a transition J J. By using Eq. (1), the
oscillator strength of the various observed transitions are evaluated. Next step, through Eq. (2) to
determine parameters by a standard least-squares fitting method. Finally, the theoretical
oscillator strengths, Pcal, are determined by using Eq. (2) and .
3.2 Radiative transition rate
From the measured oscillator strength for the excited initial transitions, we can estimate the
radiative transition rate, which is reciprocal to lifetime of the excited state. The electric Sed and
magnetic Smd dipole strengths are calculated from the formula [8]:
Sed e2
2,4,6
2 2
J U ' J '
(3)
Smd (e h /16 2m2c 2 )(J L 2S ' J ')2
(4)
The radiative transition probability A for a J J transition is given by
A(J , J ')
64 4 3 n(n2 2)2
Sed n3Smd
3h(2 J 1)
9
(5)
Total spontanneous emission probability AT is related to the R as.
AT
A(J , ' J ')
(6)
'J '

0.4
1
Absorbance
The absorption spectra of

Gd3+ doped Li2B4O7 glass for the
region of 200-500 nm are shown
in Fig.1
For the absorption spectra
there exist the transitions from
initial state 8S7/2 to 6P, 6I, 6D.
The 8S 6P transitions appeared
in the spectral range 310- 330
nm, 8S 6I in 270 290 nm and
8
S 6D in 250- 265 nm ranges.
1 mol %
2 mol %
3 mol %
0.2
2
0.0
250
300
Wavelength (nm)
Fig.1. Absorption spectra of Gd3+-doped Li2B4O7 glass
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Table 1: Energies of the observed band for Gd3+-doped Li2B4O7 glass
Transition from 8S7/2
Wavelength (nm)
Energy (cm-1)
P7/2
312
32017
P5/2
I9/2 , I17/2 , I11/2
6
D7/2 , 6D1/2
6
D3/2 , 6D5/2
306
274
253
246
32620
36401
39467
40598
6
6
The Fig. 1 shows that the shape and energies of the peaks are not changed, while the
intensities changed with different concentrations of Gd3+ in the host matrix. The strongest
absorption peak was at 287 nm, matched with 6I transition. The 6P and 6D transitions are weak.
The experimental oscillator strength Pexp of each of observed transitions is determined using
formula (1). The experimental oscillator strength includes the magnetic dipole Pmd and electric
dipole Ped . The Ped(cal.) were calculated by formula (2) with the doubly reduced matrix
elements of the unit tensor operator of Carnal [2] and Pmd (cal.) from formula (2a) with
L 2 S of Detrio [4]. With Gd3+ concentration of 3 and 5 mol%, the calculated and experimental
oscillator strengths were obtained and presented in table 2 and 3, respectively.

We noticed that electric dipole transition from 8S7/2 to the 6P and 6D states are dominated by
the 2 parameters, while those to the 6I states are dominated by the 6 ones.
Table 2. Measured and calculated oscillator strength for the 3 mol% Gd3+- doped LBO glass
Excited level
P7/2
P5/2
I9/2, I17/2, I11/2

6
6
Pexp
Pmdcal.
Pedexp.
Pedcal.
1.86E-07
7.44E-08
1.11E-07
1.01E-07
7.78E-08
4.20E-08
3.58E-08
4.11E-08
4.25E-06
4.25E-06
4.25E-06
3.97E-07
7.75E-09
3.90E-07
5.47E-07
5.62E-07
4.08E-09
5.58E-07
D7/2, D1/2
D3/2, D5/2
4.22E-07
3+
Table 3. Measured and calculated oscillator strength for the 5 mol% Gd - doped LBO glass
Excited level
Pexp
Pmdcal
Pedexp
Pedcal
P7/2
2.20E-07
7.44E-08
1.46E-07
1.18E-07
P5/2
8.64E-08
4.20E-08
4.44E-08
4.80E-08
I9/2, 6I17/2, 6I11/2
4.57E-06
4.57E-06
4.57E-06
4.06E-07
7.75E-09
3.98E-07
6.38E-07
5.96E-07
4.08E-09
5.92E-07
4.93E-07
6
6
D7/2,6D1/2
6
D3/2, D5/2
The intensity parameters were determined by a standard least-squares fitting method. The
results were shown in table 4.
Table 4. Judd-Ofelt parameters ( x 10-20cm2) for Gd3+-doped LBO glass
Gd concentration
Gd3+(3mol%)
Gd3+(5mol%)
Remark
14,9
5.47
2 > 6
17.4
5.88
2 > 6
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In order to investigate the sensitive of the transitions when the host matrix was changed, the
LiB3O5 (LTO) glasses doped Gd3+ with the same concentrations were investigated. The intensity
parameters were shown in table 5.
Table 5. Judd-Ofelt parameters ( x 10-20cm2) for Gd3+-doped LTO glass
Gd concentration
Gd3+(3mol%)
Gd3+(5mol%)
Remark
12,7
4.43
2 > 6
15,9
5.30
2 > 6
The calculated and experimental oscillator strengths for LiB3O5 glasses were obtained and
presented in table 6 and 7, respectively.
Table 6. Measured and calculated oscillator strength for the 3 mol% Gd 3+- doped LTO glass
Excited level
P7/2
P5/2
I9/2, I17/2, I11/2

6
6
Pexp
Pmdcal.
Pedexp.
Pedcal.
1.68E-07
7.44E-08
9.41E-08
8.59E-08
7.04E-08
4.20E-08
2.84E-08
3.50E-08
3.44E-06
3.44E-06
3.44E-06
3.33E-07
7.75E-09
3.25E-07
4.66E-07
5.01E-07
4.08E-09
4.97E-07
3.60E-07
D7/2, D1/2
D3/2, D5/2
3+
Table 7. Measured and calculated oscillator strength for the 5 mol%Gd - doped LTO glass
Excited level
Pmdcal.
Pedexp.
Pedcal.
P7/2
2.07E-07
7.44E-08
1.33E-07
1.08E-07
P5/2
7.92E-08
4.20E-08
3.72E-08
4.38E-08
I9/2, 6I17/2, 6I11/2
4.12E-06
4.12E-06
4.12E-06
D7/2,6D1/2
4.10E-07
7.75E-09
4.03E-07
5.83E-07
D3/2, 6D5/2
5.53E-07
4.08E-09
5.49E-07
4.50E-07
6
6
The results form table 4 and

table 5 show that the value of the
2 were changed when the host
matrix was changed. The value 2
> 6 prove that the chemical bonds
are substantial covalent character. .
The 6 parameter is related to the
rigidity of the medium in which
lanthanide ions were embedded and
considered as an indicator of
viscosity. As concentration of Gd
ions increases, the effect of medium
decreases and 6 increase.
The
comparisons
between
experimental and calculated values
of oscillator strength for all
observed transitions of LBO glass
were illustrated in the fig. 2. The
agreement is quite good.
Exp. 3 mol%
Cal. 3 mol%
Exp. 5 mol%
Cal. 5 mol%
-6
4.0x10
-6
3.0x10
Pexp
-6
2.0x10
-6
1.0x10
0.0
6P7/2
6P5/2
6I
6D7/2,6D1/2 6D3/2, 6D5/2
Levels
Fig. 2.Comparision between experimental and calculated

values of oscillatorstrength of LBO glass
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The electric dipole and magnetic dipole strengths (Sed and Smd), transition probabilities AT,
lifetime for the 6P7/2 transition of the Gd3+-doped lithium tetraborate glasses with Gd3+
concentration of 3 and 5 mol% were shown in table 8..
Table 8. The values of Sed, Smd, transition probabilities A and lifetime of 6P7/2.
Level
Sed
Smd
Amd(s-1)
Aed(s-1)
A(s-1)
(ms)
P7/2 (3 mol %)
3.44E-41
4.477E-41
282.42
126.2
440.81
2.45
P7/2 (5 mol %) 4.01E-41
5.17E-41
282.42
147.38
472.15
2.32
5. Conclusions
The study presents the spectroscopic evaluation of Gd3+ doped Li2BO7 glasses. The results
derived from the absorption spectral data show that the experimental results were in good
agreement with the calculated data by Judd-Ofelt theory. The value 2 > 6 prove that the
chemical bonds are substantial covalent character. The transition 6P7/2 is hypersensitive transition
but with the host matrix Li2O-B2O3 this transition does not clearly shown.
Although the vibration intensity in the glass is weaker than in the crystal but with the Lithium
tetraborate doped Gd3+ can be stronger, where the emission rate for transition 6P7/2 8S7/2
amount to 440 s-1
References
1. C. Gorller-Walrand, K. Binemans, Spectral intensities of f-f transtions, Handbook on the
Physics and Chemistry of Rare Earth, Vol. 25, Elsevier Science, 1998 (chapter 167)
2. W.T. Carnall, P.R. Fields, K. Rajnak, Electronic energy levels in the Trivalent Lanthanide
Aquo ions, Jour. Chem. Phys. Vol.49 (1968) 4443-4446
3. W.T. Carnall, P.R. Fields, K. Rajnak, Spectral Intensities of the Trivalent Lanthanide and
Actinidea in solution., Jour. Chem. Phys. Vol.49 (1968) 4412-4423
4. J. A. Detrio, Line Strengths for Gd3+ at a C4 site in SrF2, Phys. Rev. B. 4 (1971) pp. 14221427
5. S.M. Kacmarek, Cz. Koepke, M. Grinberg, A. Majchrowski, K. Wisniewski, M. Czuba,
Optical properties of Li2B4O7 glasses doped with rare-earths and transition metal ions,
Proceedings of SPIE Vol. 4412 (2001) 389-395
6. G. Blasse, Laser excited spectroscopy of Gd3+ ions in crystalline and glass borate hosts with
comparable composition, chapter in Luminescence of metal ions in the crystalline and in the
glass phase (1982) 31-50
7. B.R. Judd, Optical Absorption intensities of Rare Earth Ions, Phys. Rev. 137 (1962) 750-761
8. A. Renuka Devi, C. K. Jayasankar, Optical properties of Nd 3+ ions in lithium borate glasses,
Materials Chemistry and Physics, 42 (1995) 106-119
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EFFECT OF HEAT TREATMENT ON THE PROPERTIES OF GREEN-EMISSION

(La,Gd)PO4:Tb3+ PHOSPHOR PREPARED BY SOL-GEL METHOD
Duong Thanh Tunga, Bui Van Haob, Tran Ngoc Khiemb, Le Anh Tuana
Pham Thanh Huya,b, Pham Hong Duongc
a)
Hanoi Advanced School of Science and Technology (HAST)

International Training Institute for Materials Science (ITIMS)
Hanoi University of Technology (HUT), No 1 Dai Co Viet Road, Hanoi, Vietnam
c)
Intitute of Materials Science (IMS), Vietnam Academic of Science and Technology (VAST)
18 Hoang Quoc Viet Road, Hanoi, Vietnam
b)
Abstract: Green-emission (La,Gd)PO4:Tb3+ phosphors were synthesized by sol-gel method

from metal nitrate aqueous, the citric acid, and the diamonihydrophosphat in the water-ethanol
solvent. To obtain green-emission phosphors the gel was sintered at different temperatures. The
X-ray diffraction studies reveal that the samples are amorphous at sintering temperatures below
6000C and completely crystallized at 8000C. Under UV excitation of a He-Cd laser with
wavelength of 325 nm at room temperature, strong photoluminescence spectrum characterized
by a four-peak structure was observed. The most intensive peak at ~ 543 nm can be identified
as due to the 5D4 7F5 transition of the Tb3+ in the host matrix. The dependence of the
emission intensity on the sintering temperature will be discussed.
Keywords: (La,Gd)PO4:Tb3+, Sintering temperature, PL
1. Introduction
Over the past years, phosphors based on phosphate host matrices have become the subject of
great interest for an extensive investigation due to their wide applications in lighting and displays
with a high quantum efficiency and stability at higher temperatures [1]. LaPO4:Tb3+ has been
considered as an excellent commercial green phosphor that has been widely applied in the
development of fluorescent lamps, cathode ray tubes, field emission displays and plasma display
panels.
C. Wu et. al [2] had an idea about the phenomenon in which the host absorption will be
enhanced with the existence of Gd 3+. It is well known that the radius of Gd3+ is smaller than that
of La3+ due to the lanthanide shrinkage . With the Gd 3+ concentration increasing, the atomic
volume becomes smaller, thus the distance between the Tb3+ and the PO43 molecule will become
shorter. According to Frster's theory for energy transfer [3], the efficiency of energy transfer
between the PO43 and Tb3+ molecule will be enhanced which leading to the emission of Tb3+
being improved.
Orthophosphate phosphors have prepared by solutions based on combinatorial chemistry
method [4], solid-state reaction [5], precipitation method [7], hydrothermal reaction [2] and
spray pyrolysis [6]. Sol-gel method was selected with some advantages: The step progresses
were uniform, less toxic and lower sintering temperature compared to solid-state reaction and
many others. Grain sizes of the powder are in the range of nanometer [8].
In this paper, we report on the synthesis of Tb-doped (La,Gd)PO4 phosphor by sol-gel method
with citric acid as chelating agent. The structural, surface morphological and the optical
properties of the obtained phosphors are investigated and brought up for discussion.
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2. Experimental
La2O3,Tb4O7,Gd2O3+HNO3
Mixing
Transparent Solution
(NH4)2HPO4
Citric Acid
Transparent Sol
Heating at 80 oC
White Gel
o
Drying 100 C
Dry gel
Heating 170 oC
Sintered at 500-1200 oC for 1h
(La,Gd)PO4:Tb 3+
Fig. 1. The synthesis process for (La,Gd)PO4:Tb3+ by sol-gel method
Stoichiometric amount of La2O3 (99.99%), Tb4O7 (99.99%) and Gd2O3 with molar ratio (0.65
: 0.15 : 0.2) were dissolved in nitric acid. The transparent solution was mixed with a waterethanol volume ratio (1:7) containing citric acid as chelating agent for the metal ions. The molar
ratio of metal ions to citric acid was 1 : 2. The pH of the solution was adjusted to a low value
with HNO3 followed by the addition of stoichiometric amount (NH 4)2HPO4 (99%) [8]. The sol
changes to white opaque which had been stirring and heating to evaporate water and established
white viscous gel. After drying, the gel was heated to 1700C and it turned to black color due to
autofire reaction. Finally, the samples was annealed from 500 to 12000C to received white
powders (La,Gd)PO4:Tb3+. The synthesis process of the (La,Gd)PO4:Tb3+ is shown in Fig. 1.
The effects of sintering temperature on the crystallization degree and the particles
morphology were investigated by XRD (Siemens D5005) and FE-SEM (Hitachi S-4800).
Emission spectra at room temperature were recorded on the Microspec 2300 spectrometer,
excited by He-Cd laser.
Fig. 1 shows the XRD patterns of the (La,Gd)PO4:Tb3+ powders sintered at 600, 700, and
9000C. For the powder sintered below 6000C, no diffraction peak is observed in the XRD pattern
(not shown), indicating that the film remains amorphous at this stage. After sintering at 600 oC,
some weak and broad peaks are present in the XRD pattern. With the increase of annealing
temperature to 9000C, the diffraction peaks become sharper and stronger due to the increase of
the crystallinity and the growth of the crystallite size. From the literatures, it is known that
orthophosphates based on rare-earth element display a variety of structures [9]. They are
hexagonal, tetragonal and monoclinic modifications. On heating up to 9000C, the sample formed
monoclinic structrure with the lattice parameters were a = 0.6800 nm, b = 0.7035 nm, c = 0.6479
nm and = 103.50.
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Fig. 2. XRD patterns of the (La,Gd)PO 4:Tb3+

samples sintered at (a) 6000C; (b) 7000C; (c)
9000C.
Fig. 3. XRD pattern of the La0.65Gd0.2Tb0.15PO4

powder sintered at 12000C.
Fig. 3 shows the XRD pattern of the

La0.65Gd0.2Tb0.15PO4 powder samples annealed at
12000C. Several peaks at 2 = 21.740, 27.320, 28.920,
29.600, 46.50, 48.960 are present, which are due to the
(231), (202), (200), (120), (221), (312) and (132)
reflections of the crystalline lathanium phosphat,
respectively. This is consistent with the no. 84-0600 of
JCPDF date file.
Fig. 4. shows the FE-SEM micrograph of the
(La,Gd)PO4: Tb powder sintered at at 10000C for 1
hour. The particles with sizes ranging from 100 to 500
nm can be seen clearly from the FE-SEm image.
(a)
Fig.4. FE-SEM image of the

(La,Gd)PO4: Tb sample sintered at
10000C
(b)
Fig. 5. PL spectra of the La0.65Gd0.2Tb0.15PO4 powders (a) sintered at 500, 700, 8000C; (b) sintered at
800, 900 and 1100 oC.
Fig. 5 shows emission spectra of the La0.65Gd0.2Tb0.15PO4 powders sintered at different

temperature from 500 to 11000C under He-Cd excitation of 325 nm at room temperature. The
most intense emission peak of the La0.65Gd0.2Tb0.15PO4 powder located at 543 nm is assigned to
the 5D4 7F5 transition of Tb3+. The other peaks at 486, 584 and 619 nm are assigned to the 5D4
7F6, 5D4 7F4, 5D4 7F3 transition of Tb3+, respectively. This observation is in good
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agreement with the PL result previously reported for the (La,Gd)PO4: Tb3+ [9]. The effect of
sintering temperature on photoluminescent intensity is also shown in Fig. 5 (a) and (b). At first,
the emission intensity increases with the increase of sintering temperature. The highest PL
intensity obtained for the sample sintered at 8000C for 1 hour. Higher sintering temperatures
caused the decrease of emission intensity. In our opinion, the increase of the PL intensity when
the sintering temperature increases from 500 to 8000C can be explained as due to the better
crystallization of the powders as already shown in XRD patterns. At higher sintering
temperature, the particle tends to move in together and creating clusters. Thus, emission yield of
the phosphor decreases.
4. Conclusion
Powder of the (La,Gd)PO4:Tb3+ phosphors have been successfully prepared by a sol-gel
process using the non toxic inorganic compounds as main precursors. XRD pattern showed a
well-crystallized structure when the sample was sintered at 800 oC. The final product has the
particle morphology with sizes in the range from 200 to 500 nm. Strong photoluminescence was
observed from the sample sintered at 800 oC and showed the characteristic four-peak structure,
which corresponding to the four main transitions of Tb3+ in the host matrix.
Acknowledgement
This work is supported by the Key National Research Program in Science and Technology
KC.02.10/06-10.
Reference
1.
2.
3.
4.
5.
6.
7.
8.
9.
Phosphor Handbook, Phosphor Research Society (Japan), CRC Press, Boca Raton, (1999).
Chunfang Wu and Yuhua Wang, Materials Letters 61, 24162418 (2007).
Th. Frster, Ann. Phys,2, 55(1948).
Kee-Sun Sohn, Jae Mun Lee II, Woon Jeon and Hee Dong Park, J. Electrochem.
Soc,150,H182(2003).
R.P. Rao and J. Lumin,113, 271(2005).
Wuled Lenggoro, Bin Xia, Hiroaki Mizushima, Kikuo Okuyama and Naoto Kijima.
Materials Letters, 50, 9296(2001)..
Xueyan Wu, et al. Mater. Res. Bull, 37, 1531(2002).
M. Yu, J. Lin, J. Fu and Y.C. Han, Chemical Physics Letters, 371, 178183(2003).
U. Rambabu, N.R. Munirathnam, T.L. Prakash and S. Buddhudu, Materials Chemistry and
Physics, 78, 160169(2002)
Advances
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EFFECTS OF TIO2-NANOPARTICLES ON OPTICAL PROPERTIES OF MEH - PPV +

TIO2 CONJUGATED POLYMER NANOCOMPOSITES
Nguyen Nang Dinha, Tran Thi Chung Thuyb, Nguyen Kien Cuonga, Nguyen Thang Longa,
Nguyen Minh Nama, Nguyen Duc Diepa, Le Ha Chia, Tran Hong Nhungc
a)
College of Technology, Vietnam National University in Hanoi, Vietnam

b)
Thai Nguyen University of Education
c)
Institute of Physics, VAST
E-mail: dinhnn@vnu.edu.vn
Abstract: Optical properties of TiO2/MEH-PPV composites were studied based on different

weight ratio of TiO2 embedded in poly(2-methoxy, 5-(2-ethylhexyloxy)-1,4-phenylene vinylene
(MEH-PPV). The composites were prepared on ITO/glass substrates by spin-coating. The
composite properties were characterized by alpha-step measurement, Raman, absorption and
photoluminescence (PL) spectra. Results show that the amount of nc-TiO2 particles and the
drying vacuum procedures considerably affected both the absorption and PL spectra. The
absorption and photoluminescence spectra of MEH-PPV polymer matrix, COM-2 (20 wt%
TiO2) nanocomposite films better show conjugated length, the order of molecular chains and
delocalization of -electrons. Therefor, 20 wt% TiO2/MEH-PPV composite films with 150 nm
thickness annealed at temperature of 130 0C and time of 1h were selected as
electroluminescence-emitted polymer layers in OLED devices
Keywords: Organic light-emitting diodes (OLEDs), nanocomposites, MEH-PPV, I-V
characteristic, PL spectra, ITO.
1. Introduction
Organic light-emitting diodes (OLEDs) based on conjugated polymer and nanoparticles have
been widely studied for optoelectronic devices because their low-cost, light-weight, flexible
configuration, large-luminescence area, and their simple-processing [1-3]. It is necessary for
OLEDs to improve the light-emitting efficiency. It has known that the electrons have lower
mobility due to higher mass weight of two carriers. This leads to the unbalance of holes and
electrons injection, resulting in decreasing luminescent-emitting efficiency of OLEDs. Adding
nanoparticles like titan oxide (TiO2) into emitting polymer layer is the one of the approaches to
enhance luminescent effectiveness for OLED [4,5]. In this case, nanoparticles play a role of ptype semiconductor, and conducting polymers as n-type similar to p-n heterojunction.
Absorption and photoluminescence spectra of the nanocomposites based on the uniformed
dispersion of TiO2 in the conducting polymer were changed, in comparision with those of the
polymer matrix without adding TiO2 nanoparticles. Almost studies revealed that
photoluminescence quenching is usually coupled with the adding TiO 2 nanoparticles into
conducting polymers due to the charge separation and transfer at interfaces of inorganic
nanoparticles and polymer matrix of the composites [8-10]. It depend on the weight percentage
of TiO2 in the composites, the thickness of a composite layer as well as annealing conditions.
The characteristic of the absorption and photoluminescence spectra could give information about
polymer-chain directions, conjugated length and localization of -electrons [4,5]. An increase
in the full width half maximum (FWHM) of the PL spectra corresponding to zero-phonon
emission and vibronic spacing energy of nanocomposites is attributed to an increase of polymerchain directions and localization of -electrons of the nanocomposites compared to those of the
controlling samples (the sample made by polymers without any TiO2 particles added). On the
contrary, if FWHM of PL spectra corresponding to zero-phonon emission and vibronic spacing
energy decreased, the polymer-chain directions and localization of -electrons of the
nanocomposites reduced. In addition, the absorption and photoluminescence peaks of
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TiO2/MEH-PPV shifted to the longer wavelength (red-shift) than those of the controlling
samples. This shows that the conjugated length of polymer chains in the composite is longer
than that of the controlling polymer. In the case of the peaks (mentioned above) shifted to the
shorter wavelength (blue-shift), conjugated length of polymer chains decreased [4,5].
In this paper, we have reported the effects of embedded TiO2 nanoparticles on optical
properties of TiO2/MEH-PPV nanocomposites spin-coated on the ITO/glass substrates using
absorption, photoluminescence and Raman measurement.
2. Experiments
The solution of MEH-PPV were
Table 1. The compositions of TiO2 / MEH-PPV
prepared by dissolving 2 mg MEH-PPV in
samples
1ml xylene solvent. TiO2 nanoparticles in Sample
Weight of
Weight of Weight of TiO2
5 nm-diameter were dispersed in MEHs
MEH-PPV
TiO2(g)
to MEH-PPV
PPV solution with a weight ratio of 0, 10,
(g)
(wt%)
20, 40 and 50 wt%; COM-0, COM-1, COM-0
0.002
0
0
COM-2, COM-3, COM-4, in short, COM-1
0.002
0.0002
10
respectively,. The compositions of TiO2 / COM-2
0.002
0.0005
20
COM-3
0.002
0.0010
40
MEH-PPV samples are listed in table 1.
0.002
0.002
50
The fine-distribution of TiO2 in the COM-4
MEH-PPV matrix was performed by using the ultrasonic irradiation, and casted onto the glasssurfaces and indium-tin-oxide (ITO) substrates (area A = 3.5 cm2, thickness d = 150 nm) to
fabricate nanocomposites films. Then, the films were annealed at 130 0C for 1 hour in vacuum.
The thickness of thin films were measured by -step measurement .The interaction of TiO2
and MEH-PPV in composite films was detected by Raman spectroscopy using He-Ne laser
excitation at 325 nm. Effects of TiO2 nanoparticles on the optical and electrical prperties of
TiO2/MEH-PPV nanocomposite films were investigated by absorption, photoluminescence
spectra.
3. Results and discussion.
Fig 1 shows the absorption
spectra of pure MEH-PPV and
nanocomposites films annealed at
1300C for 1 hour in vacuum. The
absorbance configuration of MEHPPV in composites mainly remains
the same compared to that of only
MEH-PPV, corresponding to *
transition [7] with the peak at the
498 nm. The absorption spectra of
COM-1 and COM-2 nanocomposites
were slightly red-shifted compared
to those of MEH-PPV matrix, and
different from those of COM-3 and
COM-4, which show the blue-shift.
This can be attributed to the
conjugated length of COM-1, COM2 samples are longer and COM-3,
COM-4 samples are shorter than
those of precursor polymer film [4-
Tables 2. Gaussian fitting parameters for PL spectra (Fig. 2)

of MEH-PPV and MEH-PPV + TiO2 nanocomposites thin
films heated in vacuum at 130 0C for 1 hours
Samples Peak 1 (0-0 Peak 2 (0-2 Vibronic PLIpeak1/
transition)
transition)
splitting
PLIpeak2
(nm)
(nm)
(eV)
COM-0
599.28
644.28
0.12
1.12
FWHM 14.23
20.89
COM-1
602.34
639.21
0.121
1.13
FWHM 14.2
21.23
COM-2
603.71
637.81
0.122
1.22
FWHM 14.04
19.58
COM-3
597.43
634.73
0.123
1.09
FWHM 14.07
31.23
COM-4
598.33
635.45
0.121
1.08
FWHM 14.45
21.56
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6]. Photoluminescence spectra of pure MEH-PPV matrix and TiO2/MEH-PPV nanocomposites

films were presented in Fig 2. It can be seen that the photoluminescence intensity decreased
when TiO2 ratio increased due to photoluminescence quenching effect. This is attributed to the
increase in the interfacial area between TiO2 particles and polymer matrix in composites, leading
to an increase the number of the separation of charge at the interface and the transfer of the
photogenerated electrons from MEH-PPV polymer matrix to TiO2 nanoparticles. It has shown
that the photoluminescence features of nanocomposites are similar to that of MEH-PPV, except
the relative intensity between peaks was changed. The MEH-PPV film emitted red-orange at the
wavelength of 594 nm and 630 nm, assigned to 0-0, 0-1 transition, respectively [10,11].
Peak located at 594 nm was named as peak 1, the other at the 630 nm as peak 2.. The PLI of
the peak 1 were increased for COM-1, COM-2 and decreased for COM-3, COM-4 compared to
that of COM-0 (Fig. 3). The increase of peak 1 intensity, corresponding to 0-0 transition shows
that the direction of molecular chains and localization of -electrons increased [4]. These
results revealed that the direction of molecule chains of polymer matrix of COM-1 and COM-2
samples was more regular than that of COM-3, COM-4 samples.
Fig. 1. The absorption spectra of pure MEHPPV(a) and TiO2/MEH-PPV nanocomposite

films (b-e) on ITO substrates heated in vacuum
at 1300C for 1 hour
Fig. 2. The PL spectra of pure MEH-PPV(a)

andTiO2/MEH-PPV nanocomposite films (b-e) on
ITO substrates heated in vacuum at 130 0C for 1
hour
The Gaussian fitting parameters for PL spectra of

MEH-PPV matrix and TiO2/MEH-PPV nanocomposites
films heated at 1300C for 1 hour are shown in table 3.
When the TiO2 ratio increased from 0% to 20 wt%, the
full width and half maximum (FWHM) of spectra
corresponding to emitted zero-phonon decreased from
14.23 to 14.04 nm, while the vibronic spacing energy
increased from 0.120 to 0.122 eV. It has been known
that in [4,5], an increase of vibronic splitting energy
width and zero-phonon emission means an increase of
the order of molecular chains and -electron
delocalization [4,6]. Contrary to COM-3, COM-4
Fig. 3. The photoluminescence
samples, the FWHM of the spectra corresponding to
intensity (PLI) ratio of peak 1 to
zero-phonon emission increased from 14.07 to 14.45 nm
peak 2, depend on TiO2 content
while the vibronic spacing energy decreased from 0.122
to 0.121 when the TiO2 ratio went up from 40 wt% to 50 wt%. This may be attributed to the very
high TiO2 ratio leading to changes in the direction of molecular chains, thus, -electrons was
difficult to have a regular localization along the molecular chains [4,6].
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Further more, photoluminescence spectra of COM-1, COM-2 nanocomposite were redshifted, in contrary to those of COM-3, COM-4. These results coincide with those of absorption
spectra. This may be attributed to increasing conjugated length of molecular chains of COM-1,
COM-2 compared to
MEH-PPV.
For
COM-2 (20 wt%
TiO2/MEH-PPV)
samples,
the
photoluminescence
quenching is very
strong indicated that
the conjugated length,
the order of molecular
chains
and
electron
Fig 4. The absorption spectra of
Fig 5. The phtoluminescence
delocalization
spectra of COM-2 with the
increased much more COM-2 with the different thickness
different thickness.
than those of pure
MEH-PPV [4,5]. Based
on
the
analysis
mentioned above, the
COM-2 was selected for
the next characterization.
Fig 4 and Fig 5
indicate the absorption
and photoluminescence
spectra of COM-2 thin
films of 150 and 20 nm
a
b
in thickness. As the
Fig 6. The thickness of COM-2 (20 wt% TiO2): a):COM-2-150nm;
thickness decreased from
b):COM-2-20 nm
150 nm to 20 nm,
coincident with the band-gap energy Table 3. Gaussian fitting parameters for PL spectra (Fig. 8)
increased, the absorption and of MEH-PPV and MEH-PPV + TiO2 nanocomposites thin
photoluminescence spectra of COM- films dried in the air at room temperature
2 nanocomposites were blue-shifted Samples Peak 1 (0-0 Peak 2 (0-2 Vibronic PLIpeak1/
transition)
transition)
splitting
PLIpeak2
[6], and inversely were red-shifted.
(nm)
(nm)
(eV)
This maybe ascribed to the quantum
COM-0
size efficiency. Analyzing the
574.91
613.04
0.134
1.16
Gaussian fitting parameters we can
FWHM
14.29
20.79
see that the FWHM of spectra
COM-1
corresponding to the zero-photon
578.36
615.27
0.13
1.08
emission increased from 14.04 to FWHM 14.06
21.31
14.60nm while the vibronic spacing COM-2
energy decreased from 0.122 to 0.11.
603.71
617.79
0.128
1.22
This demonstrates that the order of FWHM 14.04
19.59
molecular chains and delocalization COM-3
597.43
621.72
0.127
1.08
of -electron decreased with the
21.22
decrease of film thickness from FWHM 14.07
COM-4
about few hundreds nm to about few
598.33
627.72
0.124
1.08
tens nm.
FWHM 14.45
21.23
Fig 7 and Fig 8 present the
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absorption and photoluminescence spectra of nanocomposite films, which were air dried in air at
room temperature. Compared to the absorption and photoluminescence spectra (data in the
Tab.2) of nanocomposite films annealed at 1300C for 1 hour in vacuum the non-annealed films
show a blue-shift of the spectra (data in Tab.3). It means that the changes in the order of
molecular layer on the surface and distribution of -electrons of composite films heated in
vacuum at 1300C that could be better than those of the films dried in air at room temperature
The combination of TiO2 nanoparticles and MEH-PPV polymers was studied by Raman
spectroscopy. Figure 9 shows the Raman spectra of MEH-PPV (a) and TiO2/MEH-PPV
composites (b). Peaks were located at wavenumbers of 1110, 1290, 1312, 1583cm-1,
corresponding to the bands of MEH-PPV pure. It proves that the TiO2/MEH-PPV composites
were formed as a simple mixture. Hence, many inorganic/organic boundaries were created,
making a great contribution to the change in electrical properties of MEH-PPV.
Fig 7. The absorption spectra of pure MEH-PPV

and TiO2 /MEH-PPV nanocomposite films casted
on ITO substrate, dried in air at room temperature.
Fig 8. The PL spectra of pure MEH-PPV

and TiO2 /MEH-PPV nanocomposite films
casted on ITO substrates, dried in air at
room temperature.
4. Conclusions
Optical
properties
of
TiO2/
MEH-PPV
nanostructured composite films vs. embedded nc-TiO2
concentration were investigated, with different film
thickness and annealing conditions. Compared to the
absorption and photoluminescence spectra of the pure
MEH-PPV polymer matrix, the COM-2 (20 wt% TiO2)
nanocomposite films show better conjugated length, the
order of molecular chains and delocalization of electrons, leading to the increase in spectra FWHM
corresponding to zero-photon emission and vibronic
spacing energy corresponding to the shift of absorption
Fig 9. The Raman spectra of pure
and photoluminescence peaks to the longer wavelength
MEH-PPV and TiO2 /MEH-PPV
nanocomposite films casted
(red-shift) and the increase in photoluminescent
on ITO substrates.
intensity of a peak corresponding to zero-photon
emission. Therefore, COM-2 (20 %wt TiO2) composite
films with 150 nm thickness annealed at temperature of 130 0C and time of 1h were selected as
electroluminescence-emitted polymer layers in OLED devices.
Acknowledgements
This work is supported in part by Vietnam National Foundation for Basic Scientific
Research in Physics (2006-2008), Project code: 410306. The author T.T.C.Thuy acknowledges
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the MOET for a partial financial support to Ph.D research through a project No.B2007-TN 0404.
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6. V. Sivaji Reddy, K. Das, S. K. Ray and A. Dhar. Characteristics of MEH-PPV thin films on
ITO electrode for organic light emitting diodes. Proc.of ASID06, 8-12 Oct, New Delhi 215218.
7. Fumitomo Hide, Mara A.Daz-Garca, Benjamin J. Schwartz and Alan J. Heeger. New
developments in the photonic applications of conjugated polymers. Acc.Chem.Res.1997, 30,
430-436.
8. S. A. Cater, J. C. Scott and P. J. Brock. Enhanced luminance in polymer composite light
emitting devices. Appl. Phys. Lett. 71 (9), 1145-1147,1997.
9. V. M. Burlakov, K. Kawata, H. E. Assender, and G. A. D. Briggs, A. Ruseckas and I. D. W.
Samuel. Discrete hopping model of exciton transport in disordered media. Physical Review
B 72, 075206 (2005).
10. T. Huser, M. Yan. Aggregation quenching in thin films of MEH-PPV studied by near-field
scanning optical microscopy and spectroscopy. Synthetic Metals 116 (2001) 333-337.
11. Kyu Won Lee, Kyu Hyun Mo, Jea Won Jang and Cheol Eui Lee. Photoluminescence study of
the proton-irradiated MEH-PPV conjugated polymer. Jounal of the Korean Physical Society,
Vol. 47, No. 1, July 2005, pp.130~132.
Advances
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SOL-GEL SYNTHESIS OF BAMGAL10O17:EU BLUE-EMITTING

PHOSPHOR POWDER
Nguyen Manh Cuonga, Tran Trong Ana,b, Le Anh Tuana, Pham Thanh Huya,b
and Pham Hong Duongc
a)
Hanoi Advanced School of Technology (HAST)

International Training Institute for Materials Science (ITIMS), Hanoi University of
Technology (HUT), 1 Dai Co Viet, Hanoi, Vietnam.
c)
Intitute of Materials Science (IMS), Vietnamese Academy of Science and Technology (VAST),
18 Hoang Quoc Viet Road, Hai Ba Trung District, Hanoi, Vietnam
b)
Abstract: The BaMgAl10O17:Eu (BAM) blue-emitting phosphor powders successfully prepared

by citrate sol-gel technique. Crystallinity and photoluminescence of the powders were
investigated. XRD result show that phase of the powders strongly depend on the annealing
temperatures
1. Introduction
Blue-emitting phosphors, with maximum emission in range of 440-480nm, are interesting
materials for light and display devices comprising fluorescent lights (FL), projection televisions
(PTV), plasma display panels (PDP) and field emission displays (FED). Eu2+ activated barium
magnesium aluminates (BAM) have been considered as the important blue-emitting phosphors
because of their good emission efficiency and chemical stability [1-4].
The quality of BAM phosphors is strongly influenced by crystalline, shape of particle,
additives, defects and preparing technique. Conventionally, commercial BAM phosphors are
synthesized by solid-state reaction method. However, complicated process and high energy
consumption are the big problems to fabricate in phosphors by solid-state reaction method.
Furthermore, this method also causes the inhomogeneity and large impurities in material [5,6].
For improving the disadvantages of solid-state reaction method, numbers of other techniques
have been proposed to synthesize BAM phosphors including: sol-gel route, spray pyrolysis. The
sol-gel method is able to be seen as a potential way to prepare the fine phosphor powders. In
comparison with solid-state reaction method, the well-mixing at molecule level and the
controlling of ingredients can be done easily by sol-gel method. Moreover, sol-gel technique
guarantees that this is considerable method to reach the fine particles and pure of phosphors [68].
In this work, by citrate sol-gel process, we successfully synthesize the pure well-crystallized
BAM phosphors. The influence of the annealing temperature and reduction process on the
structures and luminescent properties of BAM has been investigated. The works showed that
improving the stability of phosphor could be carried out by increasing firing temperature.
2. Experimental
The powder BaMgAl10O17:Eu2+ (BAM) blue phosphors were successfully prepared by
citrate sol-gel process that shows in figure 1. The starting reagents consists of
Al(NO3)3.9H2O(98,5%), Ba(NO3)2(99%), MgO(98%) and Eu2O3(99,99%). To obtain
Eu(NO3)3 and Mg(NO3)2 solutions, Eu2O3 and MgO were dissolved in nitric acid. Then
Al(NO3)3.9H2O and Ba(NO3)2 were added and mixed until the solution became transparency.
In the next step, citric acid was added and mixed continuously to gain homogeneous solutions.
The solutions were heat at 800C, in this process, the water was slowly evaporated. Because of the
removing water, solutions were converted into the white gel ultimately. After drying at 1200C for
2h and heating at 2000C for a day in a muffled oven, dried puffy and porous gels were obtained.
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These gels were calcined at 900,1000,1100,1200 and 13000C for 3h and cooled to room
temperature in air. Finally, the samples were annealed at 900, 1000, 1100 and 12000C in a
reductive gas consisting of 90% argon and 10% hydrogen for 1 h.
To characterize the crystal structure of these powders, Siemens D5005 X-Ray diffractometer
with Cu-K radiation system was performed. The shape of particles was observed by scanning
electron microscopy (Hitachi S-4800 FE-SEM). Emission spectra at room temperature were
conducted on spectrometer excited by He-Cd laser.
Al(NO3)3.9H2O, Ba(NO3)2
Eu2O3, MgO + HNO3
Solution
Mixing
Transparent Solution
Citric Acid
Transparent Sol
Heating at 800C
White Gel
0
Drying 120 C
powder
0
Heating 200 C
Reducing with
10%H2/Ar for 1h
Calcining at 100013000C for 3h
BaMgAl10O17:Eu3+
BaMgAl10O17:Eu2+
Fig. 1 The process of BAM by sol-gel synthesis

XRD patterns of powders annealed at temperatures between 1000 and 13000C are shown (In
Fig. 2). At 10000C and 11000C of the calcining temperature, the precursors were crystallized
and. Three Three peaks (19.6030, 28.2820 and 34.3180) correspond to BaAl2O4 (200), BaAl2O4
(202) and BaAl2O4 (220) due to the transformation of precursors to BaAl2O4. As we annealed
samples at 12000C and 13000C, the phase of BaMgAl10O17 (BAM) that shown at
31.7810(110), 33.1790(107) and 35.6000(114) was appeared. In addition, it can be seen that
increasing of annealing temperature lead to higher peaks due to the enhanced crystallinity. In
comparison to conventional solid-state reaction method with 15000C of preparation, BAM
crystals can be synthesized at lower temperature (13000C) by sol-gel method.
(202)
(110)
(107)
(220)
(114)
(200)
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Intensity (au)
1300 C
1200 C
1100 C
1000 C
20
30
40
50
60
70
2q/(deg)
Fig. 2 XRD patterns of the BAM samples calcined

at different temperatures
Fig. 3 FE-SEM micrograhs of the BAM samples

calcined at 13000C and reduced with 10%H2/Ar at
12000C for 1h
Eu
Eu
400
Fig.4. 3 FE-SEM image of the BAM samples

calined at 13000C and reduced with 10% H2/90%
Ar at 12000C for 1 h
6
455 nm 4f 5d -> 4f
intensity (a.u)
1: 1300 C reduced 900 c

o
o
2: 1300 C reduced 1100 C
o
o
3: 1300 C reduced 1200 C
=325
nm
ex
2
1
400
500
600
700
800
Wavelength (nm)
Fig. 6 Emission spectra of obtained BAM for the

samples after reduction
l ex=325 nm
2+
intensity (a.u)
Eu
3+
500
600
3+
700
800
Wavelength (nm)
Fig. 5 Emission spectra of obtained BAM for the

samples calcined at 11000C and reduced with
10%H2/Ar at 11000C
The morphology of the BAM powder was

examined by FE-SEM. As shown in Fig. 3,
particles with sizes ranging from 100 to 700
nm were observed for the sample cancined at
13000C and then reduced in a mixed gas of
10% H2/90% Ar at 12000C for 1 hour.
The photoluminescence (PL) spectrum is a
simple and useful tool to characterize and
evaluate quality of the phosphors. The PL
measurements were performed at room
temperature using a He-Cd laser with a
wavelength of 325 nm. Fig. 4 shows the PL
spectra of the BAM powders, which were
fired at different temperatures in the air. The
PL spectrum of the BAM powder (without
reducing in H2/Ar gas) is characterized by a
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multi-peak structure in the visible from 550 to 900 nm with the two most intensive peaks located
at around 618 and 700 nm. From the literature, these two emission bands can be identified as due
to the transitions 5D0 7F2 and 5D0 7F4 of Eu3+ in the host matrix, respectively. The intensity
of their emission bands increased with increasing firing temperature from 1100 to 13000C. At the
same time the position of the peaks shifted to 610 and 683 nm, respectively.
One should note that when the BAM powder was fired at a temperature below 12000C, the
main crystal phase in the host is BaAl2 O4, as shown by XRD in Fig. 2. At higher firing
temperature, there was a gradual transformation of the crystal phase to BaMgAl10O17. This phase
transformation leads to the change in the crystal field of the host and thus leads to the shift of the
two main emission peaks to 610 and 683 nm. It is interesting to mention that the goal of this
study is to synthesis BaMgAl10O17:Eu2+ with the Eu ion in the divalent state (Eu2+). However,
before annealing the powder in the mixture of H2/Ar gas, we only observed the transitions related
to the trivalent state (Eu3+) of Eu in the host matrix. It is known from the literature that the Eu 3+
ion can effectively be converted to Eu2+ by a second heat-treated step in a reductive gas. The
obtained powders were the annealed at different temperatures in a mixture of 10% H 2 /90 % Ar.
Fig. 5 shows a typical PL spectrum of BAM phosphor calcined at 1100 0C and reduced at
11000C. Beside, the two well-known peaks related to the transitions 5D0 7F2 and 5D0 7F4 of
Eu3+ in the host matrix at 610 and 683 nm, a new emission band with peak around 455 nm was
observed. This new emission band can be identified as due to the transition from the 4f65d to 4f7
of Eu2+ ions. This observation indicates that after the second firing process, not all the Eu3+ were
reduced to Eu2+ ions.
Fig. 6 shows the PL spectra of the BAM samples calcined at 13000C and reduced at 9000C,
11000C and 12000C for 1h. To our surprise, in these heat-treatment conditions, only one
emission band (at 455 nm) relating to the 4f65d to 4f7 of Eu2+ in the host was observed in the PL
spectra. The intensity of the 455 peak increased with increasing the annealing temperature in the
H2/Ar mixed gas. By varying the heat-treatment conditions, we have found that when the BAM
sample was calcined at the temperature higher than 12000C, and reduced at higher temperatures,
Eu3+ ions were transformed completely to Eu2+.
4. Conclusions
BaMgAl10O17:Eu2+ (BAM) blue phosphors were produced via a simple citrate sol-gel
process. The synthesis temperature was lower compared to solid-state method. X-ray showed a
well-crystallized, hase-pure -alumina structure BAM crystalline. The resultant BAM phosphors
had high purity, perfect crystalline morphology and exhibited a higher luminescent intensity.
When BAM were annealed to 12000C in a reductive atmosphere with 90% argon and 10%
hydrogen for 1h is better than annealed to 9000C, 10000C and 11000C.
Acknowledgement
This work is supported by Vietnamese national key Science and Technology Program, grant
No. KC.02.10/06-10.
Reference
1. Camellia Panatarani, I. Wuled Lenggoro, Naoki Itoh, Hiroyoshi Yoden, Kikuo Okuyama
Polymer-supported solution synthesis of blue luminescent BaMgAl10O17:Eu2+ particles
Materials Science and Engineering B 122 (2005).
2. Li-Te Chen, I-Lei Sun, Chii-Shyang Hwang, Shoou-Jinn Chang, Luminescence properties
of BAM phosphor synthesized by TEA coprecipitation method Journal of Luminescence
118 (2006) 293-300
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3. Shuxiu Zhang, Toshihiko Kono, Akira Ito, Taketo Yasaka, Heiju Uchiike Degradation
mechanisms of the blue-emitting phosphor BaMgAl10O17:Eu2+ under baking and VUVirradiating treatments Journal of Luminescence 106 (2004).
4. Journal of Alloys and Compounds 454 (2008) 245249 Luminescent properties and thermal
stability of BaMgAl10O17Eu2+ synthesized by solgel route
5. Shozo Oshio, Koji Kitamura, Teruaki Shigeta, Shigeru Horii, Tomizo Matsuoka, Shosaku
Tanaka, and Hiroshi Kobayashi Firing technique for preparing a BaMgAl10O17:Eu2+
Phosphor with controlled particle shape and size Journal of the Electrochemical Society,
146 (1) 392-399(1999).
6. Zhe Chen, Youwei Yan Crystallinity and luminescent properties of citrate sol-gel derived
BAM phosphor Materials Letters 61 (2007) 3927-3930.
7. Kyeong Youl Jung, Yun Chan Kang Preparation of BaMgAl10O17:Eu blue phosphor by
flame-assisted spray pyrolysis: photoluminescence properties of powder and film under VUV
excitation Materials Letters 58 (2004).
8. Kyeong Youl Jung, Dong Youl Lee, Yun Chan Kang, Hee Dong Park, Improved
photoluminescence of BaMgAl10O17 blue phosphor prepared by spray pyrolysis Journal of
Luminescence 105 (2003).
9. Kazuyoshi Yokota, Shu-XiuZhang, Katsuaki Kimura, Akira Sakamoto Eu2+-activated
barium magnesium aluminate phosphor for plasma displays Phase relation and mechanism
of thermal degradation Journal of Luminescence 92 (2001) 223-227
10. G. Bizarri, B. Moine, On BaMgAl10O17:Eu2+ phosphor degradation mechanism: thermal
treatment effects Journal of Luminescence 113 (2005).
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TiOxNy PHOTOCATALYTIC THIN FILMS FABRICATED BY THE EXTRA

UNBALANCED MAGNETRON SYSTEM
Vu Thi Hanh Thu , Nguyen Huu Chi, Le Van Hieu, inh Cong Truong,
Pham Kim Ngoc, Le Dinh Minh Tri
University of Science, 227 Nguyen Van Cu Street, 5, Ho Chi Minh City, Vietnam.
E-mail: vththu@hcmuns.edu.vn.
Abstract: In our work [1], the TiOxNy photocatalytic thin films achieve a high content of doped
Nitrogen and the band gap belonging to visible light range. However, these films still have the
low photocatalytic properties due to the high energy of bombardment ions and they are deposited
at the low pressure. According to Thornton structure model, the fabricated process have to be
carried out at pressure about 10-2 torr, so that thev films have sufficient large effective surface
area. In addition, at this pressure, the impact of particles makes energy of neutral particles
decrease and the films contain lower amount of doped Nitrogen, causing weaker light absorption
in visible light range. To solve this problem, we use the unbalanced magnetron system in which
the amplitude of magnetic field decrease from 400 Gauss to 200 Gauss. The results show that
films can not only thoroughly absorb light in the visible range but have the high photocatalytic
properties as well.
1. Introduction
Fig. 1: DC magnetron system
Fig.2: the unbalanced magnetron system
Nowadays, thin films as well as TiOxNy

films are fabricated by many methods.
However, they are arranged into two basic
methods: Physical Vapor Deposition (PVD)
and Chemical Vapor Deposition (CVD). In
our study, we are concerned about the first
method. There are many ways to fabricate
thin films by PVD method, but researchers
mainly have utilized the deposition process
from the vapor phase and sputtering method.
Specifically, we have used the reactive
sputtering combining the magnetic field (to
Fig. 3: the extra unbalanced magnetron system.
enhance the moving path of electrons) which
are created by right laid magnets (fig.1). To
achieve our purpose, we want to increase the bombardment into films while maintaining the
relative low pressure, so we have used the unbalanced magnet system[1] (fig.2). The magnetic
field has reached 400Gauss above the surface target in this system.
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Currently, the TiOxNy thin films fabricated by DC magnetron sputtering have studied by
many groups. However, most of their results show that the amount of Nitrogen doping is relative
low (lower than 2%atN)[2] or the photocatalytic properties are not effective (abs = 0.077) [3].
With the study [1], we have successfully fabricated the TiOxNy films having a relatively high
%atN ratio (25,1%N), Eg = 2,15eV. However, films have the low photoreaction (abs = 0.068)
due to the strong bombardment from ions and films have deposited with low pressure.
According to Thornton structure model, the fabricated process have to be carried out at
pressure about 10-2 torr, so that the films have sufficient large effective surface area. In addition,
at this pressure, the impact of particles makes energy of neutral particles decrease and the films
contain lower amount of doped Nitrogen, causing weak light absorption in visible light range.
To overcome this problem, we have proposed an extra unbalanced magnetron system, in
which the magnetic field decrease from 400Gauss to 200Gauss (fig.3) by lifting the target above
the surface of magnetron system about 3cm.
In this study, we have fabricated TiO xNy films by 400Gauss and 200Gauss magnetron
system. After that, we have compared their Nitrogen doping ratio and photocatalytic properties.
2. Experimental
The TiOxNy films have been fabricated by
reactive sputtering DC magnetron method with
titanium target (99.99% purity) and the size of
target is 80x80x6mm. The sputtering gas is
Argon gas (99.99%) and reactive gas is oxygen
(99.99%) and nitrogen (99.99%). They are
mixed according to sputtering ratio in the press
container and enter the vacuum chamber by
needle valve system.
The process of deposition occurs at the total
pressure 13mtorr. The distance between target
and substrate is 4cm [1] and the sputtering power
varies from 129W to 412W. The structure,
optical properties and ratio %at N of films are
characterized by X-rays, UV vis and EDX Fig. 4. The unbalanced magnetron system in
spectroscopy, respectively. The effects of
the sputtering process.
photocatalyst are examined by investigating
T
parameter abs= ln f .
Ti
Acording to the work [1], we have discovered that %atN ratio and the photocatalytic
capability increase with high sputtering power. Therefore, in this work we consider to investigate
the films made in condition of varied sputtering power.
3.1. With the 400 Gauss system
Table 1. Results of band gap Eg, stress f, particle size D, ratio %atN and the photocatalytic capability
abs when varying the sputtering power at p=13mtorr.
Sample Power (W) Eg (eV)
D(nm)
%atN
abs
f (Gpa)
at peak A(101)
after 5 hours
M57
168
3.3
-3.515
263
0
0.143
M58
193.5
3.3
-3.765
281
0
0.172
M59
215
3.2
-3.859
297
0.04
0.202
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Fig. 5: The transparent spectra of TiOxNy

films at varied power (400Gauss system)
Fig. 6: The graph ( dh )1/2 = f(h ) of TiOxNy

films at varied power (400Gauss system).
Fig. 7: XRD spectrum of TiOxNy at varied power

(400Gauss system).
Fig. 8. the degradation of MB of TiOxNy

films at varied power(400Gauss system).
Fig. 5 and 6 show that despite increasing sputtering power, films have a low content of the
Nitrogen doping into TiO2 crystal because the absorption edge has not shifted to visible light
range and Eg > 3.2eV
(Eg = 3.2eV is the band gap of bulk material of anatase TiO 2[4]).
The maximum transparency of films in the visible light range is about 85% 90%, strongly
absorbing at 350 nm (fig.5). All of films are light yellow. Films fabricated with higher power
have shifted the absorption edge to a longer wavelength, but just in a small range.
The structure of films still remains at anatase TiO 2 phase with the A(004) plane priority
oriented (fig. 7). The films have deposited with higher power and the intensity of A(004) peak is
higher, i.e. higher crystallinity.
However, at p = 13mtorr, the Nitrogen doping in films is very small with the power about
168W 215W. Nevertheless, all films have ABS > 0.14 after a 5-hour illumination. The
transparency of films after immersing in MB solution at the 650nm wavelength increases
gradually with exposing light in visible range (fig.8). It is found that the degradation of MB
increases with the higher power.
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3.2. With the 200 Gauss system

Due to of the properties of our system, we couldnt continue to increase the sputtering power
above 400Gauss. Therefore, we have improved the system until the magnetic field is down to
200Gauss and hence the power has increased remarkably.
Table 2. Results of band gap Eg, stress f, particle size D, %atN ratio and the photocatalytic capability
abs when varying the sputtering power at p = 13mtorr.
Sample
f (Gpa)
abs after 5 hours
%at N
2.5
D (nm) at
peak
A(101)
30.4
-7.67
0.080
2.4
2.35
2.25
25.3
25.4
27.7
-7.27
-7.74
-8.57
0.158
0.278
0.476
0
12.44
14.13
Power (W)
Eg (eV)
N03
260
N05
N07
N09
297
350
412.5
Fig.9 shows that the maximum transparency of films in the visible range is about 75% 80%
and the maximum absorption of those varies from 380nm 480nm wavelength. Films which
have been fabricated with higher power shift the absorption edge to longer wavelength (or
smaller Eg) (fig.9). Eg varies from 3.15eV 2.15eV (fig.10), showing that films strongly absorb
light in the visible range.
The amount of Nitrogen doping with the power P = 350W (sample N07) and 412.5W
(sample N09) is 12.44at%N and 14.3at%N, respectively (table 2). When the sputtering power is
smaller 350W, there is nearly no Nitrogen doping in films, or it is too small to be detected by
equipment.
Fig. 9: The transparent spectra of TiOxNy films

at varied power (200Gauss system)
Fig. 10: The graph ( dh )1/2 = f(h ) of TiOxNy

films at varied power (200Gauss system).
Alternatively, all films have contained the mixture of anatase phase (fig.11). The intensity of
peaks is higher and density of peaks is larger when films are deposited with higher power. At the
power 412.5W
(Vp ~ 750V), the A(211) plane grows rapidly. This is not observed in the
previous experiment due to low sputtering power.
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Fig. 11 XRD spectrum of TiOxNy films at

varied power (200Gauss system).
Fig. 12 The degradation of MB solution of

TiOxNy at varied power (200Gauss system).
.
N05,rms = 9.66nm
N07,rms = 11.91nm
N05,rms = 15.29nm
Fig.13: The AFM images of TiOxNy films at varied power (200Gauss

system).
The photoreaction of films increases with high sputtering power and exposed time. The best
of MB degradation is attained with films which are deposited at power P = 412.5W (fig.12).
The effective surface area of TiOxNy films have investigated by the roughness (rms) from
AFM images. These AFM images (fig.13) show that films have higher roughness when they are
fabricated at higher sputtering power.
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4. Conclusions
We have improved the DC magnetron system to enhance the sputtering power (from 215W
to 412W) by decreasing the magnetic field from 400Gauss to 200Gauss and have reached the
better results. The TiO xNy films have the doped Nitrogen about 14,13%atN; Eg = 2.15eV and the
photocatalytic capability is higher in the visible light range with abs = 0,476 after a 5 - hour
illumination.
References
1. Vu Thi Hanh Thu , Nguyen Huu Chi, Le Van Hieu, Dinh Cong Truong, Le Queo, Pham Kim
Ngoc, (2008), The auger neutralization process in the unbalanced dc sputtering magnetron
method when fabricated TiO2-xNx photocatalytic films, Communication in Physics, vol 18,
No.4, pp 206 212.
2. P.-G.WU, C.-H.MA, J.K.SHANG, (2005), Effects of nitrogen doping on optical properties of
TiO2 thin films, Department of Materials Science and Engineering, University of Illinois at
Urbana-Champaign, Urbana, IL 61801, USA, Appl.Phys.A81, pp 1411-1417.
3. Ming- Show Wong, Hung Pang Chou, Tien- Syh Yang, (2006), Reactively sputtered N-doped
titanium oxide films as visible-light photocalyst, Department of Materials Science and
Engineering, National Dong Hwa University, Hualien, Taiwan, ROC, Thin Solid Films 494,
pp 244 249.
4. Hans Bach, Dieter Krause, (1997), Thin films on glass, Springer - Verlag Berlin Heidelberg,
pp 137 161.
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OPTICAL CHARACTERIZATION OF DYE DOPED IN

SILICA NANOSPHERES FOR BIOAPPLICATIONS
Vu Thi Thuy Duonga, Do Quang Hoaa, Nguyen Thi Vana, Nghiem Thi Ha Liena, Bach
Nhat Hongb, J.C.Brochonc and Tran Hong Nhunga
a)
b)
Institute of Physics, VAST, Vietnam, 10 Dao Tan, Ba dinh, Hanoi

Vietnam Institute of Sicences and Technologies of Army, 17 Hoang Sam, Cau Giay, Hanoi
c)
Laboratoire de Biotechnologie and Pharmacologie Gntique Applique, ENS Cachan,
France.
E-mail: vtduong@iop.vast.ac.vn
Abstract: Dye-doped silica nanoparticles (NPs) have significant advantages over single-dye
labeling in signal amplification, photostability and surface modification for various
biological applications. The dyes: Rhodamine 6G (Rh6G) and Rhodamine B (RB) were
successfully incorporated into silica nanoparticles fabricated by micellar nanochemistry from
Trimethoxysilane CH3Si(OCH3)3 precursor. The optical characterization of dye-doped silica
NPs was studied in comparison with its of free dye in solution. The results shown that the
photostability of silica dye doped nanospheres is much improved in comparison with its of
dye in solution. Other studies of the photophysical properties such as anisotropy,
fluorescence lifetime, spectral conversion under high and UV excitation and the application
of particles for cell labeling must be done.
Keywords: Dye-doped polymers, Nanoparticles, Biolabeling
1. Introdution
Recently, we have seen the discovery of an increasing number of molecular mechanisms
underlying disease processes. Consequently, clinical diagnosis has come to depend heavily on
detection and monitoring of individual chemical interactions of smaller targets; such as
individual cells, DNA, proteins and peptides. Because these targets exist on nanoscale, probes
of equivalent dimentions have been developed, leading to the integration of nanotechnology and
biology. Of the many fluorescent labeling reagents, organic fluorophores are used most often in
these cases. The fluorophores usually have high quantum yield and can be easily used in many
different applications. However, they usually suffer from limited sensitivity and photostability.
In the last ten years or so, significant advances have led to a large variety of labeling reagents
based on nanomaterials with controlled size and shape. These nanomaterials represent an
exciting and often more effective alternative to the use of organic fluorophores
Dyes doped in silica and in polymer-based nanoparticle (PNs) have been investigated in the
last decade [1-6]. Weihong Tan et co-workers showed that silica based NPs are less aggregate
and little dye leakage in comparison with polymer based NPs. The size of silica particles remains
unchanged while changing solvent polarity [2]. In silica-based NPs dye molecules are
incorporated into the silica network, in turn silica host. Silica NPs possess three important
properties that have made them highly useful in bioanalysis: highly optical intensity, excellent
photostability, and easy surface modification with various functional groups (e.g., amine, thiol,
carboxyl). Furthermore, silica is used because it is chemically inert; it protects the embedded
dyes of the particle from the outside environments. Silica matrix is optically transparent that
allows excitation and emission light to pass through the silica matrix. Dye can be attached to the
NPs surface or can be embedded inside the particles by noncovalent or covalent bonds. These
NPs can be also modified with biomolecules for biological applications. Silica NPs applications
have been using for detection the immunogen, for cellular imaging, multiplexed bioanalysis, and
nucleic acid detection [3].
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These are two main methods used in synthesis silica based fluorescent NPs: Stober method and
use the reverse-micelle method or water in oil microemulsion system. NPs formed via Stober
method are typically large and non uniform but this method is simple to realise and can be
carried out in short time and the solvents used in this method are non toxic: water or ethanol.
Stober method has been modified to easily incorporate organic dye molecules inside the silica
NPs and reform high uniform bears. NPs produced by using the water in oil system usually give
a high degree of uniformity and are well dispersed in water but this method is only use to
incorporate inorganic dyes [3].
2. Materials and experiment
Reagents: Methyltrimethoxysilane (MTMOS), Aminopropyl triethoxysilane (APTEOS),
dimethylsulfoxide (DMSO), Clorotrimethylsilane, aqueous Ammonia solution 25% ,cosurfactant butanol-1 were purchased from Merck. Rhodamine 6 G dye was from Exiton.
Surfactant Aerosol-OT (AOT) (96%) was purchased from Fluka. Dialysis tubing,
MWCO=10000, was purchased from Sigma-Aldrich.
Synthesis: We are used the modified Stber method for the synthesis dye-doped silica
particles.
The first, we prepared a co-surfactant mixture using AOT and butanol1 with ratio AOT:
butanol 1g:1,82ml, and using supersonnic till optically clear. In order to adjust the sizes of sphere
particles, the quantities of this mixed co-surfactant have been changed [4]. Then in the 200 l of
precursor MTMOS was added with 1.25 ml above surfactant. This mixture was diluted with 20
ml double distilled and 100 l of dye in DMSO was added in the solution while stirring which
give a micellar system AOT(butanol)/DMSO/water. For void NPs, 100 l DMSO without the
dye was added. After that, we have the precursor MTMOS is diluted inside the non polar core of
micelle. MTMOS and APTEOS are used to product silica networks which have the organic
groups as methyl and aminopropyl groups remaining on their surfaces and we obtained the
ormosil NPs. APTEOS has amine groups so it plays also a role of base catalyses, furthermore
this groups exists on the surface of ormosil NPs and it give a ability bioconjugation. The
hydrolysis and condensation were stated when aqueous ammonia or APTEOS was added to the
micelle system. Ormosil NPs was formed which embedded the dye molecule within. After 1 h of
reaction, a 20 l of clorotrimethylsilane was added to quench the remaining silanol groups in the
surface of NPs. Next, this system was stirring for 20 h at room temperature. After the formation
of the NPs, the solution was dialyzed in a 10000 MWCO dialysis tubing against water for a week
in order to remove the remaining chemical agents and all the surfactant AOT and butanol-1.
High-resolution scanning electron microscopy (HSEM) Hitachi-S480 was used to determine the
shape and the size of particle. Infrared absorption spectra were recorded in Impact 410 Nicolet
FTIR spectrophotometer. Absorption spectra were measured using JASCO-V570-UV-VIS-NIR
spectrometer. Fluorescence spectra and anisotropy were measured on a spectrofluorimeter.
3. Results and discussions
The HSEM images of void and dye doped NPs are present in fig.1. It shows that the particle
shape is spherical with the average diameter of 30 nm with high monodispersion.
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b)
a)
Fig.1: HSEM image of: a) Ormosil pure NPs
0.6
intensity (a.u.)
8000
6000
Si-O2
Amino group
4000
2
2000
absorption intensity (a.u.)
Si-CH3
10000
b) Dye doped ormosil NPs
Si-O-Si
CH 3-Si
0.5
CH 3-Si
0.4
Si-O-Si
0.3
CH 3-Si
0.2
CH 3-Si
-C 2H 6NH 2
0.1
0.0
0
500
1000
1500
2000
2500
-1
wavenumbers (cm )
a)
3000
600
900
1200
1500
1800
-1
wave numbre (cm )
b)
Figure 2. a) Micro Raman spectrum of ormosil NPs without NH2 groups (blue line) and with NH2 (red
line) on the surface; b) FTIR spectrum of ormosil NPs without NH2 groups (red line) and with NH2
(green) on the surface.
Chemical composes of NPs are confirmed by analyzing micro Raman and FTIR spectra both
of void NPs with and without the amine groups. Since both our NPs with and without amino
groups which are produced from MTMOS precursor but the NPs that its surface is functionalized
by amino groups by adding a suitable quantity of APTEOS precursor.
Fig.2a. is Micro Raman spectrum, the band corresponding to siloxan networks (SiO2) is
observed at 560 cm-1. The methyl group bonding to Si atom is charactered by the strong bands at
2950 cm-1 and . The band at 911 cm-1 is attributed to amino group.
FTIR spectrum of void NPs with and without amino groups shown on Fig.2.b. The presence of
methyl group bonded to silicon atom (Si-CH3) on the ormosil NPs are observed by two strong
bands at 780 and 1270 cm-1. The bands corresponding to Si-O-Si symmetric and asymmetric
stretch are charactered at 1034 and 1113 cm-1, respectively. For NPs which are formed from
MTMOS and APTEOS precursors, the bands at 1534 and 1740 cm-1 are attributed to amino
groups. The region 1380 to 1450 cm-1 character to the deformation vibration of propyl groups. In
other works, the region 1380 to 1740 cm-1 is attributed of aminopropyl groups.
By analyzing micro Raman and FTIR spectrums indicated that the NPs structure is siloxan
networks and have the methyl groups bonded to silicon atom. Furthermore, it confirmed that NPs
are formed from MTMOPS and APTEOS has the amiopropyl group bonded to silicon atom on
the surface of NPs.
Advances
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1.0
RH6G in NPs
0.8
intensity(a.u.)
Fluoresscence intensity (a.u.)
1.0
Rh6G in H2O
0.6
0.4
0.2
0.8
0.6
0.4
0.2
0.0
0.0
350
400
450
500
550
600
650
700
400
500
wavelength (nm)
600
700
800
900
Wavelength (nm)
b)
a)
Figure 3: Comparison of optical absorption a) and fluorescence emission

b) spectra of Rhodamine 6G: in water with 0,2% DMSO (red line) and in ormosil NPs (blue line).
In order to compare the optical properties of the dye doped in NPs and bare dye, rh6G dye
diluted in water with 0.2 % DMSO(v/v). Optical absorption spectra of the rhodamine 6G in
water and in ormosil NPs were normalized, showed in fig.3.a. We can see the difference of
Rh6G maximum absorption in different media (NPs and water) but the fluorescence emission do
not change with around media, showed in fig.3.b. Fluorescence emission of dye molecules is not
influenced by ormosil host so the fluorescence emission spectra of dye doped in NPs do not
changed. The photostability of Rh6G dye doped in NPs and bare dye is also measured using laser
Nd-YAG at 532nm, frequency of 20 nm and power of 1.39 mW as excitation source. Rh6G is
known to be a photosensitive compound. To investigate whether the Rh6G molecules still
remain photosensitive when doped inside the ormosil NPs in aqueous solution, we measured
emission intensity with respect to time and excitation intensity. The result is showed on fig.4
that Rh6G doped in NPs is no photobleaching as compare to pure Rh6G in water.
normalized intensity
1 .0
0 .8
0 .6
0 .4
0
10
20
30
40
50
60
tim e (m in u te )
Figure 4: Photobleaching experiment: (green line) Rh6G doped in NPs, (red line) the pure Rh6G in
aqueous phase with a 1.39 mW, 20 Hz, 532nm laser Nd-YAG excitation source.
We are also measured the polarization anisotropy of Rh6G in water and in ormosil NPs by
using linearly polarized UV light. The polarization anisotropy is defined here as p=(II)/(I+I), where I and I are the fluorescence intensities for polarization components parallel
and perpendicular to the alignment direction[7]. The results are presented on Fig.5, we can see
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that Rh6G in water is not polarized but Rh6G in ormosil NPs is polarized with a high
polarization anisotropy (p~18%).
Fiure 5: Polarization anisotropy of Rh6G dye in water and doped in ormosil NPs , under linearly
polarized UV light.
5. Conclusion
In conclusion, we report a straightforward approach for the synthesis of monodispersion
water soluble the ormosil NPs and the function its surface by amino groups using modified
Stober method. We have been observed that the maximum absorption of dye molecules changed
with the media around but fluorescent emission spectra not change. We have been remarked that
the fluorescent intensity of dye in ormosil NPs were polarized under linearly polarized UV light.
Acknowledgments
The work was partly supported by National Program of Fundamental Research No 4 035 06
and 4 034 06
References
1. Jilin Yan, M. Carmen Rstevez, JoshuaE. Smith, Kemin Wang, Xiaoxiao He, Lin Wang, and
Weihong Tan, Dye-doped nanoparticles for bioanalysis, Nanotoday, Jun 2007, 2(3), 4450.
2. Tan, W., et al., Med.Res. Rev (2004), 24,621.
3. Joshua E. Smith, Lin Wang, Weihong Tan, Bioconjugated silica-coated nanoparticles for
bioseparation and bioanalysis, Anal. Chem., Vol. 25, No. 9, 2006
4. Indrajit Roy, Tymish Y. Ohulchanskyy, Haridas E. Pudavar, Earl J. Bergey, Alain R.
Oseroff, Janet Morgan, Thomas J. Dougherty, and Paras N. Prasad.Ceramic-Based
nanoparticles entrapping watter-insoluble photosensitizing anticancer Drugs : A novel
Drug-carrier system for photodynamic therapy, PNAS, vol.125, 2. 279-284. Nanostructures
in biodiagnostics, Nathaiel L. Rosi and Chad A. Mirkin, Chem. Rev. 2005, 105, 1547-1562
5. A. Van Blaaderen, and A. Vrij, Synthesis and characterization of monodisperse colloidal
Organo-silica spheres, J. Colloid and Iterface Science 156, 1-18 (1993)
Advances
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INFLUENCE OF SYNTHESIS CONDITIONS ON OPTICAL PROPERTIES OF

COLLOIDAL GOLD NANOPARTICLES FOR BIOMEDICAL APPLICATIONS
Nghiem Thi Ha Liena, Vu Xuan Hoaa, Tong Kim Thuanb, Nguyen Van Tinha,
and Tran Hong Nhunga
a)
Institute of Physics, VAST, 10 Dao Tan, Ba dinh, Ha Noi

Institute of Biotechnology . VAST, 18 Hoang Quoc Viet, Cau Giay, Ha Noi
b)
E-mail : halien@iop.vast.ac.vn
Abstract: The gold nanoparticle solutions are well known as an extremely sensitive biomedical
analytical tool, due to the strong dependence of their absorption in the visible range on the
environment. In this work, the colloidal nano golds were synthesized from metal precursor
chloroauric acid (HAuCl4) using trisodium citrate dehydrate (C6H5O7Na3) as reducing and
stabilizing agents. The optical characterization - absorption of colloidal gold solution have been
investigated under the different synthetic conditions such as: reducing agent concentration,
concentration of auric ion, pH, duration of reaction and aging time. The results show that the
absorption and the stability of the colloidal gold nanoparticles depend robustly on the synthetic
conditions and pH of environment.
Keywords : Colloidal gold, Nanoparticles,
Absorption, Surface Plasmon Resonance - SPR
1. Introduction
The optical properties of gold Nanoparticles (NPs) have attracted scientists since recent past
because of their applications as functional materials in optical devices [1], optical energy
transport [2], near-field scanning optical microscopy [4], surface enhanced Raman scattering
spectroscopy [3], and chemical and biological sensors [5]. Characteristically, Au NPs exhibit a
strong absorption band in the visible region and this is indeed a small particle effect, since they
are absent in the individual atom as well as in the bulk. The physical origin of the light
absorption by gold NPs is the coherent oscillation of the conduction band electrons induced by
the interacting electromagnetic field. The absorption band results when the incident photon
frequency is resonant with the collective oscillation of the conduction band electrons and is
known as the surface plasmon resonance (SPR). The resonance frequency of this SPR is strongly
dependent upon the size, shape, dielectric properties, and local environment of the NPs [6,7,8].
There are multiple strategies for synthesizing the gold NPs. The physical methods include
photochemistry, sonochemistry, radiolysis, thermolysis,There are many other approaches
based on the chemical methods use of sulfur, phosphine, phosphineoxide, amine, amino acid,
and carboxylate ligands. Protocols for the synthesis of water dispersible are extensively
developed, using multifunctional molecule oleyl amine to stabilization and surface modification
gold NPs [9-11]. Alternatively, stabilization can be achieved though compartmentalization in
micelle, microemulsions, and immobilization in silica, for instance, Liz-Marzan et al used silica
coating to stabilize nanosized gold particles and to modulate their optical properties[12]. In
Brust-Shiffrin method, using strong reducing agent NaBH4 and alkanethiols capped gold NPs
formation in a biphasic mixture in organic solvent produced the small particle sizes (2-5nm)[13].
Chloroauric acid (HAuCl4) is dissolved in water phase and phase transfer extracted into an
organic solvent followed by reduction with NaBH4. In Turkevich method [14], gold NPs are
produced by chemical reduction of a HAuCl4 with trisodium citrate in water. The trisodium
citrate first acts as a reducing agent. Later the negatively-charged citrate ions are adsorbed onto
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the gold NPs, introducing the surface charge that repels the particles and prevents them from
aggregation. Because of water dispersible, gold NPs has immediate applications in a vary fields,
particularly for biolabelling and biosensing.
In this paper, we present details of the synthesis of gold nanoparticles of good monodispersity by
the reduction of aqueous chloroaurate ions by the trisodium citrate. Citrate stabilized gold NPs
are targeted, because their syntheses are quick and easy to attain good mono-dispersed
diameters.
2. Experimental
2.1. Chemicals
The tetrachloroauric acid trihydrate 99.5 % (HAuCl4.3H2O), trisodium citrate dehydrate
(Na3C6O7.2H2O) purchased from Merck.
2.2. Synthesis of aqueous citrate reduced gold NPs
- Experiment 1: time of reaction.
90 ml of 3.10-4 M aqueous solution of chloroauric acid (HAuCl) was reduced by 3.6 ml 6.8 10-2
M aqueous solution of trisodium citrate under boiling and stirring vigorously conditions to attain
colloidal gold nanoparticles. In about 5 s the boiling solution turned colorless. During the time of
reaction, the color of solution suddenly changed to the black then pink and at red after 10
minute. After boiling one minute, a series of this solution were taked up for every 3 minutes until
28 minutes.
-Experiment 2: concentration of citrate.
In order to investigate the depending size and shape of colloidal gold NPs on the citrate
concentrations, one series of 8 solutions of colloidal gold NPs have been prepared with the
HAuCl4 concentrations 610-4 M. The molar ratio of chloroaurate ions to citrate is varied 2 to 5.5
with a step of 0.5 and the time of reactions were 12 minutes.
-Experiment 3: concentraton of chloroauric acid
In order to investigate the depend of the optical density of colloidal gold NPs on the HAuCl4
concentrations, one series of 12 solutions of colloidal gold NPs have been prepared by varying
the HAuCl4 concentrations from 1.5 10-4 to 1.8 10-3 M with a step of 1.5 10-4 M. The molar ratio
of chloroaurate ions to citrate was used 4.5 and the time of reaction was determined for each
solution. The HAuCl4 concentration increase, the time of reaction decrease.
The optical properties of citrate gold colloidal solutions were measured using the Varian
Carry-5000 spectrophotometer operated at resolution of 1 nm.
High-resolution scanning electron microscopy (HSEM) Hitachi-S480 using an accelerating
voltage of 5 kV was used to determine the shape, the size of the gold NPs. Samples for SEM
were prepared by placing a drop of gold colloidal solutions on silicon place and were dried
before the observation of image.
Fig.1. presents the UV-VIS spectra recorded from the gold colloidal solutions of experiment
1 as a function of time of reaction within trisodium citrate and chloroaurate ions. The maximum
of the absorbance spectra decreases from 550 nm (1min), 540nm (4min), 534nm (7min) and to
524nm (10 min). When the reaction terminate, the maximum of the absorbance is stable at 519
nm. A monotonic increase in the surface plasmon resonance intensity with time is observed, the
reaction accelerating from 1 to 10 minute and terminating after 13 minute of reaction. Thanks to
Advances
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1 min
4 min
7 min
10 min
13 min
16 min
19 min
22 min
25 min
28 min
Absorbance
1.0
0.8
0.6
1.4
1.2
1.0
absorbance
1.2
0.4
0.8
0.6
0.4
0.2
0.2
0.0
300
400
500
600
700
800
0.0
0
10
Wavelength (nm)
15
20
25
30
time (min)
Figure 1. UV-VIS spectra recorded as a function of time of reaction in experiment 1,

right is a plot of the absorbance corresponds to the maximum as function of time
this protocol we can determinate the time of reaction for each HAuCl4 concentrations.
All both of size and shape of these gold NPs solutions of experiment 2 were observed with the
HSEM, their results show that the gold NPs are quasi spherical and good monodipersed with the
diameters distributed around 15 nm. fig 2. is a HSEM image of one gold NPs solution in this
experiment and the particle size distribution histogram from the image. The mean size is 15.8 nm
with standard deviation is 3.8 nm. This result shows us that the molar ratio of chloroaurate ions
to citrate (2 to 5.5) do not influents to the size and shape of gold NPs. This result resemble to the
result of Chow et al [15] when they used the ratio molar of chloroaurate ions to citrate is 6.6 to
30. The diameter of their gold NPs solutions is 14 nm.
frequence (%)
30
20
10
0
10
15
20
25
30
size of the particles (nm)
Figure 2.
HSEM image of gold NPs from one gold NPs. Particle size
distribution histogram measured from the image
The fig.3. presents the UV-VIS spectra of the colloidal gold solutions prepared by experiment 3
as a function of HAuCl4 concentrations. The absorbance intensity observed around 520 nm
increases quasi linearly with the increase of HAuCl4 concentrations, on the right of fig. 3. These
results show that with optical density < 3.5, the absorbance intensity of the gold NPs solutions
were proportion with the HAuCl4concentrations.
3.6
3.6
3.2
3.2
2.8
2.8
2.4
2.4
absorbance
absorbance
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2.0
1.6
1.2
0.8
a layer at 520 nm
Linear Fit
2.0
1.6
1.2
0.8
0.4
0.4
0.0
300
400
500
600
700
0.0
0.0
800
wavelenght (nm)
Figure3.
-4
4.0x10
-4
-3
8.0x10
1.2x10
-3
1.6x10
-3
2.0x10
Auric ion concentration (M)
UV-VIS spectra recorded as a function of [HAuCl4] in experiment 2 (left), right is a plot of the
absorbance corresponds to the maximum as function of [HAuCl4]
after 1 day
after 20 days
after 85 days
0.5
optical density
0.4
0.3
0.2
0.1
0.0
300
400
500
600
700
800
wavelength (nm )
Figure 4. Stability of gold NPs. Absorbance of colloidal gold solution vs. time
5. Conclusions
We reported a protocol of synthesis to produce good monodipersed gold NPs with uniform
nanospheres of 16 nm diameter have been observed. We demonstrated the proportion linear
within HAuCl4 concentrations and optical density of gold NPs solutions. .
Acknowledgments. This work is supported by VAST project KHCN-15.
References
1. Y. Dirix, C. Bastiaansen, W. Caseri, P. Smith, Adv. Mater. 11, 223 (1999).
2. J.R. Krenn, A. Dereux, J.C. Weeber, E. Bourillot, Y. Lacroute, J.P. Coadonnet, Phys. Rev.
Lett. 82,2590 (1999) .
3. E.J. Sanchez, L. Novotny, X.S. Xie, Phys. Rev. Lett. 82, 4014(1999).
4. T. Wadayama, O. Suzuki, K. Takeuchi, H. Seki, T. Tanabe, Y. Suzuki, A. Hatta, Appl. Phys.
A 69,77 (1999).
Advances
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5. J.J. Storhoff, R. Elghanian, R.C. Mucic, C.A. Mirkin, R.L. Letsinger, J. Am. Chem. Soc. 120
1959(1998) .
6. C.A. Mirkin, M.A. Ratner, Annu. Rev. Phys. Chem. 101, 1593 (1997) .
7. D.L. Klein, R. Roth, A.K.L. Lim, A.P. Alivisatos, P.L. McEuen, Nature,389, 699 (1997).
8. U. Kreibig, M. Vollmer, Optical Properties of Metal Clusters, Springer, Berlin, 1995.
9. Lin He, Michael D. Musick, Sheila R. Nicewarner, Frank G. Salinas, Stephen J. Benkovic,
Michael J. Natan, and Christine D. Keating, J. Am. Chem. Soc 122 , 9071.( 2000).
10. Saikat Mandal, Pr Sekvakannan,, Sumant Phadtare, Renu Pasricha and Murali Sastry. Proc.
Indian Acad. Sci. (Chem. Sci.), 114 ( 5), pp 513 (2002).
11. Florian Vital, Rosa Vitaliano, Chiara Battocchio, Ilaria Fratoddi, Emanuela Piscopiello,
Leander Tapfer and Maria Vittoria Russo, J.organometallic chemistry 693, p 1043 (2008).
12. Luis M. Liz-Marzan, Michael Giersig and Paul Mulvaney, Langmuir 12, 4329 (1996).
13. M. Brust, M. Walker, D. Bethell, D. J. Schiffrin and R. Whyman, Synthesis of
Thiol-derivatised Gold NPs in a Two-phase Liquid-Liquid System J. Chem. Soc., Chem.
Commun., 1994, 801.
14. J. Turkevitch, P. C. Stevenson and J. Hillier, Trans. Faraday Soc. 11, p 55, (1951).
15. M.K Chow and C. F. Zukoski, J. Colloid and Interfece Science, 165, p97 (1994).
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PREPARATION AND STUDY THE EFFECT OF ANNEALING

ON SOME PROPERTIES OF ZnS:Cu2+ MATERIALS
Nguyen Thi Van Anha, Nguyen Minh Thuya, Nguyen Thi Thanh Nganc,
Le Thi Hong Haib, Dang Thi Thuy Chia, Nguyen Manh Nghiaa
a)
Faculty of Physics, Hanoi University of Education

Faculty of Chemistry, Hanoi University of Education
c)
E-mail: anhntv@hnue.edu.vn
b)
Abstract: ZnS:Cu2+ powder was prepared by a co precipitation technique with chemicals

Zn(CH3COO)2, Cu(CH3COO)2, Na2S. Then, the sample was annealed at different temperatures
(3000C, 4500C, 5000C, 6000C) in Nitrogen medium. The samples were characterized by X-ray
diffraction (XRD), SEM and photoluminescence (PL). The XRD, SEM results show that the
crystal sizes of samples are quite small, approximately 5 nm and they increase with the increasing
of the annealing temperature. The PL results show that the PL peak of sample without annealing is
around 510,26 nm (blue region) whereas the PL peaks of annealed samples are around 625 nm
(orange region). These peaks are not shifted by annealing. This phenomenon can be attributed to
the quantum effect appeared by the nanometer size of the samples.
1. Introduction
Recently, there have been many studies on the fabrication and optical properties of
semiconductor nanocrystals, because they will become new function materials for future
optoelectronic deviecs. In particular, the semiconductor nanocrystals doped with luminescence
centers exhibit efficient luminescence even at room temperature. Many different techniques have
been developed for the fabrication of high quality semiconductor nanocrystals [1-4].
Among the semiconductor nanostructured materials of interest, ZnS is one of the well-known
II-VI compound semiconductors which is suitable to be used as host matrix for large variety of
dopants because of its wide direct energy band gap ( 3.7eV). It is known that ZnS phosphors
have a broadband luminescence from the near ultraviolet (UV) to the near infrared (IR).
Therefore, it has been often used in the field of optoelectronic devices, such as for light
emitting diodes and flat panel displays [5]. Especially, when ZnS is doped with a small amount
of metallic ions, it emits a light in the visible region which is characteristic of the incorporated
impurity. Therefore, it forms a very important class of phosphor for the fabrication of thin film
electroluminescent devices.
In the 1920s, it was established that a small amount of copper incorporated in ZnS produces a
green luminescence. During the period from the 1950s to the 1970s, the research on the
luminescence of bulk ZnS:Cu2+ expanded. This material turned out to be a good cathode ray tube
(CRT) phosphor and was applied in for example oscilloscopes. Besides that, the
electroluminescence (EL) of bulk ZnS:Cu2+ had been widely studied for possible applications in
electroluminescence devices. Nowadays, the luminescence of nanocrystalline ZnS:Cu2+ has been
investigated [6-8]. Due to the large surface to volume ratio of the nanoparticles, charge carriers
can be injected efficiently into these materials. This could make nanocrystalline semiconductors
better suited for EL devices than bulk materials. The change of the electronic structure can be
explained by strong confinement of the charge carriers in all three dimensions. Besides the size
quantisation, surface effects are also known to influence of opticles properties of nanoparticles
[9,10].
Advances
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We know that for bulk ZnS:Cu2+, five emissions are observed: a UV, blue, green, red and IR
emission. It is generally believed that copper incorporates in ZnS on a Zn 2+ site as Cu2+ (3d9). In
the tetrahedral crystal field of the four S 2- legands, the 3d9 ground state splits into higher lying t 2
levels and lower lying e levels (in figure 1). The observed IR emission ( 1450 nm) corresponds
to the trasition from t 2 level to the e level [11]. When an electron is excited to the conduction
band, and subsequently trapped by shallow (delocalised) donor levels, a green luminescence can
occur, by recombination at the Cu impurity. The red emission (R - Cu) is assigned to the
recombination of an electron from a deep (localised) donor level (e.g., S 2- vacancy) at the copper
site. In literature, the green emission is reported on both bulk and nanocrystal ZnS:Cu2+, but the
red emission is reported only for bulk ZnS:Cu2+ and there are few paper reporting on the red
emission for nanocrystalline ZnS:Cu2+ [9].
Table 1: Samples and measurements
EC
Shallow delocalized
donor levels
Deep localized
donor level
G -Cu
R - Cu
t2
EV
IR
Fig.1: Schematic energy level

diagram of ZnS:Cu2+
Sample
Annealing
t0 (0C )
XRD
PL
SEM
TEM
M3
Not be
annealed
M3 -300
300
M3- 450
450
M3500
500
M3- 600
600
In this paper, we report on the preparation of Cu-doped ZnS based on co-precipitation

technique. The influence of annealing temperature on the crystal structure and the luminescence
of nanocrystalline ZnS:Cu2+ are studied. In addition, some results involving in the red emission
of nanocrystalline ZnS:Cu2+ is also presented.
2. Experimental
The method used for the synthesis of nanocrystalline ZnS:Cu2+ coated with sodiumphosphate
(PP) was co precipitation technique. 10 ml Zn(CH3COO)2.2H2O 1M and 1ml
Cu(CH3COO)2.H2O 0.01M were added to an aqueous solution of 6.12 g Na(PO)3 (n=6). The
total volume after the additon was 90 ml. After about 10 minutes of stirring, 10 ml of Na2S.9H2O
1M solution was injected into the solution. Immediately after the injection of the Na2S solution, a
turbid white fluid was obtained. Then the particles were centrifuged, rinsed with distilled water
and ethanol, and dried in vacuum at 80oC (sample M3). In order to study the effect of annealing
on the structure and optical properties, the sample M3 was annealed at different temperatures
(3000C, 4500C, 5000C, 6000C) in 30 minutes in Nitrogen medium.
The structure and crystal properties of samples were characterized by X-ray diffraction
(XRD) in Siemens D5005 in which an X ray wavelength of 1.54 (CuK line) used as a
diffraction angle 2 is varied from 200 to 700. The morphology and micro structure of powder
ZnS:Cu2+ were characterized by using scanning electro microscope (SEM) in FE SEM 4800
Hitachi and transmission electro microscope (TEM). The photoluminescence spectra (PL) of
samples were obtained by Jobin Yvon Spex FL 3 32 and spex 1250 fluorescence
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spectrophotometer at room temperature. The table 1 lists the names of the samples and the
mesurements which were used in this paper.
The XRD pattens of the samples M3 and M3-300 are shown in figure 2 and figure 3.
Fig.2: The XRD spectrum of sample M3
Fig.3: The XRD spectrum of sample M3-300
It is observed that, the XRD of sample M3 is found to be polycrystalline with preferential

orientation along the (002) plane ( 2
28.70 ), the other secondary peaks visible are (220) and
(112) ( 2
47.50 and 2
56.50 , respectively). All these peaks are associated with hexagonal
ZnS (wurtzite structure). In the other hand, the locations of XRD peaks of the two samples are
nearly the same. But, in compare with sample M3, we can see that in the sample M3 300, the
sharpness of the peak increases which in turn decreases the full width of the half maximum
(FWHM) of sample M3 300 or increases the crystal size of the particles in sample M3 - 300.
By using Scherrer formula, the crystal size of particles are about 10 nm and 15 nm respectively
for sample M3 and sample M3 300. This means that the crystal size of the particle increases by
the annealing process.
Figure 4 shows the SEM image of sample M3. It can be seen that the particles are
approximately spherical in shape and aggregate a little. Hence, it is hard to recognize the
boundary between particles. This is attributed to the presence of sodiumphosphate (PP) in the
sample.
In this technique, sodiumphosphate plays and important role in the synthesis of the
nanocrystal particles. We know that solubility product constant T of CuS and ZnS are much
different (TCuS = 6,3 10 36 and TZnS = 1,6 10 24 ). Thus, it is easier for CuS to dissolve in the
solution than ZnS. In this paper, we used sodiumphosphate to coat Cu 2+ particle, hence, we could
limit the dissolve of CuS in the solution and ensure the co precipitation of CuS and ZnS and
making the particles to grow with the nanometer size. After synthesis, the precipitate is rinsed in
distilled water and ethanol several times to remove the coat of particles. In the sample M3,
perhaps there still have more or less coats around the particles. This makes the boundary of
particles unclear enough to distinguish. In the figure 4, the size of the big particle is about several
tens nanometer. To confirm the size of particles in sample M3, we have taken a TEM image.
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Fig.4: The SEM image of sample M3
Table 2: The PL peaks of samples ZnS:Cu2
18000
M3d-300
M3d-450
M3d-500
M3d-600
M3
I (a.u)
Fig.5: The TEM image of sample M3
Sample
PL peak (nm)
M3
510,260
M3-300
625,005
M3-450
625,005
M3-500
626,005
M3-600
629,388
9000
0
400
500
600
700
800
900
nm
Fig.6: The PL spectra of samples
Before taking a TEM image, the sample M3 was shaken by untrasound in distilled water in
about 60 minutes to remove all the coats. The result in figure 5 shows that the size of particles is
about 5 nm. This result corresponds to the XRD result.
Figure 6 shows the room temperature PL spectra of sample M3 and annealed samples (M3
300, M3 450, M3 500, M3 - 600). It can be seen that the PL spectrum of sample M3 is
characterized by the PL peak at 510.26 nm (green region), whereas, the PL spectra of annealed
samples are all characterized by the PL peak at around 625 nm (red region). The results are listed
in table 2.
In nanocrystalline ZnS:Cu2+, the green emission probably originates from the recombination
of an electron from a shallow delocalized donor level just below the conduction band at the Cu 2+
impurity. This mechanism is similar to the one proposed for the green Cu emission in bulk
ZnS:Cu2+.
The red emission is assinged to a transition between a deep localized donor level (possibly
related to a S2- vacancy) and the Cu2+ impurity.
To give the reason for the results obtained in figure 6, we have used the fitting method using
Gaussian fuction. The result shown in figure 7 presents that in sample M3, besides the green
peak, there still have a red peak with much smaller intensity. This makes the curve unsymetrical.
When the sample is annealed at high temperature (more than 3000C), it seems to be that the
green emission has almost quenched completely and the weak red emission still exists and
becomes visible (figure 6). This result corresponds to the one reported in reference [9], in which
they find that in nanocrystalline ZnS:Cu2+, the red emission quenches at higher temperature than
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the green emission. This is also

consistent with the model proposed
14000
for bulk ZnS:Cu2+ in which the green
emission originates from shallow
12000
delocalized traps are situated just
10000
below the conduction band, these
8000
traps are thermally emptied at
6000
relative low energies. Whereas more
4000
energy is needed to empty the deep
traps responsible for the red
2000
emission. As a consequence, the red
0
300
400
500
600
700
800
900
1000
emission quenches at much higher
(nm)
temperature. As far as can be
Fig.7: The fitting result of sample
deduced, the red emission does not
shift with increasing the temperature,
until the temperature reaches an enough high value. This can be seen in the figure 6 that the PL
peaks remain the same until the annealing temperature reaches the value of 6000C.
By the ways, the result in the figure 6 seems to be different to bulk ZnS:Cu2+. For the red
emission of bulk ZnS:Cu2+, a blue shift (shift
36 meV) was reported with increasing
temperature [9]. This shift was explained with the configurational co ordinate model for
localized luminescence centre. With increasing temperature higher, vibrational levels of the
excited state will be occupied, which results in a shift of the emission spectrum to higher
energies [9]. However, in this paper, a red shift is observed for red emission in nanocrystalline
ZnS:Cu2+. This is attributed to the quantum effect appeared when the particles are nanometer.
But, this needs a further research to give a reasonable explanation.
Besides all above, it is also reported that the quenching of the red emission is dependent on
the particle size because the red emission originates from deep localized traps. Moreover,
because the red emission involved an S2- vacancy deep in the band gap and the Cu impurity, the
heat treatment may result in an increase of the S 2- vacancy concentration or lead to an increase of
association of S2- vacancies and Cu2+ ions, resulting in an increase of the red emission intensity.
In this paper, we do not mention in the PL intensity of samples. The researches in detail are
carried on by our group in order to resolve these problems.
16000
M3
fitting line of M3
st
fitting line of 1 peak
nd
fitting line of 2 peak
I (a.u)
Data: M3XZNSPL32_B
Model: Gauss
Chi^2 = 116972.15395
R^2
= 0.99488
y0
xc1
w1
A1
xc2
w2
A2
0
0
504.59532
0.65005
112.59348
1.77182
1744517.38242 111967.83924
606.74987
11.68301
178.33457
9.79805
896498.23706 114733.28726
4. Conclusion
In summary, we have prepared nanocrystalline ZnS:Cu2+ by a co precipitation technique. The
XRD studies show that all the samples have wurtzite structure and crystal sizes of particles on
samples have increased due to the annealing process. The size of the particles is about 5 nm. The
PL results show that green emission is dominated in lower temperature and this emission
quenches due to the annealing process but the red emission lasted even at high temperature. The
PL peaks of annealing samples do not shift with the increasing of annealing temperature until the
temperature reaches the value around 6000C.
Acknowledgements
This paper was supported by the project under the contract number SPHN 08 190 from
Hanoi National University of Education.
References
1. A. Ishizumi, C. W. White, Y. Kanemitsu, Physica E 26 (2005) 24-27
2. A. A. Bol, A. Meijerink, Phys. Stat. Sol. B 224 (2001) 291.
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3. M. Tanala, S. Sawai, M. Sengoku, M. Kato, Y. Masumoto, J. Appl. Phys. 87 (2000) 8535.

4. Y. Kanemitsu, H. Matsubara, C. W. White, Appl. Phys. Lett. 81 (2002) 535.
5. I. D. Desnica Frankovic, U. V. Desnica, A. Stotzler, M. Deicher, Phys. Rev. B Condens.
Matter 273 274 (1999) 887.
6. L. Sun, C. Liu, C. Liao, C. Yan, Solid State Commun. 111 (1999), 483
7. M. Wang, L. Sun, X. Fu, C.Liao, C. Yao, Solid State Commu. 115 (2000), 493
8. P. T. Huy, N. D. Chien, Proceedings of International Conference on Engineering Physics,
2006, 44 - 48
9. A. A. Bol, J. Ferwerda, J. A. Bergwerff, A. Meijerink, Journal of Luminescence, 99 (2002),
325 334
10. X. Zhang, H. Song, L. Yu, T. Wang, X. Ren, Journal of Luminescence, 118 (2006), 251
256
11. P. Peka, H. J. Schulz. Physica B 193 (1994), 57.
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PHOTOLUMINESCENT PROPERTIES OF Y2O3:Eu3+ MICROPHOSPHORS

SYNTHESIZED BY SOL-GEL PROCESS
Bui Van Hao a,b, Do Quang Trung b,c, Pham Thanh Huy b,d, Nguyen Thi Thanh Ngan e
and Pham Hong Duong e
a)
Faculty of Engineering Physics, Quy Nhon University

170 An Duong Vuong Street, Quy Nhon City, Binh Dinh Province
E-mail: haobv_itims2006@yahoo.com
b)
International Training Institute for Materials Science (ITIMS), Hanoi University of Technology
c)
Faculty of Natural Science, Quang Ninh College of Industry
d)
Hanoi Advanced School of Science and Technology (HAST), Hanoi University of Technology
e)
Abstract. In this paper, photoluminescent properties of Y2O3:Eu3+ microphosphors synthesized
by sol-gel process are reported. Different factors effecting on morphology, crystallite structure
and optical properties of the phosphors, such as sintering temperature, concentration of Eu3+ and
molar ratio of metal ions to citric acid, were examined. Crystal structure of the particles was
investigated by X-ray diffraction (XRD) technique. The results showed that the phosphor
powders completely crystallized at 600oC. The morphology of particles was observed by using a
scanning electron microscope (SEM). The particle size of the synthesized phosphors is in the
range of 1 6 m. Photoluminescence measurements of Y2O3:Eu3+ microphosphors showed red
emission at the wavelength of 612 nm, which corresponds to the transition between 5D0 and 7F 2
energy levels of Eu3+ ion. The optimal molar concentration for obtaining the highest
photoluminescent intensity for the phosphor was 7% of Eu3+ (sintered at 900 oC for 3 hours).
Keywords: Y2O3:Eu3+, phosphor, photoluminescent properties, sol-gel.
1. Introduction
In the early time of luminescent lighting (1938-1948), a mixture of two phosphors was used,
namely MgWO4 and (ZnBe)2SiO4:Mn2+. While the former has a broad bluish-white emission
band with a maximum at 480 nm and can be efficiently excited by short wavelengths in UV
radiation, the emission spectrum of (ZnBe)2SiO4:Mn2+ covers the green to red part of the visible
spectrum. A disadvantage of this kind of Mn2+-doped phosphor is its unstableness in lamp. It is
easy to be decomposed under ultraviolet radiation. In addition, beryllium is very toxic and later
not acceptable for application.
In 1948, these phosphors were superseded by one phosphor with blue and orange emission,
viz. Sb3+ and Mn2+ activated calcium halophosphate (Ca5(PO4)3(Cl,F):Sb3+, Mn2+). The color of
the light output can be adjusted by altering the ratio of the blue emitting antimony dopant and
orange emitting manganese dopant. By carefully adjusting Sb3+ and Mn2+ ion concentrations, we
can obtain a white emitting phosphor with color temperatures in the range of 6500 and 2700 K.
Though, a big problem of the halophosphate lamps is the fact that it is impossible to have
simultaneously high brightness and high color rendering index (CRI).
Koedam and Opstelten predicted that a luminescent lamp with an efficacy of 100 lm/W and a
CRI of 80-85 can be obtained by combining three phosphors which emit in narrow wavelength
intervals centered around 450, 550 and 610 nm. A few years later such a lamp was realized using
rare-earth activated phosphors. This type of lamp is known as the tricolor lamp [1].
The material Y2O3:Eu3+ has been widely used in lighting and displaying devices as a red
emitting phosphor. Its red emission is located at around 612 nm and all other emission lines have
negligible intensity in comparison with the main peak. Most of recent researches on this kind of
phosphor have concentrated on nanoscaled material which is one of the most promising red
phosphors for field emission display applications [2, 3]. N. Vu et al. [4] used combustion
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reaction method to synthesize the phosphor with the particle size estimated in the range of 10 to
20 nm. Spray pyrolysis techniques have been applied to produce nano-sized Y2O3:Eu3+ material
[5, 6]. Nanocrystalline cubic Y2O3:Eu3+ with an average particle size of only 10 nm was
fabricated using chemical vapor technique by Konrad et al. [7]. A laser-heated gas condensation
technique has also been employed to prepare nanocrystalline Y 2O3:Eu3+ with the monoclinic
crystal structure [8]. Sol-gel method was used to prepare Y2O3:Eu3+ with grain of 0.2 to 2 m in
size [9].
In this paper, we present synthesis process and optical properties of Y2O3:Eu3+ microphosphors prepared by sol-gel method. Citric acid was used as chelating agent. The initial
materials were rare-earth oxides Y2O3 and Eu2O3 and nitric acid. The phosphors we obtained
have particle size in the range of 1-6 m with high luminescent intensity. These grain sizes are
very suitable for applications in lighting and displaying devives, such as cathode ray tubes
(CRT), plasma display panels (PDP) and fluorescent lamps [10, 11].
2. Experimental
2.1. Preparation of Y2O3:Eu3+ microphosphors
Synthesis process of the microphosphors is shown
in figure 1. The initial rare-earth oxides Y2O3 and
Eu2O3 (99.99%, A.R) with different atomic ratios were
dissolved in a definite amount of diluted nitric acid
(A.R) and stirred to obtain a transparent liquid. Next,
citric acid was introduced.
Different ratios of metal ions to citric acid were
studied in this paper. The solution was then constantly
stirred in 14 hours at room temperature. In the next
step, the mixture was heated at 800C and a transparent
sol was formed. In the process of heating at 1000C, the
condensation reaction between COOH groups
occurred and led to the formation of water. The
evaporation of water made the volume of the sol
reduced quickly. When most of water was removed,
the sol turned into a gel and then a viscous resin was
formed. Finally, further heating caused the combustion
of the gel and the powder with a brownish color was
obtained, which is called dry gel. The dry gel was then
sintered at different temperatures to produce the
phosphors.
2.2. Characterization of the phosphors
Y2O3
Eu2O3
Diluted nitric acid

Transparent liquid
Citric acid
Transparent liquid
Heating
Transparent sol
Heating
Transparent gel
Drying
Dry gel
Sintering
Fig.1. Synthesis
process of Y O :Eu3+
Y2O3:Eu3+ microphosphors2 3
micro-phosphors
The IR spectra of the gels sintered at different temperatures were measured by using a
Nicolet 6700 FT-IR Spectrometer. X-ray diffraction images were studied with Brucker D8Advance XRD meter using Cu K radiation. The morphology of the particles was observed by
using ESEM FEI scanning electron microscope. Photoluminescence measurements were
performed using a continuous wave HeCd laser (325 nm) as the excitation source.
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3.1. Formation of Y2O3:Eu3+ phosphor in the sintering process
Figure 2 shows the IR spectra of
Y2O3:Eu3+ phosphors before sintering
and sintered at different temperatures.
For the dry gel before calcination, the
IR spectrum consists mainly of three
parts: the first part with a peak at
3438.5 cm-1 arises from the absorption
of OH vibration; the second part with
the main peaks at 1418.3 and 1541.2
cm-1 comes from citrate groups and
the third part with a weak peak at
845.3 cm-1 due to the absorption of
small amount of CO32-. After sintering
at 6000C, the absorption peaks from
the organic components decrease, and
a new sharp peak at 560 arises due to
the absorption of Y2O3. The
absorption peak due to Y2O3 became
stronger indicating the complete
crystallization
of
Y 2 O3 .
The
absorption of organic composition
almost disappeared after sintering at
9000C.
XRD patterns of phosphors
sintered at different temperatures are
shown in figure 3. The powders
crystallized
completely
at
the
0
temperature of 600 C. From these
results, it can be seen that crystal
structure of samples obtained single
phase body-centered cubic. Narrow
peaks indicate large particle size of the
phosphors.
Fig. 2. IR spectra of the phosphors before sintering and

sintered at different temperatures
Fig. 3. XRD patterns of the phosphors sintered at different

temperatures
3.2. Morphology of Y2O3:Eu3+ phosphor

Figure 4 shows SEM image of the powders sintered at 9000C in 3 hours. It can be seen that
nearly spherical particles of narrow size distribution are obtained and the mean particle size is
estimated from 1 to 6 m.
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Fig.4. SEM image of the powder sintered at 9000C for 3 hours
3.3. Luminescent properties of the phosphor

Emission spectra of the phosphors with Europium atom concentration of 7% sintered at
9000C for 3 hours when excited by 325 nm beam are shown in Figure 5. It can be seen that the
phosphors have an intensive fluorescence with a sharp peak at the wavelength of 611.5 nm
corresponding to the transition between 5D0 and 7F2 levels of Eu3+ ion.
Fig. 5. Emission spectrum of the phosphor sintered at 9000C for 3 hours,
ex
= 325 nm.
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Fig. 6. Concentration (left) and sintering temperature (right) dependence of emission intensity of the
phosphors
The emission intensity of the phosphors depends on europium concentration and sintering
temperature. As shown in figure 6, the strongest emission intensity corresponds to the
concentration of 7 at.%. Higher concentrations cause the decrease of emission intensity. This
effect may be attributed to the concentration quenching mechanism [12].
Effect of sintering temperature on photoluminescent intensity was investigated. Results
showed that emission intensity increases with the increase of temperature. The optimal sintering
temperature to produce high intensity is 900 oC. Higher sintering temperatures caused the
decrease of emission intensity. This can be explained that at higher temperatures, particles tend
to move into clusters, as a result, the emission intensity will be decreased.
3.4. Effect of molar ratio of metal ions to citric acid on luminescent properties of the
phosphors
Effect of molar ratio of metal ions to citric acid (1:1, 1:2, 1:3, and 1:4) on luminescent
intensity of the phosphors was studied. The results shown that when this ratio was 1:2, the
highest emission intensity was obtained. This can be explained that higher citric acid
concentration causes a higher carbon impurity left in the powder which decreased luminescent
intensity while the lower citric acid amount accelerates the rate of hydrolysis in sol-gel process,
as a result, the particles could not be homogeneous.
4. Conclusions
Y2O3:Eu3+ microphosphors have been synthesized by simple sol-gel process. The phosphors
have single phase BCC crystallite structure. Effect of europium concentration and sintering
temperature on luminescent properties of Eu3+ doped Y2O3 have been investigated. The optimal
Europium concentration is 7at.%. The photoluminescent intensity increases with the increase of
sintering temperature up to 9000C. Higher sintering temperatures can cause the decrease of
emission intensity. The particle size of the phosphor is in the range of 1-6 m. The best ratio of
metal ion to citric acid to obtain the highest luminescent intensity was 1:2.
Acknowledgments. This work is supported by the National Key Science and Technology
Program Grant number KC.02.10/06-10.
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References
1.
2.
G. Blasse, B.C. Geiabmaier, Luminescent Materials, Springer, Berlin, 1994, p.115

X. Jing, T. Ireland, C. Gibbons, D.J. Barber, J. Silver, A. Vecht, G. Fern, P. Trowga, D.C.
Morton, J. Electrochem. Soc. 146 (1999) 4654.
3. M.H. Lee, S.G. Oh, S.C. Yi, D.S. Seo, J.S. Yoo, J. Electrochem. Soc. 147 (2000) 3139.
4. N. Vu, T.K. Anh, G. Yi, W. Strek, J. Lumin. 122123 (2007) 776779
5. Adrian Camenzind, Reto Strobel, Sotiris E. Pratsinis, Chem. Phys. Lett. 415 (2005) 193
197
6. C. H. Lee, K. Y. Jung, J. G. Choi, Y. C. Kang, Mater. Sci. Eng. B. 116 (2005) 5963
7. A. Konrad, T. Fries, A. Gahn, F. Kummer, U. Herr, R. Tidecks, K. Samwer, J. Appl. Phys.
86 (1999) 3129.
8. H. Eilers, B.M. Tissue, Chem. Phys. Lett. 251 (1996) 74.
9. J. Zhang, Z. Zhang, Z. Tang, Y. Lin, Z. Zheng, J. Mater. Pro. Tech. 121 (2002) 265268.
10. R.P. Pao, J. Electrochem. Soc. 143 (1) (1996) 189196.
11. A. Mored, N.EL. Khiati, J. Electrochem. Soc. 140 (7) (1993) 20192022.
12. L.R. Singh, R.S. Ningthoujam, V. Sudarsan, I. Srivastava, S.D. Singh, G.K. Dey and S.K.
Kulshreshtha, Nanotechnology 19 (2008) 055201 (8pp).
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LUMINESCENT MEASUREMENTS AND DECAY TIME

OF SILICA TITANIA AND SILICA ZIRCONIA DOPED ERBIUM
Le Quoc Minha,b, Tran Thu Huong a and Tran Kim Anha
a)

18 - Hoang Quoc Viet Road, Road, Cau Giay Distr., Hanoi, Vietnam;
b)
College of Technology, Vietnam National University Hanoi, 144 Xuan Thuy Hanoi
E-mail: kimanh1949@gmail.com
Abstract. In this paper, we report new results about fabrication technology of SiO2/TiO2 and
SiO2/ZrO2 doped Er3+, Yb3+ and Al3+ planar wave guide have been fabricated by the solgel
technique and multilayer coating technology. Luminescent spectra and decay time of all the
samples were studied in detail. The influence of concentration and technology conditions were
investigated. Emission in the third telecommunication window was observed for all the samples.
The Er3+ active SiO2/TiO2 and SiO2/ZrO2 waveguide has been demonstrated a high quality for
C-telecom band amplification with significantly photonic characters such as: spectral width of the
4
I13/2-4I15/2 transition of Er3+ over 40 nm, decay time of 4-7.4 ms. Optical losses of films were
measured by an m-line spectroscopic set up about <1dB/cm.
Keywords: Planar wave guide; SiO2/TiO2; SiO2/ZrO2; Luminescent spectra; Decay time.
1. Introduction
Planar light wave guide photonics is becoming increasingly important in integrated optics,
modern telecommunication and nanotechnology [1, 2]. The fabrication of a planar wave guiding
device requires the preparation of transparent multilayer films with low optical losses and
controlled refractive index. These thin multilayer film systems with high quality could be able to
design a passive planar wave guide device such as splitter, combiner or array wave guide for
WDM (Wavelength Division Multiplexing) telecommunication technology. Besides this, for
amplification or modulation of optical signals, the films need to be doped with optically active
elements. In regards to optical amplification for telecommunication in the infrared spectral region,
the active wave guides have to process some significantly optical features such as: strong
emission at around 1500 nm, third optical window, wider band width (> 40 nm), longer decay
time of fluorescence in millisecond scale and crucially lower wave guide (optical) loss as possible
[3,4,5]. At present there is a key methods in developing an active wave guiding multilayer films
and device: sol gel process. The active sol gel multilayer films and planar photonic device has
optical high transparency (low optical loss) and excellent doping capacity of activation agent such
as nonlinear optic or in near infrared luminescent one. In our laboratory we have investigated
silica based planar photonic materials from sol gel process [6, 7, and 8]. We have developed two
promising active multilayer films of silica/titania and silica/zirconia doped with erbium for optical
amplification device at third window of telecommunication around 1500nm.
In this paper, we report new results about fabrication technology of the erbium-activated
planar waveguide, based on the Silica/Zirconia (SiO2-ZrO2) and Silica/Titania (SiO2-TiO2) thick
films. We present the research for enhancing the planar active (luminescent) properties and
especial improving the optical loss of the multilayer film in the two and third telecommunication
bands at 1300 nm and 1500 nm region.
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2. Experimental
The solutions of Silica/Titania and Silica/Zirconia were prepared by sol gel method: The
starting solution was obtained by mixing TEOS [Si(OC2H5)4, tetraethylorthosilicate Aldrich], IPA
[CH3-CH(OH)-CH3 (isopropanol) Merck], HCl was added as a catalyst and water, the hydrolysis
was processed at 50oC for one hour. TPOT [Ti((CH3)2CHO)4 (Titanium iso propoxide Aldrich]
and ZOP [Zr(OC3H7)4 (Zirconium (IV) propoxide Aldrich)] hydrolyses much faster than TEOS.
So, AcAc [C5H8O2(Acetyl Acetone )] was first added in TPOT, and MAA [C4H6O2 (methacrylic
acid)] was added in ZOP to reduce its hydrolysis speed before it was mixed with the SiO2 solution,
Al(NO3)3.9H2O (Merck), Yb(NO3)3 .5H2O (Merck) and Er(NO3)3 .5H2O (Merck) are dissolved in
IPA, and then mixed with the prehydrolyzed SiO2-TiO2 solution and SiO2-ZrO2 solution.
Wave-guide films were deposited on cleaned Silicon substrates by dip coating technology and
thermal annealing from 700oC to 950oC within 2 minutes. Optical and luminescent properties of
these materials have been investigated. The optical losses result of Er3+ doped SiO2/TiO2 and
SiO2/ZrO2 multi - layer films were measured by m-line spectroscopic method. All the experiments
were carried out at the room temperature [5].
3.1. Fluorescence spectra
= 976 nm
exc
T = 300 K
2.0
Intensity (a.u.)
Intensity (a.u.)
2.5
1.5
1.0
0.5
0.0
1450
1500
1550
1600
1650
20
18
16
14
12
10
8
6
4
2
0
-2
xc= 972 nm
T = 300 K
1450
(nm)
1500
1550
1600
1650
(nm)
Fig.1: The luminescent spectra of the Er3+ doped

silica (92)/titania(08)/Al(10)/ Yb (12.5) samples
heat treated at 950oC
Fig.2: The luminescent spectra of the Er 3+ doped

Silica (83)/ Zirconia/ (17)/ Al3+ (6) / Yb3+ (1)
samples heat treated at 850oC.
350
= 514 nm
Power = 500 mW
120 T = 300 K
exc
300
90
I ntensity (a.u.)
I ntensity (a.u.)
150
60
30
0
1400
1450
1500
1550
1600
1650
(nm)
Fig.3: The luminescent spectra of 1-SiO2/TiO2
(92/08)/ Er3+ /Al (10%) and 2-SiO2/TiO2 (92/08)/
Er3+ /Al (10%) / Yb3+ (12.5%)
250
= 514 nm
exc
Power = 500 mW
T = 300 K
200
150
100
50
0
1400
1450
1500
1550
(nm)
1600
1650
Fig.4: The luminescent spectra of SiO2/ZrO2

(83/17):Er3+ : 3- Without Al3+; 2- Al3+ (6%); 1Al(6%), Yb3+ (12.5%) - 850oC
Fluorescent spectra of the samples were measured at excitation wavelength of = 976 nm and
= 514 nm. Results of the luminescent spectra of the Er 3+ doped silica (92)/titania(08)/Al(10)/
Yb (12.5) samples heat - treated at 950oC and the luminescent spectra of the Er3+ doped
Silica(83)/ Zirconia/ (17)/ Al3+ (6) / Yb3+ (1) samples heat - treated at 850oC are shown in fig. 1
and fig.2. These spectra have peak at 1530 nm for the 3rd Window of Optical
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14
I ntensity (a.u.)
12
1- 850C
2- 750C
3- 650C
4- 70C
10
8
exc=
4
2
972 nm
T = 300 K
1450
1500
1550
1600
1650
(nm)
Fig.5: The luminescent spectra of SiO2/ZrO2 (83/17) Er (0, 75%) Yb (0.825%) Al (6%)
at different temperature at excitation wavelength of = 976nm
Telecommunication. The spectral width of the emission band from the 4I13/2- 4I15/2 transition is
over 40 nm.
Three electronic levels are involved in the basic amplification process created by Er 3+ ions: a
photon with the 972 nm pump wavelength is absorbed, which promotes the excitation of an
electron from the 4I15/2 fundamental level to the 4I11/2 excited level; rapid de-excitation occurs at
the 4I13/2 metastable, and a photon with the 1530 nm signal wavelength is spontaneously emitted,
due to the final electronic de-excitation back to the fundamental level.
When only Er3+ ions are present in short waveguides, the pumping efficiency at 972 nm is not
very good, because the Er3+ absorption cross-section at this wavelength is not very high. This
problem can be alleviated by the addition of Yb3+: pumping promotes an electron from the 2F7/2
ground state to the 2F5/2 manifold; the excited Yb3+ ion then transfers its energy to the Er 3+ 4I11/2
level [fig. 3, 4]; this transfer is very efficient, since it is quasi-resonant; this is then followed by
non radioactive decay to the Er3+ metasable level 4I13/2. Since the population of the 4I13/2 level is
increased by this mechanism, the fluorescence lifetime is also increased. Two deleterious
processes can also occur: back energy transfer from Er 3+ to Yb3+ ions, or double energy transfer,
where a second excited Yb ion transfers its energy to the Er3+ ion and promotes one electron from
the 4I11/2to the 4F7/2. Based on these mechanisms, several trends may be expected: with no Yb3+
present, Er3+ ions are not screened on one another and energy transfers between them can lower
the fluorescence lifetime. When the Yb3+ concentration is increased, Er3+ ions start tosee Yb3+
ions and deleterious Er3+ Er3+ energy exchanges are progressively replaced by beneficial Yb3+
Er3+ transfers [6]. The common feature of the luminescence emission from 4I13/2- 4I15/2 transition of
Er3+ ion in the wave guides is abroad band with full with at half-maximum (FWHM) over 40nm.
The emission maximum is situated around 1530 nm.(fig.5).
3.2. The fluorescence decay spectra
100
100
3+
10
3+
Silica/Zirconia:Er (4.6ms)
7.4ms
Intensity (a.u.)
Intensity (a.u.)
Silica/Titania/Er
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
10
10 12 14 16 18 20 22 24 26
Time (ms)
Time (ms)
Fig.6: The fluorescence decay curves of the

Silica/Titania/Er3+
Fig.7: The fluorescence decay curves of the

Silica/Zirconia/Er3+
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Table 1: Decay time of some multilayer wave guides.
Samples
Silica/Zirconia(83/17)
sample (ms)
Samples
Si/Ti /Er
3.5 ms
Si/Zr/Er
4.2
Si/Ti/ Er/Yb
4.1 ms
Si/Zr/ Er/Yb
5.7
Si/Ti/Er/Yb/Al
4.6 ms
Si/Zr/Er/Yb/Al
7.4
of
Silica/Titania(92/08)
sample of
The fluorescence decay curves of the SiO2 (92) / TiO2 (08) / Al2O3 (x)/Er3+/Yb3+ and SiO2
(83) / ZrO2(17)/ Al2O3(x) /Er3+ /Yb3+ films Er3+(1mol%) doped Silica (83) / Zirconia (17)/ Al3+ (6)
and Silica (83) / Zirconia (17) / Al3+ (6) / Yb3+ (1) samples were measured.[7, 8],
Decay exponentially with a lifetime of about 2 ms. The Er3+ emission in the infrared region
provides a possibility in development of an optical amplifier operating in the third
telecommunication band. When we use high purity chemicals, lifetimes were increased. Time
resolved fluorescence of samples were measured at excitation wavelength of = 976 nm from a
pulsed SDL-MOPA System (edge steepness 10 s), perpendicular trapping of Er3+ fluorescent
photons with a 600 m tap-fiber. Detection of the fluorescent signal by an InGaAs-photodetector
connected with an oscilloscope; the life time of Er3+ doped SiO2/ZrO2 is around 3.0 to 5.0 ms,
especial, the fluorescence decay curves of the Silica/Zirconia/Er 3+ is 4.6 ms [Fig.6]; the life time of
Er3+ doped SiO2/TiO2 is around 4.0 to 7.0 ms. We can improve the life time of Er3+ in SiO2/TiO2
multilayer films up to 7.4 ms [Fig.7]. [Table 1].
3.3. Optical losses
Optical losses of Er3+ doped SiO2/ZrO2 50, 60 layers were measured by an m-line
spectroscopic set up and are shown in table 2. The excitation source was argon laser at 532 nm,
HeNe laser at 632.8nm and semiconductor laser at 1310 nm. The film with thickness d = 3.5 m,
index n = 1.49 used prism coupler measure have rather low optical loss at 0.85 dB/cm. This value
is one of the lowest losses of optical multilayer films [7]. The 60 layer film was shown optical loss
of 1.88dB/cm. This indicated very good optical properties of the multilayer light wave guide in
the infrared region.
Table 2: Optical losses of some multilayer wave guides.
Samples
d ( m) Optical loss (dB/cm)
Silica/Zirconia(83/17) 50 layers
1.46
1.70 (532 nm)

2.24 (632.8 nm)
Silica/Zirconia (83/17)Er 60 layers
3.5
0.85 (632.8 nm)

1.88 (1310 nm)
4. Conclusion
Systems Er3+ activated SiO2/TiO2 and SiO2/ZrO2 planar wave guide have been successfully
fabricated by the solgel technique and multilayer coating technology. The layers were deposited
on silicon or silica wafers by a dip coating process.
Emission in the third telecommunication window was observed for all the samples. The Er3+
active SiO2/TiO2 and SiO2/ZrO2 waveguide has been demonstrated a high quality for C-telecom
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band amplification with significantly photonic characters such as: spectral width of the 4I13/2-4I15/2
transition of Er3+ over 40 nm, decay time of 4-7.4 ms. Optical losses of films were measured by an
m-line spectroscopic set up about <1dB/cm.
This highly developed wave guide multilayer film system shows very promising one to
develop a planar optical amplification device. This research direction has intensively been
undertaken in our institutes.
Acknowledgement
This work was supported by Vietnam Basic Research Program in Physic Science, project
408806 and Key Lab of Electronic Materials and Devices.
References
1. Bernard Jacquier Photonic materials for active devices in telecommunications. Proceeding
of the international Workshop on Optical and Spectroscopy (IWOS2000) Hanoi, Vietnam,
March 30-April1, 2000. pp.335-346
2. Xavier Orignac, Denis. Barbier, Xin Min Du, Rui M. Almeida, Orla Mc Carthy, Eric Yeatman
Sol-gel silica/titania on-Silicon Er/Yb-doped waveguide for optical amplification at 1.5
m Optical materials 12 (1999) 1-18
3. Alessandro Martucci, Alessandro Chiasera, Maurizio Montagna,
Maurizio Ferrari
Erbium-doped GeO2TiO2 solgel waveguidesJournal of Non-Crystalline Solids 322,
(2003) 295299
4. Chun Jiang, Qingji Zeng Optimization of erbium doped waveguide amplifier Optics &
Laser Technology 36 (2004) 167-171.
5. E.M.Yeatman, M.M.Ahmad, O.McCarthy, A.Vannucci, P.Gastaldo, D.Barbier, P.Mongadien,
C.Moronvalle Optical gain in Er3+-doped SiO2-TiO2 waveguides fabricated by the Sol-gel
technique Optical Communications 164, (1999)19-25
6. Tran Thu Huong, Tran Kim Anh, Carlos Barthou, Vo Thach Son and Le Quoc Minh
Fluorescent properties of Silica(92)-Titania(08) / Alumina (X) and Silica(83)-Zirconia(17) /
Alumina (X) doped with Er3+ and Yb3+. Proceedings of the Sixth German-Vietnamese
Seminar on Physics and Engineering, Chemnitz, 25 - 31, May, 2003. pp.172-176.
7. Tran Thu Huong, Tran Kim Anh, Johannes Kirchhof , Claudia Aichele and Le Quoc Minh
Preparation and photonic features of Erbium- activated Silica-Zirconia multilayer films
derived from sol gel process International Conference on Engineering Physics ICEP2006,
Hanoi; October 09-12, 2006, pp 79-82
8. Tran Thu Huong, Tran Kim Anh, Martin Becker, Anka Schwuchow and Le Quoc Minh
Luminescence, Lifetime and Optical Losses of Active Wave Guide Systems SiO2/TiO2 and
SiO2/ZrO2 Derived by Sol Gel Process 1st IWOFM-3rd IWONN Conference, Ha long, Vietnam,
December 3-10, (2006) 544-547.
Advances
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OPTICAL PROPERTIES OF CuInS2 THIN FILMS

PREPARED BY SPRAY PYROLYSIS
Tran ThanhThaia,c, Vo Thach Sona, Vu Thi Bichb and Pham Phi Hunga
a)
Institute of Physics Engineering, Hanoi University of Technology

No 1, Dai Co Viet Road, Hanoi, Vietnam
b)
Center for Quantum Electronics, Institute of Physics and Electronics, VAST
10, DaoTan Road, Badinh District, Hanoi, Vietnam
c)
Department of Technique and Technologies, Quy Nhon University
170 An Duong Vuong Street, Quy Nhon, Vietnam
E-mail: thaittdhqn@gmail.com
Abstract: Polycrystalline CuInS 2 absorber films for solar cells have been prepared by spray
pyrolysis of aqueuos solution of copper chloride, indium chloride and thiourea onto heated glass
substrates. By optimizing the spray parameters, such as the temperature of the substrate and molar
ratio of Cu/In in spray solution, the optical characterization of films which are well matched to the
solar spectrum were obtained. Transmission measurements were performed to examine the optical
properties of the films, the absorption coefficient and the optical band gap of the films were
calculated by transmission spectra. The absorption spectra of the films showed that this compound
is a direct band gap material and gap values varied between 1.35 - 1.78eV. Those thin films were
analysised by XRD in order to understand the effect of layers structure on their optical properties.
Keywords: CuInS2, Spray pyrolysis.
1. Introduction
The CuInS2 compound belongs to the family of direct band gap I-III-IV2 chalcopyrite
semiconductor. This compound exhibits a large fundamental absorption coefficient ( 105 cm-1)
and a band gap (Eg 1.55eV) optimally close to the peak of the spectral distribution of solar
energy [2,5,6,7,9,13,14]. No high toxic component is included in this compound semiconductor.
The highest reported efficiency of CuInS2 based solar cells is close to 12% [1,5,6,7,8,15].
However, at the present time, the main fundamental physical parameters important for practical
application of this material and among them, the band gap, are known only approximately. This
is primarily caused by the fact that the growth of high-quality CuInS2 chalcopyrite
polycrystallines and films presents technological problems.
There are various methods for the preparation of CuInS 2 such as chemical vapour transport
[10,13], chemical bath deposition [5,6,14], solvothermal route [3,4], wet chemical process [1],
sol-gel spin-coating [15], spray pyrolysis [2,7,8,9,11], etc. Among these methods, spray
pyrolysis, used in the present study, is an inexpensive technique which proved its convenience to
deposited homogeneous films over a large area [2,7,8,9].
In this present work, we have studied the optical properties of spray CuInS 2 films depend on
the preparation conditions as growth temperature and molar ratio of Cu/In in spraying solution.
2. Experiment
In the present study, hydrated copper chloride CuCl2.2H2O, indium chloride InCl3 and
thiourea CS(NH2)2 were used as initial chemicals. Deionised water was used for solution. Copper
to indium molar ratio in the solution was varied in the range of Cu/In = 0.85 - 1.25, while S/Cu
ratio was always maintained constant ( 3.6) for all the cases. The nozzle to substrate distance
was about 40cm. The solution was sprayed onto a heated glass substrates at temperature of 320410oC 5oC and nitrogen was used as carrier gas.
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The optical transmittance spectra of the films were measured using a Carry 100 UV-VIS
Spectrophotometer in the wavelength region of 200-900 nm. X-ray diffraction patterns were
recorded with a PANalytical Diffractometer using the Cu-K radiation. The thickness of the
films were measured using an Alpha-Step IQ profilometer.
3.1. Structural properties
(112)
(112)
(116)/(312)
(204)/(220)
TS=410 C
(204)/(220)
Intensity (a.u)
Intensity (a.u)
(116)/(312)
TS=380 C
(004)
TS=360 C
Cu/In=1.25
(004)
Cu/In=1.1
x
?
o
Cu/In=1.0
TS=340 C
TS=320 C
20
Cu/In=0.85
30
40
2 theta (degrees)
50
60
20
30
40
50
60
2 theta (degrees)
Fig.1. a) XRD patterns of CuInS2 films deposited at different substrate temperatures.

b) XRD patterns of thin films deposited from spray solution with a Cu/In ratio
between 0.85 and 1.25
The influence of the substrate temperature and the variation of Cu/In molar ratios on the
crystallinity of CuInS2 films was studied by the X-ray diffraction (XRD) (Fig. 1). We have
indexed the XRD peaks according to the crystallographic orientations of the chalcopyrite
structure (ASTM card - No 00-027-0159).
The XRD spectra shown in Fig. 1a is for films of CuInS2 deposited at temperatures between
320 and 410oC with solution in with Cu/In = 1.1 and S/Cu = 3.6. Accordingly to the chemical
composition analysis as reported in [11], the spectra correspond to those films with copper
excess relative to the stoichiometric composition. It was found that the substrate temperature had
great effects on the growth of polycrystalline CuInS 2 films. When the growth temperature
increases, the films are polycrystalline with preferred (112) orientations together with (004) and
the splitting of the (204/220) and (116/312) peaks. CuInS2 films growth at 340-380oC are considered
to have tetragonal chalcopyrite structure. These extra reflections (marked by +) close to the (112)
peak in CuInS2 films growth at low temperature TS = 320oC are obviously caused by the formation of
other phases beside CuInS2 in the Cu-In-S system formation [2,8]. Beside, the films growth at 340oC
also contains additional the (215) diffraction peak (marked by ?), it is considered that the formation of
chalcopyrite structure of ternary compound at higher temperature is explained by additional energy
require to order the atoms from disordered sphalerite phase [2,7]. Hence, these extra reflections
disappear with increasing the growth temperature. Notice that, the films are deposited at TS = 320oC
and 410oC, the splitting of the (204/220) and (116/312) reflection cannot be indentified by the XRD
pattern because of the low crystallinity of the films [2,7,11].
In Fig. 1b , we show the XRD spectra of thin films prepared at 360oC from solutions where the
ratio S/Cu was maintained constant at 3.6, but changing the ratio of Cu/In from 0.85 to 1.25.
For films prepared from solution with Cu/In 1.1 all the significant peaks correspond to the
tetragonal structure as discussed above. However for Cu/In 1, in addition to these peaks,
there appears another diffraction peak at 2 = 26.7o which may be related to the phase of In2S3
(ASTM card - No 00-033-0623). Beside, the spraying of indium excess solutions (In/Cu >1)
does not show a very good crystallinity due to the presence of a secondary chemical phase [2,7].
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The improvement of crystallinity when Cu/In ratio is increased is an effect which has been
attributed to copper mobility [3,4,6]. According to our result [11], this optimum value for Cu/In
is 1.1.
3.2. Optical properties
3.2.1. Transmission and reflection spectra
50
50
b)
a)
40
a
Transmission (%)
Transmission (%)
40
30
o
320 C
o
340 C
o
360 C
o
380 C
o
410 C
20
30
20
10
10
Cu/In = 0.85
Cu/In = 1.0
Cu/In = 1.1
Cu/In = 1.25
0
300
400
500
600
700
800
300
900
400
500
600
700
800
900
Wavelength (nm)
Wavelength (nm)
Fig.2. a) Optical transmittance spectra of the films at different substrate temperatures.

b)Optical transmittance spectra of the films at various Cu/In ratios
Optical transmission for thin films was measured in the range 300 - 900nm. The transmission
of these films are shown in Fig. 2.
In Fig. 2a the CuInS2 film presents at lower temperature (320oC) lower transmission. The
further increase in growth temperature increases the transmittance of sprayed films due to the
changes in the thickness or in the structure in the film. The films thickness has a tendency to
decrease with increasing the growth temperature as it was found also for the spray pyrolysis ZnO
and CdS films [2,8].
Fig. 2b shows the optical transmittance spectra of the films at different Cu/In ratio in the
range of 0.85-1.25. It is evident that an increase of the ratio of Cu/In leads to the decrease of the
optical transparency of the films in the visible region because of copper excess starting solution
lead to the recrystallization and larger crystallites.
3.2.2. Absorption coefficient
a)
b)
-1
4
30
Cu/In = 0.85
Cu/In = 1.0
Cu/In = 1.1
Cu/In = 1.25
30
Absorption coefficient (10 cm )
320 C
o
340 C
o
360 C
o
380 C
o
410 C
-1
Absorption coefficient (10 cm )
40
20
10
20
10
0
300
400
500
600
700
Wavelength (nm)
800
900
300
400
500
600
700
800
900
Wavelength (nm)
Fig.3. a) Absorption coefficient as a function of photon energy, for thin films prepared at different
substrate temperatures.
b) Absorption coefficient of CuInS2 thin film prepared at various Cu/In rati
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The absorption coefficient of the films have been calculated from the following relation
[12]:
T
(1 R ) 2 exp( d )
1 R 2 exp( 2 d )
where R and T are the spectral reflectance and transmittance, d is the film thickness.
For greater optical density (d > 1), the interference effects due to internal reflections as well
as reflectance at normal incidence are negligible and the previous equation can be approximated
as:
T ~ exp(-d)
Optical absorption coefficient is given by the approximate formula [12,14]:
1
1
ln
d
T
Where d is the film thickness and T the transmittance measured. We have calculated the
absorption coefficient for CuInS2 thin films having the average thickness values that various
between 231 - 592nm.
Fig. 3a,b show the absorption coefficient () of CuInS2 thin films with different substrate
temperatures and different Cu/In ratios. In the range of visible light, the order of their
absorption coefficient reaches 10-5 cm-1 and decreases with the increase of wavelength. This
value is close to reported values [5,7,10,13,14]. Summing up the law, increases with increment
of substrate temperature keeping Cu/In and S/Cu molar ratios constant. In addition, increases
with increment of Cu/In molar ratio keeping S/Cu molar ratio constant. Beside, the soft variation
of the absorption coefficient at the absorption threshold and its high value for energies below
suggest that there is a contribution of transitions from states within the band gap to light
absorption.
3.2.3. Determination of the gap energy
The fundamental absorption edge of semiconductor corresponds to the threshold for charge
transitions between the highest nearly filled band and the lowest nearly empty band. The
absorption is very small for photon energy much less than the energy gap and increases
significantly for higher photon energies.
For an allowed direct band gap transition [1-14], the absorption coefficient () can be
related to the incident energy (h) by the following equation:
(1)
h
C (h
Eg )1/ 2
where C is a constant, Eg is the optical band gap and h is the Planck constant. For a direct band
gap semiconductor, the (h )2 versus h characteristic is predicted to be a straight line with a
photon energy axis intercept giving the value of the band gap.
A plot of (h )2 against the photon energy h for CuInS2 thin films deposited at different
substrate temperatures is presented on Fig. 4a.
From substrate temperatures ranging from 3200C to 4100C, a decrease in band gap values was
observed. This compound is a direct band gap material with value of 1.78eV at 3200C, 1.69eV at
3400C, 1.58eV at 3600C, 1.51eV at 3800C and 1.35eV at 4100C substrate temperature (Fig. 4a).
A possible cause for this effect may be carrier degeneracy in CuInS 2 due to defect in the
crystalline lattice and the presence of secondary phases which have been confirmed by XRD
[2,7,9,11]. From these observations, the influence of both the film thickness and substrate
temperature on Eg values is clearly evident.
Fig. 4b shows the (h)2 versus photon energy h of CuInS2 films deposited at various Cu/In
molar ratios of the starting solution. It can be observed that the band gap decreases from 1.72 to
Advances
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200
200
( h ) (10 cm eV )
150
( h ) (10 cm eV )
-2
150
100
-2
100
320 C
o
340 C
o
360 C
o
380 C
o
410 C
50
50
Cu/In = 0.85
Cu/In = 1.0
Cu/In = 1.1
Cu/In = 1.25
0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
0
Energy (eV)
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
Energy (eV)
Fig.4. a) A plot of (h)2 vs h for CuInS2 films at different substrate temperatures.

b) A plot of (h)2 vs h for CuInS2 films at various Cu/In ratios.
1.30 eV when the Cu/In molar ratio increases from 0.85 to 1.25. The value of band gap 1.58eV
for Cu/In = 1.1 is close to 1.55eV, which is the reported value for bulk crystalline [2,7,14]. It
may be noted that the lower Cu/In molar ratio leads to the increase of the optical band gap [3,6].
The deviations from stoichiometry in CuInS 2 result in some defects in crystalline lattice, such as
copper, indium and sulphur vacancies (VCu, VS), interstitial sulphur (Si), substitutional copper in
indium sites (CuIn), and also substitutional indium in coper sites. When Cu/In increases, the Cu In
and VIn defect densities may increase which make the materials p-type degenerate, but when the
products become indium-rich, the most probable defects are VS, InCu, which can introduce
shallow donor levels and also the defect VCu is responsible for introducing an acceptor levels
[3,7].
In the present study, the decrease of optical band gap of CuInS 2 thin films may be attributed
to the presence of unsaturated defect, which increase the density of localized states in the band
gap. This decrease in optical band gap is attributed to variation of stoichiometric [6,9].
4. Conclusion
The thin films of CuInS2 with chalcopyrite structure have been prepared by varying of Cu/In
ratio in spray solution at growth temperatures of 340 - 380oC. The optical studies reveal that
these films have a direct band gap and the band gap energy varies from 1.35 to 1.69eV, which
accords with the requirement of solar cell. It is observed that the band gap decrease with the
increase of the substrate temperature or with the increase of Cu/In molar ratio. Having all this
information we expect that these properties can be controlled in order to achieve high
efficiencies when making solar cells based on this material.
Acknowledgements
We thank the Laboratory of Physical Analysis and Measurement, Institute of Engineering
Physics, Hanoi University of Technology, Vietnam for his help and excellent working conditions.
References
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P. Guha, D. Das, A.B. Maity, D. Ganguli, S. Chaudhuri, Solar Energy Materials & Solar
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K. Das, S.K. Panda, S. Gorai, P. Mishra, Materials Research Bulletin 43 (2008) 2742-2750.
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M.D. Mahanubhav, L.A. Patil, P.S. Sonawane, R.H. Bari, V.R. Patil, Sensors &
Transducers Jounal, Vol.73, Issue 11 (2006) 826-833.
M.O. Lopez, A.M. Acevedo, Thin Solid Films 330 (1998) 96-101.
J. Gonzalez-Hernandez, P.M. Gorley, P.P. Horley, O.M. Vartsabyuk, Yu.V. Vorobiev,
Thin Solid Films 403-404 (2002) 471-475.
B. Altiokka, S. Aksay, Journal of Arts and Sciences Say: 3 / Mays 2005, 27-34. Solid
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M. Abaab, M. Kanzari, B. Rezig, M. Brunel, Solar Energy Materials & Solar Cells 59
(1999) 299-307.
Thai T.T, Son V.T, Bich V.T, Proceedings of the Eleventh Vietnamese-German Seminar
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A. Bouzidi, N. Benramdance, A. Nakrela, C. Mathieu, B. Khelipha, Material Science and
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Advances
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RAMAN SCATTERING OF Ga1xMnxAs

Nguyen Van Minh and Luc Huy Hoang
Center of Nano Science and Technology, and Department of Physics, Hanoi National
University of Education, 136 Xuan-Thuy Rd., Cau Giay, Hanoi
E-mail: minhsp@yahoo.com
Abstract. Ga1xMnxAs samples with various Mn concentrations grown on GaAs substrates by
low temperature molecular beam epitaxy were studied using Raman spectroscopy. Here we report
a spectroscopic measurement of Ga1xMnxAs layers at room temperature using a Raman
scattering intensity analysis of the coupled plasmon-LO-phonon mode and the unscreened LO
phonon. The hole density determined from Raman scattering shows a monotonic increase with x,
exhibiting a direct correlation to the observed T c. This technique provides an useful tool to study
spintronic semiconducting materials.
1. Introduction
For many years, Mn-containing diluted magnetic semiconductors (DMSs) based on II-VI
compounds have been the subject of intense fundamental studies because of the strong exchange
interaction between the half filled 3d shell of the Mn2+ ions (S=5/2) and the charge carriers [1].
The recent progress in growth techniques made cubic (Ga,Mn)As available, and the discovery on
its ferromagnetism made this material attractive for fundamental studies as well as for
applications in devices based on spin-related phenomena [2,3]. The origin of ferromagnetism in
diluted (Ga,Mn)As is not yet well understood, as illustrated by the large number of recent
publications devoted to theoretical investigations of this problem. The attempts to explain the
ferromagnetic behavior in (Ga,Mn)As have used the following approaches: hole-mediated
Ruderman-Kittel-Kasuya-Yoshida (RKKY) type interaction between local Mn moments, [4,5,6]
Zener mode virtual electron excitation from the magnetic impurity to the valence band. To fully
understand the origin of ferromagnetism in (Ga,Mn)As it is necessary to clarify the electronic
configuration in which Mn enters GaAs in the diluted regime. In addition, type and density of
free charge carriers are important parameters for the ferromagnetic MnMn-interaction. In nonmagnetic materials the carrier densities are usually determined by Hall measurements. However,
in Ga1xMnxAs the ordinary Hall effect is superimposed by an anomalous Hall effect which is
proportional to the magnetization M and to the spin polarization. Therefore, the hole
concentration can only be derived from the Hall resistance under high magnetic fields above 20
T, where M saturates.
Looking for an alternative method for the determination of carrier type and density in
Ga1xMnxAs Raman scattering by the coupled modes of longitudinal optical (LO) phonons and
electron or hole plasmons may be taken into account. It is well known that in n-type GaAs two
coupled plasmon-LO-phonon modes (CPLOM) L and L+ can be observed in the Raman
spectrum [7]. The L+ mode strongly shifts to higher frequencies with increasing carrier density
for n 5 1017 cm3, allowing an accurate determination of the electron density from its Raman
shift. In p-type GaAs only one phonon-like coupled mode LS is observed because of the strong
damping of the hole plasmon [8]. Its frequency shifts from the LO-phonon position to the
transverse-optical (TO) phonon position with increasing hole concentration p. For a plasmon
damping 2000 cm1 and for hole densities 5 1018 cm3 p 1020 cm3 the LS mode appears
as a broad band between the TO and LO positions. Beyond these limits its line width approaches
that of the LO phonon with decreasing or increasing carrier density, respectively.
The aim of this paper is to present a set of Raman spectra recorded from Ga1xMnxAs
samples with different Mn concentrations and to tentatively estimate the type and density of free
charge carriers from a line shape analysis of the Raman spectra.
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2. Experiment
Ga1xMnxAs (x = 0.00, 0.03, 0.05, 0.07) thin films were grown by molecular-beam epitaxy
on a GaAs substrate. Raman scattering spectra were recorded by using T64000 Raman
spectrometer (Jobin-Yvon) using 514.5 nm line Ar+ laser excitation at the room temperature. All
spectra reported here were measured in backscattering geometry on the (001) growth surface of
the samples.
3. Result and discussion
Intensity (a.u.)
The scattering efficency per unit crystal

CPLOM
length per unit solid angle at a temperature
T can be written [9]:
ULO
z (YY ) z
2 s4 N 2
2
S
(n0 1) | es .R j .ei |
4
c
j
(1)
z ( xy) z
Where s is the frequency of the scattered
light, N is the number of the primitive cells
z ( xx) z
per unit volume, no is the Bose-Einstein
z (YX ) z
factor, is the density, c is the velocity of
light, and
is the phonon frequency. The
vectors e i and e s represent the polarization
260
280
300
-1
Raman
shift
(cm
)
of the incident and the scattered light and Rj
is the Raman tensor, the subindex allowing
Fig 1. Raman spectra of Ga1-xMnxAs with 5% Mn
for phonon degeneracy. In the case of the
with different polarization configurations
zone-center optical phonon in tetrahedral
semiconductors Rj has the three
components:
0 a 0
0 0 a
0 0 0
R3
a 0 0 ,
R2
0 0 0 ,
R3
0 0 a
(2)
0 a 0
0 0 0
a 0 0
GaAs is a polar material and therefore has the LO-TO splitting. Thus for propagation along
directions other than the crystal axes the appropriate combination of the tensors of Eq. (2) must
be considered for either TO or LO scattering.
Typical Raman spectra of Ga1-xMnxAs with 5% Mn at room temperature in backscattering
geometry with different polarization configurations are shown in Fig.1, where z = [001] is the
growth direction and x = [100], y = [010], X = [ 1 1 0] and Y = [110]. According to the Raman
selection rule for a zinc-blende crystal, the LO phonon is allowed for z (YY ) z and z ( xy) z but
forbidden for z ( xx) z and z (YX ) z , whereas the TO phonon is forbidden for all the scattering
configurations employed in Fig. 1. The Raman feature near 278 cm-1 is very strong in z (YY ) z
and z ( xy) z , whereas it is extremely weak in z (YX ) z and z ( xx) z where LO modes are
forbidden. The very weak Raman signal near 270 cm-1 in z (YX ) z configuration is the disorderinduced TO phonon that should exist as a weak background Raman intensity [10] for all the
other configurations employed in Fig. 1. Therefore, the Raman feature at 278 cm -1 is a CPLOM
in Ga0.95Mn0.05As. We did not observed any signal at high frequency that can be attributed to L +.
This indicates that the free carrier is a hole. The exists the shouder on the high frequency side of
the CPLOM is due to ULO in the depletion layer near the surface.
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(1)
1
p 2
Where d is the depletion layer thickness. S
is the static dielectric constant and B is the
surface potential barrier. We use S =12.8
[11] and B =0.5 [10]. In addition, we have
the formula [10]:
1
A
(2)
d
ln 1
2
S
where A AL / AP is the ratio of the

integrated intensity of the ULO to that of
the CPLOM in the Raman spectrum,
is
the absorption coefficient, and S I L / I P
is the relative Raman scattering efficiencies
of the ULO and CPLOM in a unit volume.
Intensity (a.u.)
0%
x=3%
5%
7%
220
240
260
280
300
-1
320
Raman shift (cm )
Fig. 2 Superimposed Raman features can be

decomposed into CPLOM and ULO parts by fitting
data using two Lorentzian
290
-1
1
2
z(YY)z
Raman shift (cm )
The superimposed Raman features can

be decomposed into CPLOM and ULO
parts by fitting the experimental data using
two Lorentzian oscillators as shown in Fig.
2, where Raman spectra of Ga1-xMnxAs for
x = 0.00; 0.03, 0.05, 0.07 in a z (YY ) z
scattering configuration are shown. The
reference (x =0.00) exists only one
Lorentzian oscillator. The ratio of the ULO
and CPLOM decreases as the Mn content
increases. Seong et.al. [10] indicated that as
Mn content increases the Raman intensity
of ULO rapidly decreases. In our result,
only the ratio of ULO and CPLOM
intensity is in agreement with Seongs
suggestion. The ULO frequency linearly
decreases with increasing Mn content. Two
reasons can be appeared in this case. One is
the lattice constant changes and the other is
alloying effect. Therefore, there appears a
blue shift in ULO frequency. The position
of ULO and CPLOM of Raman spectra vs.
Mn concentration was shown in Fig. 3 and
Table.1.
We assume that the phonon frequencies
of the TO and LO do not change with
doping because dopant concentrations are
too small to change most of the physical
parameters of GaAs used for the line-shape
analysis. The depletion layer thickness d for
p > 1018 can be calculated as a function of
hole concentration p at zero temperature:
ULO
CPLOM
280
270
0.000
0.025
0.050
0.075
Mn concentration x
Fig. 3 Position of ULO and CPLOM vs. Mn
concentration
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By equating (1) and (2), p is given by:

p
2
0
B
2
e ln 1
(3)
A
S
And thus calculated hole concentrations are listed in table 1, with an uncertainty less than 15%.
Table 1. Result of calculated hole concentration
Mn(%)
0
3
5
7
ULO (cm-1)
291
289.7
288
286.7
CPLOM (cm-1)
0
268.7
266.6
265
d(A )
60
20
10
p (cm-3)
1.3 1019
1.9 1020
2.7 1020
In summary, we have presented one way to determine the room temperature carrier concentration
in Ga1-xMnxAs for various content of Mn using Raman intensity analysis of the CPLOM and
ULO phonon. This result shows that, unlike standard Hall measurement, Raman scattering
provides an useful method of determining the hole density in Ga1-xMnxAs that can be profitably
exploited for gaining a better understanding of the origins of ferromagnetism in ferromagnetic
semiconductors.
Acknowledgment
This work was supported by Basic Research Program in Natural Science of Vietnam.
References
1. J.K. Furdyana, J. Appl. Phys. 64, R29 (1988).
2. H. Ohno, H. Munekata, T. Penney, S. von Molnar, and L.L. Chang, Phys. Rev. Lett. 68,
2664 (1992)
3. H. Ohno, A. Shen, F. Matsukura, A. Oiwa, A. Endo, S. Katsumoto, and Y. Iey, Appl. Phys.
Lett. 69, 363 (1996).
4. H. Akai, Phys. Rev. Lett. 81, 3002 (1998).
5. J. Konig, H.-H. Lin, and A.H. MacDonald, Phys. Rev. Lett. 84, 5628 (2000).
6. T. Dietl, H. Ohno, and F. Matsukura, Phys. Rev. B 63, 195205 (2001).
7. G. Abstreiter, M. Cardona, A. Pinczuk, in: M. Cardona, G. G.untherodt (Eds.), Light
Scattering in Solids IV, Springer, Berlin, p. 5 (1984).
8. G. Irmer, M. Wenzel, J. Monecke, Phys. Rev. B 56, 9524 (1997).
9. M. Grimsditch and A.K. Ramdas, Phys. Rev. B 14 1670 (1976).
10. M.J. Seong, S.H. Chun, H.M. Cheong, N. Samarth and A. Mascarenhas, Phys. Rev. B 66,
033202 (2002).
11. J.S. Blakemore, J. Appl. Phys. 53, R123 (1982).
Advances
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THERMOELECTRIC PROPERTIES OF BI1.8SB0.2TE3.0 SINGLE

CRYSTALS UNDER HIGH PRESSURE.
Ngo Thu Huong, Do Thi Kim Anh
Faculty of Physics, Hanoi University of Science, VNU
334 Nguyen Trai, Thanh Xuan, Hanoi.
Abstract: The single crystals Bi1.8Sb0.2Te3.0 were prepared by a Gradienze Freeze method. In this
paper, we have report the thermoelectric properties of Bi 1.8Sb0.2Te3.0 single crystals under high
pressure. A strong anisotropy was confirmed in the electrical resistivity and thermopower for p
and n -types Bi1.8Sb0.2Te3.0. The electrical resistivity is decreased linearly with pressure at 297 K
for p and n-types. The n-type Bi1.8Sb0.2Te3.0 exhibits a larger decrease in the electrical resistivity
with pressure at a rate of -35 %/GPa along the a and c-axes. The pressure dependence of
thermopower has been shown to be anisotropic depending on the crystallographic direction for
both p and n-types at 297 K. The thermopower value at 297 K is increased with pressure at a rate
of 29.4 VK-1 /GPa (+13.9 %/GPa) along the a -axis and is approximately constant along the caxis for p-type Bi1.8Sb0.2Te3.0. At 297 K, the absolute value of the thermopower is decreased with
pressure at a rate of -15.2 VK-1 /GPa (-17 %/GPa) and -20.8 VK-1/GPa (-35.5%/GPa) for n type Bi1.8Sb0.2Te3.0 along the a and c-axes, respectively. The power factor is increased largely
with pressure for p-type, while it is approximately constant for n-type at 297 K. The
thermoelectric performance is improved by pressure for p-type while it is pressure independent
for n-type.
1. Introduction
The search for improved thermoelectric materials has renewed interest in fundamental as
well as applied physics. It should be stressed the search for optimum conditions. The p-type and
n-type Bi1.8Sb0.2Te3.0+ alloys exhibit high thermoelectric performance below room temperature.
A strong anisotropy was found in the resistive behavior, whereas the thermopower was isotropic.
Thermoelectric perfomance is much better along the a-axis than the c-axis. The power factor
exhibited a maximum value of 35 Wcm-1 K-2 around 200 K for p-type. However, it is only one
half magnitude of recently reported value for n-type Bi1.8Sb0.2Te3.0 [1]. In this paper, we present
the effect of pressure on the thermoelectric properties of p and n-types Bi1.8Sb0.2Te3.0 alloys.
2. Experimental
The single crystals of Bi1.8Sb0.2Te3.0 alloys were prepared from pure elements of Bi,Sb
and Te with the purity of 99.9999 % (6N).We have added an excess amount of Te element by
ranging from 0.0 to 0.25 in the starting chemical formular of Bi1.8Sb0.2Te3.0+ to control the
carrier concentration in the ingots to prepare. These starting elements were melted at 610 oC for
12 hours in an electric furnane and were cooled to room temperature. Then, the Bi1.8Sb0.2Te3.0
ingots were grown by using the Bridgman method in a Gradient Freeze (GF) furnace. We used
the DC four-probe method for the electrical resistivity measurement under high pressure. The
hydrostatic pressure up to 1.2 GPa was generated by using a clamp-type piston cylinder
apparatus. The temperature range for the electrical resistivity measurement extends from 80 K to
300 K. The thermopower measurement under high pressure was performed by a steady-state
longitudinal heat flow method. Hydrostatic pressure up to 0.5 GPa was generated by the high
pressure pump system.
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3.1. Effect of pressure on electrical resistivity
b)
a)
Fig. 1: Temperature dependence of electrical resistivity for p-type Bi1.8Sb0.2Te3.0
along the a and c-axes at various presures.
a)
b)
Fig. 2: Temperature dependence of electrical resistivity for n-type Bi1.8Sb0.2Te3.0

along the a and c-axes at various presures.
The temperature dependence of the electrical resistivity (T) is shown for ptype
Bi1.8Sb0.2Te3.0 along the a and c-axes at various pressures in Fig. 1a and Fig. 1b, respectively.
The electrical resistivity decreases with increasing pressure in all the investigated temperature
range from 80 K to 300 K for p-type Bi1.8Sb0.2Te3.0 samples. The electrical resistivity increases
with increasing temperature and takes a maximum at around 180 K along the c-axis. This
behavior may be explained by the mixed conduction [2]. The electrical resistivity values are 1.6
and 4.1
cm at zero pressure and room temperature for p-type Bi1.8Sb0.2Te3.0 along the a and
c-axes, respectively. These results are in good agreement with the previous report [3].
For n-type Bi1.8Sb0.2Te3.0, the electrical resistivity is found to be decreased with pressure in
the temperature range from 80 K to 300 K (Fig. 2). A peak appears in the (T ) curves at around
210 K and 185 K along the a and c-axes, respectively and is shifted appreciably to higher
temperature with pressure.
The electrical resistivity of p-type Bi1.8Sb0.2Te3.0 along the a and c-axis is plotted in Fig. 3a
and Fig. 3b, respectively, as a function of pressure at 297 K and 80 K. At 297 K, the electrical
resistivity is decreased linearly with increasing pressure. The reduction rate of is - 429
cm/GPa (-26 %/GPa) along the a-axis and -1191
cm/GPa (-29 %/GPa) along the c-axis,
respectively. The decrease in the electrical resistivity at 80 K is smaller than that at 297 K along
the a-axis, while it is larger than that at 297 K along the c-axis.
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a)
b)
Fig. 3: Electrical resistivity of p-type Bi1.8Sb0.2Te3.0 along the a and c-axes

as a function of pressure at 297 K and 80 K
a)
b)
Fig. 4: Electrical resistivity of n-type Bi1.8Sb0.2Te3.0 along the a and c-axes

as a function of pressure at 297 K and 80 K
The similar behavior has also been observed for n-type Bi1.8Sb0.2Te3.0 (Fig. 4). The electrical
resistivity value at 297 K decreases at a rate of -891
cm/GPa (-35 % /GPa) and -2126
cm/GPa (-35 %/GPa) along the a and c-axes, respectively.
3.2. Effect of pressure on thermopower
Figures 5a and 5b show the pressure dependence of the thermopower and power factor for ptype Bi1.8Sb0.2Te3.0 along the a -axis at 297 K. At zero pressure, the thermopower value S along
the a-axis is +216 VK-1, which is in good agreement with previous report [3]. Along the c-axis
the value of S at zero pressure is +130 VK-1 which is one half of that reported by Huong et
al.[3].
The magnitude of the thermopower along the a-axis increases with pressure at a rate of +29.4
VK-1/GPa (+14%/GPa). While the measured thermopower along the c-axis is approximately
constant with increasing pressure (Fig. 5b). Thus, it is concluded that the pressure dependence of
the thermopower is highly anisotropic depending on the crystallographic direction for p-type
Bi1.8Sb0.2Te3.0. The increase in the thermopower with pressure may be associated with a change
in the electronic band structure which has a major impact on transport properties [4-8].
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a)
b)
Fig. 5: Dependence of thermopower and power factor on pressure

for p-type Bi1.8Sb0.2Te3.0 along the a and c-axes at 297 K.
a)
b)
Fig. 6: Dependence of thermopower and power factor on pressure

for n-type Bi1.8Sb0.2Te3.0 along the a and c-axes at 297 K.
Figures 6a and 6b show the pressure dependence of the thermopower for ntype
Bi1.8Sb0.2Te3.0 along the a and c-axes at 297 K, respectively. At zero pressure, the thermopower
values are -89.2 and -61.4 VK-1 along the a and c-axes, respectively.
The absolute value of the thermopower for n-type Bi1.8Sb0.2Te3.0 is found to be decreased
with pressure. Along the a-axis the decreasing rate of the thermopower is -15.2 VK-1/ GPa (17.0% /GPa). A larger decrease in the absolute value of thermopower is found along the c-axis at
a rate of -20.8 VK-1/GPa (-35.5%/GPa).
3.3. Total thermoelectric performance under pressure
The thermoelectric performance under high pressure will be discussed in this section. The
power factor P.F.=S2/ is evaluated from the thermopower and the electrical resistivity data
measured under high pressure, and plotted in Fig. 5 for p-type Bi1.8Sb0.2Te3.0 and Fig. 6 for n
type Bi1.8Sb0.2Te3.0. The power factor is found to be increased largely with increasing pressure
for p-type Bi1.8Sb0.2Te3.0 along the a and c-axes, respectively. For ntype Bi1.8Sb0.2Te3.0, a very
small change in the power factor is found and the thermoelectric performance is admitted to be
pressure independent.
To estimate the figure of merit Z under pressure, the thermal conductivity measurement
under pressure is necessary, but it is so difficult to measure thermal conductivity under pressure.
Instead, we only take into account the change of the electronic thermal conductivity e with
pressure.
The electronic thermal conductivity e and electrical conductivity are connected by the
Wiedemann-Franz law,
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e = L0 x T x
where L0 is the Lorentz number, T is the absolute temperature. When we assume L0 is
temperature independent [7]. Thus, the electronic thermal conductivity e is obtained and the
lattice thermal conductivity l can be estimated by subtracting the electronic contribution from
the total thermal conductivity .
For p-type Bi1.8Sb0.2Te3.0 the electrical resistivity at zero pressure and 298 K is 0.0016 cm
(625 S/cm). The electronic thermal conductivity e is calculated to be 3.1 mW/cmK. It is readily
shown that the electronic contribution e to the total thermal conductivity is only 25%. At P =1
GPa, the electrical coductivity is increased by a factor of 1.25 (i.e., from 625 to 789 S/cm).
Therefore, according to the Wiedemann-Franz law, the electronic thermal conductivity will be
increased by a factor of 1.25 to 3.72 mW/cmK at 1 GPa. It should be noted that this increase in
e under pressure could not be so significant when we consider large enhancement of P.F.by
more than 50 %/GPa with pressure.
The lattice contribution l may be also increased with pressure. For certain semiconductors
such as CsI, the lattice thermal conductivity increases by more than a factor of 2 in an extreme
case at pressure less than 2 GPa [8]. We may expect that many materials may shift their phonon
frequency to higher values under pressure, so the contribution of l should be more or less
appreciable under pressure.
4. Conclusion
The following conclusions can be drawn from the investigation of the effect of pressure on
the electrical resistivity and thermopower in the p-and n-types Bi1.8Sb0.2Te3.0 alloys.
- A strong anisotropy was confirmed in the electrical resistivity and thermopower for both p and
n-types.
- The electrical resistivity is decreased linearly with pressure at 297 K for p and n-types,
respectively. The n-type Bi1.8Sb0.2Te3.0 exhibits a larger decrease in the electrical resistivity
along the a and c-axes.
- The pressure dependence of thermopower has been shown to be anisotropic depending on the
crystallographic direction for both p and n-types at 297 K. The thermopower value at 297 K is
increased along the a-axis and is approximately constant along the c-axis for p-type. At 297 K,
the absolute value of the thermopower is decreased for n-type along the a and c-axes,
respectively.
- The power factor is increased largely with pressure for ptype, while it is approximately
constant for n -type at 297 K.
Acknowledgment: This work is supported by the Japan Advanced Institute of Science and
Technology (JAIST).
References
1. N. T. Huong, Ph. D. thesis, JAIST (2003).
2. D. B. Hyun, J. S. Hwang, T.S.Oh, J. D. Shim and N.V.Kolomoets, J. Phys. Chem. Solids, 59
(1998) 1039.
3. N. T. Huong, Y. Setou, G. Nakamoto, M. Kurisu, T. Kajihara, H. Mizukami and S. Sano, J.
Alloys Compound , 368 (2004) 44.
4. N. B. Brandt, M. Yu Lavrenyuk, N. Ya Minina, A. M. Savin, W. Kraak and R. Herrmann,
Phys. Status Solidi b,143 (1987) 601.
5. X. F. Chen, G. X. Tessemaand, M. J. Skove, Phys. Rev. B 48 (1993)13141.
6. T. A. Davis, W. Schaffer, M. J. Skove and E. P. Stillwell, Phys. Rev. B 39 (1989) 10094.
7. T. M. Tritt, E. P. Stillwell and M. J. Skove, Phys. Rev. B 34 (1986) 6799.
8. Y. T. Tseng, G. X. Tessema and M. J. Skove, Solid State Commun., 94 (1995) 867.
Advances
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SYNTHESIS OF LONG AFTERGLOW PHOSPHORS MAl2O4( M: Ca, Sr,Ba) CODOPED WITH RARE EARTH IONS BY COMBUSTION METHOD AND THEIR
OPTICAL PROPERTIES.
Nguyen Manh Sona, Le Thi Thao Vienb, Nguyen Ngoc Traca
a)
Department of Physics, College of Sciences, Hue University

b)
Department of Physics, Qui Nhon University
Abstract: Long afterglow phosphors MAl2O4 (M: Ca, Ba, Sr) co-doped with rare earth ions
(Eu2+, Dy3+, Nd3+, Gd3+) were synthesised by combustion method using nitrate metals and urea
at 5400C for 5 minutes. The crystalline structure of samples was monoclinic phase (-phase)
and was analyzed by XRD using CuK radiation. The average size of particles is about 80 nm
and determined by TEM. The emission spectra of these phosphors were the broad bands due to
transitions from the 4f65d1 to the 4f7 configuration of the Eu2+ ion. The emission color of these
materials depends on the earth alkaline ion in the MAl2O4 lattice. The decay time of afterglow
depended not only on the RE3+ rare earth ion but also influenced by the earth alkaline ion in the
lattice. The influence of second RE3+ ion on the luminescent properties in the MAl2O4 lattice
had been investigated.
1. Introduction
Long afterglow phosphors MAl2O4 (M: Sr, Ca, Ba) co-doped with rare earth ions (Eu2+ and
Dy , Nd3+) have attracted much attention of sciences [1, 2, 3 ,4] since they show excellent
properties, such as: high radiation intensity, color purity, longer afterglow, chemically stable,
safe and no radiation, etc. Beside, the emission color of these phosphors depends on alkaline
metal in aluminates lattice and the long afterglow of phosphors depends on co-doped rare earth
ions. With the development of scientific technologies on materials, there are several chemical
synthesis techniques, such as: coprecipitation [4], sol-gel [10, 13], solid state reaction [1, 6]
and combustion [8, 12] methods have been applied to prepare MAl2O4: Eu2+, RE3+. In this paper,
we synthesis these phosphors by combustion method using urea as reducer and fuel, nitrate
precursors as oxidizer at 5400C for 5 min. The combustion process to prepare these powders,
however, is very facile and only takes few minutes which have been extensity applied to the
preparation of various nano-scale oxide materials. These phosphors resulted from combustion
method have optical properties like those resulted from the other method and the sintering
temperature of the sample prepared by the combustion method is much lower than that of one
prepared by solid state reaction or sol-gel method.
The spectroscopy properties of the phosphors will be presented in this paper. The long
afterglow of phosphors were influenced by the second doped RE3+ ion in the lattice and the
emission color influenced by the concentration ratio between Sr and Ca or Ba in aluminate
lattice.
3+
2. Experimental
The starting materials included: Al(NO3)3 9H2O, M(NO3)2 (M: Ca, Sr, Ba), Nd2O3, Eu2O3,
Dy2O3, B2O3, CO(NH2)2 and HNO3 (1.4 g/ml). Small quantities of B2O3 were used as a flux;
amounts of urea were added as reducer and fuel, metal nitrates were used as oxidizer. The choice
of oxidizer and fuel in the stoichiometric ratios are dictated by the propellant chemistry
principles.
Firstly, Al(NO3)3 9H2O, M(NO3)2, B2O3 and CO(NH2)2 were dissolved into enough
deionized water to obtain transparent solution, Eu2O3, Dy2O3 were dissolved into concentrated
nitric acid to form nitrate solution, then mixed the two solutions together to get the
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DTG %/min.
TG / %
Heatflow/V
80
stoichiometric and stirred for 4 h at 70 C.
60
The process of heat treatment was study by
60
0
40
DTA in the fig. 1. After that, the precursor
40
20
solution was introduced into a Lenton
-20
0
20
furnace maintained at 540 C. Initially, the
0
0
solution boiled and underwent dehydration,
-40
-20
followed by decomposition with escaping
-20
large amounts of gases (oxides of carbon,
-40
-40
-60
nitrogen and ammonia), then, spontaneous
-60
-60
ignition
occurred
and
underwent
smouldering combustion with enormous
-80
-80
-80
0
100 200 300 400 500 600 700 800
swelling, producing white foamy and
Temperature ( C)
voluminous ash, the whole process was
Fig.
1:
The
DTA of the sample SrAl2O4
over within less than 5 min, after the
product was cooled to room temperature,
milled the ash slightly and the phosphor obtained.
Crystal structure and phase composition of the sample were checked by means of a Burker
D8 (Bruker Co., German) X-ray diffractometer using CuK radiation, = 1.5406 . The
morphology and particle size of the prepared phosphor powders were observed by transmission
electron microscopy. The excitation and emission spectra were measured at room temperature on
a luminescence spectrophotometer equipped at Hue University. The decay curves and the glowcurve of the sample were recorded to determine afterglow characteristics.
0

3.1. Structure
250
200
Lin (Counts)
150
100
1
50
2
3
0
20
25
30
35
40
45
50
55
2 t h e t a - s c a le
Fig. 2: X-ray diffraction diagram of the phosphor

(1): SrAl2O4: Eu2+, Dy3+, (2): CaAl2O4: Eu2+, Nd3+, (3): BaAl2O4: Eu2+, Dy3+.
A typical X-ray diffraction pattern of the resultant SrAl2O4: Eu2+, Dy3+, BaAl2O4: Eu2+, Dy3+
and CaAl2O4: Eu2+, Nd3+ powders are shown in Fig. 2. As can be seen from the figure, pure
monoclinic phase diffraction peaks of SrAl2O4, CaAl2O4, BaAl2O4 are predominant in the XRD
pattern, which are similar with the sample resulted from the solid state reaction method. SrAl2O4,
CaAl2O4 powders are all low-temperature monoclinic phase (-phase), lattice constants of
SrAl2O4 are a = 8.442 , b = 8.822 , c = 5.160 , = 93.415, and of CaAl2O4 are
a = 8.698 , b = 8.092 , c = 15.208 , = 90.14. BaAl2O4 powders are hexagonal phase,
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lattice constants of those are a = 10.447 , b = 10.447 , c = 8.794 , = 900. It was found that
the single-phase MAl2O4 was form at 5400C, which is 3000C lower than that required for the solgel method [10] and 7000C lower than the solid-state reaction method [1,4]. In fact, the volatile
combustible gases ignite and burn with a flame and thus provide conditions for formation of
phosphor lattice with dopant. No other products or starting materials are observed, implying that
the little amount of doped rare earth ions have almost no effect on the MAl2O4 phase
composition. In fact, -MAl2O4 can melt with metal ions in a wide range; this gives enough
space for doped rare earth ions entering.
3.2. Phosphor morphology
In order to determine phosphor morphology and size of the sample, a typical transmission
electron microscope (SEM) were carried out. Fig. 3 displays a typical transmission electron
microscope image of the prepared alkaline earth aluminate powder under combustion at 540 C
for 5 minutes.
Fig. 3: SEM photograph of the sample SrAl2O4: Eu2+, Dy3+.
The phosphor powders are irregular spherical particles, the surfaces of the foams show a lot
of cracks, voids and pores formed by the escaping gases during combustion reaction. It reveals
that the mean size is about 80 nm. Compared with the phosphor prepared via the traditional
ceramic method, the grain size is greatly smaller but has bad crystallinity. In fact, the large
amount of escaping gases dissipates heat and thereby prevents the material from sintering and
thus provides conditions for formation of nanocrystalline phase. It is ascribed to solid state
reaction requires a high calcining temperature, which induces sintering and aggregation of
particles, and it is an advantage for perfect crystal formation.
7
3.3. Spectroscopy Charactistics
3+
2+
3+
2+
3+
(2). BaA l 2O4: Eu , Dy
(3). CaA l 2O4: Eu , Nd
2
Intensity (a.u)
The emission spectra at room temperature

of MAl2O4: Eu2+, RE3+ (M: Sr, Ca, Ba)
prepared by combustion method are shown in
fig. 4, using the excitation wavelength 365nm.
The emission spectra of these phosphors
showed that all are broad band due to
4f65d1 4f7 transition of Eu2+ [3, 5, 6], and
the main emission peaks of SrAl2O4: Eu2+,
Dy3+, BaAl2O4: Eu2+, Dy3+ and CaAl2O4: Eu2+,
Nd3+ phosphors were at 516 nm, 496 nm and
450 nm, respectively.
2+
(1). SrA l 2O4: Eu , Dy
0
400
450
500
550
600
650
700
W avelength (nm)
Fig. 4: PL Spectra of MAl2O4: Eu2, RE3+
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It is well known that in MAl2O4: Eu2+, RE3+ (M: Sr, Ca, Ba) phosphors, Eu2+ ions are the
luminescent centers, the photoluminescence is considered to be due to the transition from 5d
level to 4f level of Eu2+. The emission spectra of the phosphors was not observed the
luminescence of the RE3+ ions. Therefore, RE3+ ions work as hole traps and play an important
role for the long afterglow. The emission of Eu2+ varies from blue to green, depends on the
structure it is built into. In many cases, the emission of Eu2+ ion in the alkaline earth aluminates
is in the blue-green region.
Using for this characteristic of Eu2+ in alkaline earth aluminates, we have prepared alkaline earth
aluminates co-doped with rare earth ions which have changeable color from wavelength 450nm
to 520nm by combustion method.
The figure 5 showed the emissiom spectra and the figure 6 presented the decay cuvers of the
alkaline earth aluminate doped with Eu2+ and Dy3+ that there are two alkaline earth ions in the
lattice. It was showed that the emission maximum of the Sr1-xCax Al2O4: Eu2+, Dy3+ phosphors
shifts to shorter wavelength when x increases from 0.1 to 1 but the PL intensity and the long
afterglow decrease.
4.5
4.0
(1): x
(2): x
(3): x
(4): x
(5): x
3.5
3.0
2.5
2.0
=0
= 0.1
= 0.2
= 0.5
=1
(1): x=0.1
(2): x=0.2
(3): x=0.5
(4): x=1
3.5
3.0
2.5
Intensity (a.u)
PL Intensity (a.u)
4.0
1.5
5
1.0
1
2.0
2
1.5
3
1.0
4
0.5
0.5
0.0
0.0
(a)
(b)
-0.5
-0.5
400
450
500
550
600
650
700
350
400
450
500
550
600
650
700
Wavelength (nm)
wavelength (nm)
2+
Fig. 5: PL spectra of MAl2O4: Eu , Dy by combustion method at 5400C

(a): Sr1-xCaxAl2O4 : Eu2+, Dy3+, (b): Sr1-xBaxAl2O4 : Eu2+, Dy3+
(1). x = 0
(2). x = 0.1
(3). x = 0.2
(4). x = 0.5
(5). x = 1
2.71828
PL Intensity (a.u)
2
3
0.36788
(1).
(2).
(3).
(4).
2.71828
PL Intensity (a.u)
3+
4
5
x
x
x
x
=
=
=
=
0
0.2
0.5
1
1
2
0.13534
3
4
0.04979
(a)
-100
100
200
300
Time (s)
400
500
600
700
(b)
-100
100
200
300
400
500
600
700
Time (s)
Fig.6: The decay curve of Sr1-xCaxAl2O4 : Eu2+, Dy3+ and Sr1-xBaxAl2O4 : Eu2+, Dy3+ using the irradiation
365nm for 1 minute
The transfer of the emission peak and a change of PL intensity was found for the Sr1Eu2+, Dy3+ phosphors but the changes were not too strong. Especially, The long
afterglow of these phosphors desrease faster.
As it is generally considered that the Eu2+ ions entered the M2+ site in the MAl2O4 hosts.
Because the ionic radius of Ba2+ (0.135 nm) and Sr2+ (0.127 nm) are roughly equivalent to that of
Eu2+ (0.130 nm), but the radius of Ca2+ (0.112 nm) is smaller than of Eu2+, so that the
xBaxAl2O4:
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crystallographic distortions will influence the

4.0x10
(1). BAO: Eu (1%), Dy (2%)
crystal field at the Eu2+ site as well as the
(2). SAO: Eu (1%), Dy (2%)
(3). CAO: Eu (1%), Nd (2%)
emission spectra. The schematic energy level
2+
1
of the Eu ion in MAl2O4 host as a function
2
of the crystal field strength could be used to
3
2.0x10
explain [5,6]. However, the long afterglow
was ifluenced strong by the depth and
concentration of trap. In the alkaline earth
codoped with Eu2+ and Dy3+, the Eu2+ ions
0.0
were the luminescent centers, the Dy3+ ions
were the hole traps. The trap depths were
determined from the glow curve that showed
0
50
100
150
200
250
in fig. 7. The experimental results of the
Nhit ( C)
decay curve and the glow curves of the
Fig. 7: Glow curve of MAl2O4: Eu2+, Dy3+
MAl2O4: Eu2+, Dy3+ showed that the Dy3+
after irradiation 365 nm, 1 min. with heating rate 1,80C/s
ions in these hosts created hole traps.
The trap depth was at 0.67 eV that was suitable as well as for the long afterglow of the SrAl2O4:
Eu2+, Dy3+ phosphor. But it was shallow or deep for BaAl2O4: Eu2+, Dy3+ and CaAl2O4: Eu2+,
Dy3+.
4. Conclusion
-6
2+
3+
2+
3+
2+
3+
C-ng TL
-6
Based on the above research, the long afterglow phosphor MAl2O4: Eu2+, RE3+ (M: Sr, Ca,
Ba) was successfully synthesized by combustion method. Analytical results implied that the
phosphor powders have monoclinic phase (SrAl2O4, CaAl2O4) and hexagonal phase (BaAl2O4),
emission color of these phosphors depends on alkaline metal in aluminates lattice. The phosphors
resulted from combustion method have optical properties like the phosphors resulted from the
other method but the sintering temperature of the sample prepared by the combustion method is
much lower than that of one prepared by solid state reaction or sol-gel method.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
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12.
13.
T. Matsuzawa, Y. Aoki and N. Takeuchi et al., J. Electrochem. Soc. (8) (1996), pp. 2670
2673.)
W. Jia, H. Yuan and L. Lu et al., J. Cryst. Growth 200 (1999), pp. 179184.
G. Blasse, W.L. Wanmaker and A. Bril, Philips. Res. Rep. 23 (1968), pp. 201206.
G. Groppi, C. Cristiani and P. Forzatti, J. Mater. Sci. 29 (1994), pp. 34413450.
Y. Lin, Z. Zhang, Z. Tang, J. Zhang, Z. Zheng and X. Lu.Materials Chemistry and Physics
70 (2001), pp.156-159.
Nguyen Manh Son, Journal of Science, Hue University. No 38, 4-2007, pp.85-93
J. Hls, J. Hgne, M. Lastusaari and J. Niittykoski, J. Alloys Comp. 323324 (2001), pp.
326330.
X. Yu, C. Zhou, X. He, Z. Peng and S. Yang, Mater. Lett. 58 (2004), pp. 10871091.
D. Ravichandran, S.T. Johnson, S. Erdei, R. Roy and W.B. White, Displays 19 (1999), pp.
197203.
L.K. Kurihara and S.L. Suib, Chem. Mater. 5 (1993), pp. 609613.
Y. Lin, Z. Zhang, F. Zhang, Z. Tang and Q. Chen, Mater. Chem. Phys. 65 (2000), pp. 103
106.
T. Peng, H. Yang, X. Pu, B. Hu, Z. Jiang and C. Yan, Mater. Lett. 58 (2004), pp. 352356
Y. Lu, Y. Li, Y. Xiong, D. Wang and Q. Yin, Microelectron. J. 35 (2004), pp. 379382.
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INFLUENCE OF TEMPERATURE ON THE PHONON CHARACTERISTICS

OF CdSe/CdS CORE/SHELL NANOSTRUCTURES
Le Ba Haia,b, Nguyen Xuan Nghiaa, Pham Thu Ngaa, Nguyen Thi Thu Tranga
a)

18 Hoang Quoc Viet Rd., Cau Giay Dist., Hanoi, Vietnam.
b)
Le Qui Don upper high school, Khanh Hoa, Vietnam
E-mail: nghianx@ims.vast.ac.vn
Abstract: CdSe/CdS core/shell nanostructures with the different shell thicknesses were prepared
by chemical method in octadecene. Raman scattering spectra of CdSe cores and CdSe/CdS
nanostructures were comparatively investigated in the temperature range of 78300 K. Both the
core- and shell-related phonon peaks reveal a common blue shift, narrowing and enhancement with
lowering the temperature. The temperature dependence of the phonon frequency of CdSe cores are
well described by considering the contributions from thermal expansion and lattice anharmonicity.
For CdSe/CdS nanostructures, the temperature dependence of core-related phonon frequencies is
different in dependence on the shell thickness. A narrowing of the core-related phonon peak upon
passivation is assigned to a diminished scattering of the phonons at the core/shell interface, as
compared to the free surface of CdSe core. Negligible temperature dependence of the
exciton-phonon coupling in CdSe core is deduced from a small constant 2LO/1LO intensity ratio
(~ 0.2) in the investigated temperature range.
Keywords: CdSe/CdS core/shell nanostructure, Raman scattering, temperature, exciton-phonon
coupling.
1. Introduction
Semiconductor nanocrystals have attracted great interest over the past years because their
properties can be tailored by a judicious control of particle composition, size, and surface [1].
These characteristics arise from several phenomena (quantum confinement of charge carriers,
surface effects, and geometrical confinement of phonons) and have turned semiconductor
nanocrystals into promising materials for many applications. At present, information on their
fundamental physical properties is scarce, and much more information will be required for further
progress. In order to elucidate the transition process of the carriers, knowledge of the vibrational
states will be necessary and the exciton-phonon interaction in the nanocrystals must be considered.
Raman scattering is one of the most important techniques used to obtain information on the
vibrational states [2].
The frequency and width of the phonon lines in the light scattering spectra depend on the
temperature. The shift of the phonon lines during heating are a manifestation of the
phonon-phonon interaction and the measurement of the temperature dependence of this shift
allows studying the anharmonicity of the lattice vibrations [3]. The temperature-dependent Raman
study of the exciton-phonon coupling in semiconductor nanocrystals could also help separating
the homogeneous and inhomogeneous contributions to the phonon peak broadening, as well as
finding the factors governing the homogeneous contribution in nanocrystals. One of the purposes
of the present temperature-dependent Raman study was to find out whether this narrowing is
related to the change of the phonon scattering condition at the nanocrystal surface or core/shell
interface after passivation. The systematic study of the exciton-phonon coupling strength is of
particular interest, because it affects the shape and width of the absorption and emission bands of
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the nanocrystals, as well as the separation between the absorption and emission maxima (Stokes
shift) [4].
In this work, we report results on temperature-dependent Raman scattering from CdSe/CdS
core/shell nanostructures with the different shell thicknesses. From the analysis of the frequency
shift and linewidth of CdSe core-related phonon peak as a function of temperature, we have been
discussed the contributions from thermal expansion and anharmonicity of lattice vibrations, the
stress caused by the different thermal expansion coefficient between core and shell material, and
the change of the phonon scattering condition in core/shell nanostructures, as well as temperature
dependence of the exciton-phonon coupling in CdSe nanocrystals.
2. Experimental
The CdSe/CdS core/shell nanostructures were prepared by chemical method in octadecene.
The synthetic procedure is described in more detail in [5].
The Raman spectra of CdSe core and CdSe/CdS nanostructures were collected on
LABRAM-1B spectrometer, fitted with the Argon ion laser of wavelength 488 nm. The Raman
scattering measurements in the temperature range of 78-300 K were performed using Linkam 600
microthermometric cell. All samples were purified and dried.
Figure 1 presents the room-temperature photoluminescence (PL) spectra of CdSe core with
size of 4.8 nm and CdSe/CdS core/shell nanostructures with the different shell thicknesses. All
spectra are normalized in the intensity and vertically translated for clarity. The PL full width at
half maximum (FWHM) of CdSe core and CdSe/CdS nanostructures with the shell thicknesses of
1 and 3 ML is 22, 23, and 25 nm, respectively, indicating a narrow size distribution of the
obtained nanocrystals. The surface emission band disappears due to the passivation of CdSe core
surface by the outer CdS shell layer. As can see in Figure 1, the increase of shell thickness leads to
a redshift of emission peak of CdSe/CdS nanostructures, reflecting an increased leakage of the
exciton into the thicker shell [6].
The effect of the passivation on the Raman spectrum showed up as an additional peak in
wavenumber range of 280-300 cm-1 and a slight redshift of the CdSe core-related phonon peak
frequency (Figure 2). The relative intensity of this additional peak increased with increasing the
CdS shell thickness. The redshift of the CdSe core-related phonon peak upon passivation is
attributed to the reduction of the pure CdSe volume in nanocrystals after intermixing, which
increases the confinement of phonon in CdSe core. The peaks at about 420 cm-1 are attributed to
the second order LO phonon scattering of CdSe core.
Remarkably, for CdSe/CdS nanostructure with the shell thickness of 1 ML, the LO shell peak
position at 282 cm-1 is very far from that of small CdS nanocrystals, proving that the outer shell
material is not CdS, but is an alloy of CdS and CdSe [7]. From our previous studies it was found
that this CdSe1-xSx layer was formated from dissolved CdSe quantity when CdSe nanocrystals
were loaded into hot ODE and from Cd2+ and S2- precursor injected into CdSe solution. In
addition, in the shell growth at high temperature, the interdiffusion of Se- and S-atoms between
core and shell also contributes to create the CdSe1-xSx layer. In the case of CdSe/CdS
nanostructure with the shell thickness of 3 ML, the LOshell peak maxima shifts up to 300 cm-1 and
the low frequency shoulder of this peak increases in the intensity. This variation indicates that the
LOshell peak is due to the contributions of phonons scattered from CdSe1-xSx interface and exterior
CdS layer.
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1LOCdS-like
1LOCdSe
3ML
1ML
1LOCdS
2LOCdSe
3ML
1ML
0ML
0ML
550 600 650 700 750 800

Wavelength (nm)
Fig. 1. Room-temperature PL spectra of CdSe core
and CdSe/CdS core/shell nanostructures
with the shell thicknesses of 1 and 3 ML
1LO
LOCdSe
0 ML
160
240 320 400

-1
Raman shift (cm )
480
Fig. 2. Raman spectra of CdSe core and CdSe/CdS

nanostructures with the different shell thicknesses at
78 K. The spectra were normalized in intensity
LOCdSe
1 ML
3 ML
25000
150
2LO
15000
78 K
120 K
160 K
200 K
220 K
280 K
300 K
300
450
600
-1
Raman shift (cm )
10000
5000
0
150
LOCdS-like
78 K
90 K
120 K
160 K
200 K
280 K
310 K
200 250 300 350

-1
Raman shift (cm )
Intensity (a. u.)
20000
LOCdS
20000
Intensity (a. u.)
Intensity (a. u.)
40000
78 K
120 K
140 K
180 K
200 K
240 K
280 K
160
240
320
400
-1
Raman shift (cm )
Fig. 3. Temporal evolution of Raman spectra of CdSe core and CdSe/CdS nanostructures
with the shell thicknesses of 1 and 3 ML in the temperature range of 78300 K
The temporal evolution of Raman spectra of CdSe core and CdSe/CdS nanostructures with
the different shell thicknesses in the temperature range of 78300 K is shown in Figure 3.
Lowering temperature has similar effects on the Raman spectra for both CdSe core and
CdSe/CdS nanostructures commonly observed for bulk and nanocrystal semiconductors [4,8]:
increase of the absolute intensity, upward shift of the peak maxima, and narrowing of the
linewidth. However, in the case of CdSe/CdS nanostructure with the shell thickness of 3 ML, the
intensity of LOCdS peak increases as the temperature increases. This can be explained by the
Raman scattering resonance for LOCdS mode due to the gradual decrease of the band gap energy
of outer thin CdS shell layer with increasing temperature.
The temperature dependence of frequency shift of 1LOCdSe modes for CdSe core and
CdSe/CdS nanostructures with the different shell thicknesses are represented in Figures 4. The
phonon frequency shift with temperature is assigned the effect of thermal expansion and
anharmonicity of the lattice vibrations (phonon-phonon coupling), and can be described by
expression [9]:
(1)
T
0
1 T
2 T
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0
-1
Raman shift (cm )
-1
Raman shift (cm )
214
212
210
208
0 ML
1 ML
3 ML
0 ML
-1
-2
-3
-4
206
100 150 200 250 300

100 150 200 250 300
Temperature (K)
Temperature (K)
Fig. 4. Frequency shift of 1LOCdSe modes for CdSe Fig. 5. Temperature dependence of experimental
core and CdSe/CdS nanostructures as a function of frequency shift (symbol) and volume-induced
temperature. The solid lines are guide for eyes.
(dashed lines) and anharmonic (dotted line)
contributions to the frequency shift of CdSe core.
where 0 + 2(0) is the Raman frequency as temperature approaches 0 K, 1(T) represents the
volume dependence of the frequency due to the thermal expansion of the nanocrystals and 2(T)
specifies the contribution of anharmonic coupling to phonon of other branches.
1(T) can be written as
T
1
exp
T ' dT '
(2)
where (T) is the coefficient of linear thermal expansion, is Gruneisen parameter of the LO
phonon. The coefficient (T) for CdSe is taken from the linear interpolation, and =1.1 [10].
The purely anharmonic contribution to the frequency shift can be modeled as:
2
A 1
1
e
x1
1
1 e
x2
(3)
which represents the optical phonon coupling to two different phonons (three-phonon processes).
Here, A is the anharmonic constant, x1 h 1 k BT , x2 h 2 k BT , kB is Boltzmann constant.
The temperature dependence of the frequency shift for 1LOCdSe mode of CdSe core was fitted
by means of the equations (1)(3) with A, 0, 1, and 2 as adjustable parameters, keeping the
sum, 1+ 2 = 0 (energy conservation). In order to estimate the contributions of the thermal
expansion and lattice anharmonicity to this frequency shift, we have calculated separately the
thermal expansion contribution 1(T) from the equation (2) and the purely anharmonic
contribution 2(T) from the equation (3) to the frequency shift for 1LO CdSe mode of CdSe core
using the values of adjusted parameters A, 0, 1, and 2 obtained above. The variations of 1(T)
and 2(T) as a function of temperature are given in Figure 5 together with the experimental
frequency shifts. The obtained result shows that the frequency shifts induced by the two effects
are comparable in the investigated temperature range.
As can see in Figure 4, the slope of the temperature-dependent curves of the frequency shift
for CdSe/CdS nanostructures decreases as the shell thickness increases. This variation is assigned
to the stress caused by the different thermal expansion coefficient between CdSe core and CdS
shell material.
In Figure 6, the linewidths of the 1LOCdSe peaks for CdSe core and CdSe/CdS nanostructures
are plotted as a function of the temperature. The broadening of the linewidth with increasing
temperature is confirmed for all samples.
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17
0.3
15
I2LO/I1LO
FWHM
-1
(cm )
16
0.4
0ML
1ML
3ML
14
0.2
0.1
13
12
0.0
100 150 200 250 300
Temperature (K)
100
200
300
Temperature (K)
Fig. 7. The 2LO/1LO intensity ratio for

Fig. 6. Linewidths of 1LOCdSe peaks for CdSe core and
CdSe core vs. temperature
CdSe/CdS nanostructures as a function of temperature.
The best-fit results are shown by solid lines
For the bulk crystal, the temperature Table 1. The homogeneous ( 0) and
dependence of the Raman linewidth is inhomogeneous ( 1) parts of the 1LOCdSe peak
explained by decay of the optical phonon to found by fitting the dependence in Figure 6 by
two acoustic phonons [11]. In the case of equation (4)
-1
-1
CdSe nanocrystals, the linewidth
is the
Sample
0 (cm )
1 (cm )
geometrical sum of the intrinsic width 0,
CdSe core
4.2
13.2
determined by the phonon- phonon scattering,
CdSe/CdS(1ML)
4.4
11.9
and the additional width 1 due to size
CdSe/CdS(3ML)
4.5
12.1
dispersion of nanocrystals and relaxation of
phonon at the surface of nanocrystals. The intrinsic width 0 depends on the temperature, and the
additional width 1 does not depend on the temperature. The full Raman linewidth is given by
[12]:
2
2
2
2
2
(4)
(T )
0 1
1
ex 1
where x LO / 2k BT , LO is the frequency of the LO phonon at the zone center.
The fitting curves to the experimental points using the equation (4) are shown by solid lines in
Figure 6. 0 and 1 values, found from fitting the dependence in Figure 6, are given in Table 1.
As the passivated nanocrystals revealed 0 even slightly larger than CdSe cores, the observed
reduction of the total width exp of the LO peak upon passivation (Figure 7) is not due to a
diminished decay of the LO phonon in core/shell nanostructures. The most probable reason is a
reduced scattering of these phonons at the core/shell interface, as compared to the free surface of
the CdSe core, which is reflected in the
reduced inhomogeneous broadening 1.
In general, the intensity of the Raman peaks increases with lowering the temperature. The
exciton-phonon coupling strength (the Huang- Rhys factor) is determined by the intensity ratio of
the second and first order LO phonon peak (2LO/1LO). For the CdSe nanocrystals, the LO mode
has the Cd anh Se atoms vibrating out of phase within each unit cell. Since the Cd-Se bond is
relatively polar, the LO mode interacts with charge distributions within the crystallite through the
Frohlich interaction [13]. In our experiment, the 2LO/1LO intensity ratio for CdSe core is about
0.2 and almost is not various in the temperature range of 78-300 K (Figure 7), indicating a
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relatively week exciton- phonon coupling strength.

4. Conclusions
CdSe/CdS core/shell nanostructures with the different shell thicknesses were prepared by
chemical method. Raman scattering spectra of CdSe cores and CdSe/CdS nanostructures were
comparatively investigated in the temperature range of 78300 K. Both the core- and shell-related
phonon peaks reveal a common blue shift, narrowing and enhancement with lowering the
temperature. The temperature dependence of the phonon frequency of CdSe cores is well
described by considering the contributions from thermal expansion and lattice anharmonicity. The
obtained results show that the frequency shifts induced by the two above effects are comparable in
the investigated temperature range. Negligible temperature dependence of the exciton-phonon
coupling in CdSe core is deduced from a small constant 2LO/1LO intensity ratio (~ 0.2) in the
whole investigated temperature range, indicating a relatively week electron-phonon coupling
strength.
For CdSe/CdS nanostructures, the temperature dependence of core-related phonon
frequencies is different in dependence on the shell thickness. The slope of the
temperature-dependent curves of the frequency shifts decreases as the shell thickness increases.
This variation is assigned to the stress caused by the different thermal expansion coefficient
between CdSe core and CdS shell material. A narrowing of the core-related phonon peak upon
passivation is assigned to a diminished scattering of the phonons at the core/shell interface, as
compared to the free surface of CdSe core.
Acknowledgement
This work was financially supported by the National Fundamental Research Foundation of
Vietnam and by the Institute of Materials Science, Vietnamese Academy of Science and
Technology.
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LARGE-SCALE SYNTHESIS AND OPTICAL PROPERTIES OF ZnO

NANOPARTICLES
Pham Van Tuan a, Le Anh Tuan a, Pham Thanh Huya,b, Le Hong Hac
a)
b)
Hanoi Advanced School of Science and Technology (HAST)

International Training Institute for Materials Science (ITIMS), Hanoi University of
Technology, No 1 Dai Co Viet, Ha Noi
c)
Faculty of Physics, Hanoi University of Science, Hanoi National University
No 334 Nguyen Trai, Thanh Xuan, Ha Noi
E-mail: tuanphamvan1982@yahoo.com
Abstract: In this work, ZnO nanoparticles were prepared by hydrothermal method. The
structural, surface morphology and optical properties of the ZnO products were investigated by
X-ray diffraction (XRD), Field emission scanning electron microscopy (FE-SEM),
photoluminescence excitation (PLE) and photoluminescence (PL) measurements. The obtained
results of FE-SEM images indicate that varying shapes and sizes of ZnO nanoparticles were
observed in the sample and the sizes of the nanoparticles were in the range from 50 to 100 nm for
the small nanoparticles and 200 to 300 nm for the large nanoparticles. The XRD analysis shows
that the ZnO nanoparticles possess hexagonal wurtzite structures. The PL spectra exhibit a near
UV emission and a green emission. It has been demonstrated that the morphology, particle sizes
and photoluminescence of the ZnO nanoparticles were strongly dependent on the synthesis
conditions.
Keywords: ZnO nanoparticles; Hydrothermal; Photoluminescence
1. Introduction
Recently, there are much interest in preparation and investigation of properties of nano-scale
particles such as metals, metal sulfides, and oxides. Zinc oxide is a well-known semiconductor
with a wide direct band gap (3.37 eV) and a large exciton binding energy of 60 meV at room
temperature [1]. ZnO has been a promising candidate for room temperature UV LED and laser
because its exciton binding energy exceeded the room temperature energy (26 meV). In addition,
it can be also used for various applications such as gas sensor [2], antibacterial activity [3],
varistor [4], ceramics [5] and solar cells [6].
A photoluminescence (PL) spectrum of ZnO exhibits a near-band-edge emission in the near
UV region and a broad defect-related visible emission mostly in the green partly in the yellow
and red spectral region. For device application, such as high efficiency UV light emitting
devices, it is important to suppress the visible emission.
In the present study, the hydrothermal method was employed to fabricate ZnO nanoparticles.
The sizes, morphologies, crystallinities and optical properties of the ZnO nanoparticles were
studied. The effects of synthesis conditions on the morphology, size as well as the optical
properties of ZnO nanoparticles were also investigated.
2. Experimental
ZnO nanoparticles were prepared by hydrothermal method. The synthesis process for
preparing ZnO nanoparticles as previously described in Ref. [7]: ZnCl2 powder were dissolved in
deionized water and then NaOH powder was slowly added into the solution. After stirring for 1
hour, the solution was transferred to a Teflon-lined autoclave with about 100 ml capacity. The
hydrothermal temperature varied from 100 to 2000C where as the hydrothermal time changed
from 2 to 40 h. After hydrothermal process, the autoclave was cooled to room temperature
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naturally. The as-formed white precipitate was filtered off, washed with deionized water and
absolute ethanol several times, and then dried in the air at 100 C.
The synthesized ZnO nanoparticles were characterized by Field emission scanning electron
microscopy (FE-SEM, Hitachi S4800). The shapes and the mean particle sizes of ZnO
nanoparticles were observed and also determined by FE-SEM micrographs. The optical
properties of ZnO nanoparticles were investigated by Photoluminescence (PL) and
Photoluminescence excitation (PLE) spectra (JOBIN YVON SPEX FL-3-22 fluorescence
spectrophotometer). The crystal structure of ZnO nanoparticles was studied by X-ray diffraction
(XRD, SIMEMS D 5000).
(101)

4000
2000
1500
1000
20
30
40
50
(103)
(200) (112)
(201)
2500
(102)
Intensity (a.u)
3000
(110)
(100)
(002)
3500
60
70
80
Fig. 1. XRD pattern of the ZnO nanoparticles
Fig. 2. FESEM image of the as-prepared ZnO

nanoparticles
The typical XRD pattern of the ZnO nanoparticles prepared by hydrothermal method was
shown in Fig. 1. It can be seen that all the peaks observed in the figure can be indexed to the
known wurzite structure of ZnO. The strong and narrow diffraction peaks indicate that the
material has a good crystallinity. No characteristic peaks from impurities were found in the
pattern. For investigating the surface morphology and determining the size of ZnO nanoparticles,
the samples were investigated by the FE-SEM microscopy as displayed in Fig. 2. One can
clearly see from Fig. 2 that there are varying shapes and sizes of the ZnO nanoparticles observed
in the sample. The sizes of the small nanoparticles were in the range of 50 to 100 nm while that
of the large nanoparticles were in the range of 200 to 300 nm.
Next, the effects of varying synthesis conditions of pH value, hydrothermal temperature,
hydrothermal time on the shape, size and surface morphology of ZnO nanoparticles were also
studied by means of the FESEM images as shown in Figs. (3-5).
(a) pH = 8
(b) pH = 10
(c) pH = 12
(d) pH = 14
Fig 3. FESEM images of ZnO nanoparticles prepared by hydrothermal method at different pH values
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(a) T = 1000C
(b) T = 1200C
(d) T = 1800C
(c) T = 1500C
Fig 4. FESEM images of ZnO nanoparticles prepared by hydrothermal method at different

hydrothermal temperatures
(b) t = 20 h
(a) t = 2h
(c) t = 40 h
Fig. 5. FESEM images of ZnO nanoparticles prepared by hydrothermal method at different

hydrothermal times
As observed in these figures, it is clear that the synthesis conditions affected on the shape and
size of ZnO nanoparticles. In other word, the synthesis conditions, such as pH value,
hydrothermal temperature, hydrothermal time are the predominate factors for controlling mean
sizes and morphology of the nanoparticles.
373
1000000
2500000
600000
400000
2000000
1500000
380
Intensity (a.u)
Intensity (a.u)
800000
565
3000000
1000000
200000
500000
0
0
320
360
400
440
480
Wavelength (nm)
Fig. 6. PLE spectrum of the as-prepared ZnO

nanoparticles
350
400
450
500
550
600
650
Wavelength (nm)
Fig. 7. PL spectrum of the as-prepared ZnO

nanoparticles
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300000
200000
180000
160000
88000
1: pH = 8
2: pH =10
3: pH =12
4: pH =14
1: t = 2h
77000 2: t = 20h
3: t = 40h
66000
150000
100000
140000
120000
100000
80000
60000
50000
3
1
55000
2
44000
33000
22000
40000
Intensity (a.u)
3
Intensity (a.u)
Intensity (a.u)
1: T = 100 C
o
250000 2: T = 120 C
o
3: T = 150 C
200000 4: T = 180 oC
11000
20000
350
400
450
500
550
600
650
Wavelength (nm)
Fig. 8. PL spectra of ZnO

nanoparticles prepared at
different hydrothermal
temperatures
0
350
400
450
500
550
600
650
Wavelength (nm)

nanoparticles prepared at different
pH values
360
400
440
480
520
560
600
wavelength (nm)

nanoparticles prepared at
different hydrothermal times
The optical properties of as-prepared ZnO nanoparticles were studied by PLE and PL spectra
as shown in Fig. 6. From this figure, it can be seen that there is the only peak of the PLE
spectrum located at 373 nm. The PL spectrum of the ZnO nanoparticles in Fig. 7 measured at
room temperature indicates that there are characteristic two emission peaks, one is narrow nearUV peak (380 nm) and other is broad green peak (565 nm). The narrow near-UV emission at 380
nm agrees with the band gap of bulk ZnO material [8], which comes from the recombination of
free excitons [9]. The broad green peak at 565 nm is related to the defects-related deep level
emission, such as oxygen vacancies and Zn interstitials [1012].
In order to study the effect of the hydrothermal temperature on the luminescence of ZnO
nanoparticles, the PL spectra of the samples prepared by hydrothermal method at different
hydrothermal temperatures from 100 to 1800C were measured as displayed in Fig. 8. As
observed in the figure, the intensity of the visible emission is much stronger than that of the nearUV emission, this indicates that there are many defects in the samples. Moreover, it was found
that the relative intensity of the near UV emission and the visible emission strongly depend on
the hydrothermal temperature. As the hydrothermal temperature increases the intensity of the
near-UV emission increases, whereas that of the visible peak decreases. In other word, the
relative intensity of the near-UV emission and the visible emission increases with the increasing
hydrothermal temperature. This implies that with increasing the hydrothermal temperature the
improved crystalline quality of the sample.
Finally, others effects of synthesis conditions, such as pH value, hydrothermal time on
photoluminescence of ZnO nanoparticles were also studied. The PL spectra of ZnO nanoparticles
prepared at different pH values were shown in Fig. 9. As clearly seen in the figure, it is also
found that the relative intensity of the near-UV emission and the visible emission varies with the
variation of the pH value. Fig. 10 displays the PL spectra of ZnO nanoparticles prepared at
different hydrothermal times. It can be seen that as increasing the hydrothermal time, not only
the relative intensity of the near-UV emission and the visible emission varies but also the
maximum position of the visible emission varies. This indicates that the photoluminescence of
ZnO nanoparticles was strongly dependent on the synthesis condition.
4. Conclusions
In the present work, ZnO nanoparticles were successfully prepared by the hydrothermal
method. Varying shapes and sizes of ZnO nanoparticles in the sample were observed by the
FESEM image. The sizes of the ZnO nanoparticles were in the range of 50 to 100 nm for the
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small nanoparticles and from 200 to 300 nm for the large nanoparticles. The optical properties of
ZnO nanoparticles were also studied. The PL spectra of ZnO nanoparticles exhibited two
emission bands: a near-UV emission and other visible emission (green emission). The near-UV
emission was related to recombination of free exicitons and the green emission was due to the
defect related deep level emission such as oxygen vacancies and Zn interstitials. The analysis
of the hydrothermal temperature on the luminescence of ZnO nanoparticles revealed that the
relative intensity of the near UV emission and the visible emission increased with increasing the
hydrothermal temperature, this was attributed to the improved crystalline quality of the sample.
In addition, the other synthesis conditions, such as pH value, hydrothermal time, also
considerably affected on shape, size and photoluminescence of ZnO nanoparticles. This
indicated that the synthesis conditions play an important role in controlling shape, size and
crystalline quality of ZnO nanoparticles.
Acknowledgement: This work was financially supported by KC.02/06-10 national key science
and technology programme. The authors are thankful for support from ITIMS and HAST
directors.
References
1. Y. S. Kim,W. P. Tai, S. J. Shu, Thin Solid Films 491(2005) 153160.
2. Chandra Sekhar Rout, A. R. Raju, A. Govindaraj, C. N. R. Rao, Solid State Communications
138 (2006)136.
3. K. H.Tam, A. B. Djurii, C. M. N. Chan ,Y. Y. Xi, C. W. Tse, Y. H. Leung, W. K. Chan, F.
C. C. Leung, D. W. T. Au, Thin Solid Films 516 (2008) 6167.
4. N. T. Hung, N. D. Quang, S. Bernik, Journal of Material Research 16 (2001)2817.
5. L. Gao, Q. Li, W. L. Luan, Journal of American Ceramic Society 85 (2002)1016.
6. U. Rau, M. Schmidt,Thin Solid Films 387 (2001) 141.
7. A. Elkhidir, Y.W. Tang, X. Zhang, Z.J. Jia, J. Appl. Sci. 6 (2006)1298.
8. E.M. Wong, P.C. Searson, Appl. Phys. Lett 74 (1999) 2939.
9. V. Stikant, D.R. Clarke, J. Appl. Phys 83 (1998) 5447.
10. W.D. Zhou, X. Wu, Y.C. Zhang, Mater. Lett. 61 (2007) 20542057.
11. S. Kar, A. Dev, S. Chaudhuri, J. Phys. Chem. B 110 (2006) 1784817853.
12. Y.C. Zhang, X. Wu, X.Y. Hu, J. Cryst. Growth 280 (2005) 250254.
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OPTICAL PROPERTIES OF CdS QUANTUM DOTS AND CdS QUANTUM DOTS

PASSIVATED BY ZnS SHELL
Chu Viet Haa, Vu Thi Kim Lien a, Le Tien Ha b, Pham Thai Cuong b, Nguyen Nhu Dat c
a)
Thai Nguyen University of Education (TUE), Thai Nguyen, Vietnam

b)
Hanoi University of Mining and Geology, Hanoi, Vietnam
c)
Institute of Physics, Vietnamese Academy of Science and Technology, Hanoi, Vietnam
Abstract: In this paper, we present results about the synthesis and optical properties of CdS and
CdS passivated by ZnS shell (CdS/ZnS core/shell) semiconductor nanocrystals quantum dots. The
CdS quantum dots were produced ranging from about 2.5 to 4 nm in diameter depending on the
concentration of surfactant agent. The absorption spectra of CdS quantum dots show a narrow
size distribution. The photoluminescence spectra include two bands, the intrinsic emission of CdS
nanocrystals and the emission of surface states. There is noticeable increase of the
photoluminescence emission intensity and subsequent photostability in CdS/ZnS quantum dots
samples compared with CdS quantum dots samples without the ZnS shell.
Keywords: CdS quantum dots, absorption spectra, narrow size distribution, photoluminescence.
1. Introduction
Nanocrystal quantum dots are nanometer-sized semiconductor crystals with size-dependent
optical and electronic properties. Semiconductor nanocrystal quantum dots have been
investigated from physical properties of low-dimensional systems to their application such as
labeling and other functional materials. Efficient luminescent quantum dots form an important
and interesting class of luminescent materials. The nanocrystal quantum dots exhibit excellent
optical properties and higher photochemical stability than most organic emitters [1, 2]. The
spectral broad absorption coupled to a narrow emission band is tunable with their size. One of
the most interesting applications is the use of quantum dots as luminescent labels for optical
sensors. They can be used as fluorescent label sources for biological imaging applications [1, 35].
Among approaches to prepare nanocrystals, the direct solution chemical routes have widely
been used for synthesis of semiconductor quantum dots because this methods allow us to create
the quantum dots with a narrow size distribution [6]. In this work, we used a reverse micelle
method to synthesize CdS quantum dots. In the method, a reverse micelle solution is created by
three components, surfactant molecules, water and a non-polar organic solvent. The polar heads
of the surfactant molecules are directed toward the interior of a water-containing sphere, whereas
the aliphatic tails are oriented toward the non-polar organic phase. The size of the CdS quantum
dots can be controlled by changing the ratio of water to the surfactant agent. We have studied the
optical properties of CdS and CdS/ZnS core/shell semiconductor nanocrystal quantum dots. The
core/shell nanocrystal structures show the enhanced luminescence and photostability.
2. Experimental
The CdS semiconductor nanocrystal samples were synthesized by a reverse micelle method
with sodium bis (2-ethylhexyl) sulfosuccinate (AOT) used as the surfactant agent and heptane
used as the solvent [6, 7, 8]. To obtain two micellar solutions with the aqueous solution
encapsulated within the reverse micelles formed by surfactant in oil, we prepared two identical
mixtures of heptane and AOT, and then one of the mixture was added by an aqueous solution of
Cd(CH3COO)22H2O, while the other mixture was added by an aqueous solution of Na2S9H2O.
After addition of one micellar solution containing Cd2+ ions into the other micellar solution
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containing S2 ions in a vigorously stirring condition, CdS nanocrystal quantum dots were
yielded in the nanometer-sized water pool within the reverse micelles. The size of the
nanocrystals can be controlled by changing the molar ratio, W (= [H2O]/ [AOT]). The value of W
was 2.5, 5, 7.5 and 10.
To passivate the CdS quantum dots, a ZnS shell layer was grown on CdS core nanocrystals
by using two aqueous solutions of Zn2+ and S2- ions which were obtained by dissolving the
compounds Zn(CH3COOH)2.2H2O and Na2S9H2O into water. The aqueous solutions of Zn2+
and S2- were mixed with two identical AOT/heptane stock solutions respectively. Then two
micellar solution containing Zn2+ and S2- ions were injected at a very slow rate into the CdS
nanocrystal micellar solution which was prepared before. The obtained solution was then stirred
vigorously, so that ions Zn2+ and S2- could hang on the drops containing CdS quantum dots
forming the ZnS shell layer. The CdS/ZnS core/shell semiconductor nanocrystal samples were
dispersed in organic solvents such as methanol and heptane.
Optical absorption spectra (UV-VIS) of nanocrystal samples were performed in the region
300 - 750 nm wavelengths with Jasco V-600 (Japan). A monochromatized 450 W Xe light
source (200 nm < exc < 900nm) with FS 920 Edinburgh (England) was used for
photoluminescence (PL) spectra and photoluminescence excitation (PLE) spectra at room
temperature.
The prepared CdS and CdS/ZnS core/shell quantum dots were clusters which were protected
by surfactant agent (AOT) layer dispersed in heptane solvent. Fig. 1 presents the absorption
spectra of CdS quantum dots samples with W = 5 grown with different times (15 min., 60 min.,
and 180 min.). The absorption spectra show a significant note that there is no shift in the
absorption spectra when the time preparation increases. The absorption curves are the same. This
result shows an ability of the role of surfactant agent AOT versus the aggregation of
nanocrystals, and an ability of preparing nanocrystals in the short time. This is different from
other colloidal methods, such as the synthesis of CdSe nanocrystals by using organometallic
precursors in standard airless condition at high temperature [1]. So we can control the size of
nanocrystals just by changing the value of W.
Fig. 2 presents the absorption spectra of the CdS nanocrystals dispersed in solutions with the
molar ratio of water to surfactant agent W = 2.5, 5, 7.5 and 10. There is large shift of absorption
edge of all nanocrystal quantum dots from the bulk Eg value towards shorter wavelength (or
higher energy) compared with that of bulk CdS crystal (bulk ~ 500 nm corresponding to Eg
2.48 eV at room temperature [9]). This blue shift agreed with theory about the values of the
effective ban gap of semiconductor quantum dots. That is an increase in the band gap of the
semiconductor with a decrease in the particle size. Observed clear absorption peaks are explained
by the exciton confinement. The exciton energy in quantum dots is explained well by the
electron-hole individual confinement model, where R, the nanocrystal quantum dots radius, is
smaller than aB, the Bohr exciton radius. Many different theoretical approaches have been
employed to account for the variation in the electronic structure of quantum dots as function of
their size [1]. We used the formulation Brus [10] to estimate the size of the CdS nanocrystals:
h 1
1 2
e2
E ( R ) = E g + * + * 2 - 1.786
- 0.248E*R
2 me
mh R
R
y
where Eg is the band gap of bulk CdS. The second term is the kinetic-energy term containing the
*
*
effective masses, m e and m h of electron and hole, respectively. The third term arises due to the
Coulomb attraction between electron and hole, and the fourth term due to the spatial correlation
*
between electron and hole which is generally small compared to the other two terms [11]. E R y is
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the bulk exciton binding energy, R is the radius of the quantum dots, and is the Planks
constant. Eg of bulk CdS is 2.48 eV at 300K. The large shift from the bulk Eg value is observed
according to the value of W: 3.875 eV (320 nm) for W = 2.5, 3.594 eV (345 nm) for W = 5, 3.38
eV (378 nm) for W = 7.5, and 3.024 eV (410nm) for W = 10. The mean radii of CdS quantum
dots are estimated from absorption peak energy to be 1.2, 1.4, 1.6, and 2.0 nm for W = 2.5, 5, 7.5
and 10, respectively.
CdS QDs
Absorbance (a.u.)
Absorbance (a. u.)
CdS QDs
w=5
15 min.
60 min.
180 min
W = 10
W = 7.5
W= 5
W = 2.5
Bulk CdS
500 nm (2.48 eV)
300
350
400
450
500
550
Eg Bul k CdS= 2.48 eV

(500 nm)
250 300 350 400 450 500 550 600
600
Wavelength (nm)
Wavelength (nm)
Fig. 1. Absorption spectra of CdS quantum dots
samples with W = 5 grown with different times.
Fig. 2. Absorption spectra of CdS quantum dots

with different values of the molar ratio of water
to surfactant agent AOT
Fig. 3 presents of the absorption spectra of the CdS and CdS/ZnS core/shell nanocrystal
quantum dots dispersed in solution with the molar ratio of water to surfactant agent W = 5. There
is a red shift (lower energy) in the absorption spectra after overcoating the ZnS shell outside the
CdS core. This can be explained that there is a partial leakage of the exciton into the ZnS matrix.
This red shift is more pronounced in smaller dots where the leakage of the exciton into the ZnS
shell has a more dramatic effect on the confinement energies of the charge carriers [1]. This shift
is of the order 294 meV (31 nm) for the core size 2.8 nm (corresponding to W = 5).
7000
(1) CdS
(2) CdS/ZnS
W=5
6000
PL Intensity (a. u.)
Absorbance (a. u.)
(1) CdS
(2) CdS/ZnS
W=5
2
1
5000
4000
3000
2
1
2000
1000
250
300
350
400
450
500
550
600
Wavelength (nm)
Fig. 3. Absorption spectra of CdS and

CdS/ZnS quantum dots samples with W = 5
350
400
450
500
550
600
650
Wavelength (nm)
Fig. 4. PL spectra of CdS and CdS/ZnS core/shell

nanocrystals quantum dots under excitation of 330 nm
at room temperature
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PL intensity (a. u.)
The photoluminescence (PL)

7000
measurements of the CdS nanocrystal
CdS/ZnS QDs
quantum dots were carried out under
W=5
continuous excitation with 330 nm
6000
wavelength of Xe light. For all of our
CdS nanocrystal samples, the PL
5000
spectra include two bands, the
intrinsic
emission
of
CdS
nanocrystals and the emission of
4000
surface states. (We do not show all
of PL spectra here). Fig. 4 shows the
PL spectra of CdS and CdS/ZnS
3000
core/shell quantum dot in condition
of W = 5. The emission of CdS
350
400
450
500
550
600
650
quantum dots without ZnS shell
(curve 1 in fig. 4) includes two
Wavelength (nm)
bands, a narrow band peaked at 410
Fig. 5. PL spectra of CdS/ZnS core/shell nanocrystals
nm and a broad band peaked at 620
quantum dots after washing and centrifugation under
nm. Emission band centered at 410
excitation of 330 nm at room temperature
nm is attributed to the intrinsic
emission of CdS quantum dots (or the band-to-band transition in CdS nanocrystals), and the
other emission band centered at 620 nm is attributed to the emission of surface states due to the
small size of nanocrystals. When the CdS quantum dots are overcoated by a ZnS shell, the
intensity of intrinsic emission of CdS quantum dots increases significantly and is stronger than
the emission of surface states (curve 2 in fig 4). This shows the passivation of the ZnS shell: the
shell ZnS makes the emission of the surface states decrease, so that the intrinsic emission of the
CdS nanocrystals is enhanced. However, the emission of surface states is quite strong for
CdS/ZnS quantum dot samples. This can be expalined that may be there are a surplus of some
compounds that did not react and small ZnS quantum dots formed in solution, so that the density
of surface states is high.
In order to only obtain the intrinsic emission of CdS quantum dots in PL spectra, besides
passivating the quantum dots by ZnS shell, the prepared quantum dots were precipitated and then
were washed and centrifuged by methanol. Fig. 5 presents the PL spectra of CdS/ZnS core/shell
quantum dots after washing and centrifugation. We can see that the intensity of intrinsic
emission of CdS quantum dots is enhanced while the emission of surface states decreases
significantly.
4. Conclusions
The CdS and CdS/ZnS nanocrystals quantum dots were synthesized by a reverse micelle
method. We have presented shortly our results about the preparation and optical properties of the
CdS and CdS/ZnS nanocrystals. The mean diameters of the CdS nanocrystals are about from 2.5
to 4 nm. The absorption spectra of CdS quantum dots show the narrow size distribution. The
photoluminescence spectra include two bands, the intrinsic emission of CdS nanocrystals and the
emission of surface states. There is noticeable increase of the photoluminescence emission
intensity and subsequent photostability in CdS/ZnS quantum
dots samples compared with CdS quantum dots samples without the ZnS shell. By washing and
centrifugation after peparation, the emission of CdS/ZnS quantum dots is enhanced significantly.
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Acknowledgments: This work is supported in part by the Natural Science Research Project
(2006-2008) and the Asia Research Center, Vietnam National University, Hanoi. We thank Prof.
Nguyen Van Hieu, Prof. Phan Hong Khoi, and Prof. Vu Ngoc Tu for their encouragement.
References
1. P. T. Nga et al, Proceeding of the IEEE SENSORS 2006, Daegu, Korea / October 22~25,
2006, pp 22-25.
2. V.I. Klimov, A.A. Mikhailovsky, S.Xu, A.Malko, J. A. Hollingsworth, C.A. Leatherdale,
H.J. Eisler, M.G Bawendi, Science 290, 314 (2000).
3. R. E. Bailey, A.M. Smith, S.Nie, Physica E 25, 1-12 (2004).
4. C. B. Murray, D. J. Norris, and M. G. Bawendi, J. Am. Chem. Soc. 115, 8706 (1993).
5. V. I. Klimov, J. Phys. Chem. B 104, 6112 (2000).
6. D.G. Kim, N. Teratani and M. Nakayama, Jpn. J. Appl. Phys., Vol. 44 (2002) pp. 5064-5068,
Pt. 1. No 8.
7. Atsushi Ishizumi and Yoshihiko Kanemitsu, Adv. Mater. (2006), 18, 1083-1085.
8. Heesun Yang, Paul Holloway, H., Gary Cunningham, and Kirk S. Schanze, Journal of
Chemical Physics, vol. 121, No 20, (2004), 10233-10239
9. Woggon, U. (1996), Optical properties of semiconductor quantumdots, Springer Tract in
modern physics, vol. 136, Springer. Berlin.
10. L.E. Brus, J. Chem. Phys. 80, 4403 (1984).
11. S. Sapra and D.D. Sarma, Phys. Rev. B 69, 125304 (2004)
12. B. O. Dabbousi, J. Rodriguez-Viejo, F. V. Mikulec, J. R. Heine, H. Mattoussi, R. Ober, K. F.
Jensen, M. G. Bawendi, J. Phys. Chem. B, 101, 9463-9475 (1997).
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STUDY OF OPTICAL PROPERTIES OF YVO4:EU3+ NANOMATERIALS PREPARED

BY HYDROTHERMAL METHOD
Dinh Xuan Loc a, Nguyen Vu a, Pham Thi Minh Chau b, and Tran Kim Anha
a)
Instistute of Materials Sciences - Vietnam Academy of Sciences end Technology.

18 Hoang Quoc Viet Road, Cau Giay District, Ha Noi, Viet Nam
b)
Instistute of Geography - Vietnam Academy of Sciences end Technology. A27 building,
18 Hoang Quoc Viet Road, Cau Giay District, Ha Noi, Viet Nam
Abstract: Nanocrystals of YVO4:Eu3+ were prepared by hydrothermal method. The samples
were characterized by scanning electron microscopy, photoluminescence (PL), and time-resolved
luminescence measurements. The PL spectra are described by using the well known 5D0 - 7FJ
transitions (J = 1, 2, 3, 4) of Eu3+ ions. The dependence of PL intensity of Eu3+ concentration has
been investigated. The application potential will be discussed.
Keywords: YVO4:Eu3+, Photoluminescence, Nanoparticles
1. Introduction
Yttrium orthovanadate (YVO4) doped with rare earth ions such as Nd, Er, Eu, Sm has been
used as an laser host material, cathode ray tube display for more than 30 years. Bulk YVO4: Eu3+
can be prepared by differencial chemical methods as solid state reaction [1], sol gel process [2],
spray pyrolysis [3], hydro-thermal synthesis [4]. Inrecently, nanosize fluorescent have been
found many potential applications for devices [5], optical amplifiter [6], biolabels [7, 8], ect.
Luminescent materials emiting visible colors by the excitation near ultra violet (UV) light
around 365 nm are extensively used in the fields of security, because it is more harmless to
human bodies in comparison of near-UV-light with UV light [9].Vanadate nanoparticles of rare
earth ions can crystallize at low temparature through hydrothermal synthesis [4] to develop
monodisperse nanocrystals with shape control, some another have been used the high
temperature solution phase synthesis as high boiling solvent act a stabilizer [10]. In tendency use
nanoparticles powder Eu as a material for control labels. We investigate a process for the
synthesis of nanoparticles europium doped yttrium vanadate using hydrothermal method. Some
physical charaterizations of the obtained nanomaterials will be disscussed.
2. Expermental
Materials:Y(NO3)3, Eu(NO3)3, NH4VO3 and NaOH (analytical reagent of Merk) were used as
starting materials and ethanol (Prolabo Chemical reagent) as solvent for the preparation and
cleaning YVO4.Eu3+ nanorystalline powders.
Y(NO3)3 and Eu(NO3)3 was prepared dissolving Y2O3 and Eu2O3 (both 99.999%) in nitric
acid. The process to synthesis of YVO4.Eu3+ nanoparticles powders is following:
The amount of Y(NO3)3.6H2O and Eu(NO3)3.6H2O were dissolved in 15ml of distilled water,
and the solution was poured into a Teflon vessel. During stirring, 15ml NaOH 1M were rappidly
added to the solution which become a white suspension. To the well - stirring suspension, the
amount of Na3VO4.10H2O dissolved in 30 ml of distilled water was added. Finally, the reaction
mixture pH should be reached 12.5 by using NaOH 1M. The Teflon vessel containing the
suspension was loosely capped and placed in an autoclave (Roth, 200ml) and heated at 2000C
for 1h. After 1h the autoclave was quenched in cold water and the suspension was removed.
The suspension was centrifuged at 3000g for 10 min. The supernatant was discarded. The
precipitate was suspended in 40ml distilled water and centrifuged again. As prepared
nanoparticles can be easily redispersed in the ethanol, in water at room temperature or in TOPO
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(trioctylphosphore oxide) solution with toluen at 2400C. The powder of the nanoparticles was
obtained by removing the ethanol which treated in dryven at 600C for several hours.
UV-Vis absorption of the nanoparticles solutions was measured in UV-Vis JASCO 500
(Japan). Photoluminescent spectra of the YVO4:Eu nanoparticles were determined by using a
spectrometer system HORIBA JOBIN YVON IHR 550. The obtained signals were treated
through didital sofware program. The SEM images were obtained in the FESEM (HITACHI S
4800) system.
Table 1: The doping concentrations of Y3+, Eu3+ and VO43- ions in YVO4 host
T
T
1
2
3
4
Sample
Y0.99Eu0.01VO4
Y0.97Eu0.03VO4
Y0.95Eu0.05VO4
Y0.93Eu0.07VO4
X
mol
1%
3%
5%
7%
Y(NO3)36H2O
g
mmol
1.85
4.83
1.81
4.71
1.76
4.59
1.71
4.46
Eu(NO3)36H2O
g
mmol
0.02
0.05
0.06
0.14
0.11
0.24
0.15
0.33
Na3VO4.10H2O
g
mmol
1.69
4.65
1.77
4.87
1.76
4.83
1.75
4.80
3. Result and Discussion

3.1. Morphology properties
Figure 1 shows scaning electron micrographs (SEM) of the YVO4: Eu3+ nanoparticles
prepared by wet chemical hydrothermal synthesis. As can be seen from the figure that the
YVO4: Eu3+ sample occur through the aggregation of the nanocrystals which the sizes were
exhibited about 30 to 50 nm.
3.2. Photoluminecent properties
The absorption spectrum of dilute water
solution of YVO4:Eu3+ nanoparticles show the
broad banks peaking at 272 nm are attributed to
a charge transfer inside the VO43- ion [8]. The
emission spectrum of YVO4: Eu 3+ (5%) is
shown in figure 2. The most intense transtion
observed in the emission spectrum origirate
from the 5Do level. Which is consequence of the
absence of an inversion symmetry at the Eu3+
latlice site (D2d symmetry). The intensity of
transitions between different J-number leves
Fig. 1: Scaning electron micrograph (SEM) of
depends on the symmetry of the local
the YVO4: Eu 3+
environment of the europium ion and can be
discribed interms of the Judd - Ofelt Theory [11]. In bulk YVO4 the Eu3+ site has D2d symmetry.
For this point group the splitting of the energy levels has been calculated and the selection rules
for transitions between the sublevels are well-known. Our obtained results for YVO4 : Eu
emission spectra are good agreement with the optical transitions actually observed in bulk YVO4
: Eu [12].
Upon UV excitation, europium doped YVO4 nanoparticles exhibit strong red luminescence
cause by transition within the f electron shell of the europium ions [12]. From the 5Do level
there are a magnetic dipole level allowed transitions to a sublevel of 7F1, two electric dipole
level transitions to the sublevels of 7F2, three magnetic dipole transitions to sublevels of 7F3.
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30000
20000
592
593
595
10000
580
590
609
Intensity (a.u)
D0 - F2
615
5 % Eu
619
40000
600
610
620
630
640
Wavelength (nm)
Fig. 3: The energy schem of YVO4: Eu3+.

Excitation, emission, and energy transfer
processes
Fig. 2: The emission spectrum of YVO4: Eu 5%
50000
Intensity (a.u)
Intensity (a.u)
30000
7 % Eu
5 % Eu
3 % Eu
1 % Eu
20000
10000
0 s
20
80
100
180
280
40000
30000
20000
10000
580
590
600
610
620
630
640
Wavelength (nm)
Fig. 4: The comparision of the emission

spectra change from 1 mol % to 7 mol %
YVO4: Eu3+ nanoparticles
0
580
600
620
640
Wavelength (nm)
Fig. 5: Time-resolved emission spectra of the

YVO4: Eu3+ (5%) nanoparticels, upon 337 nm
excitation, with variable time delays.
The most intense luminescence lines coresponding to the 5Do - 7F2 emission (619 nm) in
YVO4: Eu3+ nanoparticles similar in bulk materials. The consideration difference within the
emission bands of the nanocrystals and bulk materials YVO4: Eu are found the larger with of
emission band. Which could be given by the small size of the particles
In YVO4: Eu3+ material, all europium ions are excited via energy transfer from vanadate
groups, the later indicates un upper limit of about 250ns for the energy transfer rate to europium
[4]. The 5D1 level of europium is not populated directly but via a relaxation process involving
several higher states of europium (see figure 3).
Figure 4 shows the comparision of the emission spectra change from 1 mol % to 7 mol %
Eu3+ in YVO4: Eu3+ nanoparticles. Similar to bulk materials [11] the quantum yield shows a
maximum at a doping level at about 5 mol % europium and decreases at higher (7 mol %)
europium concentrations.
It is a quenching effect of the luminescence at high concentrations in lanthanid-doped systems.
This typical properties is observed when neighboring distance between europium ion decreases
below a critical value. The nonlinear variation of the quantum yield shows in figure 4 provides
additional proof that the obtained sample consists of doped YVO4:Eu3+ particles which are not a
mixture of EuVO4 and YVO4 particles.
Figure 5 presents the room temperature time-resolved emission spectra of the YVO4: Eu3+
(5%) nanoparticels upon 337 nm excitation and with variable time delays. The maximum
intensity corresponding to the 5D0 - 7F2 transition of Eu3+ is observed in a time delays of 100 s.
As the time delays increases from 100 s the emission intensity correspond to the 5D0 - 7F2
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transition of Eu3+ decreases. This is due to the fact that the decay time of the 5D0 - 7F2 transition
of Eu3+ ion is in the s range. The decay curve at 619 nm of the YVO4: Eu3+ (5%) nanoparticels
is shown in fig. 6. For the 5% Eu3+-doped sample, the 1/e decay time is about 340 s.
4. Conclussions
Intensity (a.u)
The YVO4 :Eu3+ nanoparticles have been

successfully synthesized via wet chemical
hydrothermal synthesis. The particles have a
size from 30 to 50 nm. YVO4.Eu3+
nanoparticles of all systems investigated
show the strongest luminescence. Spectral
position of the transition of the luminescence
transition correspond to the Eu3+ ion
occupying a site with D2d symmetry. The
low-temperature hydrothermal synthesis at
0
300
600
900
1200 1500 1800 2100
2000C in 1 hour, the dopant ion occupies the
T im e ( s)
same site as in the bulk material. The most
Fig. 6: PL decay curve of YVO4: Eu3+ (5%)
intense transition observed in the emission of
3+
nanoparticels at 619 nm, upon 337 nm excitation.
the YVO4.Eu particles originate from the
5
Do level. The room temperature timeresolved emission spectra of the YVO4.Eu3+ nanoparticels upon 337 nm excitation and with
variable time delays indicates that the 1/e decay time is about 340 s for the 5% Eu3+-doped
sample.
Acknowledgments: This work is supported in part by Instistute of Materials Sciences - Vietnam
Academy of Science and Technology (VAST). A part of the work was done in the National Key
Laboratory for Electronic Materials and Devices, Institute of Materials Science, VAST.
References
1.
U. Rambabu, D.P. Amalnerkar, B.B.Kale, S.buddhudu. J.Electrochem. Mater. Res. Bull.,

Vol.35, No.6, (2000) 929 936
2. M.Yu.J. Lin, S.B.Wang. Appl.Phys. A, Vol.80, (2005) 353 - 360
3. Y.H. Zhou, J.Lin. Optical Mater, vol.27, (2005) 1426 - 1432
4. K. Riwotzki and M.Haase.J. Phys. Chem.B 102, (1998), 10129 - 10135
5. J.W. Stouwdam, G.A. Hebbink, J. Huskens, F.C.J.M. Vanveggel. Chem. Mater. Vol.15,
No.24 (2003) 4604 4616
6. D.B. Barker, C.R. Pollock, L.L. Beeczoft, C.K. Ober. Opt. Lett. Vol.22, No.16(1997)1247
1249
7. E. Beaurepaire, V.Buissetle, M.P. Sauviat, D. Giaume, K.Lahlil, A.Mercuri, D.Casnova, A.
Huinard, J.L.Martin, T.Gacoin, J.P.Boilot, A.lexandzou. Nano.lett.vol.4,no.11(2004) 2079
2083
8. Juan Kang, Xin-Yue Zhang, Ling-Dong Sun, Xin-Xiang Zhang, Talanta, Volume 71, Issue
3, 28 February 2007, Pages 1186-1191
9. Satoru Takeshita, Tetsuhiko Isobeand Seiji Niikura, Journal of Luminescence, Article in
Press, Corrected Proof (2008).
10. C.Feldman. Soid Stat Sci., Vol.7(2005) 868 873
11. (a) Judd, B.R. Phys. Rev. 127(1962) 750. (b) Ofelt, G.S.J. Chem. Phys.37 (1962) 511
12. F.C Palilla., A.K Levine, M.Rinkevics, J. Electrochem.SOC. 112 (8) (1965) 776
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INTERACTIVE KINETIC THEORY IN THERMOLUMINESCENCE

Truong Quang Nghia, Phan Thi Minh iep, Hoang Th Thu
Department of Solid State Physics Department,
University of Natural Sciences of Ho Chi Minh City
E-mail: phanthiminhdiep@yahoo.com
Abstract: With our model of three electron traps and two recombination centres, the interaction
(competetion) between traps was considered which was not be taken into account in popular
kinetic theory nowadays. Computation results by fourth order Runge-Kutta method indicate
that the computed glow curve is in good agreement with that of first order kinetic theory in case
in which the retrapping probability was neglected in comparation with the recombination
probability. Contrarily, in cases in which the retrapping probability has the same order of
recombination one, the computed glow curve has different shape and behaviour from that of
second order kinetics. In conclusion in fitting technique, one should be care in application of
second order kinetics.
1. Introduction
Nowadays in thermoluminescence one still uses widely first order kinetics (neglecting
retrapping effect), second order kinetics (having retrapping with an assumption in which the
retrapping rate equals to the recombination one) and general order kinetics (developed from
second order kinetics with the kinetic parameter b varies in the range 12).
However, all the above models have the same assumptions.
Models have only one trap and one recombination centre.
Using the assumptions of quasiequilibrium state of charge during specimen heating.
That means: nc 0 and dnc / dt 0
With these above assumptions there is no interaction between traps. That means when one
elctron leaves a certain trap, coming up to the conduction band, it can only retrap at the same
trap. This does not reflect perfectly a truth that when one electron reaches the conduction band, it
can be trapped at T1, T2, ...Tn traps as the case when electron is trapped during irradiation.
To overcome above discussion we used a model of three electron traps and two recombintion
centers and considered the interaction between traps. We also do not use the assumptions of
quasiequilibrium state during thermal scanning.
2. Rate equations describing the flow of charges
To limit the programming length and caculation time, we only use three electron traps which
have the same retrapping rate Ani (i =1,2,3) and two recombination centers which have the same
recombination rate Amnj(j=1,2).
Putting Ni is the concentration of electron traps ith
ni is the concentration of trapped electrons in trap ith
mj (j=1,2) is the concentration of holes in recombination center jth
nc is the concentration of electrons in the conduction band
We have rate equations describing the flow of charges.
dn1
E
= n1s1 exp 1 + nc ( N1 n1 ) An1 = F1 ( n1 , s1 , E1 , nc , N1 , An1 , T )
(1)
dt
kT
dn2
E
= n2 s2 exp 2 + nc ( N 2 n2 ) An 2 = F2 (n 2 , s 2 , E 2 , n c , N 2 , An 2 , T )
(2)
dt
kT
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dn3
E
= n3 s3 exp 3
dt
kT
+ nc ( N 3 n3 ) An 3 = F3 (n 3 , s 3 , E 3 , n c , N 3 , An 3 , T )
dm1
= nc m1 Amn1 = J 1 (n c , m1 , Amn1 , T )
dt
dm2
= nc m2 Amn 2 = J 2 (n c , m 2 , Amn 2 , T )
dt
dnc
E
E
E
= n1s1 exp 1 + n2 s2 exp 2 + n3 s3 exp 3
dt
kT
kT
kT
(3)
(4)
(5)
nc {m1 Amn1 + m2 Amn 2 + ( N1 n1 ) An1 + ( N 2 n2 ) An 2 + ( N 3 n3 ) An 3 }

(6)
= L (n c , m1 , m 2 , n1 , n 2 ,..., T )
where si (i=1,2,3) is the frequency factor of electrons in trap Ti.
(Ni - ni) (i=1,2,3) is the number of empty traps in trap ith.
Ei (i=1,2,3) is the trap depth ith (from the bottom of conduction band)
Ani (i=1,2,3) is the retrapping rate at trap ith
Amnj (j=1,2) is the recombination rate at recombination centre jth
It is clearly seen that these above aquations are not independent. The kinetic theories now must
use different assumptions mentioned so far in order to separate these equations into independent
equations. Since then one can find analytic solutions. Contrarily, in our model, we do not use any
assumptions, so we can only approximately solve these equations by digital method.
3. The fourth order Runge-Kutta method

The fourth order Runge-Kutta method is applied widely in solving differential equations. This
method bases on the fact that if we know the value of y(T) we will find the value of y(T+h), (h is
the increasing step of T). The computed accuracy will increase 16 times if h step lessens half. By
this way one can continue to deduce h step until the expected accuracy will be taken. Of course
the time for calculation is longer.
We apply the fourth-order Runge-Kutta method. Sometimes one can apply higher order (sixth
order) Runge-Kutta method in order to save the calculation time. In our case we wrote the
program in LabVIEW language for 12000 steps of h and the calculation time is about 5 to 6
seconds.
The fourth order Runge-Kutta method is as follows:
1
yi (T + h ) = y i (T ) + (K 1 + 2 K 2 + 2 K 3 + K 4 )
(7)
6
Coefficents K1, K2, K3 and K4 are given by:
K1i = hFi (T0 , ni , m j , nc )
(i = 1, 2,3; j = 1,2)
K
L
h
K 2i = hFi To + , ni + 1i , nc + 1
2
2
2
K
L
h
K 3i = hFi To + , ni + 2i , nc + 2
(8)
2
2
2
K 4i = hFi (To + h, ni + K 3i , nc + L3 )
Coeficients J1, J2, J3, J4, L1, L2, L3 and L4 are calculated in the same way as for Ki (i=1,2,3,4).
The glow curve intensity is calculated by:
dm dm
I (T ) = 1 + 2
dt
dt
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It should be noted that these obtained solutions are mathematical solutions not be physical
ones (which must be satisfied physical conditions). Therefore we have to add the physical
requests for which these solutions must be satisfied.
4. The imposed physical conditions

The physical conditions are imposed following.
nc can not have the value exceeding initial value (n01+n02+n03), and not having negative
value.
n1, n2, n3 can not receive negative values
charge neutrality m1+m2=nc+n1+n2+n3 must be satisfied during thermal scanning.
5. Results and discussions

Solving the set of equations (1) (6) with these above imposed conditions, the received
results are following:
Figure 1 introduces the computed glow curve using the interactive kinetics (the full line), the
sum of three first order kinetic peaks () and the sum of three second order kinetic peaks (o). The
parameters were used to compute the interactive glow curve and the sum curve of first order and
second order kinetics are listed in table 1.
Table 1. The initial values of used parameters in glow curve calculation.
Trap N01
Trap N02
Trap N03
N1=1.1010 m-3
n1=1.109 m-3
E1=-0,95 eV
s1=1.107s-1
An1=1.10-12 s-1
N2=1.1010 m-3
n2=1.109 m-3
E2=-1.2 eV
s2=1.108s-1
An2=1.10-12 s-1
N3=1.1010 m-3
n3=1.109 m-3
E3=-1,42 eV
s3=2.108s-1
An3=1.10-12 s-1
Recombination
center 1
Recombination
center 2
m1=1,5.109 m-3
Amn1=1.10-9 s-1
m2=1,5.109 m-3
Amn2=1.10-9
nc
Figure 1. The computedglow curve using the interactive kinetics (the full line)
and the sum of three first order curves ().
As be seen in this case the retrapping effect is very small in comparision with the
recombination effect (An=1.10-12 << 1.10-9=Amn), the interactive glow curve fits the sum of three
first order curves well. The remarkable point is that the intensity of peaks 3 in the interactive
kinetics is smaller than that of first order kinetics. Qualitatively we can explain that due to
retrapping effects in traps. Note that the electrons that leave trap 3th by thermal energy can be
retrapped at trap 1th and trap 2th. Therefore after thermal scanning a lot of electrons is kept in
these traps.
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Figure 2 represents the case in which the retrapping rate gradually increases (An=1.10-10s-1;
Amn =1.10-9s-1) and all other parameters are remained the same as in figure 1. The interactive
glow curve changes not only intensity but also shape and behaviour. The three peaks remain
sepatarely but the first two peaks have lower intensities whereas the intensity of the third peak
gradually increases. In all cases it has remarkable departures from that of second order kinetics.
Figure 2. The computed glow curve using the interactive kinetics (the full line) and the sum of three first
order curves (), second order curves (o) calculated with the same condition.
In general we can conclude that in cases where the retrapping effect is neglected the
interactive glow curve follows well that of first order kinetics. When retrapping effect is taken
into account, the interactive glow curve has its shape and behaviour differ strongly not only the
second order kinetics and first order kinetics also. In all cases there are great departures from the
interactive glow peak with that of second order kinetics. Therefore in fitting technique one
should be care in application of second order kinetics.
Our model has several limitations. Firstly, nowadays we do not know the values of An and
Amn so they were chosen randomly. Secondly, after thermal scanning a lot of electrons and holes
are still captured at their centres and in conduction band. This fact is in disagreement with
experiments in which no signal is observed in second thermal scanning. The main reason may be
in our model the presence of thermally disconnected traps does not be taken into account.
6. Conclusions
The interactive kinetics makes good a part of kinetics popularly used in thermoluminescence
now. Due to the difficulty of the problem and limitations in choosing the unknown physical
parameters corresponding to traps and recombination centers, the results and conclusions in this
report only be referential.
References
1. S. W. S Mc Keever, Thermoluminescence of Solids, Cambrige University Press, 1985.
2. Trng quang Ngha, Thermoluminescence and Applications (in Vietnamese), VNU-HCM
Publishing house, 2007.
3. R. Chen, S. W. S Mc Keever, Theory of Thermoluminescence and Related Phenomena,
World Scientific, 1997.
4. Trng Quang Ngha, Phan Th Minh ip, Hong Th Thu, Researching on
Thermoluminescence at University of Natural Sciences of HCMC (in Vietnamese), reported
at the 4th internationnal school and workshop on Thermoluminescence and Luminescent
Detectors Quangbinh University, July 6 - 7, 2008.
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SYNTHESIS AND CHARACTERIZATION OF SnO2: Sb NANOPOWDERS

Nguyen Ngoc Long, Le Thi Thanh Binh, Nguyen Thanh Binh,
Nguyen Thi Hanh, Nguyen Tu Niem, Nguyen Viet Duc
Faculty of Physics, Hanoi University of Science, VNU
334 Nguyen Trai Road, Thanh Xuan Distr, Ha Noi, Viet Nam
Abstract: Nanopowders of antimony - doped tin oxide have been received by hydrothermal
method. The products were characterized by means of EDS, X- ray diffraction, scaning electron
microscopy (SEM). Results indicate that the SnO2: Sb has a rutile structure with diameters about
range from 4 nm to 5 nm. From the absorption spectra, it was found that the bandgap energy of
SnO2: Sb varied from 3.98 eV to 4.12 eV with variation of Sb dopant concentration. The
luminescence properties of the samples have been influenced by the Sb dopant concentration.
1. Introduction
Tin dioxide is an n-type and wide band gap semiconductor. It has many important
applications in technology of constructing electronic and optoelectronic devices. The novel
properties of SnO2 in nanoscale have been stimulated potential application of the material.
Moreover, doping tin dioxide with electronic donors as F or Sb yields a high conductivity
without significant changes in its optical transmittance. The dependence of electrical and optical
properties on SnO2 grain size always attracted attention of many scientists on the world. SnO2
nanostructures can be received by many techniques such as solgel [1], r.f. magnetron sputtering
[2], simple thermal evaporation [3], thermal CVD [4], hydrothermal [5, 6, 7, 8] etc.
In this paper, we present our success in syntheses of SnO2: Sb nanoparticles by hydrothermal
method with the Sb dopant concentration changing from 1 to 3 % at and some characterization of
the material.
2. Experimental
The samples of SnO2: Sb nanoparticles were prepared by hydrothermal method from initial
materials of SnCl4.5H2O, C2H5OH, NH3 anf SbCl3. The solution was obtained by dissolving
SnCl4.5H2O and SbCl3 in distilled C2H5OH. The solution was stirred in 30 minutes. Aqueous
ammonia (NH3) was added dropwise until a pH value of 910 was reached. Then the white
precipitate was washed several times with distilled water until no Cl ion could be detected. The
white precipitate was in 150 ml of distilled water and then put into teflon liner hydrothermal
autoclave. The autoclave was put into the electrical oven Mermert - 500 and kept constantly at
2000C. The time of hydrothermal process was varied in 24 h. The reactions can be as follows:
mSnCl 4 + nNH 3 (SnCl 4 )m (NH 3 )n
(SnCl 4 )m (NH 3 )n mSn 4+ + nNH 3 + 4mCl

NH 3 + H 2 O NH 4 OH
4+
Sn + 4 NH 4 OH SnO2 +4 NH 4+ + 2 H 2
After the oven was cooled to room temperature, white powders were obtained in the bottom
of the teflon liner hydrothermal autoclave. The powders has been washed several times in
absolute ethanol and distilled water until the pH = 7. After that, the powders were dried at 1000C
in 10 h. The last products are SnO2: Sb powders with the dopant concentration change from 1- 3
% at.
The crystal structure of the samples was analyzed by X-ray diffraction using DX 5005
diffractometer and TEM images using JEM 1010 microscope. Optical properties of the samples
were investigated at room temperature. Absorption spectra of the samples were measured on
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UV-VIS 2450 spectrometer. Photoluminescent emission and excitation spectra of the samples
were measured on Fluorolog FL3-22 spectrofluometer.
3. Discussion
The X-ray diffractions patterns of the SnO2: Sb samples synthesized with the Sb dopant
concentration change from 1- 3 % at are shown in Fig.1 and Fig. 2. The XRD patterns clearly
indicate that all nanoparticle SnO2: Sb samples possess a polycrystalline tetragonal rutile
structure with lattice constant of a = b = 4.74 and c = 3.19 . The patterns are consistent with
the standard JCPDS card of SnO2 (JCPDS 21-1250). No other crystalline phase was detected in
any of the XRD patterns.
Fig.1. XRD patterns of the SnO2: Sb nanoparticles

samples with 3% Sb
Fig.2. XRD patterns of the SnO2: Sb nanoparticles

samples synthesized with the dopant concentration
change from 1- 3 % at
Table 1.The lattice parameter of SnO2 powder with different Sb concentration
The sample
a = b()
c ()
SnO2:1%Sb
4.74
3.187
SnO2:1.5%Sb
4.71
3.20
SnO2:2%Sb
4.77
3.181
SnO2:2.5%Sb
4.73
3.192
SnO2:3%Sb
4.73
3.192
Table 2.The particle size of SnO2: Sb powders
The samples
Size of particles (nm)
SnO2: 1%Sb
SnO2:1.5%Sb
SnO2:2%Sb
SnO2: 2.5%Sb
SnO2: 3%Sb
5.12
5.12
5.08
5.05
4.83
The table 1 shows the lattice parameter of SnO2: Sb powders have almost no change when Sb
concentration is varied. Its werent depended on the Sb doping concentration.
The average grain size of the powder was calculated by using the Scherrer formula:
d=
0.9
cos
(1)
Where is the X-Ray wavelength, is the Bragg diffraction angle and is the linewidth at half
maximum of diffraction peak. The particle size of nanoparticles SnO2: Sb samples are presented
in table 2.
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Fig.3. Particle size of SnO2: Sb powders

dependence on the dopant concentration
Fig.4. EDS spectrum of the SnO2: 1% Sb powders
In the table 1 and figure 3, it can be seen the upward tendency of the nanoparticle size with
the dopant concentration. The increasing concentration of antimony then the slower the crystal
grain growth, and the smaller the grain size. However the quantitative change is small and the
rule is not affirmed clearly.
In the EDS spectrum of the 1% Sb sample, the peaks of O, Sn and Sb are obviously
observed. However, the elements of Al and Si appear in the spectrum (Fig.4). Its can be taken
SnO2 nanoparticles coating on hollow glass microspheres [6].
Fig.5. TEM image of SnO2: Sb powders with 1% and 3%
The morphology of the samples was observed by TEM. A typical TEM image of SnO2: Sb
sample with 1% and 3% synthesized by hydrothermal is shown in Fig.5, from which it can be
seen that the powder consists of a large quantity of nanoparticles. The average sizes of the
particles from sample 3% are about 5nm.
In order to investigate the absorption property of the SnO2: Sb nanoparticle, the powders
have been dispersed into absolute C2H5OH. Absorption spectra were measured at room
temperature. For the direct band gap semiconductor with allowed transition, the absorption
coefficient near the fundamental absorption edge is given by equation:
1
= A(h E g ) 2
(2)
2
The straight line plot of (h) vs (h) indicates the dominance of direct transition. Figure 6
shows the photon energy dependence of (h)2 for SnO2: Sb sample synthesized with 0% Sb.
The band gap of the material can be determined from the plot. The band gap energies of SnO2:
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Sb nanoparticles synthesized in variable the Sb doping concentration are tabulated in table 3.

The band gap of the nanoparticle is changed in the range from 3.98 eV to 4.12 eV with
variable Sb dopant concentration of hydrothermal process.
No
The samples
Eg(eV)
SnO2
4,12
SnO2:1%Sb
4,01
SnO2:1.5%Sb
4,0
SnO2:2%Sb
3,89
SnO2:2.5%Sb
3,98
SnO2:3%Sb
3,98
Fig.6. The photon energy dependence of (h)2 for
SnO2 sample 0% Sb
Table3. Band gap energy of SnO2: Sb
Fig.7. Emission spectra of SnO2 samples

synthesized with different
Fig.8. Excitation spectra of SnO2 samples

synthesized with different Sb concentration
Photoluminescent emission (PL) and excitation (PLE) spectra of the samples were measured
at room temperature. Figure 7 shows emission spectra of SnO2: Sb samples with excitation
wavelength at 267 nm. All PL spectra of the samples synthesized exhibit an emission band in the
UV region. The PL spectra present peak at 340 nm (3.6 eV), 396nm (3.14 eV), 415 nm (3.0 eV),
439 nm (2.83 eV), 451 nm (2.74 eV) and 468 nm (2.66 eV). The origin of these broad peaks
need for further argument. However, to interpret the nature of this UV emission region, the
recombination mechanism of a conduction band electron with a Vo center can be used [1].
The PLE spectra of the samples have been investigated in some emission peak positions.
Figure 8 illustrated the PLE spectra of the samples with maximum emission wavelength fixed at
439 nm. It well known that for a semiconductor sample, a peak of PLE spectra corresponds to an
absorption process occurred in the sample
4. Conclusions
In summary, SnO2: Sb nanopowders were fabricated hydrothermal method using
SnCl4.5H2O, C2H5OH, NH3 anf SbCl3 as source material with the Sb dopant concentration
change from 1- 3 % at. From X-ray measurements, the average grain size of the powder is in the
range of 4 nm 5 nm. The band gap energy of the SnO2: Sb nanoparticles vary from 3.98 eV to
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4.12 eV. The photoluminescence of the nanoparticles was investigated in the UV region at room
temperature.
Acknowledgement: This work was supported by Natural Science Council, Ministry of Science
and Technology of Vietnam (project 4 055 06).
References
1. F.Gu, S. F. Wang, M. K. L, G. J. Zhou, D Xu, and D. R. Yuan, J. Phys. Chem. B, 108,
(2004), 8119-8123
2. J. Ma, Y. Wang, F. Ji, X. Yu, H. Ma, Mater. Lett., 59, (2005), 2142-2145
3. J.Q. Hu, Y. Bando, D. Golberg, Chem. Phys. Lett., 372 (2003) 758 -762
4. J. Jeong, S. P. Choi, C. I. Chang, D.C. Shin, J. S. Park, B. T. Lee, Y. J. Park and H. J. Song ,
Solid State Commun., 127, (2003), 595-597
5. H. Zhu, D. Yang, G. Yu, H. Zhang and K. Yao, Nanotech., 17 (2006) 2386- 2389
6. J. Xu, H. Yang, Q. Yu, L. Chang, X. Pang, X. Li, H. Zhu, M. Li and G. Zou, Matt.. Lett 61
(2007)1424-1428
7. J. Zhang, L. Gao, Mat. Chem. Phys. 87 (2004) 10-13
8. H. Miao, C. Ding, H. Luo, Microelectronic Engineering 66 (2003) 142-146
Advances
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RESEARCH AND DEVELOPMENT OF VISUAL IMMERSIVE ENVIRONMENT FOR

THE CAR DRIVING SIMULATOR WITH STEREOSCOPIC TECHNOLOGY
Pham Hoang Minh a, Chu Anh Tuan a, Pham Hong Quang b, Pham Canh Duong b,
Nguyen Duc Thanh a, Pham Hong Duong a, M. Mikhailiuk c and V.N. Reshetnikov c
a)
Institute of Material Sciences, Vietnam Academy of Science and Technology,

18 Hoang Quoc Viet Hanoi.
b)
Institute of Mathematics, Vietnam Academy of Science and Technology,
18 Hoang Quoc Viet Hanoi.
c)
Institute of Microprocessors, Russian Academy of Sciences.
E-mail: duongphamhong@yahoo.com
Abstract: Advanced immersive environment for traffic simulation was realized by real time
dynamic stereoscopic visualization. To present a stereoscopic motion picture, two images are
projected superimposed onto the same screen through orthogonal polarizing filters. The viewer
wears eyeglasses which also contain a pair of orthogonal polarizing filters. In this work, we
report on the realization of a 3D stereo car driving simulator. The hardware components such as
non-depolarized screen, 3D polarized eyeglasses, projector frames are fabricated with available
materials in the Vietnam market with the affordable cost. The influence of its parameters on the
image quality and stereoscopic effect are discussed. Visual dynamic effects such as bumping
shock, obstacle collision and glare illumination give different impressions under mono and stereo
projections. The precise depth perception due to binocular vision requires more accurate
construction of models, avatar and environment. The prospects and challenges of this technology
in the near future will be discussed.
Keywords: 3D projection, car driving simulator, virtual reality
1. Introduction
Computer used as a 3D interactive simulation tool is widely applied in many domains. In
United States, both of aerial and automobile industries have used the Virtual Reality technology
since many years, due to the pilot and driver training using the simulator indicates that's a highly
effective methodology [Lathan 2002]. The manufacturers hope that by using these simulators,
they can save significantly the consumed energy, protect the environment and enhance the
training quality.
The driving simulators are typically classified into 3 major categories based on the technical
features and display quality [Staffan 2003]. The low-level simulators cost tens thousands USD,
are similar the video games, consists of a computer with simulation program, seat, steering
wheel, and 30 inches 2D display monitor. The mid-level simulator which are used in the driving
training centers have some significant upgrades of electrical mechanic, such as the steering
wheel can turn 2 rounds on the left and 2 rounds on the right; the wide viewing angle display
system consists of 3 screens, and advanced software. The high-level simulators cost millions
USD, are designed with the most advanced features, like the wide screen stereo display system,
the hydraulic system to generate the vibration and crash, synchronized with the software with the
appropriate kinetic effects.
In Vietnam, some kinds of simulators such as MIG BT-21 airplane handling cabin, tank
handling cabin, ship handling cabin was built by different groups, and are applied in the research
and education works. The simulation images of these systems are projected on the screen by one
or three projectors to increase the viewing angle. However, all the display systems are based on
2D projection technology, hence all the effects of binocular vision such as the 3D depth , rivalry
effect and disparity effect can not be percepted by the trainees.
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For the first time in Vietnam, with the cooperation with the colleagues coming from
Institute of Microprocessors, Russia Federation, we have built successfully a driver training
simulation system, with the kinetic and crash effects, which can bring the nearly real impacts to
the driving trainee. Almost all the components for producing this system were purchased in
Vietnam with significant lower price, compared with the price of the equivalent system in
abroad.
Fig.1: The stereoscopic car driving simulator
2. Hardware design
The simulator consists of 3 main parts:

+ A mechanic framework with the a driver seat and control components, including the startup
key, brake pedal, clutch pedal, accelerator pedal, gear stick and steering wheel.
+ A computer equipped with a 3D graphic card. The NVIDIA GeForce 7600 is suitable for
our work. It supports 2 outputs: one
VGA output and one DVI output, so
the motion pictures can be exported
simultaneously to two display
devices.
+ A stereo display system
consisting of 2 identical projectors
and a special screen. Two images are
projected superimposed to this screen
through orthogonal polarizing filters,
set at 450 and 1350. The viewer wears
eyeglasses with a pair of orthogonal
polarizing filters, hence only the light
beam having parallel polarization can
be viewed. Two images rendered
from two virtual cameras are seen
separately, then will be fused in the
viewers
brain,
giving stereo
perception.
Fig.2: Cross section of simulator
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3. Software design
The virtual environment is programmed by the 3D modeling language. The models were
built using Auto Cad and 3DStudioMax tools, and the interactive motion pictures were rendered
by OpenGL. All the data and scenario was packed into an auto-run program running on the
Linux OS.
The most important upgraded features of the software using for 3D projection, compared
with the previous version designed for conventional 2D projection is the use of 2 virtual cameras,
located at 2 view points. The real-time scenario is captured and rendered simultaneously by this
pairs of cameras. This dual video streams are send separately to two display devices (i.e. 2
projectors) via 3D graphic card.
In reality, the perception of each viewer to the stereoscopic visualization is different. The eye
strain or viewer discomfort may occur, because of high parallax or excessive 3D cues of images.
So the amount of parallax of the stereo images must be adjusted [Janusz, 1999].
In our simulator, the adjustment can be done
manually by varying the distance d between the
pairs of virtual cameras and convergence angle
(by pressing keys on keyboards). The distance
d is chosen to be the distance between two eyes
of the viewer. The larger d means larger parallax
and vice versa. When the value of change the
convergence point is shifted closer or farther,
the stereo image gets closer or farther to the
viewer. A default value was chosen by the
developers, but each user can find the suitable
parallax for him to get best viewing comfort in
stereoscopic visualization.
Fig.3: The parallax adjustment
4. Fabrication of 3D projector screen

For the stereo projection with polarized light, the screen must have a non-depolarized
surface. The solution is to coat conventional screen with micro-size metallic paint, which permit
the light keep its polarization after diffused from screen surface. The substrate used to fabricate
the screen is a large composite sheet initially coated with a diffused aluminum layer on the
surface. This material can be found easily on the market. However, the aluminum surface of this
sheet is not satisfied the diffusion quality for stereo projection. To improve it, we have to coat
the surface with a diffused aluminum layer. The coated layers must be uniform that the diffuse of
light occurs primarily on the surface of each aluminum grains, and only very small part occurs
on the sinking membrane of adhesive. The polarized filters and eyeglasses were fabricated from
the large polarized plastic sheets which can be purchased in the market with affordable cost.
In order to evaluate the quality of the screen and of the polarized filters after fabrication, a
measurement of ghost quotient was done. This parameter is defined as the ratio of luminous
intensities of crossed polarizer and parallel polarizer configurations. The lowest value means that
the separation of left and right image is almost absolute and the stereo quality is good enough.
In the experiment shown in Fig. 3, the filter 2 serves as analyser, and the filter 1 (polarizer)
was rotated 3600 around the horizontal axis. Light intensities was recorded by a luxmeter. The
other important parameter to evaluate the quality of screen is the reflectance. By using the
integral sphere, combined with an Optical Multi channel Analyser (OMA), a measurement of
this parameter is also done.
Normalized Intensity (%)
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Fig.4: Schematic diagram illustrates the

polarization measurement
100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
0
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
Angle (Degree)
Fig.5: Ghost quotient under polarization angles
5. Results and analysis

1.0
Reflectance
Fig. 4 shows the plot of the normalized

0.9
light intensity as a function of the angle
0.8
between the axis of the polarizer and
0.7
analyzer, arranged as shown in Fig. 3. The
0.6
0.5
result shows that the ghost quotient is only
0.4
3% for the perpendicular polarization. This
0.3
value is small enough (<5%), it means that
0.2
the ghost effect generated from the polarized
0.1
projection on our stereo display system can be
0.0
400
450
500
550
600
650
700
ignored for the human vision. By other word,
wavelength (nm)
the separation of left and right image is good
Fig.6: Reflection spectrum of the screen
enough.
For the second experiment, the graph shows that the reflection spectrum is flat and stable on
the visible spectrum band. It means that the screen is fairly neutral or has a good whiteness for
the visible light. The average reflectance 0.65 indicates that one third of light lost after scattering
from the screen surface. The aluminum coated screen is slightly grayer than the conventional
projector screen.
6. Stereoscopy for driving simulator: Prospects and challenges
What are the advantages of stereoscopic simulator? What does the visual immersive
environment mean? Stereoscopic simulator is a system that can generate binocular vision (or
stereopsis), which is probably evolved as a means of survival. Some animals, usually predatory
animals, have their two eyes positioned on the front of their heads, thereby reducing field of view
in favor of stereopsis. Examples include eagles, cats, tigers, snakes and human. With stereo
vision, we can see where objects are in relation to our own bodies with much greater precision,
especially when those objects are moving toward or away from us in the depth dimension. We
can see a little bit around solid objects without moving our heads and we can even perceive and
measure "empty" space with our eyes and brains. Other animals, usually prey animals, have their
two eyes positioned on opposite sides of their heads to give the widest possible field of view.
Examples include rabbits, buffalos, and antelopes. In such animals, the eyes often move
independently to increase the field of view. Even without moving their eyes, some birds have a
360-degree field of view.
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Our stereo driving simulator respects of course

this natural law. The stereo display brings us a
sensation as like as we are inside a real car and see
the real scene with our binocular vision. In this
immersive environment, we can estimate easily the
distance from us to the virtual object on the road as
trees, terrain hazard, traffic lights, and other cars.
When a car moves towards ourself, so close that
feeling we can "touch" it, and a crash can bring us
a small visual shock. With binocular vision, we can
have an impressive feeling of bumping shock when
our car wheel runs over road bead. These visual
kinetic effects aren't obvious with convention 2D
display simulator. In brief, the stereoscopic display
means a higher fidelity in driving simulation.
Fig.7: Binocular vision
However, is it clear that higher fidelity yields a higher training effectiveness? Driving is a
task where the visual system plays a dominant role. Mollehauer (2004) states that a stereo
presentation is often associated with positive reactions, an increased sense of realism, and feeling
of presence, which could positively affect the training effectiveness. Sachsenweger and
Sachsenweger (1991) indicate that stereoscopic is essential in road traffic within a range up to
20m. Kemeny and Panerai (2003) report that stereoscopy is effective for near space distance
cueing, but its effectiveness more distantly is controversial. Furthermore, Mollehauer (2004)
indicates that stereo presentations are frequently associated with an increase of simulator
sickness due to cue conflicts or artifacts.
While the debate of effectiveness of stereoscopic is inconclusive, in order to reduce as much
as possible the viewer discomforts of stereoscopic, we need to improve the image quality by
many ways. The lost of intensity in the projection, due to polarization, is considerable. But
following the principle of visual physiology, the high contrast is more important than high
intensity for the visual cue perception. So we need to improve the contrast of projected image by
minimize the outer light coming to the screen. A darkened room seems to be the only interim
solution [Bennett, 2000].
The uniform and matte of aluminum coated layer of screen is also important. There must be
no any glare portion on the screen and the entire surface of screen must be non-depolarization to
avoid the ghost effect. Otherwise, the individual differences of stereo perception are
considerable, and the accommodation-convergence from separated images is not easy for some
people, which can yields an eye strain during the training. Solution: the parallax can be adjusted;
each individual can choose an appropriate image disparity for himself. Furthermore, our
simulator is dual-use; the trainee can switch between stereo vision mode and mono-vision mode
by turning off one projector and removing the polarized filters and eyeglasses.
7. Conclusion
1. For the first time in Vietnam, a complete car driving simulator with stereo polarization
display was investigated.
2. The self-fabricated screen with aluminum coated satisfies the optical requirements for 3D
projection, such as uniform and matte non-depolarized surface, no glare, very small ghost
effects that can be ignored, acceptable intensity and contrast of projected images. The cost to
manufacture our entire 3D projection system is reduced significantly in compare with the
same system in abroad.
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3. Good image quality was obtained in our system, such as high contrast, neutral color gamus,
large view angle.
4. Many solutions were applied to improve the 3D perception, for example: parallax adjustment;
switch between stereo / mono mode.
5. The stereo presentation brings a higher fidelity to the trainee, which could positively affect
the training effectiveness. This stereo projection system shows a very large potential for
application. It can be applied not only for driving simulator but also for stereo cinema
projection with 10-20 audiences.
Acknowledgement: This work is supported by Convention Program between Vietnamese
Academy of Science and Technology and Russian Academy of Sciences.
Reference
1. Lathan C. E., in Stanney, K. M. (2002): Handbook of Virtual Environments, Lawrence
Erlbaum Associates, Inc., New Jersey, United States, pp.404-414
2. Staffan Starnevall, PhD thesis (2003), Traffic Simulation in Virtual Reality with Possible
Application in Rehabilitation, Lund University, Sweden
3. anusz Konrad, Enhancement of viewer comfort in stereoscopic viewing: Parallax adjustment,
IS&T/SPIE Symposium on Electronic Imaging Stereoscopic Displays and Virtual Reality,
USA (1999)
4. De Winter, et al. (2007): Driving simulator fidelity and training effectiveness in Proceedings
of the 26th European Annual Conference on Human Decision Making and Manual Control,
Lyngby, Denmark.
5. Mollehauer, M.A: Simulator Adaptation Syndrome Literature Review, Michigan: Real time
Technology, Inc.
6. Dan Bennett, et al. (2000): A Low Cost Commodity Based System for Group Viewing of 3D
Images in Proceedings of Visualization Development Environments
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Hi ngh Quang hc Quang Ph ton quc ln th V

Nha Trang Vit Nam, 10-14/9/2008
STRUCTURAL PROPERTIES OF VISIBLE-LIGHT PHOTOCATALYSIS TiO2/CdS

NANOCOMPOSITE MATERIALS
V. T. T. Thuya, N. T. M. Huong b, T. T. Duc b, N. N. Trung c, L. L. Anh c ,V. T. Son c,
N. T. Binh a and V.T.Bicha
a)
Center for Quantum Electronics, Institute of Physics, VAST

10, Daotan Road, Badinh District, Hanoi, Vietnam
b)
Institute of Applied Physics and Scientific Instruments, VAST
18 Hoang Quoc Viet Road, Caugiay District, Hanoi, Vietnam
c)
Institute of Engineering Physics, HUT, Hanoi, Vietnam
1, Dai Co Viet, Hanoi, Vietnam
Abstract. In this paper we have systematically carried out the synthesis of pure TiO2, pure CdS
and CdS coupled TiO2 nanocomposite by employing reverse micelle process. The TiO2/CdS
nanocomposite was characterized by X-ray diffraction (XRD), SEM-EDS techniques and by
Resonance Raman spectroscopy and also UV-visible measurements. All these results confirm the
presence of coupled TiO2/CdS system in which the TiO2 in anatase form and the CdS in cubic
geometry. It is a cause significant absorption shift to the visible region compared to pure TiO2
powder to use the main part of the solar irradiation.
Keywords: XRD; SEM-EDS; Raman; UV-Vis, Titanium dioxide; Cadmium sulfide
1. Introduction
The efficient utilization of solar energy is one of major goal modern science and engineering.
Of the materials being developed for photocatalytic applications, titanium dioxide remains the
most promising. A disadvantage of the use of TiO2 as a photocatalyst is due to its relatively large
band gap (Eg=3.2 eV for anatase phase): its efficiency depends on the presence of radiation with
relatively low wavelength, in the ultra-violet spectral region. Due to this limitation, the
preparation of photocatalysts that can be excited in the visible range is of great interest for
development of photocatalytic processes that use solar radiation for degradation of organic
pollutants. The convert the TiO2 absorption onset from the UV to the visible region has many
methods. Here we are associated TiO2 with cadmium sulfide (CdS) which is a semiconductor
material with a band gap in the visible range (2.42 eV). The synthesized visible-light TiO2/CdS
nanocomposite was characterized in terms of its structure (by the X-ray diffraction XRD and
SEM-EDS techniques) and in terms of the electronic interaction between both semiconductors
(by Raman spectroscopy and UV-visible measurements).
2. Experimental methods
2.1. TiO2/ CdS nanocomposite preparation.
The chemicals used for the synthesis of TiO2 /CdS nanocomposite are of the purest quality
and are used as received: cadimium acetate (Cd(CH3COOH)2.2H2O), thioacetamide (C2H5NS) ,
C6H16O3SSi (MPS), methanol (MeOH), titanium isopropoxide ( Ti (OC3H7)4), 2- propanol are
obtained from Meck.
Initially, Cd(Ac)2.2H2O is dissolved in MeOH to create the 1M solution. Adding an amount
of C6H16O3SSi (MPS) into the solution with vigorous stirring at room temperature to form the
solution containing Cd2+ ion. In the next step, dissolving C2H5NS in MeOH to create the 1M
solution, stirring strongly to form the solution containing S2- ion.The microemulsions of Cd2+ and
S2- ion are mixed and vigorously stirred in 30 minutes to produce CdS yellowish microemulsion.
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Another TiO2 colloid solution were prepared by hydrolysis of Ti (OC3H7)4 as follows: Under
a stream of dry nitrogen, Ti(OC3H7)4 was added to 2- propanol. The mixture was added to
distilled deionized water, stirring vigorously. During the hydrolysis a white precipitate formed.
Nitric acid was added to the hydrolysis mixture, still stirring vigorously. The mixture then stirred
for 8 h at ~ 80oC. The 2- propanol (and some water) was allowed to evaporate during this time.
A stable TiO2 colloid sol resulted from this procedure.
The TiO2 colloid solution and CdS microemulsion are finally mixed and vigorously stirred to
form TiO2 x wt.% CdS ( x = 10,50).
2.2. Apparatus.
The photocatalyst material was characterized by using the X-ray diffraction (XRD)
measurements which were performed on a Siemens/ D5005 X-ray diffractometer using CuK
radiation. The surface morphology of samples were obtained on a Field Emission Scanning
Electron Microscope (SEM), S-4800, Hitachi. The Raman spectra were carried out on a
Renishaw in via Raman microscope (RENISHAW-UK) in the 100- 4000 cm-1 range by 514 nm
exciting line of the Ar+ laser and 633 nm exciting line of the He-Ne laser. Unresolved bands
were decomposed using a curve-fitting technique by OriginPro V7.5 software.
3.1. Structural and microstructural characterization.
The structural characterizations for the phase identification of observed nanocomposit
powder have been studied by X- ray powder diffraction technique. The XDR profile for TiO2,
CdS and TiO2 /CdS (50wt.% CdS) samples are shown in Fig.1. It is show presence of coupled
TiO2/CdS system in which the TiO2 in anatase form with very little amount of rutil form and the
CdS in cubic geometry. The microstructural
characterizations such as surface morphology and
chemical composition were performed using
scanning electron microscope SEM both in
imaging and EDS modes (Fig.2). Genesis software
has been used to analyze the microstructures and
elemental composition of the TiO2 /CdS
nanocomposites. The estimated values of cadmium
and sulphure are 6.12 weight % (1.34 atomic %)
and 1.44 weight % (1.08 atomic %). The calculated
and experimentally determined amounts of Cd and
Fig.1. Powder x- ray diffraction (XDR)
S are found to be in close agreement with each
pattern of TiO2 (a); CdS (b) and
other. The chemical component in the observed
TiO2/CdS (50wt.% CdS) (c)
nano powder are summarized in table 1.
(a)
Fig.2. SEM structure image (a) and powder SEM-EDS spectrum of TiO2/CdS
(in the case 50wt.%) (b)
(b)
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Table 1. Observed elements in the nanocomposite

TiO2/CdS podwer
Element
O
K
S
K
Ti
K
Cd
L
Totals
Weight % Atomic %
51.58
77.23
1.44
1.08
40.71
20.36
6.27
1.34
100.00
Fig. 3. UV-VIS spectral responses for pure TiO2
and TiO2/CdS nanocomposite films
3.2. Spectral analyses.

3.2.1. Optical transmission studies
The optical transmission spectrum of the pure TiO2 and TiO2 /CdS nanocomposite was
recorded in the UV Visible region from 200700 nm and is presented in fig. 3. It is observed
that the onset of transmittance starts below 300 nm and a sharp transition occurred at around 350
nm for the pure TiO2 anatase structure. Whereas for the case of TiO2 /CdS nanocomposite, the
spectral curve extends to the visible light region. The absorption edge of TiO2 in TiO2 /CdS
nanocomposites observed above 500 nm indicates a significant blue shift of the bandgap
energy compared to pristine TiO2. This may suggest that the nanocomposite coupled
semiconductor (TiO2 /CdS) is expected to increase photogenerated charge carriers under the
irradiation of visible light.
Table 2. Observed Raman frequencies in (cm-1) of nanocomposite TiO2/CdS podwers
(exc = 514 nm and 633 nm)
322
397
TiO2/CdS
exc =
514nm
633nm
147
198
199
246
247
300
320
400
399
516
515
452
519
452
515
638
800
639
600
640
640
TiO2
CdS
exc =
exc =
exc =
514nm
633nm
146
197
246
514nm
196
245
300
322
396
450
480
600
Assignment
exc =
Eg TiO2 Anatase
Eg TiO2 Anatase
LO
B1g TiO2 Anatase
Eg TiO2 Rutil
Ti-O
Ti-O
A1g +B1g Anatase
LO
Eg TiO2 Anatase
Bg of TiO2 Anatase
902
985
Ti-O-Cd
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3.2.2. Raman spectral analysis

Raman spectra excited at 514.5 nm of TiO2,
CdS/TiO (500 C)
CdS and TiO2 /CdS composites with high and
=514 nm
30000
low concentrations of CdS are displayed in Fig.
4. In comparison with all Raman spectra excited
CdS
20000
at 632.8 nm, a strong resonance effect for the
CdS phase is expected, since the band gap for
CdS/TiO high
bulk CdS 2.42 eV is very close to the
10000
excitation laser energy at 514.5 nm (2.41 eV).
CdS/TiO low
Raman spectrum for CdS particles is dominated
TiO
by an intense band at 300 cm-1, assigned to the
0
200
400
600
800
1000
1200
first-order longitudinal optic phonon (1 LO) and
-1
Wavenumber (cm )
the second-order LO phonon peak at 600 cm .
Fig.4. Raman spectra for TiO2, CdS and
The TiO2 spectrum in the 2001200 cm-1 region
-1
TiO
2 /CdS composites with high and low
is dominated by the 397, 516 and 640 cm
of CdS in the 2001200 cm1
concentrations
bands, characteristic of the TiO2-anatase phase.
range. Laser excitationwavelength at 514 nm
A weak feature can be seen at 450 cm-1,
(E laser = 2.41 eV).
indicating the presence of a small amount of
rutile modification of TiO2. Raman spectra of the
TiO2 /CdS composites show a combination of the two semiconducting characteristic bands and
an new feature at 983 cm-1 could attributed to Ti-O-Cd bonds. All observed Raman frequencies
of the obtained composites are listed in Table 2.
300
3mW
985
518
1mW
983
400
300
Intensity (a.u.)
902
600
640
ex
3mW
1mW
-1
4. Conclusions
We have systematically carried out the synthesis of pure TiO2, pure CdS and CdS coupled
TiO2 nanocomposite by employing reverse micelle process. The obtained TiO2 /CdS composites
was studied by XRD, SEM, resonance Raman spectroscopy, which gave information about the
structural characteristics of the nanosized TiO2 /CdS mixed catalysts. It was found that: i)
affirmation of the exist of CdS in the matrix of TiO2; ii) Raman spectra are sensitive to variations
in charge density which results from chemical interactions, and allowed the study of electronic
interaction between the two associated materials; iii) the X-ray phase analysis of these systems
shows evidence for the formation of TiO2/CdS nanocomposite structure. The microstructural
investigation of the nanocomposite envisages the correct stoichiometry of CdS to TiO2 and
homogeneous surface morphology. The TiO2/CdS nanocomposite extends the absorption band
edge into the visible region as observed from the UV-Vis measurements. The as-synthesized
nanocomposite materials will give better photoactivity under visible light irradiation than that of
pure TiO2.
Acknowledgments: This work is financially supported by The National Fundamental Research
Program on Physics, N.4030 06.
References
1. Fujishima K. et al., TiO2 Photocatalysis Fundamentals and Applications, BKC, Tokyo
(1999)
2. Tran Thi Duc, Phan Thi Binh, Nguyen Trong Tinh , Phung Thi Xuan Binh and Tran Xuan
Hoai, Preparation and Characteristics of Porous Nanocrystalline TiO2 ; Proceedings of the
Third International Workshop on Materials Science ( IWOMS 99), Hanoi, November (1999)
617
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3. Jiaguo Yu et al., Effect of surface structure on photocatalytic activity of TiO2 thin films
prepared by sol-gel method, Thin Solid Films 379 (2000) 7p
4. L.Miao et al., Fabrication, characterization and Raman study of anatase TiO2 nanorods by
heating sol-gel template process, J. Cryst. Growth 264 (2004) 246
5. V. T. Bich, T. T. Duc, N. T. Tinh, T. B. Ngoc, N.L.Lam, V.T.M.Hanh and T.X.Hoai, Visible
Light Photocatalysis in Nitrogen doped Titanium Oxides for Environmental Applications;
Physics & Engineering in Evolution Ed. Do Thac Cat, Nguyen Chau, Vo Thach Son
(2005) 86
6. Juliana C. Tristao, Fabiano Magalhaes, Paola Corio,Maria Terezinha C. Sansiviero,
Electronic characterization and photocatalytic properties of CdS/TiO2 semiconductor
composite, J. of Photochemistry and Photobiology A: Chemistry 181 (2006) 152
7. Trn Th c, Nguyn Th Mai Hng, Nguyn nh Dng, V Th Bch, Nguyn Trng
Tnh v Nguyn Ngc Long, nh hng ca SiO2 v c ch t sch ca mng nanocomposit
TiO2/SiO2, Tuyn tp bo co ti Hi ngh Vt l cht rn ton quc ln th V, Vng Tu,1214/11(2007)751
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POSSIBLE ORIGINS OF FERROMAGNETISM IN Co-DOPED ZnO THIN FILMS

P.V.Hai a, P.T.Huy b, N.D.Lam a, N.T.Khoi a and L.H.Hoang a
a

International Training Institute For Materials Science, Hanoi University of Technology
Abstract: Co doped ZnO films were formed on glass and Si substrates using spin coating
technique. Their structure and magnetic properties have been examined. All of the Co-doped ZnO
films exhibit ferromagnetic behaviors at room temperature. The saturated magnetization of Codoped ZnO films on Si substrates is larger than on glass substrate. Additionally, magnetization on
both substrates increases with increasing Co content. The XRD and EDS results suggest that the
magnetic properties of Zn1-xCoxO films with x < 0.10 are due to indirect exchange interaction
between Co magnetic ions. Evidence of a link between room-temperature ferromagnetism and the
incorporation of Co like Co-metal clustering was found in the Zn1-xCoxO films (on both glass and
Si substrates) with x greater than 0.10. Our calculations based on density functional theory (DFT)
showed the consistence with experimental results.
Keyword: Diluted magnetic semicondutor, ZnO, spin-coating, Density Functional Theory (DFT).
1. Introduction
Diluted magnetic semiconductors (DMSs) have attracted considerable attention as promising
materials for spintronic devices. Following the theoretical prediction [1] and experimental
realization [2] of ferromagnetism in Co-doped ZnO, numerous reports have been published on
this system. Pulsed-laser deposition (PLD) [2-6] magnetron sputtering sol-gel coating [9,10] and
other methods have been used to fabricate Zn1-xCoxO films, and many studies seem to
substantiate the existence of a ferromagnetic phase above room temperature. Park et al. reported
ferromagnetism (FM) above room temperature [9] by using sol-gel coating, while Jin et al. found
no indication of FM by utilizing laser molecular beam epitaxy [11] This difference in results may
originate in the growth method used and/or from the growth conditions (vacuum pressure,
oxygen environment, annealing temperature , etc. . . ). In the particular case of the spin-coating
technique, the magnetic properties of the prepared films may also depend on the substrate ,
which has not been considered up to this point.
For this purpose, we present our study on structural and magnetic properties of ZnO films
doped with Co magnetic ions grown by spin-coating technique on glass and Si(111) substrates. It
was found that there is a strong dependence of magnetic property on both the Co concentration
and the substrates.
Co-doped ZnO thin films were prepared by a sol-gel coating route using
Zn(CH3COO)2.2H2O and Co(CH3COO)2.4H2O as starting precursors and a 9:1 mixture of
ethanol and diethanolamine (DEA) as a solvent. The 0.5 M coating solution was dropped and
spin coated on the substrate with 3000 rpm for 30 s in air. The precursor film specimen was dried
at 450 oC in air for 10 min. The procedures were repeated 10 times until the desired thickness of
400-450 nm of the films was reached. The Co-doped ZnO with concentrations of (0 %, 5 %, 10
% and 12 % ) on both glass and Si(111) substrates were prepared. The films were then annealed
at 4500C for 2 h in air environment. X-ray diffraction (XRD-Siemens D5000) using
monochromatic CuK radiation (=1.5406) and field emission scanning electron microcopy
(FESEM - Hitachi S4800) were used to determine the structure and surface morphology of the
Zn1-xCoxO films. The film composition was measured using energy dispersive spectroscopy
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(EDS). Vibrating sample magnetometer (VSM - PPMS 5000) was used to investigate the
magnetic properties of these samples.
The typical XRD patterns of ZnO and Co-doped ZnO films on both glass and Si(111)
substrates were shown in Fig. 1. The subsequent XRD showed that the doping does not change
the wurtzite structure of ZnO for doping concentrations below 10% and, furthermore, we could
not find any Co cluster and/or secondary phase in the XRD. In both cases, however, the intensity
of the XRD with high 2 angles (above 400 ) decreases when the Co doping concentration
increases to 12%. We remark that the adhesive ability of ZnO sol solution to the substrates
decreases with the increase of Co concentration. The crystallite size of ZnO and ZnO:Co films
calculated by the Scherrer's equation from the width of the (110) XRD peaks was around 10-20
nm.
Fig.2 shows the SEM images of the undoped ZnO thin prepared on glass and Si(111)
substrates. It can be observed that the substrate preparation significantly affects the obtained film
morphology, which is in good agreement with the previous reports [13]. It shows that ZnO film
reveals a smooth surface, consisting of nano-size crystallites having a size of 35-60 nm. It is
interesting to note that the crystallite sizes observed from SEM is different from the grain size
determined by using XRD. This confirmed that the grains seen in the SEM are the domains
formed by aggregation of nanosize crystallites.
(b)
(a)
x= 0 .1 0
x = 0 .1 2
Intensity (a.u)
Intensity (a.u)
x= 0 .1 2
x= 0 .1 0
x= 0 .0 5
x= 0 .0 5
x= 0
x= 0
30
40
50
60
2 (deg ree)
70
80
40
60
80
2 (degree)
Figure 1: X-ray diffraction patterns of ZnO and Zn1-xCoxO films on glass substrates a)
and Si(111)substrate b)
Figure 2. SEM micrographs of nanocrystalline ZnO film on

a) glass subtrate and b) Si(111) substrate.
The SEM images of the Zn on Si(111) as revealed by SEM shows that the films with Co
concentration 10% (Fig.2a) and 12% (Fig.2b) have agglomerated with particle sizes of 2050nm and 50-100nm, respectively. The increasing doping concentration leads to the trend of
increasing particle sizes.
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Figure 3. SEM micrographs of nanocrystalline Zn0.88Co0.12O film on

(a) glass substrate and b) Si(111)substrate.
A representative energy dispersive X-ray spectrum (EDS) of the Zn1-xCoxO thin films is
shown in Fig. 4 with the peaks associated with Si, Zn, O and Co in the film. The Si peaks
originate from the substrate. The Co content in the Zn1-xCoxO films was estimated to be about
4.5%, 7.8%, 14.3% on glass and 4.3%, 7.6% and 17.3% on Si(111) from a quantitative fit for x
= 5%, 10% and 12% , respectively. We believe that the EDS taken at a number of locations
throughout the specimens reveal a solid solution of Co in ZnO, with Co concentrations ranging
from 0.10 to 0.12 incorporated into the lattice.
Figure 4. EDS spectrum of the Zn films Zn0.88Co0.12O on Si substrate
Fig.5 shows MH curves of Zn1-xCoxO films with x = 5%, 10%, 12% at 300 K temperature.
The ferromagnetic hysteresis loop was observed.
Figure 5. The MH curve of Co-doped ZnO films with doping concentration

of 5%, 10% and 12% measured at 300 K shows hysteresis loops
We find that the saturation magnetization of the films increases slowly up to 10% but
increases sharply with 12% Co doping concentration sample. The values of MS are 0.26, 0.42
and 1.41 emu/cm2 for x = 0.05, 0.10 and 0.12, respectively. The increment of the saturation
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magnetization with increasing doping concentration below 10% seems to be caused by the
increasing of the concentration on Co ions. On the other hand, 12% Co doping sample shows
evidences of weak crystallization in XRD, and inhomogenous distribution in SEM. For this
sample, we suggest that the origin of the large saturation magnetization originate from the
magnetic behavior of Co ion clusters.
Total energy and electronic structure calculations of Zn1-xCoxO were performed using the
numerical basis of density functional theory as implemented in the DMol package [11, 12] .
Brillouin's zone integrations were performed by using 4x4x2 Monkhorst and Pack special point
grids. We approximated the exchange-correlation functional PWC [13] with local spin density
approximation ( LSDA). In order to achieve realistic experimental dopant concentrations we
used a periodic 2x2x2 wurtzite supercell of ZnO which consists of 32 atoms in a unit cell.
Substitution of one Zn atom and two Zn atoms by transition metal ion give a dopant
concentrations of 6.25% and 12.5%, respectively.
8
a)
b)
6
6
4
Energy (eV)
Energy (eV)
-3
2
0
Majority
Minority
-2
M ajo rity
M ino rity
-4
-6
-6
-8
-1200
-800
-4 00
400
8 00
120 0
-1200
-800
-400
400
800
1200
DO S
DOS
Figure 6. The density of states of Zn1-xCoxO as calculated from density functional theory
a) x = 0 b) x = 0.625
Fig. 6 shows that the density of state of spin up is balanced by spin down, so ZnO is nonmagnetic material, while there is no such a symmetry in ZnO:Co 6.25%, and the magnetic
moment was estimated as 2.54 B/Co. On the other hand, the magnetic moment is distributed in
far configuration and therefore the origin of ferromagnetism was caused by indirect interaction
between magnetic ions via carrier electrons.
When two Co atoms are included in a 32 atom unit cell (giving a 12.5% doping
concentration), a number of different magnetic and positional arrangement are possible. Here we
adopt two different pairs of Co positions; the 'near' configuration, in which the Co ions in the
same unit cell are separated by a single O ion, and the 'far' configuration in which they are
connected via -O-Zn-O- bonds. For both configurations we calculate the relative energies of the
ferromagnetic and antiferromagnetic spin alignments, as shown in Table 1.
Table 1. The calculated total energies and differences between FM and AFM states by 'near' and 'far'
configuration, respectively.
Configuration
Near
Far
Enear-far (eV)
EFM (eV)
EAFM (eV)
EFM-AFM (eV)
-784516.3698
-784516.1573
-0.2125
-784516.3954
-784516.1624
-0.233
0.0256
0.0051
Our calculation showed that the near configuration is more energetically favorable than the
far one by around 0.2125-0.2330 eV, suggesting that the Co ions are likely to cluster together
during growth, rather than distribute themselves evenly throughout the lattice.
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From theoretical predictions, we see that the origin of ferromagnetism was caused by
indirect interaction between magnetic ion via carrier electrons in sample doped with 6.25% of
Co ion, while Co ions are likely to cluster together to form antiferromagnetic state in 12.5%
sample. Those results had good consistence with the evidences on above experiments.
4. Conclusion
In summary, we have characterized Zn1-xCoxO thin films fabricated by solgel process and
found that at dopant concentration below 12%, no secondary phase was observed.
SEM and EDS results showed that the films are homogeneous when doped with Co at
concentration below 5%wt and particles aggregatedly distributed with Co concentration above
10%.
The Co-doped ZnO thin films showed ferromagnetism above 300 K. The theoretical
calculation confirmed that at Co concentration 6.25%, the origin of ferromagnetism is the
indirect interaction between magnetic ions, while at 12.5 %, the antiferromagnetism is favorable
Acknowledgements: This work was supported by Hanoi National University of Education
Research Project SPHN-08-184 and Asia Research Center VNU Research Project
References
1. K. Sato and H.Katayama-Yoshida, Jpn. J. Appl. Phys.39, L334 (2000).
2. K. Ueda, H. Tabata, T. Kawai, Appl. Phys. Lett. 79, 988, (2001).
3. K. Rode, A. Anane, R. Mattana, et al., J. Appl. Phys. 93, 7676 (2003).
4. W. Prellier, A. Fouchet, et al., Appl. Phys. Lett. 82, 3490 (2003).
5. S. Ramachandran, A. Tiwari, et al., Appl. Phys. Lett.84, 5255 (2003).
6. M. Venkatesan, C.B. Fitzgerald, et al., Phys. Rev. Lett. 93, 1206 (2004).
7. Y.M. Cho, W.K. Choo, H. Kim, et al., Appl. Phys. Lett.80, 3358 (2004).
8. A. Dinia, G. Schmerber, C. Meny, et al., J. Appl. Phys.97, 1208 (2005).
9. J.H. Park, M.G. Kim, H.M. Jang, et al., Appl. Phys.Lett. 84, 123 (2004).
10. H.-J. Lee, S.-Y. Jeong, C.R. Cho, et al., Appl. Phys. Lett. 81, 4020 (2002).
11. Z. Jin, T. Fukumura, M. Kawasaki, et al., Appl. Phys.Lett. 79, 3824 (2002).
12. C. Dubourdieu, M. Rosina, et al., Thin Solid Films 400,81 (2001).
13. M. Guo, P. Diao, S. Cai, J. Solid State Chem. 178, 1864 (2005).
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PREPARATION OF ZnO, ZnO:Tb3+ POWDERS

AND STUDY OF THEIR STRUCTURAL AND OPTICAL PROPERTIES
Ngo Ngoc Hoa a, Nguyen Minh Thuy a, Nguyen The Khoi a, Pham Thu Nga b,
Pham Thi Duyen a and Nguyen Thi Lam a
a)
Faculty of Physics Ha Noi National University of Education

136 Xuan Thuy Cau Giay Ha Noi.
b)
Institute of Materials Science, Viet Nam Academy of Science and Technology
Abstract: The optical material ZnO:Tb3+ contains Tb3+ ions, which have the role of
photoluminescence centre. XRD and SEM diagrams show that ZnO, and ZnO:Tb3+ samples have
zinc oxide hexagonal wurzite structure and the size of particles is about 15 nm. The absorption
spectra show that the fundamental absorption edge moves towards higher energy with increasing
of Tb3+ content. The photoluminescence excitation spectrum shows that the green emission of
ions Tb3+ has a highest intensity at excitation wavelength of 488 nm. With the excitation
wavelength of 488 nm, the photoluminescence emission spectra of ZnO : Tb3+ has characteristic
emission peaks at 543 nm, 584 nm and 619 nm originating from the intraionic transitions of Tb3+
(from 5D4 to the basic states 7Fj with j = 4, 5, 6).
1. Introduction
It is well-known that ZnO is an important semiconductor AIIBVI, n-type, with a wide bandgap
(Eg=3.3 eV, at room temperature) that has versatile practical applications in quantum optical
devices, solar cells As we have known, rare- earth ions are a special kind of photoactive
centers that have large Stokes shifts, narrow emission bandwidths and long emission lifetimes,
so it is significant to focus on the properties of rare- earth ions doped zinc oxide luminescent
materials [1,2]. In terms of energy transfer from ZnO to the RE3+ ions, RE3+ ions characteristic
luminescence will be acquired [3]. The luminescence efficiency of these materials is often
limited by the dynamics of the rare earth ion, which depends on the interactions with the host
[4]. Rare-earth ions are good candidates for luminescent centers due to their special 4f intra-shell
transitions, for example the narrow characteristic emission bands make RE-doped materials
bright colored fluorescent materials. If RE ions are incorporated in semiconductors nanocrystals,
optical properties of nanocrystals are expected to be modified remarkably; consequently REdoped nanocrystals are a new class of nanosized materials with potential application in flat panel
display.
In this study we have prepared Tb3+ doped ZnO nanocrystals by forced hydrolysis method.
We analyzed the conditions of preparation aiming to reduce the crystalline size, thereby improve
the luminescence quality of the materials.
2. Exprimental
For a typical preparation of ZnO powders, 100 ml of ethanol solution containing 2.195 g of
Zn(CH3COO).2H2O, is stirred for 3h to get the Zn-O-Zn precursor. The precursor was then
hydrolyzed in an ultrasonic bath at 00C by addition of 0.84 g LiOH.H2O powder into the flask
for 20 min. The resulted colloidal suspension was concentrated and then precipitated by adding
of hexane. The nanoparticles were redispersed in ethanol and then centrifuged and separated
from ethanol by precipitation for several times. The sample was obtained by drying the
precipitate at room temperature for a day, then annealing at 200oC for 1h.
The ZnO and ZnO:Tb3+ samples were fabricated by hydrolysis method following this
diagram (see Fig.1).
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Tb(CH3COO)3
Zn(CH3COO).2H2O
C2H5OH
Stir in 3 h
Addition of LiOH and the

precursor was hydrolyzed in
ultrasonic bath in 20 min
Addition of hexane
Centrifuged and separated

from etanol for 4 times
Annealing at
200C in 1h
The synthesis of ZnO:Tb was performed

similarly, but by adding Tb(CH3COO)3.H2O
to Zn(CH3COO).2H2O solution. Samples
with different Tb concentration have been
prepared by varying the amount of
Tb(CH3COO)3.H2O present in the precursor
solution (Tb mol %: 2.5, 5, 7.5 and 10). The
Zn2+ concentration was in each case reduced
to keep constantly the total concentration of
metal ions in solution.The microstructure and
crystallinity of the products were further
examined by scanning electron microscopy
(SEM), energy dispersive X-ray spectroscopy
(EDX) and X-ray diffraction (XRD). Optical
properties of samples were investigated using
Raman spectrum (RS), optical absorption and
photoluminescence measurements (PL).
Powder of
ZnO:Tb3+
Fig 1. Schema of the preparation of ZnO:Tb

nanomaterials

The XRD patterns of three samples
doped with the molar ratio of Tb to Zn of 0,
2.5 and 5% are shown in Figure 2. The
diffraction peaks show that the samples have
the hexagonal wurtzite structure of ZnO.
For the pure ZnO sample, the lattice
parameters are a = 3.254Ao and c =
5.2246Ao. The lattice parameters of Tbdoped ZnO are slightly larger than those of
undoped ZnO. No XRD peaks related to
Tb3+ ions were obtained in the XRD patterns
of doping samples. This can be related with
the fact that Tb3+ ions occupy Zn2+ sites or
interstitial sites in the ZnO lattice.
Fig 2. XRD patterns of ZnO:Tb with the molar
The crystalline size of the samples was
ratio of Tb to Zn: a 0%, b 2,5% and c 5%.
calculated from the Scherrer formula.
The results show that the crystalline size of the samples is approximately 12 nm.
Figure 3 shows the SEM image of ZnO:5 %Tb (top) and 7.5 %Tb (bottom). One can see that
the particle size is approximately 10 - 20 nm
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Fig. 4. Optical absorptione spectra of ZnO:Tb

with Tb concentration: a) 0%; b) 2.5% and c) 5%.
Fig. 3. SEM micrograph of ZnO:Tb with

the molar ratio of Tb to Zn: 5% (top) and
7,5%(bottom
Fig 5. Photoluminescence spectrum of the

sample ZnO:5%Tb with excitation wavelength of
325nm
Fig 6.a. PLE spectra of the same sample with the

molar ratio of Tb to Zn: 2.5%, 5% and 7.5% detected
at 544 nm
Fig.6b. Energy levels of ZnO and Tb3+ ion
The optical absorption spectra of ZnO:Tb samples are presented in Figure 4. From the
fundamental absorption edge, we can define the value of the band gap of the sample.
With increase in the molar ratio of Tb to Zn, the value of band gap of the samples ZnO:Tb
increased. Following [10] this trend can be explained by the BursteinMoss effect (the band gap
of doping material can be larger in comparison to the original host crystal due to the lowest
states of the conducting band are blocked) [2,10].
Photoluminescence PL spectrum of the sample ZnO:5%Tb with excitation wavelength of
325 nm is given in Figure 5. One can see that the emission peaks originated from Tb3+ 4f 4f
transition appear at 434, 490, 543, 587 and 620nm on the background of a broad band.
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To clarify the origins of the characteristic emission of ion Tb3+, we realized the
photoluminescence excitation (PLE) spectra of the samples ZnO:Tb with the molar ratio of Tb to
Zn: 2.5%, 5% and 7.5% detected at 544 nm. The result is presented in Figure 6.
Fig.7. PL spectra of the sample ZnO:Tb under

excitation wavelength of 488nm
Element
Weight%
Atomic%
OK
Cl K
Zn K
31.12
3.45
57.67
65.42
3.28
29.66
Tb L
7.76
1.64
Fig 8. The energy dispersive X-ray spectra of the

ZnO:5%Tb sample.
The excitation spectra have a stronger peak at 488nm and another peak at 380nm. The peak
at 380 nm represents band gap absorption of ZnO. The peak at 488 nm represents absorption
transitions in 4f energy levels of Tb3+( 5 D4 7 F6 ). It is known that electric dipole (ED)
transitions between 4f states in the free RE ions are parity forbidden, the ED transitions are
partially allowed with weak intensity while RE ions occupy lattice or interstitial sites in the
condensed matter such as ZnO, which has large absorption transition probabilities due to direct
band gap [9]. So most excited carriers trapped at Tb centers come from band-gap absorption in
ZnO matrix and a small part result from 4f-4f absorption transitions in Tb3+ ions, see following
energy schema.
The high intensity of the 488 nm peak in this PLE spectrum indicates that the excitation
efficiency at 488 nm is higher than that at 370 nm for Tb3+ emission at 544 nm. Figure 7 shows
the emission spectra of ZnO:Tb samples under the excitation of 488 nm. These spectra show the
characteristic emission peaks at 543, 585 and 620nm corresponding to the transition 5 D4 7 F j
(j= 5,4 and 3 respectively). Since the PL spectra also show a broadband emission, it is suggested
that some excited carriers on Tb3+ centers relax to surface states, which is similar to the result of
Ref. [5].
We note that the above concentration of Tb is the calculated nominal concentration in the
preparation process which can be more than the real content of Tb in the obtained ZnO:Tb
crystal. Fig. 8 shows the energy dispersive X-ray spectrum of the sample ZnO:5%Tb. From the
inserted table of results, we see that the real molar ratio of Tb is in range 1,6%, which lest more
2 times than the value of nominal content.
4. Conclusion
Tb3+ doped ZnO nanocrystals were synthesized by forced hydrolysis method. The samples
have hexagonal wurtzite structure of ZnO. The particle size is approximately 10 - 20 nm.
Emissions from both Tb3+ ions and surface states of nanocrystals were observed in
luminescence studies.
Acknowledgements: The authors would like to thank Hanoi National University of Education.
This work was supported by the Natural Science Council of Vietnam.
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References
1. Xi Chen, Bing Yan, Induced synthesis of ZnO:Tb3+ green hybrid phosphors by the assembly
of polyethylene glycol matrices, Materials Letters 61 (2007), 17071710.
2. X. M. Teng, H. T. Fan, S. S. Pan, C. Ye, and G. H. Lia, Influence of annealing on the
structural and optical properties of ZnO:Tb thin films, Journal of Applied Physics 100
(2006), 053507.
3. B. S. Barros et al., Photophysical properties of Eu3+ and Tb3+doped ZnAl2O4 phosphors
obtained by combustion reaction, J Mater Sci (2006), 47444748.
4. Lei Yang, Yan Li, Yanhe Xiao, Changhui Ye, and Lide Zhang, Synthesis of Tb3+ -doped ZnO
Nanowire Arrays Through a Facile SolGel Template Approach, Chemistry Letters Vol.34,
No.6 (2005), 828 829.
5. A S Pereira, M Peres, M J Soares, E Alves, A Neves, Synthesis, surface modification and
optical properties of Tb3+-doped ZnO nanocrystals, Nanotechnology 17 (2006), 834 839.
6. W.D.Yu et al., Self catalytic synthesis and photoluminescence of ZnO nanostructures on
ZnO nanocrystal substrates, Applied Physics Letters volume 84, number 14 (2004), 2658
2660.
7. Lin Guo and Shihe Yang, Synthesis and characterization of Poly(vinypyrrolidone)
Modified zinc oxide nanoparticles, Chem.Mater 12 (2000), 2268 2274.
8. Shu Man Liu et al., Correlated structural and optical investigation of terbium doped zinc
oxide nanocrystals, Physics Letters 271 (2000) 128 133.
9. R.Boyn, Physica Status Solidi B 148, 11(1988).
10. Z.B.Fang et al. Materials Letters 59 (2005) 2611-2614.
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SPECTROSCOPIC CHARACTERIZATION OF TOURMALINES

Le Thi Dunga, Nguyen Van Hunga, Luc Huy Hoanga, Nguyen Trong Suub,
Nguyen The Khoia and Nguyen Van Minha*
a
Center of Nano Science and Technology, and Department of Physics, Hanoi National
University of Education, 136 Xuan Thuy Road, Cau Giay, Hanoi, Vietnam
Secondary Education Department, Ministry of Education and Training, 49 Dai Co Viet, Hanoi.
E-mail: minhsp@yahoo.com
Abstract. Structure and vibrational spectra of two different tourmalines: green and pink
coloured minerals from Luc Yen, have been investigated by X-ray diffraction, EDX and
Raman spectroscopy. The band positions in the spectra of green and pink tourmalines
differ slightly due to compositional variations. Experimentally, a number of cation
oxygen vibrational modes in the Raman spectra could be observed in the low
wavenumber region 1200200 cm-1. Raman spectra of both tourmalines vs. temperature
as the evidence of order-disorder and phase transform were also analyzed. EDX and XRD
analysis permits to identify the pink and green tourmalines as Liddicoatite and Dravite,
respectively.
Key words: Tourmaline, Raman spectroscopy, structure
1. Introduction
Tourmaline is a structurally and chemically

complex borosilicate mineral with the general
formula XY3Z6Si6O18(BO3)3W4, where X = Na+,
Ca2+, K+, vacancy ( ); Y = Mg2+, Fe2+, Mn2+, Al3+,
Fe3+, Mn3+, Cr3+, Li+; Z = Al3+, Mg2+, Fe3+, Cr3+,
V3+, and W = O2, OH, F, Cl. In this structure,
corner-sharing tetrahedral form hexagonal rings
and are principally occupied by Si, although
minor amount of IVAl is found in some cases [1].
Boron is in triangular coordination and has no
known substitutes [2]. There are two types of
octahedra: the Y octahedra and the slightly
smaller, distorted Z octahedra. The Y and Z
octahedra share edges to form brucitelike
fragments, and the Z octahedra also share edges
with other Z octahedra in a helical linkage parallel
to the c axis [3]. Al, B and Na ions serve in
different ways to tie together the central cores of
composition Y3OH4Si6O21 (Fig. 1). OH groups
occupy two structurally distinct positions: the
center of the hexagonal rings and the corner of
brucite-like fragments of three edgesharing
octahedral [4]. Although extensive solid solution
is possible, the main compositional varieties in
nature are Na- and Mg-rich dravite, Na- and Ferich schorl, Ca- and Mg-rich uvite and Na- and
Li-rich elbaite [5].
Fig. 1 (a) View of the tourmaline structure

showing the relative positions of OH,
X (Na+), Y (Fe2+ or Li+, Al3+), and
Z (Al3+) sites. (b) Projection on the ab
plane of the tourmaline structure (modified
after Gonzales et al. 1988).
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Mn-rich tourmalines have been extensively investigated and the studies have focussed mainly on
composition and geological environments [6]. Burns et al. [3] described the crystal structure of a
number of Mn-rich tourmalines whose composition varies from 0.35 to 6.23 wt.% MnO.
Hawthorne and Henry [7] reviewed crystal-chemical aspects of substitutions including lighter
elements and structural features in tourmaline. The crystal chemistry of tourmalines was studied
by Camara et al. [8] and they explained the difficulties in determining lighter elements with high
accuracy in tourmalines. Such elements in tourmalines are crucial to the further understanding of
chemical substitutions and orderdisorder schemes. A recent study of crystal chemistry and
optical spectra of Mn-rich tourmaline from Austria has revealed the compositions of MnO and
FeO ~ 8.5 and 0.15 wt.%, respectively [9]. And its optical absorption spectra were attributed to
Mn3+, and Mn2+ in the visible region where as near infrared cited to ferrous ion with no
assignment of the bands. Gasharova et al. [10] reported Raman spectra of different tourmalines
in the finger print region (spectral range 1500150 cm-1) where the spectra differ in intensity
from each other studied, due to the different optical parameters. These authors treated BO and
AlO vibrational modes as combined BAlO network modes [9]. One observed mode at 750
cm-1 is attributed to the BO stretching vibration [9]. The intensity of the vibrational modes was
proven to be dependent on the polarizability tensor [9]. This paper reports the structure and
vibrational spectra of two different tourmalines; pink and green coloured minerals from Luc Yen,
Vietnam. OH stretching bands are highlighted here since they are very sensitive to crystal
structural changes. Raman spectroscopy displays a number of bands in the fingerprint region,
1200 200 cm-1, due to cationoxygen vibrational modes. The data from XRD and EDX
indicated that, the pink and green tourmalines from Luc yen belong to Liddicoatite and Dravite
types, respectively. In addition, the effect of annealing on the structure and optical properties of
two tourmalines also investigated.
2. Experiment
Intensity (a.u.)
Intensity (a.u.)
The
two
natural
tourmaline
samples
(b)
(a)
were collected from
Luc Yen mine (North
Vietnam). The samples
were fired in air at
different temperatures
(200, 400, 600, 800 and
Natural
Natural
0
940 C) for 10 mins.
940 C
940 C
Structural
20
30
40
50
60
70
20
40
60
was
characterization
2-theta (degree)
2-theta (degree)
performed by means of
Fig. 2 XRD patterns of pink (a) and green (b) tourmalines
X-ray diffraction using
before and after annealing 940 0C
a D5005 diffractometer
with CuK radiation.
Micro Raman measurements were performed in a back scattering geometry using Jobin Yvon
T64000 triple spectrometer using 514.5 nm line of an argon ion laser.
0
3. Result and discussion

3.1. Structure of tourmaline
XRD pattern of pink tourmaline was shown in Fig. 2a. The compositions of sample are also
confirmed by an energy-dispersive X-ray analysis (EDAX), which reveals the presence of C, O,
F, Na, Al, Si, Ca and some of Mn and Pb impurities (Fig. 3a and Table 1a). This result proves
Nhng
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that pink tourmaline is Liddicoatite.

However, there remains the small
amount of Mn and Pb in the
sample. This differs to tourmaline
in the same type from other areas.
The similar analysis is also applied
for green tourmaline (Fig. 2b, 3b
and table 1b) and it is clear that the
green tourmaline belongs to
Dravite. Based on this result we
can identify two tourmaline types
in Vietnam, the pink one is
Fig. 3 EDAX of pink (a) and green (b) tourmalines
Liddicoatite
(Ca(Li2Al)Al6the
(BO3)3Si6O18(OH)4),
and
remain one is Dravite (Na(Mg,V)Al6(BO3)3Si6O18(OH)4).
After annealing, the Liddicoatite
Table 1. Composition of (a) pink and (b) green tourmalines
became Al4B2O9 with orthohombic
(a)
(b)
structure, whereas the Dravite seems
Weigh Atom Element Weigh Atom
to be remained own structure but some
Element
%
%
%
%
peaks were disappeared (correspond to
0
0
C
2.31
3.59
C
8.25
12.44
d=2,9037 A ; d=1,8784 A ).
3.2. Vibrational spectroscopy
56.67
64.16
59.80
69.85
3.02
2.88
Na
2.20
1.79
The crystal structure of tourmaline

Mg
6.92
5.32
Na
1.12
0.89
belongs to the space group C3v5 R3m,
Al
14.3
9.90
Al
16.38
11
and each Bravais unit cell contains one
Si
14.17
9.43
formula unit. The OH groups are
Si
12.53
8.08
distributed into two different sites.
Ca
0.15
0.07
Ca
0.94
0.43
One, designated OH1, is located at the
V
0.16
0.06
center of hexagonal rings, and its
Mn
0.18
0.06
oxygen atom is coordinated by three Y
Pb
0.92
0.08
cations. The other site, designated
OH3, is located at the border of the rings, and one Y and two Z cations coordinate its oxygen
atom (see Fig. 1). Site symmetries of the OH1 and OH3 groups are C3v and CS, respectively.
Table 2. Correlation diagram irreducible representations, and symmetry coordinates for OH group
5
R3m, ZB = 1)
( C3v
Site Group
Point Group
C3v
C3v
A1
A1
C3v
Cs
A1
Site Group
C3v
A1
C3v
N
1
1
Activity
IR, R
S
S1 = r1
1
( r2 + r3 + r4 )
3
1
A1
IR, R
(r2 r3 r4 )
6
E
1 IR
Note: N = numbers of the internal stretching modes for each species; IR = Infrared, R =
Raman.
S1 is the symmetry species.
r1 = internal coordinates for OH1; r2, r3, r4 = internal coordinates for OH3.
OH1 = 1 A1
3OH = A1 + E
Advances
_____________________________________________________________________________________
Raman
According to the factor group
200
400
600
800
940
Natural
0
0
0
0
0
Mode
C
C
C
C
C
analysis for internal vibrations of
the OH groups (Table 2). Three
226
225
225
225
225
1 (cm-1)
IR active fundamental modes are
-1
287
2 (cm )
expected, one for the OH1 and
two for the OH3 groups.
328
3 (cm-1)
Symmetry coordinates allow an
350
4 (cm-1)
approximate description of the
-1
376
376
376
376
376
5 (cm )
fundamental modes (Table 2).
Raman spectra of green and pink
410
6 (cm-1)
tourmalines vs. temperature in
515
511
511
511
7 (cm-1)
the low wavenumber range
-1
-1
639
640
640
640
8 (cm )
1200200 cm are represented in
Fig. 4a and b. The vibrational
713
709
711
711
711
9 (cm-1)
types
are
calculated
by
1060 1061 1074
10 (cm-1)
Mihailova et al. [11,12]. Due to
-1
1234 1234 1234 1234
11(cm )
the different optical parameters
-1
of the tourmalines, their Raman
1300 1300 1302
12(cm )
spectra differ in intensity from
each other. Raman groups of
Table 4. Raman mode of green tourmaline at various
bands and their assignments are
temperatures
given in Tables 3 and 4 along
200
400
600
800
940
Mode
with a selected tourmalines
Natural
0
0
0
0
0
studied by Gasharova et al. [10].
Raman
C
C
C
C
C
There is a close relationship
-1
221
221
220
221
221
217
1 (cm )
between the data of the type
-1
275
270
269
269
264
2 (cm )
reported and the present study of
green and pink tourmalines,
372
372
372
372
370
373
3 (cm-1)
since they belong to the same
-1
452
452
452
452
452
452
4 (cm )
series of tourmalines. The first
521
521
520
521
522
5 (cm-1)
group of broad bands arise from
-1
SiO stretching, the second from
677
677
676
677
677
676
6 (cm )
BO stretching, bending modes
727
727
727
727
727
713
7 (cm-1)
of OBO and BOAl and
763,
765,7
symmetrical
SiOSi
767
767
767
8 (cm-1)
774
74
deformations. The sharp peak
with marked intensity at 375 cm1
in both the spectra of the
samples implies strong bonding of AlO. The lowest wavenumber band at 225 cm-1 originates
from MgO and a shoulder of this band at 250 cm-1 on higher wavenumber side represents O
AlO bending mode. The effect of Fe impurity is seen on this band in green tourmaline (Fig. 4b )
and its intensity is depleted. The same band is resolved in pink tourmaline into three sharp peaks
at 275, 250 and 225 cm-1. This feature differentiates green and pink tourmalines (Fig. 4a).
Comparing to previous data [13], in the present Raman results there showed some new peaks
around 287, 350, 515, 639 cm-1 for pink tourmaline and around 521, 677,726, 765 cm-1 for green
tourmaline. These are some different evidences to tourmaline from other areas
Nhng
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(b)
(a)
940 C
800 C
800 C
Intensity (a.u.)
Intensity (a.u.)
940 C
600 C
0
400 C
0
200 C
600 C
Natural
400 C
300
600
900
1200
-1
1500 200
Raman shift (cm )
400
600
800
-1
Raman Shift (cm )
Fig. 4 Raman spectra vs. temperature of pink (a) and green (b) tourmalines
4. conclusions
From the data here presented, it is concluded that:
Tourmalines from Luc Yen can identify as Liddicoatite for pink tourmaline and Dravite for green
tourmaline, respectively.
Raman spectroscopy also confirms the change in structure as samples were treated at different
temperatures. For pink tourmaline, there appears structural change when temperature around 900
0
C, and become Al4B2O9 with orthorhombic structure, whereas the Dravite seems to be remained
own symmetry but structure changed when temperature reaches 600 0C, that can related to
appearance of order-disorder in sample.
The colour of pink tourmaline became colourless and then opaque white after heating at 800 0C.
For green tourmaline, the colour is still kept until 800 0C but faded at higher temperature.
Acknowledgments : This work was supported, in part, by Basic research Program of Vietnam.
References
P.E. Rosenberg, and F.F. Foit, Mineralogist, 64, 180186 (1979).
P. Povondra, Acta Universitatis Carolinae, Geologica, 3, 223264 (1981).
P.C Burns, D.J. Mac Donald, and F. Hawthorne, Canadian Mineralogist, 32, 3141 (1994).
C.T. Gonzales, M. Fernandez, and J. Sanz, Physics and Chemistry of Minerals, 15, 452460
(1988).
5. R.V. Dietrich, The Tourmaline Group, 300 p. Van Nostrand Reinhold, New York (1985).
6. G.R. Rossman, S.M. Mattson, Am. Miner. 71 599 (1986).
7. F.C. Hawthorne, D.J. Henry, Eur. J. Miner. 11 201 (1999).
8. F. Camara, L. Ottolini, F.C. Hawthorne, Am. Miner. 87 1437 (2002).
9. A. Ertl, J.M. Hughes, S. Prowatke, G.R. Rossman, D. London, E.A. Fritz, Am. Miner. 88
1369 (2003).
10. B. Gasharova, B. Mihailova, L. Konstantinov, Eur. J. Miner. 9 935 (1997).
11. B. Mihailova, N. Zotov, M. Marinov, J. Nikolov, L. Konstantinov, J. Non-Cryst. Solids 167
265 (1994).
12. B. Mihailova, B. Gasharova, L. Konstantinov, J. Raman Spectrosc. 27 829 (1996).
13. Cristiane Castaneda, E. F. Oliveira, N. Gomes and A.C.P. Soare, American Mineralogist, 85
15031507, (2000).
1.
2.
3.
4.
Advances
_____________________________________________________________________________________
TNG HP HT NANO ZNO BNG PHNG PHP HO S DNG

VI BA LM XC TC
P.. Chunga, T.. Hia, L. P. Thoa, P.V. Hia, N.H.Hib, N.T.Khia and L.H.Honga
a)
Khoa Vt l, H S Phm H Ni, 136 Xun Thy, Cu Giy, H Ni, Vit Nam
Trung tm khoa hc vt liu, H Khoa Hc T Nhin, H Quc Gia H Ni,
334 Nguyn Tri, H Ni, Vit Nam
E-mail: phamdochung@gmail.com
b)
Tm tt: Cc ht nano ZnO c ch to bng phng php ha c h tr ca vi ba t cc tin

cht l NaOH, Zn(CH3COO)2 v Triethanolamine (TEA). nh hng ca iu kin to mu ln
cu trc v tnh cht quang ca vt liu c nghin cu bng php o nhiu x tia X, chp
nh SEM v php o ph hp th. Ph nhiu x tia X cho thy tt c cc mu u c cu trc a
tinh th dng wurtzite. Ph hp th cho thy mu ZnO thu c c cht lng tt v khng c
tm tp quang hc trong mu. Hnh thi b mt ca mu thay i theo cng sut vi ba chiu vo
v lng TEA trong mu.
1. Gii thiu
Km xit (ZnO) l bn dn c di cm rng (Eg = 3,37 eV) v nng lng lin kt exciton
ln (60 meV). Do , vt liu ZnO ha hn c ng dng ch to pin mt tri, cm bin
kh, linh kin quang in t, v cc linh kin dn sng [1-3]. Gn y, vt liu ZnO kch thc
nanomt c quan tm nhiu hn bi nhiu ng dng nh lm vt liu p in, in cc trong
sut, it pht quang, laser t ngoi nhit phng [1, 2] C nhiu phng php ch to vt
liu nano nh: bc bay xung laser, lng ng pha hi ha hc (CVD-chemical vapor deposition),
Cc phng php ny yu cu thit b kh t tin nn nhn chung cn kh thc hin ti iu
kin Vit Nam. V vy, nhiu nhm nghin cu s dng phng php sol-gel ch to vt
liu nano vi chi ph thp hn [1-4]. Nhng nm gn y, vi ba (sng cc ngn) c s dng
nh mt phng php t nhit nhm h tr, thc y cc phn ng ha hc trong phng php
sol-gel tng hp vt liu kch thc nanomt vi cht lng tt hn. y l mt phng
php c th to ra lng sn phm ln, cht lng n nh, thi gian to mu ngn, tit kim
nng lng, d dng ng dng trong sn xut qui m cng nghip v thn thin vi mi
trng [1, 4]. Trong bi bo ny, chng ti s dng phng php tng hp c s h tr ca vi ba
ch to ht nano ZnO dng bt v xc nh cht lng mu thu c thng qua vic nghin
cu cu trc cng nh tnh cht quang ca mu.
2. Thc nghim
Cc ht nano ZnO c tng hp theo cc bc sau: ha ln 25 ml dung dch km axtat 0,2
M vi 25 ml dung dch NaOH 0,4 M. Sau khi dung dch trn c khuy t trong mt vi pht,
dung dch 1,2 ml triethanolamine (TEA) c nh t t vo. Tip tc khuy trong 10 pht, ta thu
c mt dng dch c mu trng c. Dung dch thu c trn c chiu vi ba vi cng
sut 300W v thi gian chiu t 5 pht n 20 pht. Kt thc qu trnh chiu vi ba, kt ta trong
bnh c thu li bng phng php quay li tm. Hn hp sau c nung () trong 2h nhit
600oC. Mu thu c sau khi nung c dng bt mu trng. Cc mu nghin cu c chia
thnh hai h: c s dng TEA lm dung mi v khng s dng TEA. Chi tit v iu kin ch
to ca cc mu c lit k trn bng 1. Ph nhiu x tia X ca mu c o trn h my
D5005-SIEMENS s dng bc x K ca ng vi Cu = 1,54056 . nh SEM ca mu c
chp trn my JMS 5410 Jeol. ph hp th ca mu bt ZnO c thc hin trn Ph k Jasco
V-670.
Nhng
_____________________________________________________________________________________
Bng 1. Cc mu c ch to v nghin cu trong bi bo.
K hiu mu
S1
S2
S3
S4
N1
N2
N3
N4
Triethanolamine (TEA) (ml)
1,2
1,2
1,2
1,2
Thi gian chiu vi ba (pht)
10
15
20
10
15
20
3. Kt qu v tho lun
Kt qu o ph nhiu x tia X ca mu S1 c trnh by trn hnh 1. Trn ph c 9 nh
nhiu x. Cc nh ph u c tnh i xng cao, chng t mu kt tinh tt. So snh vi th
chun s 36-1451 ca pha wurtzite, ta thy rng cc nh nhiu x thu c u trng khp v v
tr v ph hp v cng tng i vi cc nh ph chun. iu ny cho thy mu thu c
hon ton n pha v c cu trc wurtzite. Cc nh nhiu x c xc nh ln lt l: (100),
(002), (101), (102), (110), (103), (200), (112), (201).
Hnh 1: Ph nhiu x tia X ca bt ZnO c

chiu vi cng sut 300 W trong 5 pht (S1)
Hnh 2: Ph nhiu x tia X ca mu S1 (a), S2 (b),

S3 (c) v S4 (d).
Ph nhiu x tia X ca cc mu S1S4 c tng hp trn hnh 2. Cc kt qu ny cho thy

cc mu ZnO thu c u c ph nhiu x tia X ging nhau v s lng v v tr nh ph. Nh
vy cc mu u c cu trc lc gic wurtzite v kt tinh tt vi thi gian chiu vi ba trn 5
pht. Thi gian chiu vi ba khng lm nh
hng n qu trnh kt tinh ca mu. S dng
kt qu o ph nhiu x tia X ca mu, t v tr
ca cc nh (100) v (002) ta tnh c kch
thc mng ca pha wurtzite l a = 3,25 v c
= 5,20 . Cc gi tr ny khng khc bit nhiu
so vi ca mng chun, do mu nghin cu
kh ng u v c cu trc tinh th tt.
Ph nhiu x tia X ca cc mu N1N4 c
trnh by trn hnh 3 cho thy v tr v s lng
cc nh nhiu x hon ton ging nh ph
nhiu x tia X ca cc mu S1S4. Nh vy cc
mu ZnO thu c khi khng cho thm TEA
trong qu trnh tng hp c cu trc tinh th
Hnh 3: Ph nhiu x tia X ca mu

N1 (a), N2 (b), N3 (c) v N4 (d).
Advances
_____________________________________________________________________________________
Hnh 4. nh SEM ca mu N1 (a), N2(b), S1 (c), S2 (d), S3 (e) v S4 (f).
Hnh 5. Ph hp th ca mu
S1, S2, S3 v S4.
Hnh 6. o hm hp th theo bc
sng nh sng chiu ti ca mu S1.
Nhng
_____________________________________________________________________________________
dng lc gic wurtzite. Tuy nhin, cng tng i ca cc nh ph (100), (002), (101),
(102), (110), (103), (112) l khng ging so vi ph nhiu x tia X ca cc mu S1S4. iu
ny chng t rng khi khng c TEA, mu ZnO thu c mc hn n v kt tinh khng c
phng u tin. Nh vy vic cho thm TEA gip thu c sn phm c cu trc tinh th tt
hn.
Hnh 4 trnh by nh SEM ca cc mu N1, N2 v S1S4. Hnh 4.c-f cho thy h mu S1S4
c cc ht ZnO dng hnh cu ng u v kch thc trung bnh ca cc ht l kh ln. Kch
thc ht trung bnh ca mu S1 (4.c), S2 (4.d) khong 120 nm v ca mu S3 (4.e), S4 (4.f) l
khong 80 nm. So vi kt qu nghin cu ca N. F. Hamedani v F. Farzaneh [4] kch thc ht
ZnO thu c trong bi bo ny ln gp 2 n 3 ln, nhng ng u v kch thc th tng
ng. Nh vy, mu c thi gian chiu vi ba di hn, th kch thc ht c gim nhng khng
ng k. Hnh 4.a v 4.b cho thy, b mt ca cc mu N1, N2 c cc ht hnh cu xen ln vi
nhiu mnh dng khi hoc que. Kt qu ny cho thy cc mu N1N4 c qu trnh to ht xy
ra khng hon ton do vy vn cn tn ti nhiu mnh vt liu dng khi v que. V vy, ph
nhiu x tia X ca cc mu ny khng th hin r phng kt tinh u tin l kt qu hp l. Kt
qu ny chng t TEA c tc dng phn tn vt liu v gip qu trnh to ht ZnO din ra ng
u hn.
Ph hp th quang hc ca cc mu c trnh by trn hnh 5. Kt qu cho thy, cc mu
ch c mt b hp th c bn ng vi hp th gia cc di (vng-vng) m khng c nh hp
th ph ca cc tm quang hc. iu ny chng t rng mu thu c khng cha cc tm tp
quang hc. Vic s dng TEA khng lm thay i nhiu tnh cht quang ca mu. hnh 6 biu
din s ph thuc ca o hm hp th theo bc sng ca mu S1.
Hnh 6 cho thy trn ph c mt nh duy nht ti bc sng 381 nm. y l bc sng kch
thch gy ra chuyn mc vng-vng mnh nht trong mu (Hon ton khng ng!!). Ch cn
da vo bin hp th l xc nh c Eg. Khng cn ly o hm. Da vo kt qu ny, chng
ti xc nh c b rng vng cm ca mu nghin cu l Eg = 3,26 eV. Kt qu thu c l
ph hp vi cng b ca Yong Cheol Hong v cc ng nghip cng nh nhiu nghin cu khc
[1, 3, 4].
4. Kt lun
Bt nano ZnO c ch to thnh cng bng phng php sol-gel c h tr ca vi ba.
Mu thu c c cu trc wurtzite v kt tinh rt tt. TEA c tc dng lm b mt ca mu ng
u v tinh th nh hng tt theo cc phng u tin ca cu trc wurtzite. Cc mu S1S4 c
ng knh ht trung bnh t 80 n 120 nm. Kch thc ht gim khi tng thi gian chiu vi ba.
Ph hp th ca mu ch ra rng mu ZnO ch to c l tinh khit v khng c tm tp quang
hc trong mu. B rng di cm ca mu l 3,26 eV thu c t kt qu o ph hp th. Cc kt
qu nghin cu cho thy mu c ch to bng phng php sol-gel s dng vi ba lm xc tc
c thi gian ch to ngn hn v cho cht lng tt hn so vi phng php sol-gel thng
thng.
Li cm n
Cc tc gi chn thnh cm n s h tr kinh ph ca Trung tm H t Nghin cu Chu
& Qu gio dc Cao hc Hn quc v ti nghin cu khoa hc m s SPHN-08-184 cp
Trng i hc S phm H Ni
Ti liu tham kho
1. Yong Cheol hong, Jong Hun Kim and Han Sup Uhm, Japanese Journal of Applied Physics 45
(2006), 5940-5944
Advances
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2. Xian-Luo Hu, Ying-Jie Zhu, Shi-Wei Wang, Materials Chemistry and Physics 88 (2004) 421426
3. Jieming Cao et al., Chemistry Letters 33 (2004), 1332-1333
4. N. Faal Hamedani and F. Farzaneh, Journal of Sciences, Islamic Pepublic of Iran 17(3)
(2006), 231-23.
Nhng
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NH HNG CA DUNG MI LN TNH CHT CA VT LIU ZnS:Cu,Al

C CH TO BNG PHNG PHP NG KT TA
Nguyn Bch Phng a, Nguyn Minh Thyb
a)
Khoa Vt l, Trng i hc s phm ng Thp

Khoa Vt l, Trng i hc S phm H Ni
b)
Tm tt: Bt ZnS:Cu,Al c ch to bng phng php ng kt ta vi cc dung mi

khc nhau l ethanol v formamide. Cc mu c kho st bng nhiu x tia X, SEM, DSC
v hunh quang. Mu bt cho di pht quang rng trong vng kh kin 410 590 nm v b
nh hng bi nhit . S nh hng ca dung mi ln cc tnh cht pht quang ca mu
cng c nghin cu.
1. M u
ZnS l vt liu bn dn thuc nhm AIIBVI c cc nh khoa hc quan tm nghin cu t
lu bi nhng tnh cht c bit ca n nh: vng cm thng, nng lng vng cm ln (Eg =
3,7eV), c kh nng t kch hot v pht quang trong di rng t vng gn cc tm (UV) n
vng gn hng ngoi (IR) [1] v c ng dng rng ri trong vic ch to cc linh kin in t,
pin mt tri, thit b in hunh quang [2]
Khi ZnS c pha mt lng nh tp kim loi th n c th pht ra nh sng c trng cho
ion tp pha vo. Khi pha cc tp cht Cu, Al vo tinh th ZnS th Cu ng vai tr l tp cht
axepto cn Al ng vai tr l cc cc dono.Ngi ta cho rng trong trng tinh th ca 4 ion S2-,
Cu2+ (3d9) th vo v tr ca Zn2+ trng thi c bn b tch thnh hai mc t2 (ng vi nng
lng cao hn) v mc e (ng vi nng lng thp hn). Cn i vi cc dono Al, trong tinh th
ZnS, ion Al3+ t hp cng vi cc nt khuyt v sai hng ring ca mng tinh th hnh thnh nn
cc mc dono nng v su nm trong vng cm. Di xanh lc c ngun gc t s ti hp ca
in t b by ti mc dono nng vi l khuyt Cu2+ ti mc t2. Di l s ti hp ca in t
mc dono nh x su vi l khuyt t2. Nhng tnh cht th v ca ZnS:Cu,Al hin ang c
ng dng rng ri trong cng ngh ch to mn hnh hin th hay trong cc thit b in hunh
quang.
Vng dn
Mc dono nng
Mc dono su
xanh da tri
xanh lc
da cam
t2 ca Cu2+
e ca Cu2+
Vng ha tr
S chuyn mc nng lng ca ZnS:Cu,Al.

Trong nhng nm gn dy, vt liu ZnS nano tinh th c nhiu tnh cht mi m nh hiu
sut pht quang cao gp nhiu ln v cc di pht quang c nhng quy lut khc vi mu khi
m ra kh nng ng dng ln hn nn ZnS vn tip tc c nghin cu.
Trong bo co ny, chng ti trnh by nh hng ca dung mi, nhit ln cu trc, kch
thc ht v tnh cht pht quang ca vt liu ZnS:Cu,Al c ch to bng phng php ng
kt ta
Advances
_____________________________________________________________________________________
2. Thc nghim
2.1. Ch to mu bt
Mu bt ZnS:Cu,Al c ch to bng phng php ng kt ta vi cc ho cht ban u
l: ZnCl2, CuCl2, AlCl3, dung dch (NH4)2S 38%. Nng tp cht kch hot Cu l 0,025% v Al
l 0,05%. Dng cc dung mi l ethanol (C2H5OH 99%) v formamide ( CH3NO 99,99%) ha
cc mui trn theo t phn tnh ton ri trn u. Tin hnh lc ra cc kt ta v sy nhit
800C trong mi trng thi kh Ar trong 6h. Nung mu cc nhit khc nhau t 600 n
7500C trong mi trng Ar.
2.2. Cc phng php kho st mu
Cc mu bt c kho st cu trc bng gin nhiu x tia X trn mySiemen D5005,
kho st hnh thi b mt bng nh hin vi in t qut (SEM), ph TG, DSC. Tnh cht hunh
quang ca cc mu c kho st bng ph hunh quang.
3.
Kt qu v tho lun
Trn ph nhiu x tia X ca

cc mu cho thy bt
ZnS:Cu,Al (hnh 1), dng dung
mi ethanol cc nhit
khc nhau t 6000C 7500C,
trong mi trng kh Ar c cu
trc lc gic Wurtzite 2H v
Wurtzite 8H, l mt trong
nhng cu trc tinh th c trng ca bn dn ZnS thng xut
hin nhit cao. i chiu
vi th chun, cc nh tng
ng vi ch s Miller sau: (100),
(002), (101), (110), (103),
(112).Tuy nhin, ngoi cu trc
lc gic c trng ca ZnS cn xut hin cu trc Zincite c trng ca ZnO. iu ny c th l
do bung mu cha tht kn hoc do kh Ar cha sch khng kh c ht kh oxi nn mt phn
ZnS b oxi ha nhit cao chuyn thnh ZnO.
T ph tia X, ta dng cng thc Debye - Scherrer nh gi ng knh trung bnh ca ht
tinh th; vi mu nung 6000C dtb 100 nm v mu nung 7000C dtb 150 nm. Kt qu
ny cho thy nhit cng tng th mu kt tinh tt v kch thc ht cng tng. nh SEM
(2a,2b) cho ta hnh nh ht kh ng u v ph hp vi kt qu tnh ton trn.
Khi thay dung mi ethanol bng dung mi formamide, t ph XRD ca mu bt ZnS:Cu,Al ti
6000C v 7000C (hnh 3a,3b) chng ti thy trong mu tn ti c hai cu trc wurtzite v
sphalerite, cu trc Zincite c trng ca ZnO hnh thnh rt t. Kch thc ht tinh th tnh theo
cng thc Scherrer vi mu nung 6000C, dtb 30 nm, mu nung 7000C, dtb 50 nm. Mu
dng dung mi formamide c kch thc nh hn (gim gn mt na) so vi mu dng dung mi
ethanol, iu ny cho thy dung mi formamide c th dng lm cht hm kch thc ht. Ta c
th gii thch nh sau: khi cc vt liu hnh thnh, dung mi s bao quanh chng ngn s to
khi. i vi formamide, cc ht to thnh d phn tn trong dung mi, kh nng dung mi bao
bc cc ht tt hn do khng ch kch thc ht hiu qu nht. Theo cc kt qu nghin cu khi
kch thc ht gim ti vi chc nm, vt liu ZnS c xu th tn ti pha cu trc sphalerite v vy
trong mu tn ti ng thi hai cu trc ca ZnS. Mu dng formamide khi nung nhit cao
s oxi ho to thnh ZnO kh xy ra hn so vi mu dng ethanol, chng ti vn cha l gii
c hin tng ny.
Nhng
_____________________________________________________________________________________
Hnh 2a: Anh SEM ca mu bt ZnS:Cu,Al

ti 6000C.
Hnh 2b: Anh SEM ca mu bt ZnS:Cu,Al

ti 7000C.
Hnh 3a: Ph XRD ca mu ZnS:Cu,Al dng

dung mi formamide ti 6000C
Hnh 3b: Ph XRD ca mu ZnS:Cu,Al dng dung

mi formamide ti 7000C.
Kt qu nh SEM (hnh 4a,4b) mt ln na cho thy dung mi formamide khng ch kch

thc ht rt hiu qu. Ht mu ZnS:Cu,Al dng dung mi formamide ti 7000C l hnh cu,
ng u, kch thc ht c 50 nm.
Hnh 4a: nh SEM ca mu ZnS:Cu,Al dng dung

mi ethanol ti 7000C.
Hnh 4b: nh SEM ca mu ZnS:Cu,Al dng dung

mi formamide ti 7000C.
Vi cc nghin cu gn y, nhit chuyn pha gia sphalerite v wurtzite trong ZnS tinh
khit khong 10200C nhng nhit ny s thay i, ph thuc vo cht pha tp vo ZnS v mi
trng nhit. Vi nng Cu 0.025% cc mu bt ZnS: Cu,Al cho nhit chuyn pha
wurzite (tn ti bn) TF thp. Kt qu o DSC, TG ca mu dng dung mi ethanol vi tc
gia nhit l 200C /pht trong mi trng Ar ( hnh 4).
Advances
_____________________________________________________________________________________
T kt qu ca ph DSC, nh thu nhit

TCH = 559.790C (ti nhit ny mu nhn
thm nhit chuyn t pha sphalerite sang
wurtzite) v nh ta nhit TF = 756.970C
(ti nhit ny mu hon ton kt tinh ti
pha wurtzite). Do , chng ti chn
nhit cho mu t 6000C 7500C nu
nhit di 6000C th mu d ht m, bo
qun kh v trn 7500C th kch thc ht s
ln.
Kt qu o hunh quang ca cc mu
bt ZnS:Cu,Al ti cc nhit 6000C,
7000C v 7500C dng dung mi ethanol
Hnh 5: Ph hunh quang ca mu
c kch thch bi bc x 325 nm, o ti
ZnS:Cu,Al lm bng dung mi ethanol
nhit phng vi thi gian chiu sng l
6000C, 7000C, 7500C.
100 ms c trnh by nh hnh 5.
T ph hunh quang chng ti c nhn xt cc mu u pht quang mnh trong vng kh
kin c bc sng t 470 nm - 620 nm thng ng vi cc bc x xanh da tri, xanh lc v da
cam, hnh dng ph khng i xng v cc nh ng vi nhit cng cao th lch v pha bc
sng . Ngun gc ca cc bc x ny l s chuyn di dono - axepto c cp nh trn.
Tuy nhin cc mc dono v axepto thc t u b nho ra khng ch mt hay hai mc m l
mt di cc mc nm gn nhau do s c nhiu chuyn di bc x ca cc cp dono v axepto.
V vy ph hunh quang l mt di rng bao gm rt nhiu nh gn nh lin tc v mang tnh
bt i xng. T nhng kt qu ca cc nghin cu trc, chng ti d on s bt i xng ca
ph hunh quang c th l s chng chp ca hai nh pht quang.
Hnh 6: ng fit theo ng Gaussian cc nh pht quang ca cc mu ethanol

nhit 6000C, 7500C.
T cc ng fit (hnh 6), ta c th nhn xt nh

sau: nh sng xanh dch v pha nng lng thp,
nh sng vng da cam dch chuyn v pha nng
lng cao khi nhit tng, kt qu ny ph hp vi
cc nghin cu trc [4]. iu ny c th gii thch
nh sau: khi nhit tng th di dn v by nng
dch chuyn v pha nng lng thp, do dch
chuyn ng vi nh sng xanh s dch v pha nng
lng thp. Cn i vi bc x vng da cam, bc x
ny ph thuc vo v tr ca cc tm hunh quang;
khi nhit tng, mc dao ng mnh hn ca trng
thi kch thch s b chim nn kt qu l bc x
vng da cam s dch chuyn v pha nng lng cao
[4].
Hnh7:7:Ph
Ph hunh
hunh quang
Hnh
quangca
cacc
ccmu
mu
lmlam
bng
dung
mi mi
formamide
6000C,
bng
dung
forrmamide
0
7000C, 750
600CoC, 700oC, 750oC
Nhng
_____________________________________________________________________________________
Hnh 8: ng fit theo ng Gaussian cc nh pht quang ca cc mu formamide

nhit 6000C, 7500C.
Kt qu o hunh quang ca cc mu bt
ZnS:Cu,Al ti cc nhit 6000C, 7000C v
7500C s dng dung mi formamide cng iu
kin nh vi cc mu ethanol c trnh by nh
hnh 7.
Cc mu u pht quang mnh trong vng kh
kin v tri rng hn so vi h mu ethanol. Theo
kt qu chp XRD, h mu dng dung mi
formamide ng tn ti 2 cu trc sphalerite v
wurtzite nn vi ph khng i xng ta c th d
on nh nhn c l do s chng chp ca 3
Hnh 9: Ph hunh quang ca cc mu
nh ng vi 3 bc x: xanh l cy, vng da cam v
N - 7500C (ethanol) ,
(thm mt nh do cu trc sphalerite to thnh)
F - 7500C (formamide).
[5]. Qua ng fit ca cc mu (hnh 8) bc x
xanh, vng da cam v dch chuyn theo ng qui lut ca h mu ethanol.
Ngoi ra ta nhn thy khi nhit tng th cng nh sng tng. iu ny c
Shinoya gii thch: nh sng l do s kt hp ca l trng mc su S- v ion Cu2+. Khi nhit
tng th nng l trng S- tng v s kt hp ca S- v Cu2+ cng nhiu dn n cng
nh sng tng.
So snh s pht quang cc mu nhit 7500C trong mi trng kh Ar nhng s dng
hai dung mi ethanol v formamide nh hnh 9.
Ta thy mu F-750 c vng pht quang rng hn so vi mu N-750, xu hng m rng v
pha bc sng di. Ph hunh quang ca mu F -750 c s bt i xng hn so vi mu N-750,
v trong mu F-750 tn ti 2 cu trc sphalerite v wurtzite do trong ph hunh quang s tn
ti nhiu nh hn mu N-750. nh bc x l do s chuyn di tng i t VS di ho
tr hoc t hp dono - axepto (D - A) t VS VZn [5].
Mt khc ta thy cng pht quang ca mu F-750 mnh hn nhiu so vi mu N-750;
iu ny c th do kch thc ht trong mu F-750 nh hn N-750 nn s pht quang mnh hn
[6, 7, 8, 9].
4. Kt lun
Bt hunh quang ZnS:Cu,Al c ch to thnh cng bng phng php ng kt ta.
Mu cho pha cu trc v cng pht quang tt nht l mu dng dung mi formamide v ti
nhit 7500C, pht hunh quang tt vng bc sng 410-590 nm v c th c dng lm
vt liu nn phc v cc nghin cu tip sau.
Li cm n: Cc tc gi chn thnh cm n trng HSP H ni, Trng HSP ng thp v
cc ng nghip to iu kin thun li cho vic tin hnh nghin cu ny.
Advances
_____________________________________________________________________________________
Ti liu tham kho

1. Agreeth A.Bol, Joke Ferwerda, Jaap A.Bergwerff, Andries MeijerinK (2002), Luminescence
of nanocrystalline ZnS:Cu2+, Luminescence 99, pp 325-334
2. Tadao Sugimato, Sixin Wu, Hiroyuki Itoh, Takashi Kojima (2003), Well-defined fluorescent
particles of ZnS:Cu(I) preparation and effects of annealing, Journal of Collid and Interface
Science 257, pp 47-55.
3. Mingwen Wang, Lingdong Sun, Xuefeng Fu, Chunsheng Liao, Chunhua Yan (2000),
Synthesis and optical properties of ZnS:Cu(II) nanoparticles, Solid State Communications
115, pp 493-496.
4. Lai Qui, (2003), Synthesis and characterization of ZnS:Cu,Al phosphor prepared by a
chemical solution method, Journal of Luminescence 104, pp 261-266.
5. J.C.Lee, D.H.Park (2003), Self defects properties of ZnS with sintering temperature,
Materials Letters 57, pp 2872-2878.
6. Duong Ngoc Huyen, Nguyen Truong Luyen (2006), Effect of concentration of Cu doping on
cubic hexagonal transition in ZnS, Proceedings of the 1st IWOFM 3rd IWONN Conference,
Ha Long, pp 635-637.
7. Th Sm, Nguyn Minh Thy, Nguyn Th Khi (2006), Ch to v nghin cu tnh cht
ca vt liu ZnS:Cu,Al, Bo co hi ngh quang hc quang ph ton quc ln th IV, Cn
Th.
8. Xiaobo Zhang, Hongwei Song, Lixin Yu, Tie Wang, Xingguang Ren, Xianggui Kong,
Yuhua Xie, Xiaojun Wang (2006), Surface states and its influence on luminescence in ZnS
nanocrystallite, Journal of Luminescence 118, pp 251-256.
9. A. Ishizumi, C.W.White, Y.Kanemitsu (2005), Photoluminescence properties of impurity doped ZnS nanocrystals fabricated by sequential ion implantation, Physica 26, pp 24-27.
Nhng
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NGHIN CU CH TO BT PHT QUANG Zn1-xAlxS BNG PHNG PHP

GM V KHO ST MT S TNH CHT QUANG CA CHNG
Phm Vn Bn, Phan Trng Tu, Nguyn Th Thanh
Khoa Vt l,Trng i hc Khoa hc T nhin, i hc Quc gia H ni
Tm tt: Cc bt pht quang Zn1-xAlxS (0 x 10 mol%) c ch to bng phng php gm
vi nhit nung t 700oC n 1100oC. nh SEM cho thy cc ht pthn b ng u, kch
thc ht vo khong 8 m . Ph pht quang ca chng ph thuc vo bc sng kch thch. Khi
kch thch bng cc bc sng 325 nm ca laser He-Cd v 337 nm ca laser N2, trong ph pht
quang ca Zn1-xAlxS 300 K xut hin mt di rng c cng ln vi cc i tng ng
khong 467 nm v 440 nm. Di 467 nm l do s dch chuyn bc x ca cc in t t do vng
dn xung cc mc acceptor trong acceptor l cc nt khuyt ca Zn lin kt vi Al [VZn-Al];
cn di 440 nm c trng cho s ti hp bc x ca cc cp donor-acceptor trong donor l Al,
cn acceptor l cc nt khuyt ca Zn lin kt vi Cl [VZn-Cl]. nh hng ca nng Al, nhit
nung, thi gian nung v mt cng sut kch thch ln cu trc tinh th, ph pht quang
ca Zn1-xAlxS cng c nghin cu.
1. Gii thiu
ZnS l hp cht bn dn vng cm rng (Eg = 3.67 eV 300 K) c ng dng nhiu trong
cc dng c quang in t, cc thit b hin th Trong vng nhn thy, ph pht quang ca ZnS
300 K gm hai di c bn: di mu xanh lam khong 460 - 480 nm v di xanh l cy
khong 520 - 540 nm. Cc di pht quang ny c trng cho cc nt khuyt ca Zn lin kt vi
Cl [VZn Cl] hoc Al [VZn-Al] v mt s tp cht khng kim tra c trong ZnS [1,2].
Ph pht quang ca ZnS pha Al gm cc di: SAL 370 nm, IB 425 - 428 nm v SA 460
- 474 nm. Di SAL c trng cho s ti hp bc x ca exciton lin kt trn cc tm cch ly in
hoc ca cc in t - l trng ca cc cp donor nng v tm cch ly in. Di IB v SA c
trng cho s ti hp bc x ca cc in t vng dn vi cc l trng mc acceptor v ca
cc cp donor acceptor lin quan n Cl, Al v cc nt khuyt ca Zn lin kt vi Cl [VZn Cl]
hoc Al [VZn Al] [ 3,5].
Khi tng nng Al, cng di SA tng dn, t cc i ri sau gim dn. Cc ion
3+
Al nm l lng trong mng tinh th ZnS ng vai tr nh cc donor, cn Al lin kt vi nt
khuyt ca Zn [VZn-Al] ng vai tr nh cc acceptor to ra cc by bt in t. V th khi pha
tp Al vi nng thch hp s lm tng hiu sut pht quang ca ZnS do tng xc sut ti hp
DAP [6]. Trong cng trnh ny, bng phng php gm chng ti ch ng pha tp Al vo
ZnS vi cc nng khc nhau v nghin cu nh hng ca nng Al, nhit ,thi
gian nung n ph pht quang ca ZnS, t lm sng t thm mt vi c ch ti hp bc x
trong ZnS:Al.
2. Quy trnh ch to mu v thit b thc nghim
2.1. Quy trnh ch to Zn1-xAlxS (ZnS:Al) bng phng php gm
Cc mu Zn1-xAlxS (0 x 10 mol%) c ch to bng phng php gm trong khng
kh, trong Al c a vo ZnS di dng mui AlCl3.6H2O theo quy trnh nh sau: u tin
sy kh ZnS vi thi gian 30 pht trong l sy chn khng (khong 80oC), sau cn, trn
AlCl3.6H2O vi ZnS theo cc nng x = 0; 0.3; 0.7; 1.0; 1.5; 2.2; 8.0; 10 mol%. Tip theo,
hn hp c nghin trong 4 gi ri c nung nhit t 700oC n 1100oC, trong thi gian
t 5 pht n 30 pht v ngui t nhin.
Advances
_____________________________________________________________________________________
2.2. Thit b thc nghim

Php phn tch gin nhiu x tia X (XRD) ca cc mu c thc hin trn my D8
Advance Bruker dng bc x CuK ( = 1.5046 Ao, 2 =10o-70o). Kch thc ht tinh th v
ph tn sc nng lng (EDS) ca cc mu bt c ghi trn my JEOL5410-VL. Ph pht
quang (PL) ghi ti 300 K trn ph k Acton SpectraPro 2300i dng bc sng kch thch 325
nm ca laser He-Cd. Ph kch thch pht quang c ghi trn ph k Jobin-Yvon Fluorolog FL322 dng bc x lin tc ca n xenon 450W.
3. Kt qu v bin lun
3.1. Cu trc tinh th, nh SEM v ph EDS ca ZnS:Al
(013)
(a)
(112)
(110)
(011)
(010)
(002)
Gin XRD ca ZnS (hnh 1a) cho thy mu kt tinh dng a tinh th, ch yu c cu
trc lc gic Wurtzite 2-H ng vi nhm khng gian P63mc v cc hng s mng a = b = 3.81
Ao, c = 6.23 Ao. Cc mt phn x chnh l: (010), (002), (011), (110), (013) v (112).
(b)
H.2. nh SEM ca ZnS (a) v ZnS:Al ( x = 1.5

mol%) (b) nung 9000 C trong 15 pht
H.1. Gin XRD ca ZnS (a) v ZnS:Al ( x

= 1.5 mol%) (b) nung 900oC trong 15 pht
cps
cps
Khi pha Al vo ZnS (x = 1.5 mol%) (hnh 1b) hng s mng a, b hu nh khng i nhng
hng s mng c b gim (c 6.21Ao). iu ny chng t Al c nh hng ln cu trc tinh th
ca ZnS. Cc ion Al3+ c th thay th v tr ca cc ion Zn2+ trong mng tinh th ZnS. Hng s
mng b gim i l do bn knh ca ion Al3+ (0.54 Ao) nh hn bn knh ion Zn2+ (0.74 Ao).
Hnh 2 l nh SEM ca ZnS v ZnS:Al (x = 1.5 mol%) nung 9000 C trong 15 pht. Cc ht
c kch thc trung bnh khong 8 m v phn b tng i ng u. Ph EDS ca ZnS,
ZnS:Al (x = 1.5 mol %) nung ti 900o trong 15 pht cho thy trong ZnS xut hin cc vch c
trng cho cc nguyn t Zn, S, O (hnh 3) cn trong ZnS:Al cn xut hin thm vch c trng
cho Al vi t l phn trm nguyn t cc nguyn t Zn, S, Al, O tng ng l 48.76 %, 45.78
%, 0.71 %, 4.75% (hnh 4).
S
keV
H.3. Ph EDS ca ZnS nung 9000C

trong 15 pht
keV
H.4. Ph EDS ca vi ZnS:Al ( x = 1.5 mol%)

nung 9000 trong 15 pht
Nhng
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3.2. Ph kch thch pht quang ca ZnS:Al

Hnh 5 l ph kch thch pht quang ca
ZnS:Al (x = 1.5 mol%) 300 K ly ti 512 nm khi
qut bc sng t 320 nm n 400 nm. Ph kch
thch ny xut hin mt nh 336 nm (3.687 eV),
gi tr ny ph hp vi rng vng cm ca ZnS
(3.670 eV 300 K). V th chng ti cho rng
nh 336 nm c trng cho s hp th vng vng ca ZnS[2].
3.3. Ph pht quang ca ZnS:Al
a. S ph thuc ph pht quang ca ZnS:Al vo

nng Al
a.
b.
c.
d.
e.
f.
g.
h.
H.5. Ph kch thch pht quang m 512

nm ca ZnS:Al (x =1.5 mol%) 300K
x=0
x = 0.3 mol %
x = 0.7 mol %
x = 1.0 mol %
x = 1.5 mol %
x = 2.2 mol %
x = 8.0 mol %
x = 10 mol %
H.6. Ph pht quang ca ZnS:Al 300 K vi

nng Al thay i: 0 x 10 mol%
H.7. S ph thuc ca cng nh 467nm

vo nng Al
Hnh 6 l ph pht quang ca ZnS:Al (0 x 10 mol%) 300 K c nung 9000 C trong

15 pht khi kch thch bng bc x bc sng 325 nm ca laser He-Cd. Trong ph pht quang
ca ZnS (hnh 6a) xut hin hai di rng: di mu xanh lam khong 467 nm v di mu xanh l
cy khong 533 nm c cng gn bng nhau, chng khng hin r thnh nh v b ha vo
nhau thnh mt di rng. Hai di ny c trng cho cc nt khuyt ca Zn lin kt vi Al [VZn
Al] hoc Cl [VZn-Cl] v mt s tp cht trong ZnS nh Cu,[1,2].
Khi pha tp Al vo ZnS vi nng x = 0.3 mol% trong ph pht quang ca ZnS:Al vn tn
ti hai di trn (hnh 6b). Tuy nhin, di 467 nm c cng ln hn v hin r thnh nh. Khi
tng nng Al n 10 mol %, cng di ny cng tng dn, t cc i ti
x = 1.5
mol% (hnh 6e) nhng v tr ca n khng thay i. iu ny chng t di 467 nm lin quan n
Al, cn di 533 nm lin quan n tp no c trong ZnS. y, Al lin kt vi nt khuyt ca
Zn [VZn-Al] ng vai tr l tm acceptor su trong c ch ti hp bc x ca di 467 nm.V th
khi tng nng Al th s tm acceptor cng tng, lm cho xc sut ti hp in t t vng dn
xung cc mc acceptor ny cng tng ln, dn n cng pht quang ca di 467 nm tng
ln. Khi tip tc tng nng Al (x > 1.5 mol%) cng di 467 nm gim i (hnh 6e,f,g,h)
nhng v tr ca n vn khng thay i. y chnh l hin tng tt pht quang v nng m
nguyn nhn l khi nng Al ln c th xy ra tng tc gia cc ion Al3+ vi cc ion ca
mng tinh th hoc gia cc ion Al3+ vi nhau lm xc sut ti hp khng bc x tng ln, dn
n gim cng ca di ny [6]. S ph thuc cng ca di 467 nm vo nng Al c
dn ra hnh 7.
Advances
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b. S ph thuc ph pht quang ca ZnS:Al vo nhit nung, thi gian nung, mt cng
sut kch thch v thi gian tr
Hnh 8 l ph pht quang ca ZnS:Al (x = 1.5 mol%) 300 K c nung cc nhit khc
nhau (7001100oC) trong khong thi gian 15 pht khi c kch thch bng bc x ca laser
He-Cd bc sng 325 nm. Ph pht quang ny xut hin mt di rng t 400 nm n 580 nm
phn b khng theo i xng Gauss. Di pht quang ny thc cht l s chng chp ca hai di.
Dng phn mm tch ph Peakfit cho mu ZnS:Al nung T = 1000oC chng ti xc nh c
v tr ca hai di ny tng ng khong 467 nm v 531 nm (hnh 8f1, f2). Di pht quang xanh
l cy 531 nm lin quan n tp Cu trong ZnS [1,2]. Khi tng nhit nung t 700oC n
1100oC ta thy cng di 467 nm tng dn v t cc i T = 850oC sau gim dn.
467 nm
H.8. Ph pht quang ca ZnS:Al (x = 1.5 mol

%) 300K nung t 700oC n 1100oC.
H.9. Ph pht quang ca ZnS:Al (x = 1.5 mol%) 300

K nung 9000C vi thi gian nung t = 5 30 pht
Hnh 9 l ph pht quang ca ZnS:Al vi x = 1.5 mol% 300 K c nung 900oC trong
khong thi gian t 5 pht n 30 pht khi kch thch bng bc x ca laser He-Cd bc sng
325 nm. Trong ph pht quang ny ch yu xut hin di xanh lam 467 nm. Khi tng thi gian
nung mu, cng di xanh lam tng dn v t cc i ti t = 17 pht sau gim dn khi
tip tc tng thi gian nung n 30 pht.
Khi tng nhit v thi gian nung mu, xc sut cc ion Al3+ thay th cc ion Zn2+ trong
mng tinh th ZnS tng, do cng ca di xanh lam tng. Khi nhit v thi gian nung
mu ln c th dn ti s tng tc gia cc ion Al3+ vi nhau v vi cc ion ca mng tinh th
nn dn n s xo trn trong cu trc tinh th ca ZnS v lm gim cng pht quang ca
di ny [6].
H.10. Ph pht quang ca ZnS:Al (x = 1.5

mol%) 300 K vi cc mt cng sut
kch khc nhau ca laser He-Cd.
H.11. S ph thuc ln (I) ca m 467 nm

vo ln (Jkt) khi thay i mt cng sut kch
thch
Nhng
_____________________________________________________________________________________
nghin cu k hn bn cht cc c ch pht quang trong ZnS:Al, chng ti tin hnh kho
st ph pht quang ca ZnS:Al (x = 1.5 mol%) theo mt cng sut kch thch v thi gian tr.
Hnh 10 l ph pht quang ca ZnS:Al( x = 1.5 mol%) 300 K c nung 900oC trong 15
pht vi nhng mt cng sut kch thch khc nhau ca laser He-Cd. Khi tng mt cng
sut kch thch Jkt t 0.006 W/cm2 n 0.501 W/cm2 th v tr ca di 467 nm ny hu nh khng
thay i nhng cng ca n tng ln theo quy lut Ihq = A.Jkt
(hnh 11).
Hnh 12 l ph pht quang phn gii theo thi gian ca ZnS:Al (x = 1.5 mol%) vi cc thi
gian tr 30, 40, 50, 70 v 90 ns khi kch thch bng bc x 337 nm ca laser N2 vi rng xung
l 6 ns v tn s lp li l 10 Hz. Ph ny gm hai di c bn: di rng khong 425 - 440 nm
v di hp khong 460 nm. Khi tng thi gian tr t 30 ns n 90 ns, v tr ca nh ca di
rng dch v pha sng di t 425 nm n 440 nm (khong 77 eV) v cng ca di ny gim
dn. y chnh l c trng in hnh ca ti hp donor-acceptor. Khi thi gian tr nh, cc cp
donor-acceptor gn vi thi gian sng ngn ti hp trc. Khi tng thi gian tr cc cp donoracceptor xa vi thi gian sng di ti hp sau v xc sut ti hp gim dn v th nh ca di
b dch chuyn v pha nng lng thp v cng ca di ny b gim. Vi nhng c im
trn c th xem rng di pht quang 425 - 440 nm l do s ti hp bc x ca cc cp donor
acceptor, trong donor l Al , cn acceptor l cc nt khuyt ca Zn lin kt vi Cl [VZn Cl ]
hoc Al [VZn Al ] [5]. Vi di hp 467 nm, khi tng thi gian tr, cng ca di cng b
gim dn nhng v tr nh ca n hu nh khng thay i. V th chng ti cho rng di pht
quang 467 nm c trng cho hi phc bc x ca cc in t t vng dn xung mc acceptor
su to bi cc nt khuyt ca Zn lin kt vi Al [VZn-Al] [6]. Thi gian sng ca cc in t t
do trn vng dn khong 48 ns c xc nh t ng cong tt pht quang ca di 467 nm
(hnh 13). Kt qu ny cng ph hp vi cc cng trnh c cng b [7].
H.12. Ph pht quang phn gii theo thi

gian ca ZnS:Al (x = 1.5 mol%) 300 K
H.13. ng cong tt dn pht quang

ca di 467 nm ca ZnS:Al ( x= 1.5 mol%)
4. Kt lun
Bng phng php gm chng ti thnh cng trong vic ch ng pha tp Al vo ZnS
(0 x 10 mol%) vi nhit nung t 7000C n 11000C v thi gian nung t 5 pht n 30
pht trong khng kh. Kt qu cho thy vi nng 1.5%mol, thi gian nung 17 pht v nhit
nung 850oC cng di 467 nm t gi tr cc i. Cc mu kt tinh dng cu trc lc gic
wurtzite-2H, nhm pha P63mc. Ph pht quang ca cc mu ny ch yu xut hin hai di: di
440 nm c trng cho s ti hp bc x ca cc cp donor-acceptor, trong donor l Al, cn
acceptor l cc nt khuyt ca Zn lin kt vi Al [VZn Al ] hoc Cl [VZn-Cl]; di 467 nm l do
s ti hp bc x ca cc in t t do t vng dn vi l trng acceptor su l cc nt khuyt
ca Zn lin kt vi Al [VZn Al ]. Al pha tp nm l lng gia cc nt mng tinh th to ra
nhng mc nng lng xc nh trong vng cm ca ZnS v ng vai tr nh cc tm donor lm
tng hiu sut pht quang ca ZnS.
Advances
_____________________________________________________________________________________
Li cm n: Chng ti xin chn thnh cm n ti QG.07.45 h tr kinh ph thc hin bi

bo ny.
Ti liu tham kho
1.
2.
3.
4.
5.
6.
7.
L. Brus, J. Phys. Chem., 90 (1986) 2555

J. Tanaka et al., Jpn. J. Appl. Phys., 15 (1976) 2359
H. Y. Lu, S. Y. Chu, S .S. Tan, J. Cryst. Growth, 269 (2004) 385
W. G. Becker, A. J. Bard, J. Phys. Chem., 87 (1983) 4888
T. Yasuda, K. Hara, H. Kukimoto, J. Cryst. Growth, 77 (1986) 485
P. Prathapetal et al (2008), Solid State Science, In press
Y. Hattori, T. Isobe, H. Takahashi, S. Itoh, J. Lumin, 113 (2005) 69-78
Nhng
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CdSe
Khng Ct Cnga, Trnh c Thina, Phm Vn Hia, Nguyn Phi Hnga,
Bi Th Phng Thanha, Nguyn Vn Hnga, Phm Thu Ngab,
V c Chnhb, V Th Hng Hnhb
a)
Trng i hc S phm H Ni, 136 Xun Thy, Cu Giy, H Ni

b)
Vin Khoa hc Vt liu, Vin Khoa hc v Cng ngh Vit Nam
: Trong bo co ny, chm lng t CdSe c tng hp t tin cht trioctylphosphine

oxide cadmium (TOPOCd) v trioctylphosphine selenide (TOPSe) trong dung mi
trioctylphosphin oxide- hexadecyamine (TOPO-HAD) nhit cao. Cc mu c ly tng
ng vi thi gian pht trin t 1, 5, 10 v 15 pht. Ph hunh quang ca chm lng t CdSe
ch ra thi gian pht trin ht nh hng ca n s dch nh pht x. S dch nh cng ln
khi thi gian pht trin ca mu tng ln.
Kch thc ca chm lng t CdSe c xc
nh bi cng thc Brus da trn ph hp th thu c t thc nghim. Kch thc ca chm
lng t CdSe trong khong t 2,5 nm n 3,1 nm tng ng vi thi gian nui mu thay i t
1 pht n 15 pht.
1.
Chm lng t (QDs) l cc nano tinh th c kch thc b gii hn ba chiu, kch thc ca
chng di 10 nm (<10-8 m). Cc electron v l trng b giam gi trong chm lng t bn dn
lm cho nng lng ca chng trong cc vng c php b lng t ha tch thnh cc mc
nng lng ring bit. Hiu ng giam gi lng t dn n mt s tnh cht ca chm lng t
khc vi vt liu khi. Tnh cht quang hc ca chm lng t bn dn c nghin cu nhiu
nht l ph hunh quang ph thuc kch thc; kch thc gim, nh hunh quang dch chuyn
v pha sng ngn.
Nhng chm lng t c tp trung nghin cu l cc hp cht thuc nhm A2B6 nh
CdSe, ZnS, CdTe Trong s cc hp cht , cc nghin cu cho thy CdSe pht hunh quang
rt mnh, ngoi ra khi c bc thm lp v ZnS tnh cht pht quang c tng cng. Kch
thc ca chm lng t ph thuc vo nhiu yu t nh t l gia cc tin cht Cd:Se, nhit
mi trng, thi gian nui tinh th.
Trong bo co ny, chm lng t CdSe c ch to bng phng php phn hy cc tin
cht hu c kim loi m c M.G. Bawendi [1] xut. Cc mu kho st c thi gian mc
tinh th khc nhau. Cc mu dung dch sau ch to c o ph hp th, ph hunh quang trn
h o c xy dng khoa Vt l Trng i hc S phm H Ni. S dch nh hunh quang
v nh hp th v pha sng ngn ca cc mu ph thuc vo kch thc chm lng t. Da
trn mi lin h gia kch thc trung bnh ca ht v bc sng ti nh hp th exciton th
nht ca ph hp th, kch thc trung bnh ca chm lng t CdSe
.
Ch to chm lng t CdSe: hnh thnh chm lng t CdSe cn phi to ra cc ion
Cd v Se2 v to mi trng cho cc ion ny lin kt vi nhau. Mui cadmium acetate
Cd(CH3COO)2.2H2O c ha tan vo trong trioctylphosphine oxide C24H51OP (TOPO)
cho vo bnh kn sc kh N2 un ti nhit 800C th thu c tin cht TOPOCd. Bt
selen (Se) cng vi trioctylphosphine C24H51P (TOP) cng c ha trn nhit 800C nh
trn nhn c tin cht TOPSe. Cc tin cht hu c kim loi TOPSe v TOPOCd
tim
vo mi trng ch to chm lng t l cht hu c c khi lng phn t ln TOPO-HAD
(hexadecyamine C16H35N) t trong bnh cu sc kh N2 c un ti nhit 3000C. Trong mi
2+
Advances
_____________________________________________________________________________________
trng ny tin cht b phn hy gii phng cc ion Cd2+ v Se2. Cc ion ny va chm v kt
hp vi nhau to thnh cc mm tinh th ban u. Theo thi gian, cc mm tinh th to thnh cc
chm lng t v kch thc ln dn ln. Cc mu c ch to vi thi gian to mm trong 1
pht, 5 pht, 10 pht, 15 pht sau cho ngui nhanh v nhit phng. Vi thi gian nui tinh
th khc nhau, cc mu c mu khc nhau, ngha l kch thc chm lng t ca cc mu khc
nhau.
Ph hp th ca cc mu dung dch c kho st trn thit b Jasco 670, ph hunh quang
c o trn h quang hc a nng c lp rp ti B mn Vt l Cht rn Khoa Vt l
Trng
. Ngun kch thch s dng laser He-Cd KR 1801C hng
KIMMON KOHA (Japan) pht bc x 325 nm cng sut cc i 200mW, h tn sc l ph k
Model 9490 hng SCIENCETECH (Canada) vi cch t
1200 vch/mm vng ph phn
tch t 180 nm n 50 m, u thu dng ng nhn quang in KA 5134 hng Hamamatsu
(Japan).
3. K
CdSe l bn dn loi n, nhit phng (~ 300 K) rng vng cm l 1,74 Ev. Bc x
bc sng
700 nm. Nhng mu dung dch
hunh quang ca CdSe dng khi ng
sau ch to c kch thch bng n t ngoi, chng pht ra nh sng c mu t xanh thm,
xanh da tri, vng ti da cam tng ng vi thi gian nui tinh th ko di hn. Nhn mu sc
ca cc dung dch c th nhn nh rng cc chm lng t bn dn c hnh thnh v phn
tn trong dung dch.
Hnh 1. Ph hp th ca cc
chm lng t CdSe
Hnh 2. Ph hunh quang ca cc

chm lng t CdSe
Ph hp th ca cc
CdSe m cc tinh th mc theo cc thi gian khc nhau
(hnh 1) cho thy rng b hp th ca cc mu dch chuyn v pha sng di (530, 557, 561 v
574 nm) tng ng vi thi gian nui tinh th tng. Ph hunh quang (hnh 2) ca cc
u dch chuyn v pha sng di (539, 562, 579 v 589 nm) tng ng vi dch
Stokes l 9, 5, 18, 15 nm so vi ph hp th. Cc kt qu ny hon ton ph hp vi nh lut c
bn v mi quan h gia ph hp th v ph hunh quang.
gii thch cc chm lng t pht quang dch v pha xanh so vi s pht quang ca vt
liu khi CdSe ta da trn s mc nng lng trnh by trn hnh 3.
Trong vt liu khi, in t t do v l trng tng ng ch yu tp trung y vng dn v
nh vng ha tr. Khi c kch thch, cc lectron t vng ha tr hp th nng lng
Nhng
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ln vng dn, t vng dn, in t tr v vng ha

tr ti hp vi l trng
pht ra phton c nng
lng tng ng vi rng vng cm
hunh quang b vng, mi cht bn dn c
c bc sng
rng vng cm xc nh
hunh quang xc nh (vi CdSe bc sng ny
khong 700 nm). Khi in t - l trng b giam
gi, cc mc nng lng b lng t ha. in t
t do v l trng phn b cc mc nng lng
c lng t ha nm su hn trong cc vng
. Khi ti hp, nng lng c gii
phng ln hn nng lng b vng, trng thi
giam gi cng mnh (kch thc chm lng t
gim) khong cch gia cc mc nng lng ca
cp in t - l trng (exiton) cng tng dn n
pht x dch chuyn v pha xanh.
Effros, Brus, Kayanuma a ra biu thc
Hnh 3. S cc mc nng lng ca

cp in t - l trng trong vt liu khi
(A1) v trong chm lng t (A2)
nh sau [2]:
2
Eg a
Eg
2 1
2a 2 me*
1
mh*
1, 786
e2
0, 24 R*y
a
trong Eg(a) l nng lng ca

trng thi exciton kch thch th
nht ng vi chm lng t c bn
knh a, Eg l rng vng cm tng
ng ca vt liu dng khi. me* v
mh* tng ng l khi lng hiu dng
ca in t v l trng, v Ry* tng
Hnh 4. ng cong chun xc nh kch thc chm
ng l hng s in mi v nng
lng t CdSe
lng Rydberg exciton ca vt liu.
Xut pht t l thuyt ny, nhiu
bo co xc nh kch thc a ca cc chm lng t trong cc mu bng cch nhp cc gi
tr Eg a nhn c t ph hp th, tra cu cc thng s ca bn dn CdSe thay vo biu thc
trn hoc xy dng cc cng thc tnh kch thc chm lng t t cc thng s thc nghim
[3].
Ngoi suy thm cc gi tr nng lng Eg a ngi ta xy dng c ng cong chun
xc nh kch thc a ca chm lng t CdSe khi bit nng lng b hp th.
Da trn ng cong chun ny, chng ti xc nh kch thc chm lng t ca cc
mu c ch to.
Bng 1: Kch thc trung bnh ca QDs thay i theo thi gian nui mu.
T l
Cd:Se
1:8
(2800C)
Tn mu
CdSe
CdSe
CdSe
Thi gian nui

mu (pht)
1
5
10
CdSe
15
nh hp th ecxiton Kch thc trung bnh

th nht (nm)
(nm)
530
2,5
557
2,8
561
2,9
574
3,1
Advances
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Bng 2: Tnh n phn tn ca mu theo thi gian nui tinh th.
T l
Cd:Se
1:8
(280oC)
CdSe
CdSe
CdSe
Thi gian nui

mu (pht)
1
5
10
nh hunh quang
(nm)
539
562
579
bn rng ca nh
hunh quang (nm)
25,5
24,5
34
CdSe
15
589
34
Tn mu
T bng thng k cc kt qu thc nghim cho chng ta mt s nhn xt sau:

+ Thi gian nui tinh th cng di, kch thc chm lng t tng v nh h
dch v
pha (bng 1).
+ Bng 2 cho thy ng vi thi gian nui tinh th ngn (1 pht n 5 pht) bn rng ca
nh ph hunh quang hp khong 25 nm ng vi cc chm lng t CdSe to thnh c tnh n
phn tn cao v kch thc. Ko di thi gian nui mu (10 pht n 15 pht) tnh n phn tn
v kch thc gim i th hin thng qua s tng bn rng ca ph hunh quang ti 34 nm.
Kt qu ny cho thy cc mu ch to c n phn tn v kch thc cao, ph hp vi cc kt
qu cng b [4].
4. K
Cc chm lng t CdSe phn tn trong dung dch c ch to bng phng php phn
hy cc tin cht hu c kim loi. Ph hp th v ph hunh quang ca cc mu nhn c
chng t thi gian nui tinh th cng di, kch thc chm lng t CdSe cng ln. Bc sng
hunh quang ca cc chm lng t bn dn c iu chnh thng qua thay i kch thc
chm lng t bng cch ko di thi gian nui tinh th. Cc chm lng t CdSe ch to c
tnh n phn tn cao v kch thc v gim dn khi ko di thi gian nui tinh th.
Cc tc gi chn thnh cm n ti nghin cu khoa hc cp B B2008-17-128 h tr

kinh ph chng ti hon thnh bo co ny.
T
1. M.G. Bawendi, et al, Evidence of photo and electrodarkening of (CdSe) ZnS quantum dot
composites, J. Applied Physics June 15, 2000, Vol. 87, Issue 12, 8526-8534.
2. S.V. Gaponenko, Optical properties of semiconductor nanocrystals, Cambridge University
Press 1998 (USA).
3. W. William Yu, Lianhua Qu, Wenzhuo Guo, and Xiaogang Peng, Experimental
Determination of the Extinction Coefficient of CdTe, CdSe, and CdS Nanocrystals; Chem.
Mater. 2003, 15, 2854-2860
4. Marcel Bruchez Jr., Mario Moronne, Peter Gin, Shimon Weiss, A. Paul Alivisatos;
Semiconductor Nanocrystals as Fluorescent Biological Labels; Science 281 (1998), 20132016
Nhng
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TNH CHT QUANG CA CC HT NANO ZnS CH TO

BNG PHNG PHP THY NHIT
Trn Th Qunh Hoa, Nguyn Ngc Long, T nh Cnh
Khoa Vt l, Trng i hc Khoa hc T nhin H Ni
334 Nguyn Tri, Thanh Xun, H Ni
E-mail: tranthiquynhhoa@gmail.com
Tm tt: Cc ht nano ZnS c ch to thnh cng bng phng php thy nhit. Ph nhiu
x tia X cho thy cc ht nano ZnS c cu trc lp phng. nh hin vi in t truyn qua cho
thy cc ht nano c dng hnh cu vi ng knh trung bnh c 13 nm. Kch thc ca cc ht
nano ZnS ph thuc vo nhit v t s mol ca cc vt liu ngun. Ph hp th UV - Vis cho
thy mt s dch nh v pha nh sng xanh da tri so vi mu khi. S dch nh ny c cho l
do hiu ng giam cm lng t. Ph hunh quang (PL) ca cc mu cng xut hin mt di bc
rng c nh ti 451 nm v 485 nm v 500nm. Cc nh ny c th lin quan n cc trng thi b
mt v vacancy S. Ph kch thch hunh quang ca mu c kho st theo trong di nhit
t 12 K n nhit phng.
T kha: Phng php thy nhit, ht nano ZnS, tnh cht hunh quang.
1. Gii thiu
Trong nhng nm gn y, vt liu bn dn ZnS ang c quan tm nghin cu mt cch
ph bin bi v n c nhiu c tnh c bn qu bu nh rng vng cm ln (3,72 eV i
vi pha lp phng v 3,77 eV i vi pha lc gic ti 300 K), chuyn mc thng v nng
lng lin kt exciton ln (40 meV) [1]. ZnS c mt di pht quang rng t cc tm (UV) ti
cn hng ngoi (IR). V vy, n thng c s dng trong cc thit b in t v quang t
nh cc transistor pht x trng nhit phng, cc bng hin th phng, cc thit b in
pht quang, cc ca s cn hng ngoi, cc diot v laze UV... c bit, ZnS c cu trc nano
khng chiu (0D) ang thu ht c nhiu s quan tm v chng c th c s dng trong
vic pht hin v nh du t bo sinh hc [2].
Hin nay nhiu nghin cu v ZnS cu trc nano v ang c thc nhin nhm iu
khin kch thc, hnh thi hc, s kt tinh thay i cc tnh cht vt l ca n. Nhiu
phng php c s dng ch to cc ht ZnS nh l sol-gel, lng ng in ha, in
ha siu m, thy nhit,
Trong bi bo ny, chng ti trnh by qui trnh ch to v tnh cht quang cc ht ZnS
tng hp bng phng php thy nhit di cc iu kin khc nhau. y l mt phng
php n gin ch to tinh th di nhit v p sut cao. Mc ch quan trng ca
nghin cu ny l tm ra nh hng ca nhit thy nhit ln tnh cht quang ca sn phm
ZnS.
2. Thc nghim
H thng thy nhit gm mt ni hp hnh tr bng thp dy c kh nng chu c nhit
v p sut cao trong mt thi gian di. Trong lng ni hp c mt ng Teflon c s
dng chng s n mn ca ha cht. ng ny c ng knh trong l 30 mm v th tch l
120 ml.
Tt c cc tin cht c s dng u l ha cht phn tch. Th nghim c thc hin
nh sau: vt liu ngun bt ZnSO4.5H2O v bt Na2S.7H2O c ha tan trong nc kh ion
Advances
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v c khuy t trong 30 pht. Sau chng c ha trn vi nhau bng cch nh tng
git dung dch Na2S vo dung dch ZnSO4 trong khi khuy. T l mol thnh phn Zn2+ v S2c gi nguyn trong cc th nghim l 1:0,7. Nhit c thay i ln lt l 220 oC,
2000C, 1800C, 1600C, 1400C tng ng vi cc mu 1, 2, 3, 4, 5. Phn ng ha hc c th
m t nh sau [3]:
ZnSO4 Zn2+ + SO42(1)
Zn2+ + Na2S ZnS + 2Na+
(2)
Lp gel trng thu c sau phn ng c vo trong ng Teflon, chim khong 50%
th tch ng. Ni hp c ng kn v a vo trong t sy (Mermert - 500) c khng ch
nhit . Qu trnh thc hin trong thi gian 12 h v sau ni hp c ngui ti nhit
phng. Sau qu trnh thy nhit, dung dch trong ng Teflon c ra bng cch quay ly
tm trong nc ct 2 ln b lp nc c ln cc dung mi d. Qu trnh ny c lp li
khong 10 ln loi b tp cht ra khi mu. Mu c sy 12 h trong khng kh, ti nhit
600C. Sn phm cui cng c mu trng.
Cu trc tinh th ca cc mu ZnS c phn tch bng ph nhiu x tia X (Brucker
D5005). Hnh thi mu c phn tch qua nh hin vi in t truyn qua (JEOL JEM 1010).
Cc php o hunh quang c thc hin bng my quang ph hunh quang (FL3-22 Jobin
Yvon Spex). Ph hp th thu c nh my quang ph hp th (Shimadzu UV 2450 PC).
3. Kt qu v tho lun
(311)
(220)
(200)
C-ng (Cps)
(111)
Ph XRD ca cc mu ZnS c ch ra trn hnh 1.

th cho thy tt c cc mu u c cc nh nhiu
x ti gc 2 bng 28,60, 33,10, 47,60 v 56,40. Kt
Mu 5 (140 C)
qu ny hon ton ph hp vi s liu l thuyt ca
Mu 4 (160 C)
pha lp phng zincblende ZnS. Cc nh nhiu x ny
Mu 3 (180 C)
tng ng vi cc mt (111), (200), (220) v (311).
Mu 2 (200 C)
Khong cch gia cc mt phng mng c tnh
Mu 1 (220 C)
ton theo cng thc Vulf - Bragg v ch ra trn bng
Gc 2
1.
(3)
2d hkl sin k
Hnh 1. Ph XRD ca cc mu ZnS
vi cc nhit khc nhau
trong l bc sng, dhkl l khong cch gia cc
mt phng mng, l gc nhiu x v k l s t
nhin cho bit bc nhiu x.
Hng s mng ca cc mu ZnS c th tnh c t ph nhiu x tia X theo cng thc.
Cc kt qu ny ln hn mt cht so vi s liu chun ca pha sphalerite ZnS (a = 5,398 ).
o
20
d hkl
30
40
50
60
70
a
(h k 2 l 2 )
2
(4)
Cc s liu thu c t ph nhiu x tia X c s dng tnh ton kch thc tinh
th qua cng thc Debye - Scherrer [4]:
0.9
(5)
L
cos
trong l bn rng (FWHM) ca cc nh nhiu x.

Trong trng hp tinh th hnh cu, ng knh tinh th D 4/3L. Kch thc cc ht
nano ZnS xp x 7, 10, 13, 16, 17 nm ng vi nhit l 1400C, 1600C, 1800C, 2000C,
2200C. R rng kch thc cc ht nano ZnS ln hn khi nhit cao hn. Bng vic iu
khin nhit , kch thc tinh th c th thay i.
Nhng
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Bng 1. Tng hp cc kt qu tnh ton t ph XRD
Mu
1
Mt
(11)
(22)
(31)
(11)
(22)
(31)
(11)
(22)
(31)
(11)
(22)
(31)
(11)
(22)
(311)
dhkl ()
a ()
3,124
1,914
1,630
3,125
1,911
1,630
3,125
1,911
1,630
3,121
1,907
1,628
3,118
1,905
1,627
5,410
5,404
5,405
5,413
5,406
5,408
5,413
5.405
5,407
5,406
5,394
5,398
5,401
5,388
5,395
a ()
5,406
5,409
5,408
5,399
5,392
L ()
136,760
125,001
130,647
125,986
115,727
116.655
113,877
93,802
93,299
78,809
72,143
72,244
51,760
47,591
47,421
L
(nm)
D
(nm)
13,08
17,44
11,95
15,93
10,03
13,38
7,44
9.92
4.89
6,52
Hnh thi hc v kch thc cc ht ca ZnS cu trc nano c th c thy r hn qua

phn tch nh TEM. Hnh 2 ch ra nh TEM ca mu 1 c ch to nhit l 220 0C. Ta
c th thy mt s lng ln cc tinh th c cu to gn nh hnh cu vi ng knh trung
bnh c ~ 17 nm. Kt qu ny hon ton ph hp vi cc tnh ton t ph nhiu x tia X.
nghin cu tnh cht hp th ca cc mu, bt ZnS c rung siu m trong nc ct 2
ln. Dung dch sau c ng trong cuvette thch anh. Ph hp th c ch ra trn hnh
3.
T cc ng cong hp th, chng ta c th thy mi ph u c mt vai ti bc sng
ln lt l 320 nm, 327 nm, 330 nm, 332 nm, 333 nm khi nhit tng ng l 1400C,
1600C, 1800C, 2000C, 2200C. Cc vai ny lin quan ti hp th c bn trong cc mu ht nano
ZnS, v c th s dng chng xc nh rng vng cm ca vt liu.
T ph hp th ta c th tnh c rng vng cm ca cc mu l 3,872 eV, 3,789 eV,
3,755eV, 3,732 eV, 3,721 eV tng ng vi nhit l 1400C, 1600C, 1800C, 2000C,
Hnh 2. nh TEM ca mu 1 vi nhit l

2200C
Hnh. 3. Ph hp th ca cc mu ZnS vi cc
nhit khc nhau
2200C. rng vng cm ca cc mu ht nano ny ln hn so vi rng vng cm ca

mu khi (3,72 eV) v gim xung mt cht khi nhit tng ln. S dch nng lng vng
Advances
_____________________________________________________________________________________
cm v vng nh sng xanh da tri c th l do hiu ng giam cm lng t trong mu ZnS

c cu trc nano.
Bng 2. Cc kt qu xc nh dch b hp th
Nhit
T (0C)
220
200
180
160
140
Mu
1
2
3
4
5
S dch b hp th E c lin quan

n bn knh cc ht nano, c tnh
theo cng thc [1]:
h
8 r
1.8e
r
E (eV)
0.001
0.012
0.035
0.069
0.152
0.20
(6)
0.15
g (eV)
Eg Eg film Eg bulk
Bn knh
ht r (nm)
8.72
7.96
6.69
4.96
3.26
L thuyt
Thc nghim
220 C
trong m m /m m l khi
200 C
lng hiu dng, me* v mh* l khi
0.05
lng rt gn ca in t v l trng,
180 C
l hng s in mi ca vt liu, k l h
160 C
0.00
s t l ph thuc vo h n v. i vi
140 C
ZnS me* 0.34m0 , mh* 0.23m0 , m0 l
2
4
6
8
10
r (nm)
khi lng tnh ca in t, 8,76
(Landolt - Bornstein 1987).
Hnh 4. th s ph thuc ca Eg vo kch thc ht
Trn hnh 4 l th biu din s
ph thuc Eg vo kch thc ht tnh theo (6) v kt qu thc nghim tnh ton t ph XRD v
ph hp th. C th thy kt qu thc nghim l kh ph hp vi cc gi tr trn ng l thuyt.
iu ny khng nh s dch nh b hp th xy ra do hiu ng gim kch thc cc ht bn dn
n c nano mt.
Tnh cht hunh quang ca cc mu ZnS c kho st ti nhit phng. Ph pht x
ca cc mu ny c ch ra trn hnh 5. Bc sng kch thch l 320 nm (3,87 eV).
*
e
*
h
*
e
*
h
0.10
Hnh 5. Ph hunh quang ca cc mu vi cc

nhit khc nhau
Hnh 6. Ph kch thch hunh quang ca cc mu

vi cc nhit khc
Nhng
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Ph hunh quang c mt di pht quang rng t 450 nm n 500 nm. Di pht quang ny
c th phn tch thnh 2 nh. nh th nht ti khong 451 nm (2,75 eV) i vi tt c cc
mu. nh th hai thay i t 485 nm (2,35 eV) n 500 nm (2,48 eV) khi nhit ca mu
tng ln t 1400C n 2200C. S hnh thnh cc nh pht x rng c th do c hai yu t: s
phn b kch thc v s tng trng thi b mt v t s din tch b mt trn th tch tng i
vi cc ht nano c kch thc nh hn [1]. Theo chng ti, cc nh pht quang ca cc mu
trn c cng mt ngun gc l cc sai hng vacancy S trong mng tinh th ca cc ht nano
ZnS. Cc trng thi b mt c hnh thnh ti cc tm VS. Ti hp ca ht ti in t do qua
cc trng thi b mt bc x ra nng lng hunh quang. Mt s cng trnh nghin cu v
ZnS cng a ra kt qu v cc nh 450 nm [1, 5, 6], 490 nm [7] v 500 nm [1]. Cc tc
gi [1] quan st c nh 500 nm i vi mu thanh nan c kch thc ln c 100 nm. Cn
chng ti thu c nh 500 nm trong ph hunh quang ca mu cha cc ht nan c 17 nm.
Trong phn ln cc cng trnh, ngun gc di hunh quang min 450 nm 500 nm u c
quy cho cc VS.
Ph kch thch hunh quang c lin quan n tnh cht hp th ca mu, cc nh ph kch
thch hunh quang tng ng vi cc nh ph hp th. nghin cu c ch hunh quang
ca di pht x xanh, ph kch thch hunh quang ng vi bc sng 485 nm c thc
hin v biu din trn hnh 6.
T ph kch thch hunh quang, ta thy cc nh ti 370 nm (3,35 eV), 390 nm (3,18 eV), 395
nm (3,14 eV), 393 nm (3,15 eV) v 401 nm (3,07 eV) tng ng vi cc nhit thy nhit
1400C, 1600C, 1800C, 2000C, 2200C. Cc mc nng lng ny u thp hn gi tr nng
lng b hp th c bn ca mi mu (tnh t ph hp th) mt gi tr Ei. Nhit ch to
mu cng cao th Ei cng gim. Cc gi tr Ei ln lt l 0,8 eV, 0,64 eV, 0,62 eV, 0,55
eV v 0,37 eV. y c th l cc mc tm su trong cc mu tng ng. Qu trnh hp th
qua cc tm su ny gp phn gy ra ti hp bc x min xanh.
Khi o nhit phng, cc ph kch thch hunh quang trn hnh 6 khng th hin cc nh
gn b hp th. Nhng khi ph c o nhit thp, c th quan st c r rng s
dch nh ph gn b hp th theo nhit . Trn hnh 7 l cc ph kch thch hunh quang
ca mu 1ti bc sng 485 nm, c o cc nhit khc nhau.
C th thy nh ph kch thch hunh quang dch v pha sng di mt cch kh r. Trn
hnh 8 l th biu din s ph thuc ca nh ph vo nng lng sng kch thch. Quy lut
ph thuc nng lng nh ph vo nhit o mu tun theo cng thc Vashni:
Hnh 7. Ph kch thch hunh quang ca mu 1

o nhit thp
Hnh 8. S ph thuc ca v tr nh ph
vo nhit o
Advances
_____________________________________________________________________________________
T 2
(7)
T
T ng fit theo cc gi tr thc nghim chng ti xc nh c E0 = 3,748 eV, l nng
lng nh ph ti 0 K, cc thng s = 0,062 eV/K v = 2,01.104 (K).
E (T ) E (0)
4. Kt lun
Cc mu bt tinh th nano ZnS c ch to thnh cng bng phng php thy nhit.
Nghin cu nhiu x tia X cho thy ZnS c cu trc lp phng zincblende. Kch thc cc
ht nano tng t 7 nm ti 17 nm khi nhit tng t 1400C n 2200C. rng vng cm
tng t 3,72 eV ti 3,87 eV khi kch thc ht nano gim. Di pht x xanh l cy trong ph
hunh quang l do cc cc trng thi b mt v vacancy sunfua trong mng.
Li cm n
Bi bo ny c ti tr bi ti khoa hc c bn cp Nh nc, s 4 05 506. Chng
ti xin chn thnh cm n Trung tm khoa hc vt liu (CMS), B mn Vt l i cng Khoa Vt l trng H KHTN-HQG H Ni gip , to iu kin cho chng ti s
dng trang thit b lm th nghim v o c.
Ti liu tham kho
1.
2.
3.
4.
5.
S.Biswas and S.Kar, Nanotechnology, 19 (2008) 045710.

W.B.Tan, N.Huang and Y.Zhang, Colloid and Interface, 310 (2007) 464.
D. Denzier, M.Olschewski and K. Sattler, Appl. Phys., 84 (1998) 2841.
B.D.Cullity, Addision-Wesley Publishing Company, Inc., 1978.
P.K.Ghosh, S.Z.Jana, S.Nandy, K.K.Chattopadhyay, Materials Research Bulletin, 42
(2007) 505.
6. Y.Wang, L.Zhang, C.Liang, G.Wang, X.Peng, Chem. Phys. Lett., 357 (2002) 314.
7. S.Kar, S.Biswas, S.Chaudhuri, Nanotechnology, 16 (2005) 737.
Nhng
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HIU NG GIAM CM CA GING LNG T ZnO TRN SAPPHIRE

Nguyn Thanh Bnha, V Th Bcha, Ngac An Bangb, B. P. Zhangc; Y. Segawac
a
Vin Vt l, Vin Khoa hc v Cng ngh Vit nam

b
Trng i hc Khoa hc t nhin H Ni
c
Vin nghin cu Vt l Ha hc RIKEN Nht bn
E-mail: tbnguyen@iop.vast.ac.vn
Tm Tt: Chng ti thng bo v hin ng giam cm ca ging lng t ZnO/ZnMgO trn

Sapphire (1120) ch to bng phng php MOCVD vi rng ging thay i mt cch lin
tc. Ph quang hynh quang cho thy hai nh:mt nh c v tr khng i theo rng ging
cn nh kia thay i. Ph hunh quang phn cc chng minh rng s thay i ca nh
exciton lin quan ti s giam cm trong khng gian hai chiu (2D). S thay i v tr ca nh
pht x ny c cho l pht x exciton ca lp barrier MgZnO. S ph thuc rng ging
th c so snh vi m hnh l thuyt n gin. c bit l thi gian sng ca ht ti trn
ging lng t l 360 ps, ngn hn so vi thi gian sng ca ht ti trn lp MgZnO l 470ps
giy v hiu ng giam cm lng t.
1. M u
Oxit km (ZnO) l h vt liu y trin vng cho vic ch to linh kin pht quang trong
vng ph t ngoi. ZnO c cc tnh cht gn ging vi h vt liu GaN, tuy nhin nhit ch
to vt liu GaN thng ln hn 1000C, cao hn nhiu so vi nhit ch to ZnO (khong
500C do vic pht trin cc linh kn pht quang h ZnO thu ht c s quan tm ca cc
nh nghin cu v cng ngh.
Nhng nm gn y cng ngh nano v vt liu nano c pht trin mt cch mnh m nh
tnh cht mi ca vt liu kch thc nano mang li so vi vt liu khi. Hiu ng giam cm
lng t cho php ch to linh kin nano vi hiu sut lm vic cao hn so vi linh kin thng.
Cc ging lng t ZnO vi hiu sut quang hunh quang cao hn vt liu khi c ch to
bng phng php MBE trn ScAlMgO v bng phng php MOCVD trn GaN [1,2]. S
sai khc hng s mng gia GaN v ZnO l 2%, nh hn nhiu so vi sai khc mng gia ZnO
v sapphire (18% i vi hng s a v 31% i vi hng s c). Do s sai khc hng s mng ln
gia ZnO v sapphire nn s c mt s kh khn to ra cc lp ZnO/MgZnO lin tc to c
ging lng t cht lng cao v siu mng (superlaticle). Gn y, chng ti tm c
nhit nui thp, c th to ra cc b mt c nhm b trn sapphire (0001), tuy nhin tnh
cht quang li khng tt khi dy ln hn mt gi tr gii hn no . Tch cht quang ca cc
lp ny c ci thin hn khi nui trn sapphire (1120). Do chng ti thc hin ch
to cc ging lng t trn sapphire (1120) v s dng cc nhit nui lp m
MgZnO(buffer), lp ro (barier), v ging lng t khc nhau, ngoi ra, cc k thut nui l nh
nhau, cc lp ni lin tc trn cng mt . Trong bi bo ny chng ti thng bo v kt qu
ch to ging lng t ZnO/MgZnO trn sapphire v mt s tch cht ca n.
2. Thc nghim
Hnh 1 cho thy cu to ca mt mu ging lng t ZnO nui trn saphire (1120). u
tin trn chng ti nui mt lp buffer MgZnO, sau lp ZnO c nui gia hai lp
barrier MgZnO to nn cu trc ging lng t. K thut nui bng phng php MOCVD
c chng ti m t trong cc cng trnh trc y [3-5]. Vt liu ngun ch to cc lp
MgZnO v ZnO l diethylzinc, bism. ethylcyclopentadienyl- magnesium, kh oxy (oxygen). Khi
nit ng vai tr kh mang. Lp m Zn0.1Mg0.9O c dy khong 100 nm c nui nhit
425C, sau c trong khng kh ti 800C trong 10 gi. Cc php o hin vi lc nguyn
Advances
_____________________________________________________________________________________
t cho thy nhm (rms) b mt ca lp m

nh hn 1 nm sau khi . Lp m ny c s
dng nh nui ging lng t. nui to
ging lng t, trc ht chng ti to mt lp
barier MgZnO vi dy khong 150 ti 200
nm nhit 500C, p sut trong bung mu
c gi 5-6torr. Lp ZnO c to ra trn lp
barier th nht v mt lp barier th 2 ph ln
lp ZnO. Mu sau khi nui c u ti 700C
trong 2 gi. Trong cu trc ging lng t ny,
dy cc lp thay i t tm mu ra xung
quanh do tc nui thay ti cc v tr ny
khng ging nhau. Tc nui thay i 3 ln
vi di 3-5 mm t tm mu. Thnh phn ca
lp MgZnO c xc nh bng phng php
ph tn x tia X trn my nhiu x tia X Philips
Hnh 1. Cu trc gin lng t. ZnO/MgZnO
XPert. Ph quang hunh quang o ti nhit
nui
trn lp m MgZnO v trn sapphire
phng (300K) v nhit heli lng (4K) vi
(1120)
ngun kch thch l Laser He-Cd 325nm v thu
bng ph k ActonResearch SpectraPro-300i.
chng minh hiu ng gim cm lng t, ph hunh quang phn cc c o t mt ct ca
mu. Trong php o ny chng ti s dng ng knh hin vi hi t laser kch thch ln mt ct
mu c ln 3-5 m2 v dng chnh ng knh hin vi ny hi t nh sng hunh quang. Tm
phn cc c t sau ng knh hin vi phn cc nh sng hunh quang trc khi vo my
quang ph. Thi gian sng hunh quang c o bng streak camera Hamamatsu C5680 vi
ngun kch thch l ha ba bc ba ca laser Ti-sapphire bc sng 250 nm tn s lp li 80 MHz,
rng xung 2 ps.
3. Kt qu v tho lun
Kt qu ph nhiu x tia X cho thy rng mng ZnO nui trn Sapphire (1120) c b mt
mng song song vi mt (0001) ca tinh th [5] . Ph hunh quang t mt (0001) o ti 4K ti
cc v tr khc nhau ca mu bng cch dch chuyn vt laser hi t i 0.3 mm mi ln o. Tng
di kho st l 3mm. Ph hunh quang ca ging lng t cho thy s tn ti hai nh chnh.
Mt nh c v tr ph thuc co v tr kch thch trn mu cn nh kia hu nh khng. nh
hunh quang khng ph thuc vo v tr vt laser kch thch ti 3.54 eV ph hp vi hunh
quang ca MgZnO cha 10% Mg [6] do nh ny c th quy cho exciton trong lp MgZnO.
nh hunh quang ph thuc vo v tr c th quy cho exciton ca ging lng t ZnO. S ph
thuc nh pht x vo v tr y c cho l gy bi s thay i rng ging lng t. Hnh
2 ch ra rng nh exciton ca ging thay i trn 100meV trn ton b di mu kho st.
chng mnh hiu ng giam cm lng t chng ti cng o ph hunh quang phn cc
ca mt ct ging lng t, s dng h o vi hunh quang (micro-PL). Hnh 3 cho thy ph
hunh quang phn cc vi cc gc phn cc khc nhau. Trong php o ny gc khng biu
din vect cng in trng song song vi b mt mu. Cng hunh quang ca ging
lng t t cc i (I ) khi gc phn cc bng khng ngc li cng hunh quang bng
khng khi gc phn cc quay 90 (I ). S thay i cng hunh quang theo gc phn cc
cho thy rng y l c trng hai chiu trong cu trc ging lng t trong cc exciton c th
chuyn ng t do. Cc exciton khng th chuyn ng theo chiu vung gc vi mt mu (I )
[7] v exciton b giam cm trong ging lng t. Cng trong ph hynh quang phn cc, exciton
ca lp MgZnO hu nh khng ph thuc vo gc phn cc chng t rng cc exciton ny c
th chuyn ng t do trong cu trc ba chiu. Nng lng ca exciton ca ging lng t c th
Nhng
_____________________________________________________________________________________
Hnh 2. Ph hunh quang ca ging lng

t o ti cc v tr khc nhau 4K.
Hnh 3. Ph hunh quang phn cc o t mt ct

ging lng t vi cc gc phn cc khc nhau ti
20K. Hnh trn gc l cu hnh phn cc
so snh vi cc gi tr nng lng exciton tnh ton trn m hnh bnh phng ti thiu a vo
tnh nng lng lin kt exciton [8]. Nng lng excitong trong ging lng t c tnh bi
phng trnh:
Trong
l nng lng vng cm ca ZnO
Ee v Eh l nng lng giam cm ca in t v l trng

l nng lng lin kt exciton trong ging lng t
Hnh 4. So snh gi tr thc nghim v gi tr

tnh ton ca nng lng exciton trong ging
lng t vi m hnh l thuyt n gin.
Hnh 5. Ph hunh quang phn gii thi gian ca

ging lng t o ti 77K. Hnh b trong l ph
tch phn theo bc sng.
l 3.436 c xc nh t exciton t do l 3.376 eV v nng lng lin kt exciton ca ZnO

l 60mV. S khc nhau gia nng lng vng cm ca ZnO l lp MgZnO c xc nh t
nh hunh quang ca ZnO l 3.376 eV v ca MgZnO l 3.54 eV khi lng hiu dng ca in
t l 0.28mo, khi lng hiu dng l trng l 0.78mo, mc offset ca vng dn v vng ha tr
l 65/35 [8]. Hnh 4 cho thy gi tr nng lng exciton ca ging lng t xc nh t ph
hunh quang v gi tr tnh ton. Gi tr thc nghim ph hp tt vi cc gi tr tnh ton vi
ging lng t c rng ging b hn 40 .
Advances
_____________________________________________________________________________________
chng minh thm v hiu ng giam cm lng t, chng ti o thi gian sng hunh
quang ca exciton. Hnh 5 cho thy ph hunh quang phn gii thi gian ca ging lng t ZnO
o ti 77K. ng v ri nt l ng khp vi gi thit hunh quang phn r theo hm exponen
n (c 1 thi gian sng hunh quang). Thi gian sng hunh quang ca exciton MgZnO l
360ps v thi gian sng ca exciton ZnO trong ging lng t l 322 ps. Gi tr ny b hn so
vi thi gian sng exciton ZnO trong tnh th khi [10] iu ny phn nh tnh nhax ca
exciton trong ging lng t v nng cao xc sut ti hp ca exciton.
4. Kt lun
Ging lng t c cu trc ZnO/MgZnO c ch to bng phng php MOCVD trn
sapphire. nh exciton c trng ca ZnO trong ging lng t dch v pha nng lng cao
khi rng ging gim. Ph hunh quang phn cc chng minh rng cc exciton ZnO b gian
cm trong khng gian hai chiu. Thi gian sng hunh quang ngn hn ca exciton ZnO lm
nng cao hiu sut hunh quang ca ZnO so vi ca lp MgZnO. Gi tr nng lng ca exciton
ton ZnO trong ging c so snh vi m hnh l thuyt n gin v ph hp tt. Hiu ng
giam cm lng t trong ging lng t ZnO chng minh c th pht trin ZnO ng dng trong
linh kin quang in t.
Li cm n
Cc tc gi trn trng cm n s ti tr kinh ph t Chng trnh NCCB cp Nh nc cho ti
N0 4.031.06
Ti liu tham kho

1. T. Makino, C. H. Chia, N. T. Tuan, H. D. Sun, Y. Segawa, M. Kawasaki, A. Ohtomo, K.
Tamura, and H. Koinuma, Appl. Phys. Lett. 77,9752000.
2. Th. Gruber, C. Kirchner, R. Kling, F. Reuss, and A. Waag, Appl. Phys. Lett. 84,53592004.
3. B. P. Zhang, K. Wakatsuki, N. T. Binh, N. Usami, and Y. Segawa, Thin Solid Films
449,122004.
4. B. P. Zhang, N. T. Binh, K. Wakatsuki, N. Usami, and Y. Segawa, Appl. Phys. A: Mater. Sci.
Process. 78,252004.
5. N. T. Binh, B. P. Zhang, C. Y. Liu, K. Wakatsuki, Y. Segawa, N. Usami, Y. Yamada, M.
Kawasaki, and H. Koinuma, Jpn. J. Appl. Phys., Part 1 43,41102004.
6. A. Ohtomo, M. Kawasaki, T. Koida, K. Masubuchi, H. Koinuma, Y. Sakurai, Y. Yoshida, T.
Yasuda, and Y. Segawa, Appl. Phys. Lett. 72, 24661998.
7. M. Asada, A. Kameyama, and Y. Suematsu, IEEE J. Quantum Electron. QE-20, 7451984.
8. G. Coli and K. K. Bajaj, Appl. Phys. Lett. 78, 28612001.
9. H. D. Sun, T. Makino, Y. Segawa, M. Kawasaki, A. Ohtomo, K. Tamura, and H. Koinuma, J.
Appl. Phys. 91,19932002.
10. D. C. Reynolds, D. C. Look, B. Jogai, J. E. Hoelscher, R. E. Sherriff, M. T. Harris, and M. J.
Callahan, J. Appl. Phys. 88, 21522000.
Nhng
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NH GI S TR NHIT TRONG PHP O NHIT PHT QUANG V CC

THAM S NG HC BNG PHNG PHP THAY I TC GIA NHIT
V Th Thi Ha, Nguyn Th Qu Hia v Nguyn Ngc Longb
a)
Vin Khoa hc vt liu, 18 Hong Quc Vit, Cu Giy, H Ni

b)
Khoa Vt l, H Khoa hc T nhin H Ni
E-mail: havtt@ims.vast.ac.vn
Tm tt: Phng php thay i tc gia nhit c s dng nh gi cc thng s

ng hc ca by lin quan n nh o liu ca vt liu nhit pht quang LiF: Mg, Cu, Na, Si.
Vt liu LiF: Mg, Cu, Na, Si dng bt pha tp 0,2 mol% Mg, 0,6 mol% Cu and 2 mol% NaSi
c ch to ti phng th nghim Quang ph ng dng v Ngc hc bng phng php
phn ng pha rn. Mt ngun pht tia X c s dng chiu x. Cc ng TL c o
trn my Harshaw TLD 3500. Tc gia nhit trong qu trnh c liu c thay i t 1 K.s -1
n 30 K.s-1. Nhit cc i nh v cng ca nh o liu bin i nh mt hm ca tc
gia nhit; s ph thuc ny c s dng xc nh nng lng kch hot E v tha s tn
s s ca nh o liu. nh hng ca s tr nhit gy ra bi s tip xc khng hon ho gia
thanh t v liu k cng c xc nh. Gi tr ca cc tham s by thu c t s liu thc
nghim v s liu tnh ton sau khi hiu chnh s tr nhit c nh gi v so snh.
T kha: Phng php thay i tc gia nhit;s tr nhit, nhit cc i nh.
1. Gii thiu
Thay i tc gia nhit (heating rate) l mt phng php rt c bn trong cc php o
nhit pht quang (thermoluminescence (TL)). i vi cc vt liu o liu, liu hp th thng
c nh gi t s ph thuc ca ng p ng TL cng tch phn din tch nh TL
(hoc theo chiu cao ca nh TL). C hai thng s ny (cng TL tch phn v chiu cao
nh o liu) u b nh hng bi s thay i tc gia nhit [1]. Taylor v Lilley (1982)
ch ra rng s thay i cng nh gy ra bi s thay i tc gia nhit c th nh hng ti
vic xc nh cc tham s by E ( su by) v s (tn s thot) [2].
Khi biu din ng TL theo nhit , nhit m my ghi nhn chnh l nhit ca thanh
t, nhit ny khc vi nhit thc ca mu. S khc nhau ny gy ra bi tip xc khng l
tng gia thanh t v mu v c gi l tr nhit (temperature lag (TLA)). nh hng ca
TLA trong cc php o TL c nhiu nhm tc gi nghin cu v cho thy rng n nh
hng n gi tr ca cc tham s by ca nh pht quang [3, 4].
Mc ch ca bi bo ny l dng phng php thay i tc gia nhit v s dng cc tnh
ton m G. Kitis v J. W. N. Tuyn [4, 5] gii thiu p dng cho vt liu LiF: Mg, Cu, Na,
Si do chng ti ch to [6].
2. Thc nghim
Vt liu LiF: Mg, Cu, Na, Si dng bt do chng ti ch to c s dng trong cc th
nghim ny. My pht tia X c s dng lm ngun chiu x. Cc php o TL thc hin trn
my Harshaw TLD 3500. Tc gia nhit thay i t 1 K.s-1 (tc thp nht c th ca my
o) n 30 K.s-1.
Kitis v Tuyn [5] a ra mt phng php n gin hiu chnh tr nhit ch da vo
php o TL theo phng trnh sau:
Advances
_____________________________________________________________________________________
Tm( j )
Tm(i )
c ln
(1)
vi Tm( j ) v Tm(i ) l nhit cc i ca nh pht quang vi tc gia nhit tng ng l j v

i; c l hng s.
Cc bc thc hin c tin hnh nh sau:
- o TL theo cc tc gia nhit khc nhau. Hng s c trong phng trnh (1) c xc nh
bng hai tc gia nhit rt thp (khi TLA l khng ng k, c th b qua). Chng ti s
dng = 1 K.s-1 v 2 K.s-1, c = (Tm, = 2 Tm, = 1)/0,693.
- S dng phng trnh (1) v gi tr c tnh cc gi tr Tm ng vi cc tc gia nhit khc
nhau ( i =1 K.s-1, j = 1,., 30 K.s-1).
- tr nhit ( T) ti v tr cc i nh l T = Tg Tm vi Tg l gi tr nhit ti cc i
nh c c tr nhit (gi tr thu c bng thc nghim) v Tm l gi tr nhit tnh ton t
bc 2.
3. Kt qu v tho lun
Dng ng cong nhit pht quang ca
vt liu LiF: Mg, Cu, Na, Si c biu din
trn hnh 1. Trong khong nhit t 50
3600C, c t nht 5 nh. Tuy nhin, nh
chnh hay cn c gi l nh o liu c
cng ln hn rt nhiu so vi cc nh
cn li. Khi thay i tc gia nhit, vic xc
nh cc thng s ca nh chnh cng d
dng hn rt nhiu nn mi tnh ton trong
bi bo ny ch c thc hin cho nh
chnh.
3.1. V tr nh o liu v chiu cao nh
thay i theo tc gia nhit
Hnh 2: Nhit cc i nh chnh thay i

theo tc gia nhit
Hnh 1: ng cong TL ca LiF: Mg, Cu, Na, Si

o theo cc tc gia nhit khc nhau
Hnh 3: Cng nh thay i theo tc

gia nhit
Nhng
_____________________________________________________________________________________
ng cong TL ca vt liu o liu c o trn my Harshaw theo cc tc gia nhit khc

nhau l = 1, 2, 5, 10, 15, 20 v 30 K.s -1 ; vi mi tc gia nhit, php o c thc hin 5 ln
ly gi tr trung bnh. S thay i ca nhit cc i nh o liu c trnh by trn hnh 2.
Khi tc gia nhit tng, nhit cc i nh dch v pha nhit cao. Kt qu ny l hon
ton ph hp vi l thuyt v cc nhm tc gi khc. i vi cc vt liu o liu, s ph thuc
ca nhy ca liu k vo tc gia nhit trong qu trnh c liu l rt quan trng. nhy
ny ta c th ly theo tch phn din tch ton b ng TL hoc ly theo chiu cao nh o liu.
Vi vt liu s dng trong bi bo, chng ti ly theo chiu cao nh. Chiu cao ca nh o liu
thay i theo tc gia nhit c trnh by trn hnh 3. Kt qu thu c cho thy p ng TL
tng khi tc gia nhit tng t 1 K.s-1 n khong 20 K.s-1. So vi cc vt liu nhit pht quang
khc, xu hng nhy tng khi tng l rt him gp, tuy nhin n xy ra i vi LiF: Mg,
Ti v c Piters v Bos gii thch bi s tng tc gia cc khuyt tt trong qu trnh c tn
hiu TL [7].
3.2. S tr nhit
Cc gi tr nhit cc i nh o liu thc nghim (k hiu l Tg) c so snh vi cc gi
tr cc i tnh theo bc 2. Kt qu trn hnh 4 cho thy c mt s chnh lch ng k gia hai
gi tr ny khi tng tc gia nhit.
Hnh 4: So snh Tm thc nghim v tnh ton

theo tc gia nhit.
Hnh 5: tr nhit nh mt hm ca tc
gia nhit
T cc gi tr nhit cc i nh thc nghim v tnh ton, ta cn c th tnh c gi tr

tc gia nhit hiu dng theo cng thc m Kitis v Tuyn a ra nh sau:
Tg T0
T
eff
T0 l nhit phng (T0
Tg
T0
300 K).
Bng 1: Cc gi tr thc nghim v tnh ton khi thay i tc gia nhit

-1
(K.s )
1
2
5
10
15
20
30
Tm thc
nghim
(K)
489.78
497.54
510.27
521.55
529.76
536.54
546.27
Tm tnh ton
(K)
489.78
497.54
507.80
515.56
520.10
523.32
527.86
tr
nhit (K)
0
-0.00
2.46
5.98
9.65
13.21
18.40
hiu dng
(K.s-1)
1
2.00
4.94
9.73
14.38
18.91
27.82
Advances
_____________________________________________________________________________________
3.3. Nng lng ca nh o liu

T cc gi tr Tm thc nghim v tnh ton nh trong bng 1, v th ca ln(Tm2/) theo
1/kTm (hnh 6) ta c th xc nh c gi tr ca E ng vi nh o liu. Gi tr chng ti thu
c l E = 1.897 0.017 (eV). Theo l thuyt m Kitis v Tuyn a ra th c = TiTj(k/E), mt
khc c l mt hng s c tnh theo bc 1 nu trn, ta c th thy E l mt hm ca gi tr
cc i nh v do E bin thin theo tc gia nhit. Vi Ti l gi tr Tm khi = 1 K.s-1 v Tj
l Tm ng vi cc gi tr khc, ta xc nh c cc gi tr E bin thin theo tc gia nhit
nh trn hnh 7.
N ng l- ng kch ho t (eV)
2.05
a - Nng l-ng tnh theo cc gi tr thc nghim

b - Nng l-ng tnh khi khng c tr nhit
a
2.00
1.95
1.90
1.85
10
15
20
25
30
-1
Tc gia nhit (Ks )
Hnh 7: Nng lng kch hot E thay i

theo tc gia nhit
Hnh 6: th ln(Tm2/) theo 1/(kTm). ng (a) l

cc gi tr thc nghim; ng (b) l cc gi tr c
hiu chnh tr nhit.
3.4. nh hng ca tc gia nhit i vi tn s s.

Gi tr tn s s c tnh t cng thc s
E
E
exp
2
kTm
kTm
Bng 2: Cc gi tr ca E v s trong hai trng hp c
v khng c tr nhit
-1
(Ks )
Hnh 8: T s sg/sm thay i theo
1
2
5
10
15
20
30
E theo E theo sg tnh theo sm tnh theo

Tm thc Tm tnh Tm thc Tm tnh ton
nghim ton nghim (s-1)
(s-1)
(eV)
(eV)
1,842
1,842 8.832E17
8.832E17
1,871
1,871 1.739E18
1.739E18
1,919
1,910 4.239E18
4.259E18
1,961
1,939 8.294E18
8.391E18
1,992
1,956 1.224E19
1.247E19
2,018
1,968 1.612E19
1.653E19
2,054
1,985 2.375E19
2.458E19
Vi mi gi tr E tng ng vi gi tr Tm v khc nhau trong c hai trng hp c v khng

c tr nhit, ta thu c cc gi tr s tng ng. Cc gi tr E v s bin i theo tc gia nhit
c tp hp trong bng 2. th trong hnh 8 biu din s thay i ca t s sg/sm vi sg l gi
tr tha s tn s tnh t gi tr thc nghim (c tr nhit); sm l gi tr tnh theo cc gi tr ca E
v Tm khi khng c tr nhit. Khi thay i tc gia nhit, chnh lch gia gi tr ln nht v
Nhng
_____________________________________________________________________________________
nh nht ca nng lng kch hot E vo khong 10% v chnh lch gia cc gi tr ca s l vo
khong 96%.
4. Kt lun
Bng phng php thay i tc gia nhit v da vo vic xc nh s thay i ca v tr
cc i nh o liu xc nh c tr nhit gy ra bi tip xc khng hon ho gia thanh
t v vt liu.
V tr cc i nh dch v pha nhit cao khi tng tc gia nhit l hon ph hp vi l
thuyt v kt qu ca cc nhm nghin cu khc. Chiu cao nh o liu cng tng theo chiu
tng ca tc gia nhit, xu hng ny ch xy ra vi LiF v mt vi vt liu nn Li2 B4O7; n
hon ton tri ngc vi Al2O3:C.
T th (Tm2/) theo 1/kTm xc nh c gi tr ca E ng vi nh o liu 1,897
0,017 (eV). Gi tr ny cng nm trong khong ph hp vi cc cng b ca cc tc gi khc trn
th gii.
Khi tc gia nhit thay i, cc thng s ca by lin quan n nh o liu l E v s bin
thin nh mt hm ca tc gia nhit.
Ti liu tham kho
1. F. O. Ogundare, F. A. Balogun and L. A. Hussain, Heating rate effects on the
thermoluminescence of fluorite, Radiation Measurements 40 (2005), 60 64.
2. G. C. Taylor and E. Lilley, Rapid readout rate studies of thermoluminescence in LiF (TLD100) crystals: III. J. Phys. D: Appl. Phys. 15 (1982), 2053 2065.
3. A. S. Pradhan, Influence of heating rate on the TL response of LiF TLD-700, LiF: Mg, Cu, P
and Al2O3: C, Radiat. Prot. Dosim, Vol.58, No. 3 (1995), 205 209.
4. G. Kitis and J. W. N. Tuyn, A simple method to correct for the temperature lag in TL glow
curve measurements, J. Phys. D: Appl. Phys. 31 (1998), 2065 2073.
5. G. Kitis and J. W. N. Tuyn, Correction for temperature lag and thermal gradient effects
arising during thermoluminescence readout, Radiat. Prot. Dosim, Vol.84, Nos. 1- 4 (1999),
371 374.
6. V. T. T. Ha, N. T. Q. Hai, N. N. Long and L. V. Vu, Preparation and characteristics of LiF:
Mg, Cu, Na, Si thermoluminescent material, VNU Journal of Science, Mathematics
Physics 23 (2007) 225 231.
7. G. Kitis, C. Furetta, M. Prokic and V. Prokic, Kinetic parameters of some tissue equivalent
thermoluminesce materials, J. Phys. D: Appl. Phys. 33 (2000), 1252 1262.
Advances
_____________________________________________________________________________________
CH TO V KHO ST MNG PHT QUANG NGC S DNG LP VI

CU MICRO V NANO
Phm Hng Dnga, Ngc Chungb, Phm Thnh Huyc,
Nguyn Th Thanh Ngna v Phm Thu Ngaa
a)
Vin Khoa hc Vt liu (IMS), Vin Khoa hc v Cng ngh Vit Nam (VAST),
18 Hong Quc Vit, Cu Giy, H Ni
b)
i hc Cng Ngh, i hc Quc Gia HN
c)
Vin Tin Tin Khoa hc v Cng ngh (HAST), trng i hc Bch Khoa H Ni,
s 1 i C Vit, H Ni.
Tm tt: Mng pht quang ngc l mng c hng pht nh sng hunh quang quay tr li vi
hng nh sng kch thch. ch to mng pht quang ngc, chng ti ph mt lp mng
hunh quang mng ln thu tinh. Sau mt lp bi cu bng thu tinh hoc SiO2 c tri
u ln b mt ca lp mng hunh quang. ng knh ca ht bi cu thu tinh khong 35 m,
cn ng knh ca bi cu SiO2 khong 300 nm. Lp bi cu c tri ln b mt mng hunh
quang bng mt cch thc c bit, sao cho t nht mt phn ca b mt bi cu l ra ngoi khng
kh. Khi mng c chiu bng tia laser t ngoi, phn b cng hunh quang theo gc ca
mng lun lun c mt hng u tin, trng vi hng ca laser kch thch, d mu c b tr
theo hng no i na. Phn b cng hunh quang theo gc c o bng mt phng php
c bit, cho ta kt qu c th biu din bng th 3 chiu. S ph thuc ca s phn b theo
gc ny vo tnh cht ca mng hunh quang s c chng ti tho lun.
1. M u
Vt liu pht quang c nghin cu ng dng rng ri trn th gii trong vic ch to
tem nhn bo mt, di dng mc in dng cho cc my in phun v in offset [1, 2]. Vt liu
c dng cho mng pht quang c th l bt hunh quang cha ion t him, cht mu hay
chm lng t. Mng bo mt c ch to bng nhiu phng php khc nhau nh in phun, in
li, in offset, vi vt liu pht quang trong sut hoc c mu ln trn mu giy khng pht
quang. Khi chiu bng n nh sng en (black light 370 nm), hnh nh hunh quang ni trn
nn ti, gip chng ta phn bit tht gi. Yu cu ca loi mng bo mt ny l kh lm gi,
nhng d quan st di nh n UV, v vy cng pht quang v mu sc nh sng hunh
quang ng vai tr rt quan trng. Trong bi vit ny, chng ti thng bo v kt qu nghin
cu ca chng ti v vic to ra mt loi mng pht hunh quang c cu trc c bit sao cho
cng nh sng hunh quang mnh hn i vi ngi quan st, trong trng hp ngi
quan st eo ngun sng UV gn vi mt ca mnh. Ngun sng ny c th l mt n LED
pht UV, eo ln trn ngi quan st. Ngoi ra, nu ngi quan st thay i gc gia ngun
sng UV v mt mnh, mu sc ca mng pht quang s thay i.
Mng pht quang do chng ti ch to c gi l mng pht quang ngc, tc l mng c
hng pht nh sng hunh quang quay tr li vi hng nh sng kch thich. Mng pht quang
ngc c cu trc gn ging nh cu trc ca mng phn x ngc c dng trong bin bo
giao thng, tuy nhin, thay cho lp phn x l lp hunh quang. Mng pht quang ngc cho
cng hunh quang ln v phn b nh hng u tin theo hng kch thch.
Mng pht quang ngc bao gm 2 thnh phn chnh: lp pht quang v lp nh hng
hunh quang. Lp pht quang l loi mc hunh quang, hoc cht mu vi cc bc sng
hunh quang khc nhau. Lp nh hng c to bi cc ht bi hnh cu c kch thc vi
trm nanomet n vi chc micromet. Bi cu kch thc di micromet c th dng cho mc in
dng my in phun, trong trng hp chit sut ca bi cu cao (n=2), khi , bi cu c th trn
vo trong mc in. Bi cu ln hn i hi phng php ph ring, sau khi tri mng hunh
quang.
Nhng
_____________________________________________________________________________________
Vic kho st phn b cng theo gc c th c thc hin bng k thut m t trong
cng trnh [3], kt hp dng goniometer quay mu trn mt gi quang hc c thit k c
bit lun gi v tr c nh gia mu v u thu. Phng php ny cho phn gii tng i
cao (1 mrad) nhng di o b hn ch v ch o c gc quay theo 1 chiu. c s gi ca
GS L S ng (i hc Grenoble), chng ti xy dng c mt phng php o phn b
cng theo gc dng u thu CCD, cho ta hm phn b theo 2 chiu vi phn gii cao
hn rt nhiu so vi phng php o phn b gc thng thng. nh chp phn b cng
theo gc c phn tch v biu th 3 chiu vi phn gii cao. K thut ny cng m ra mt
trin vng mi ng dng trong vic to nh trng gn, khi dng mng vi cu thch hp thu
thp tn hiu pht ra t v tr rt gn b mt ca mu. nh trng gn hin nay c to ra bng
knh hin vi trng gn dng u d lm bng dy dn quang, c l kch thc nh cho tia laser
i qua khong vi chc nanomet [4, 5]. Khi i qua l nh ny, nh sng vi bc sng vi trm
nanomet ca tia laser b nho ra, v ch c b mt gn vi l nh ca mu tng tc mnh nht
vi tia laser. nh trng gn c ghi ln lt tng im mt, trong khi nh chp phn b
ca lp mng tri bi cu c ghi cng mt lc nh u thu CCD.
2. Thc nghim, kt qu v tho lun
Mng pht quang ngc c
cu trc nh s hnh 1, bao
gm lp vi cu, lp pht hunh
quang v . Lp vi cu c sp
xp u trn lp pht quang. Lp
pht quang l mc in hunh
quang c ph trn l thu
tinh hoc giy nh bng k thut
quay ph. Lp vi cu c ph
sao cho mt phn c l ra
Hnh 1: Cu trc mng pht quang ngc
khng kh. Trong nghin cu ca
chng ti cc mu c ch to vi hai loi vi cu khc nhau c kch thc tng ng khong
300 nm v 35 micromet.
Lp vi cu c tc dng tp trung nh sng kch thch v nh hng hunh quang. Chm
sng laser kch thch t cc gc khc nhau s hi t ti cc im nm trn tiu din ca cc vi
cu. Ti tiu im, cng pht hunh quang mnh hn. Hunh quang li c lp vi cu
nh hng v pht ngc tr li hng chm sng kch thch. Khi chm sng kch thch l mt
chm sng song song nh chm tia laser, chm tia hunh quang pht ra cng c hng u tin
song song vi tia laser. Nu v tr quan st xa mu nhng gn vi v tr chm tia kch thch,
cng hunh quang quan st c s mnh hn nhiu ln so vi trng hp mng pht
quang thng thng, khi m phn b cng hunh quang l ng u theo cc gc.
nh gi kh nng nh hng ca quang hunh quang nh vo lp vi cu, chng ti
tin hnh o s phn b cng hunh quang theo gc ca mu pht quang. Phng php o
phn b cng theo gc c dng kh ph bin trong c hai trng hp, mt l phn b
cng ca cc ngun sng (v d nh n, LED, laser) theo gc, hai l phn b cng tn
x hoc pht x nh sng ca mu khi chiu chm sng kch thch vung gc vi b mt mu.
Trong trng hp o phn b ca ngun sng, mu o c t ln mt b qut gc
(goniometer), nh sng pht ra c ghi bng mt u thu t kh xa mu. Cn trong trng
hp tn x hoc pht hunh quang, do ngun kch thch kh cng knh, cho nn ngi ta chn
gii php di chuyn u thu. Cc tc gi trong cng trnh [3] a ra mt cu hnh trong
Advances
_____________________________________________________________________________________
mu o tn x c
t ln goniometer, ngun
kch thch t ngoi m vn
m bo iu kin chiu
vung gc vi mt mu.
Tuy nhin, tt c cc
phng php trn u c
hn ch v phn gii ca
php o do kch thc mt
pht quang khng phi mt
Hnh 2: S nguyn l phng php chp nh hm phn b cng
im, do kt qu phn
theo gc
b khng hon ton l phn
b gc, hn na, kch thc u thu li kh ln, v vy phn gii khng cao.
Chng ti pht trin mt phng php o mi c phn gii cao, hn na, kt qu o
li cho chng ta hnh nh phn b cng theo hai chiu, thay v phn b theo mt chiu ca
cc phng php o m t trn. Phng php ny da trn hai bc, mt l hi t tt c cc
tia sng song song thnh mt im (bin phn b cng theo gc thnh nh phn b), hai l
sau dng u thu CCD ghi bc nh ny. Bc cui cng l x l nh v hin th thnh
th 3D theo yu cu. Phng php o c ny c thc hin nh trn s hnh 2. Xt hai
chm tia hunh quang pht ra t mu S c cng phn b theo hai hng: hng trng vi
trc ca h o c cng I1 v hng lch so vi trc ca h o gc c cng I2. Mu
c t ti tiu c ca L1, qua L1 chm tia theo 2 gc khc nhau c hi t ti 2 v tr trn
mt phng tiu din F ca L1. Nh vy, nh cng trn mt F biu th hm phn b theo gc
ca chm tia. Phn b cng ti mt F c hi t ln CCD ca my nh k thut s hoc
CCD lm lnh chuyn dng (trong trng hp cng hunh quang yu). nh phn b ti v
tr F l nh thc, v vy chng ti dng mt mn nh tn x bn trong sut lm mc chnh
nh r nt trn mn. Mn nh lm mc c b ra sau khi ly nt. Lc ny nh c chp trn
CCD l nh phn b cng hunh quang theo gc. nh chp c lu di dng file th
(Raw file) v c x l bng phn mm Origin 8.0. Kt qu phn tch c hin th 3 chiu
(3D) hoc mt ct hai chiu (2D). Vic chun ho gc c xc nh bng cch dng 2 chm
tia laser He-Ne chiu vo mt tm knh trong sut t ti v tr mu S vi mt gc nh xc nh
trc, sau thay mu vo ng v tr ny tin hnh php o.
My nh chng ti s dng l my nh Olympus C7070 c tiu c 5,7-22,9 mm, khu
2,8-4,8, kch thc CCD l 3,99 5,32 mm. Vic s dng my nh ch c th thc hin c
trong trng hp cng nh sng ln, v d nh sng trc tip pht ra t ngun sng,
hoc nh sng tn x sau khi chiu mu bng mt chm tia laser. Khi nghin cu phn b gc
ca nh sng hunh quang, cn phi s dng vt liu pht hunh quang mnh nh cht mu
hoc chm lng t. Khi cng nh sng hunh quang khng ln, chng ti phi s dng
CCD lm lnh (PI Acton PIXIS:256E), gn vi quang ph k PI Acton MicroSpec-2356 hot
ng ch to nh gng.
Phng php chp nh hm phn b cng theo gc c u im rt ln l phn gii
rt cao, c th t ti 12 Mpx, tc l 3000x4000 im nh. Hn th na, nh hm phn b theo
gc li l phn b theo gc khi, c th dng thnh th 3D, trong mt chiu l cng
nh sng, cn hai chiu kia l gc. Mt hn ch ca phng php ny l ch c th o c hm
phn b trong mt gii hn gc nht nh. Gii hn ny ph thuc vo ng knh, tiu c ca
thu knh L1, kch thc CCD ln ca khu . Ni tm li, u th tuyt i ca phng
php ny nm vic ghi nhn hm phn b theo gc nhng mu c gc nh, vi phn gii
cao. Vi my nh chng ti s dng, c th o c hm phn b cng theo gc ca mu
pht trong hnh nn c gc khi l <= 500, do thu knh L1 c ng knh 25 mm v tiu c l
30 mm.
Nhng
_____________________________________________________________________________________
Do c im ca cc
mng pht quang ngc l
pht x hunh quang
ngc tr li hng laser
kch thch nn chm tia
laser c a vo mu
bng tm chia tia c
R=50%. Laser kch thch
c bc sng 442 nm,
c b tr hi t qua L3
ti tm chia tia R, qua
Hnh 3: S th nghim chp nh phn b cng theo gc
thu knh L1 v chiu
ca mu hunh quang
song song ti mu S.
Do thu knh L1 c tiu c
ngn nn tin li cho vic b tr,
thu knh L2 c t thm to
nh 1-1 ca mt F, F l nh ca F
qua L2. Filter c tc dng ngn
bc sng 442 nm laser kch thch
vo CCD. Trong s ny, mn nh
m T c t ti F lm tng th
trng ca php o. Sau khi iu
chnh my nh sao cho ng v tr v
thu c chnh xc nh ca mt
Faraday, h o c c nh v ch
thay i cc mu cn o.
Chng ti ch to cc mu
o nh sau:
Mu D1: dng cht mu
Hnh 4: Ph hunh quang hunh quang ca giy nh (I1),
Rodamine 6G phn tn trong khi
mc in hunh quang (I2), mu M2 (I3)
PPMA, sau c thnh khi tr
ng knh 20 mm, dy 5 mm. Lp vi cu 35 m c ri u ln mt phn b mt, sau khi
dng dung dch aceton lm tan mt lp mng trn b mt PPMA, dng lm keo dnh. Mu M2:
dng mc hunh quang chuyn dng cho my in phun Epson in mt lp mng ln giy trng
bng k thut in li, sau khi mc sp kh, tri lp bi cu ln trn mt phn b mt.
Hnh 4 l th ph quang hunh quang ca mu 2 c hunh quang mu ph trn l
giy nh. ng cong I1 l ph hunh quang ca giy nh, ng cong I2 l ph hunh quang
ca mc in hunh quang ph trn giy nh khng c lp vi cu v ng cong I3 l ph mu
M2.
Lp vi cu khng lm thay i dng ca ph hunh quang, m ch lm thay i nh
hng cng hunh quang. Tuy nhin, nh lp vi cu quang hunh quang thu c bao gm
c ph ca v ph ca mc in hunh quang, cng ca tng ph ph thuc vo gc quan
st. y cng l mt c im c th s dng lm vic nhn bit trn cc tem hay nhn mc
nh du, l s thay i mu sc khi thay i gc nhn so vi ngun kch thch.
Hnh 5 cho ta th phn b 3D ca mu hunh quang khi cha c lp vi cu v c lp vi
cu biu din di dng 3D t cc file nh chp c. Trong trng hp cha c lp vi cu, s
phn b cng hunh quang theo gc ca mu D1 v mu M2 l kh u. Khi c thm lp
vi cu, cng quang hunh quang mnh hn v c s phn b nh hng theo hng laser
kch thch. Hnh 6a l th mt ct ti tm ca mt phn b cng quang hunh quang theo
gc ca mu D1 v mu M2, km theo nh chp tng ng.
Advances
_____________________________________________________________________________________
(a) mu D1 khng c lp vi cu
(b) mu D1 c lp vi cu
(c) mu M2 khng lp vi cu
(d) mu M2 c lp vi cu
Hnh 5: Biu din 3D phn b cng theo gc ca mu Dye v mu mc in hunh quang
(a)
(b)
Hnh 6. th mt ct ti tm ca phn b cng hunh quang theo gc
Hnh 6b l th h s khuch i (gain) ca cng quang hunh quang ca mu D1 v

mu M2 trong trng hp c lp vi cu so vi trng hp khng c lp vi cu. H s khuch
i c tnh bng cch ly cng ca mu c vi cu chia cho mu khng c vi cu.
T th hnh 6a ta thy cc mu D1 v M2 c lp vi cu, s phn b cng ca hunh
quang l hp hn rt nhiu v c nh hng.
Ngoi cc mu vi cu micro, chng ti tin hnh ch to cc mu vi vi cu ng knh
khong 300 nm trn cc mu mng hunh quang. Cc php o kho st c tin hnh
tng t nh i vi cc mu s dng vi cu micro. Tuy nhin, kt qu nhn c cn cha
c nh mong mun v cc mu s dng vi cu 300 nm cha c s nh hng hunh quang
r nt. Theo nhn nh ban u ca chng ti, nguyn nhn c th do k thut ph cc ht cu
nano cha ph hp, bi vi cu b chm vo mng hunh quang.
Nhng
_____________________________________________________________________________________
3. Kt lun
Chng ti ch to c mng pht quang ngc, trong lp vi cu c vai tr lm cho
cng quang hunh quang c tng cng v c nh hng pht x ngc tr li
hng laser kch thch. Tnh cht nh hng ca mng pht hunh quang ny c kho st
bng k thut chp nh phn b cng theo gc cho ta phn gii cao theo 2 chiu khng
gian. Kt qu cho thy, mng pht quang ngc dng bi cu kch thc 35 m cho ta mt s
tnh nng mi c th ng dng c trong k thut nh du. Vic to mu dng bi cu c kch
thc nh hn cn c nghin cu thm, c bit l loi bi cu c kch thc nh hn bc
sng nh sng.
Li cm n
Cng trnh ny c ti tr mt phn bi chng trnh NCCB trong lnh vc vt l.
Ti liu tham kho
1. Kuhn et al. Scientific American, April 1979, 162-178.
2. Keeling, Phys. Technol., 12 (5) 196-303 (1981).
3. D. S. Wiersmaa, Meint P. van Albada, Ad Lagendijk, Rev. Sci. Instrum., Vol. 66, No. 12,
December 1995.
4. Nanophotonics, Paras N. Prasad, Published by Wiley, (2004), p. 66
5. Near-filed Nano-Optics: From basic principles to Nano- Fabrication and Nano- Photonics.
Author: Motoichi Ohtsu, and Hirokazu Hori. (1993)
Advances
_____________________________________________________________________________________
NGHIN CU CH TO LP SILIC CACBUA XP KCH THC NAN

TRN MNG SILIC CACBUA V NH HNH PHA TP LOI p, LOI n V
TNH CHT HUNH QUANG CA N
Cao Tun Anha, o Trn Caob, Nguyn Th Thu Hb, Hunh Th Hb,
Phm Th Mai Hoab,c, Phm Hng Dngb v Nguyn Th Thanh Ngnb
a)
Vin Vt l, Vin Khoa hc v Cng ngh Vit Nam, 10 o Tn, H Ni, Vit Nam
b)
Vin Khoa hc Vt liu, Vin Khoa hc v Cng ngh Vit Nam
c)
Delft University of Technology Mekelweg 4, 2628 CD Delft, the Netherlands
E-mail: ctanh@iop.vast.ac.vn
Tm tt. Trnh by cc nghin cu ch to lp xp vi cc l xp kch thc nan trn
mng SiC v nh hnh pha tp loi p v loi n (ph ln Si) bng phng php n
mn in ho trong dung dch HF/H2O/cht hot ho b mt (Triton X-100). quan
st thy rng vi vic thay i cc iu kin n mn in ho nh nng HF, nng
Triton-X100 trong dung dch in ho, mt dng in ho, thi gian in ho, kch
thc v mt cc l xp cng nh tnh cht hunh quang ca lp aSiC xp thay i.
T kho: SiC xp, mng mng, ant ho, hunh quang
1. M u
Silic cacbua (SiC) l mt vt liu hin ang c quan tm nghin cu nhiu trn th gii
cng nh Vit Nam nh n c nhiu c tnh th v nh vng cm rng, th nh thng ln,
dn nhit tt, dng cun bo ho ca in t cao, bn vng nhit cao v tr i vi cc tc
ng ho hc. Vt liu SiC xp (PSiC) ngoi cc c tnh trn cn c mt tnh cht rt ng quan
tm na, l s pht quang vng nh sng mu xanh dng-xanh l cy. Tnh cht pht quang
ca PSiC hin nay ang rt c quan tm bi v khng ging nh s pht quang mu ca silic
xp (PSi), tnh cht pht quang ca PSiC b suy gim rt t trong khng kh nhit phng
[1,2].
Trong mt cng b nm 2007 [3], chng ti tm ra cch to ra lp SiC xp trn mng SiC
v nh hnh khng pha tp (i-aSiC) c dy ln (3-6 m). y l mt vic kh kh do mng
i-aSiC vi dy ln nh trn c in tr sut rt cao. Chng ti phn no gii quyt c
nhim v ny bng cch dng dung dch in ho gm 72% HF (48%), 27% H2O c cho thm
1% Triton X-100 ng vai tr cht hot ho b mt, km theo dng th in ho rt cao (n 500
V i vi lp i-aSiC dy 6 m). Tuy vy, do xp t c cha cao nn nm nay chng ti
tip tc nghin cu n mn in ho i-aSiC vi cc dung dch c nng HF v Triton X-100
khc nhau v cc kt qu thu c s c cng b trong [4]. Cn trong cng trnh ny chng ti
tp trung vo nghin cu n mn in ho ch to lp xp trn cc mng aSiC c pha tp loi
p hoc loi n (p-aSiC v n-aSiC) v nghin cu tnh cht hunh quang ca chng.
C hai l do chng ti la chn hng nghin cu v mng aSiC xp. Th nht, mng
aSiC xp mi ch c nghin cu rt t, trn bo ch chng ti ch tm c mt vi bi [5-7]
nghin cu v i tng ny. Cho n nay phn ln cc tc gi ch tp trung vo nghin cu mng
SiC tinh th (cSiC) xp. Th hai, mng aSiC d ch to hn, gi thnh r hn so vi mng cSiC,
nhng chc chn vn ha hn nhiu ng dng, c trc cng nh sau khi lm xp.
Nhng
_____________________________________________________________________________________
2. Thc nghim
2.1. n mn in ho mng mng aSiC loi p v loi n
Mng mng aSiC ban u vi chiu dy 3 m c ch to bng phng php PE-CVD
lng ng 400oC ln Si v trong qu trnh lng ng chng c pha tp bo (mu loi p)
hoc phospho (mu loi n). Sau Al c bc bay trong chn khng c km theo nhit ln
cc phin aSiC/Si ny c th p t in th ln mu khi n mn in ho. Tip theo, cc phin
aSiC/Si c Al trn mt sau c ct thnh cc mu vi kch thc 1,5 cm x 1,5 cm. Trc khi
n mn in ho cc mu aSiC/Si c gn ln gi v sau ph lp bo v bng
polystyrol ln 4 ra mu m bo sao cho trong sut qu trnh in ho ch c b mt aSiC tip
1% HF, 1% Triton, 30 pht
2,5% HF, 1% Triton, 30 pht
Hnh 1. nh SEM ca cc mu p-aSiC

sau khi n mn in ho trong cc dung
dch c nmg HF khc nhau, cc iu
kin khc nh nhau (cc im en l cc
v tr p-aSiC b n mn cc l xp).
xc vi dung dch in ho. Vic bo v mu bng lp ph polystyrol l mt sng to mi m

chng ti a ra trong [3]. Lp polystyrol bo v, trnh cho Si v lp Al khi b n mn bi
dung dch, nhng sau khi n mn n li c th d dng c bc i bng cc bin php c hc,
khng phi dng n dung mi ho tan, nh m khng gy bn cho b mt aSiC c lm
xp. Nu ta ghi nh rng sau khi lm xp b mt aSiC c rt nhiu l xp kch thc nan, ta s
hiu rng vic m bo sao cho b mt aSiC xp l sch, khng b dnh bn ho cht l mt vn
quan trng nh th no.
Trc ht xin ni v s n mn in ho cc mu aSiC loi p (p-aSiC). Chng ti n mn
in ho p-aSiC trong cc dung dch in ho c nng HF khc nhau vi mc ch tm ra dung
dch c kh nng xp ho p-aSiC tt nht. Cc kt qu c minh ho bng hnh 1. y l cc
nh SEM chp b mt ca cc mu p-aSiC sau khi c n mn cng mt ch (dng in
ho 1mA, thi gian 30 pht) trong cc dung dch cng cha 1% Triton, nhng c nng HF
khc nhau, tng ng l 1%, 2,5% v 5%. T hnh 1 ta d dng nhn thy rng dung dch 1%HF
c kh nng xp ho p-aSiC tt nht. Nng HF trong dung dch cng cao th mt l xp
cng tr nn tha hn. Tuy nhin cn nhn xt rng cc dung dch vi nng HF khc nhau u
cho cc l xp tng t nhau v hnh dng v kch thc, vi kch thc l xp c 20nm.
Advances
_____________________________________________________________________________________
Chng ti cng nghin cu xp ca lp p-aSiC xp ph thuc vo thi gian n mn.

Hnh 2 l nh SEM ca cc mu p-aSiC sau khi n mn vi dng 1mA, trong dung dch cha 1%
HF v 1% Triton, vi thi gian n mn thay i t 10 n 30 pht. T hnh 2 thy r rng khi
c n mn trong cng mt iu kin, mu c in ho lu hn s c mt l xp cao hn,
nhng kch thc l xp hu nh khng thay i. ng ch l nghin cu n mn i-aSiC [4]
cng cho cc kt qu tng t.
Tip theo nghin cu s nh hng ca Triton ln xp ca lp xp thc hin trn
p-aSiC. Hnh 3 l nh SEM ca cc mu p-aSiC sau khi n mn trong cc iu kin tng t
nhau, ch khc l dung dch cha 0% hoc 0,1% Triton. Hnh 3 cho thy Triton hu nh khng
nh hng n xp ca p-aSiC, c th l hnh dng, kch thc v mt l xp trn mng
p-aSiC trong cng mt iu kin in ho hu nh khng ph thuc vo nng Triton. ng
ch l iu ny rt khc vi cc kt qu chng ti thu c khi in ho i-aSiC [4]. Khi in
ho lm xp i-aSiC thy rng Triton gip cho vic lm xp vt liu ny tr nn d dng hn rt
nhiu, c th l lm tng mt l xp v lm cho hnh dng cc l xp tr nn trn hn (hnh 4).
Hnh 2. nh SEM ca cc mu p-aSiC sau khi n mn in ho trong cc khong thi gian

khc nhau, cc iu kin khc nh nhau.
p-aSiC, 1% HF, 0% Triton
p-aSiC, 1% HF, 0,1% Triton
Hnh 3. nh SEM ca cc mu p-aSiC sau khi n mn in ho trong dung dch c nng

Triton khc nhau, cc iu kin khc nh nhau.
V phn n mn lm xp cc mu aSiC loi n (n-aSiC), chng ti nghin cu nh hng

ca Triton n xp. Cc kt qu thu c khi n mn n-aSiC bng dung dch cha 0,1% v
1% Triton c minh ho trn hnh 5. Ta thy r rng, tng t nh i vi p-aSiC, Triton hu
nh khng c tc dng trong vic lm xp n-aSiC.
2.2. Hunh quang ca cc mu aSiC xp loi p v loi n.
S pht quang ca cc mu aSiC xp c nghin cu bng cch ghi ph hunh quang
(photoluminescence - PL) ca chng, khi chng c kch thch bng vch 325 nm pht ra t
laser He-Cd. Trc ht thy rng cc mu p-aSiC xp hu nh khng pht quang, trong khi
Nhng
_____________________________________________________________________________________
i-aSiC, 1% HF, 1% Triton
Hnh 4. nh SEM ca cc mu i-aSiC sau khi n mn in ho trong dung dch c nng

n-aSiC, 1% HF, 0.1% Triton
n-aSiC, 1% HF, 1% Triton
Hnh 5. nh SEM ca cc mu n-aSiC sau khi n mn in ho trong cc dung dch c nng

n-aSic, 1% HF, 1% Triton
Hnh 6. nh SEM ca cc mu
n-aSiC, i-aSiC v p-aSiC sau khi
n mn in ho trong cc iu
kin tng t nhau (cc im en
l cc v tr aSiC b n mn cc
l xp).
p-aSiC, 1% HF, 1% Triton
Advances
_____________________________________________________________________________________
cc mu n-aSiC xp pht quang tng i yu vi ph pht quang nm trong vng 450-650 nm

(c nh ti khong 520 nm). Cc kt qu ny c minh ho bng hnh 7 (th hin ph PL ca
cc mu p-aSiC v n-aSiC c n mn vi dng in ho 3 mA, trong thi gian 25 pht,
trong dung dch cha 1% HF nhng c nng Triton thay i t 0% n 1%). Hnh 7 cng cho
thy rng Triton nh hng mnh n s pht quang ca n-aSiC xp, c th l nu n-aSiC c
n mn trong dung dch cha 1% Triton th cng pht quang ca lp n-aSiC gim i hn.
Chng ti cng thu c cc kt qu tng t nh vy i vi i-aSiC [4]. Tuy vy, ng ch
l mu n-aSiC c n mn trong dung dch in ho cha 0,1% Triton li c cng pht
quang mnh hn so vi mu c n mn trong dung dch khng cha Triton.
Khi nghin cu s pht quang ca i-aSiC xp, chng ti thy rng vt liu ny c ph pht
quang vi cng kh mnh tri rng trong vng 450-850 nm (c nh trong vng 600-700 nm).
Nh vy, mt kt qu quan trng na m chng ti thu c l ph hunh quang ca cc vt
liu p-aSiC, n-aSiC v i-aSiC xp hon ton khc nhau. iu ny c minh ho bng hnh 8.
Hnh 7. Ph hunh quang kch thch bng

bc sng 325 nm ca cc mu p-aSiC v
n-aSiC in ho trong cc dung dch c
nng Triton khc nhau, cc iu kin
khc nh nhau (1% HF, 3 mA, 15 pht).
Hnh 8. Ph hunh quang kch thch

bng bc sng 325 nm ca cc mu
i-aSiC, n-aSiC v p-aSiC sau khi n
mn in ha trong cc iu kin
tng t nh nhau.
3. Kt lun
1. Nng HF trong dung dch in ho nh hng mnh n kh nng lm xp mng aSiC
(k c i vi i-aSiC, p-aSiC v n-aSiC) ca dung dch. Dung dch cha 1% HF c kh
nng n mn lm xp tt nht.
2. Cht hot ho b mt Triton X-100 trong dung dch in ho nh hng mnh n kh
nng n mn lm xp ca dung dch i vi vt liu i-aSiC, nhng li hu nh khng nh
hng n vic n mn lm xp p-aSiC v n-aSiC.
3. Vt liu n-aSiC d n mn lm xp nht, sau n i-aSiC v cui cng l p-aSiC. Trong
cc iu kin in ho tng t nhau, lp xp trn mng n-SiC s c cc l xp kch
thc ln hn v mt dy hn.
4. Ph hunh quang ca cc vt liu p-aSiC, n-aSiC v i-aSiC xp hon ton khc nhau. Vt
liu p-aSiC xp hu nh khng pht quang, vt liu n-aSiC xp pht quang yu trong
vng xanh dng v xanh l cy, vt liu i-aSiC xp pht quang mnh hn nhiu nhng
ph pht quang dch v pha nh sng .
Nhng
_____________________________________________________________________________________
5. Triton X-100 s dng trong khi n mn in ho c tc dng lm gim mnh s pht

quang ca vt liu aSiC xp (i vi c i-aSiC xp v n-aSiC xp) nu nng ca n
trong dung dch ln n 1%.
Li cm n
Cc tc gi xin chn thnh cm n ThS. Hng Mnh gip trong vic thc
hin chp cc nh SEM.
Ti liu tham kho.
1. T. Matsumoto, J. Takahashi, T. Tamaki, T. Futagi, H. Mimura, and Y. Kanemitsu, Appl.
Phys. Lett. 64, 226 (1994).
2. T. L. Rittenhouse, P. W. Bohn, and H. Adesida, Sol. St. Comm. 126, 245 (2003).
3. Dao Tran Cao, Nguyen Thi Thu Ha, Vu Thi Thanh, Huynh Thi Ha, Bui Huy, Pham Thi
Mai Hoa, and P. M. Sarro, Proceedings of the 1th International Workshop on
Nanotechnology and Application (IWNA 2007) (Vung Tau, Vietnam, November 15-17, 2007),
p. 176.
4. S ng trong K yu ca Hi ngh APCTPASEAN Workshop on Advanced Materials
Science and Nanotechnology (AMSN2008) (Nha Trang, Vietnam, September 15-21,
2008).
5. V. P. Parkhutik, F. Namavar, and E. Andrade, Thin Solid Films 297, 229 (1997).
6. E. J. Connolly, H. T. M. Pham, J. Groeneweg, P. M. Sarro, and P. J. French, Sensors and
Actuators B 100, 216 (2004).
7. E. J. Connolly, B. Timmer, H. T. M. Pham, J. Groeneweg, P. M. Sarro, W. Olthuis, and P.
J. French, Sensors and Actuators B 109, 44 (2005).
8. A. J. Stecki, J. N. Su, J. Xu, J. P. Li, C. Yuan, P. H. Yih, and H. C. Mogul, Appl. Phys.
Lett. 64, 1419 (1994).
9. C. K. Inoki, T. S. Kuan, Y. Shishkin, R. P. Devaty, W. J. Choyke, Annual American
Physical Society March Meeting 2003 (Marh 3-7, 2003).
Advances
_____________________________________________________________________________________
MT S TNH CHT VT L CA ZnAl2O4: Eu3+

TNG HP BNG PHNG PHP THU NHIT
L Hng Ha, Trn Th Duynb, Phng Th Lnha,
Nguyn Ngc Longa, Trnh Th Loana
a)
i hc khoa hc T nhin, i hc Quc Gia H ni, 334 Nguyn Tri, H Ni

b)
i hc S phm H ni, 136 Xun Thy, H Ni
E-mail: longnn@vnu.vn
Tm tt: Bt nano ZnAl2O4 pha tp ion t him Eu 3+ c tng hp thnh cng bng phng
php thy nhit nhit thp (200 0C). Kch thc ht trung bnh c xc nh t gin
nhiu x tia X v nh TEM. nh hng ca ch x l nhit v nng tp ti cu trc v tnh
cht quang ca mu c nghin cu.
T kha: Phng php thy nhit, hunh quang, ZnAl2O4: Eu3+.
1. Gii thiu
Spinel pha tp t him, kim loai chuyn tip l vt liu hunh quang c cc nh khoa hc
trn th gii quan tm bi chng c nhiu c tnh quan trng nh trong sut, bn ha hc,
c, nhit, kh nng chu nhit, hiu sut pht quang u cao, khng a nc, chua
thp.Chng c nhiu ng dng trong k thut ch to lade, cm bin ng sut c quang,
ph quang hc, mn hnh mng in hunh quang, cht xc tc, vt liu chu nhit cao[1,2,3].
Trong cng trnh ny chng ti tng hp thnh cng cc mu bt nano ZnAl2O4 pha tp
3+
Eu bng phng php thy nhit nhit thp (2000C) v tin hnh nghin cu tnh cht cu
trc v hnh thi hc qua cc php o XRD, TEM cng nh tnh cht quang ca bt nano
ZnAl2O4: Eu3+ cc ch x l nhit v ch pha tp khc nhau.
2. Thc nghim
Bt nano spinel pha tp Eu3+ theo cng thc Zn(Al1-xEux)2O4 c ch to bng thng php
thy nhit nhit thp nh sau: Bt CO(NH2)2 , AlCl3.6H2O v ZnCl2 c ha tan hon
ton trong nc ct 2 ln vi t l thch hp, kt qu nhn c l dung dch trong sut. Pha tp
Eu3+ dng mui nitrat vo dung dch trn v khuy u trong 30 pht, sau b xung vo dung
dch ny mt lng NaOH v khuy u trong 30 pht. B xung tip mt lng ru C2H5OH
980 v khuy u. Sau qu trnh trn, cho dung dch thu c vo ni hp, y kn v t trong t
sy 2000C trong 48 gi. Sau qu trnh thu nhit, ni hp c ngui t nhin xung nhit
phng. Sn phm thu c cha kt ta mu trng. Sau khi lc ra kt ta v sy kh 100
0
C ta thu c bt nano ZnAl2O4:Eu3+. Thay i nng tp Eu3+ v x l nhit cc mu ch to
s c tnh cht vt l khc nhau.
Ph hunh quang v kch thch hunh quang c thc hin trn h quang hc FL3-22 ca
hng Jobin Yvon Spex, USA. Gin nhiu x tia X c tin hnh o trn my nhiu x
D5005 ca hng Brucker, Cng ha Lin bang c vi bc x CuK ( = 1,54056 ) v nh
hin vi in t truyn qua TEM trn h JEOL JEM 1010.
3. Kt qu v tho lun
T gin nhiu x tia X trn hnh 3.1 ta thy cc mu bt cha nng tp Eu 3+ nh (0,5%
at) hon ton n pha spinel, ht t kch thc nanomt v kt tinh kh tt ti nhit cao.
Khi nng tp Eu3+ ln (15% at), mu ch to c khng cn n pha, bn cnh pha spinel
ZnAl2O4 xut hin pha Eu2O3. Bn rng cc nh nhiu x gim dn khi tng nhit x l
Nhng
_____________________________________________________________________________________
chng t kch thc ht tng dn, cc mu kt tinh tt hn khi c x l nhit cao. Kch
thc ht tnh t gin nhiu x tia X i vi mu n pha spinel vi nng Eu 3+ thp (0,5%
at) c trnh by trn bng 1.
Bng 1: nh hng ca nhit ti kch thc ht ca Zn(Al1-xEux)2O4 (x = 0,005)
Nhit x l (0C)
Khng x l
400
900
*
Lin (cps)
8000
Kch thc ht d (nm)

6
7
16
* ZnAl2O4
o Eu2O3
4000
* *
b
a
0
20
30
40
50
60
70
2 Theta - Scale
Hnh 3.1. Gin nhiu x tia X ca cc mu

Zn(Al1-xEux)2O4
a- x = 0,005 cha x l nhit;
b- x = 0,005; T = 9000C;
c- x = 0,15; T = 6000C
Hnh 3.2. nh TEM ca mu

ZnAl2O4 cha x l nhit
ch to bng phng php thy nhit
nh TEM ca mu spinel ZnAl2O4 cha x l nhit c th hin trn hnh 3.2. Ta thy tn
ti 2 hnh thi trn nh TEM: hnh thi th nht c dng lp phng kch thc khong 1213nm
v hnh thi th hai c dng gn hnh cu kch thc nh xp x 12 nm.
Ph hunh quang ca cc mu Zn(Al1-xEux)2O4 vi x = 0,005 n pha kch thch bc sng
394 nm, ch to trong 2 ngy, vi cc ch x l nhit khc nhau t nhit phng n 900 0C
c a ra trn hnh 3.3. Kt qu cho thy, di ph hunh quang trong vng 560-720 nm cha
cc nh c trng ca chuyn di in t 5D0 7Fj (j = 0,1, 2, 3, 4) ca ion Eu3+ [2,3,4]. i
vi mu cha x l nhit cc nh hunh quang rng hn, chuyn di 5D0 7F0 xy ra ti bc
sng 578,9 nm cn bc x 5D0 7F2 c cng hunh mnh nht ti 615,4 nm ng vi
chuyn di 5D0 7F2. Khi x l nhit t 4000C tr ln v tr cc nh v cu trc ph thay
i: vch n 5D0 7F0 dch ti v tr 577,5 nm cn cc chuyn di khc vi j 1 tch thnh
nhiu vch ph v cc i dch ti 611.9 nm. S tch vch tinh t trong cc di ph v s dch
nh ca chuyn mc khng suy bin 5D0 7F0 khi nhit tng lin quan n s kt tinh tt
hn ca tinh th, kt qu ny ph hp vi cng b [2, 4]. Cn lu rng bc x 5D0 7F2 kh
mnh ti vng 610-615 l chuyn di lng cc in v chu nh hng nhiu vo trng
tinh th nh x quanh ion Eu3+, trong khi chuyn mc lng cc t 5D0 7F1 t ph thuc
vo trng tinh th. Ngoi ra, t s cng hunh quang gia chng l tiu chun nh gi
Advances
_____________________________________________________________________________________
mc i xng tm o quanh ion Eu3+. Kt qu trn hnh 3.3 cho thy t s bt i xng c 4
phn nh tnh i xng thp quanh ion Eu3+ [3] v ion ny c kh nng nh x hoc trong nhm
i xng Cnv, Cn hoc Cs [2].
5
615.4
1500000
D0- F2
F0- D3
393.3
8000000
a (x2)
D0- F3
D0- F3
F0- D2
463.8
b
7
395
F0- D1
464
530
465
531
534
560
4000000
362.2 362 361.3
b (x4)
394
701.2
D0- F0
694.1
649.5
654.7
500000
D0- F1
611.9
Cuong do (cps)
577.5
578.9
585.6
591.9
597.2
Cuong do (cps)
1000000
0
600
640
680
720
Buoc song (nm)
Hnh 3.3 Ph hunh quang ca

Zn(Al1-xEux)2O4; x = 0,005; ex = 394nm
a- cha x l nhit; b- T = 4000C;
c- T = 9000C
350
400
450
500
550
Buoc song (nm)
Hnh 3.4. Ph kch thch hunh quang

ca Zn(Al1-xEux)2O4; x = 0,005;
em = 615,4 (611,4) nm
a- a-cha x l nhit; b- T = 4000C;
c- T = 9000C
Ph kch thch hunh quang ca cc mu tng hp spinel ZnAl2O4 n pha cha nng tp
Eu thp (0,5% at) cha qua x l nhit v nhit ti 400 v 9000C c trnh by trn hnh 3.4.
Kt qu cho thy cc ph kch thch hunh quang ly ti
Ph kch thch hunh quang ca cc mu tng hp spinel ZnAl2O4 n pha cha nng tp
Eu thp (0,5% at) cha qua x l nhit v nhit ti 400 v 9000C c trnh by trn hnh 3.4.
Kt qu cho thy cc ph kch thch hunh quang ly ti cc nh vng em = 615,4 nm
(mu cha x l nhit) hoc 611,9 nm (mu nhit) c dng hon ton nh nhau bao gm mt
dy cc vch hp c trng cho chuyn mc hp th ca ion Eu 3+ [2,5]. Ngoi ra tng t nh
phn trn, hnh 3.4 cho thy tn ti s khc bit gia cc mu x l nhit khc nhau: cc nh
kch thch hunh quang tng ng vi cc qu trnh chuyn di hp th 7 F0 5D3, 7F0 5D2,
7
F0 5D1 u dch v pha sng di do mc kt tinh ca tinh th tt ln khi nhit x l
mu tng t nhit phng ti 9000C.
Kt qu nghin cu nh hng ca nng tp ti tnh cht quang ca ion Eu 3+ c tin
hnh nghin cu mt cch h thng i vi cc mu bt nano spinel c kt tinh tt khi ti nhit
6000C. Ph hunh quang ca cc mu ny vi cc nng ln lt l 0,5: 8: 15 (% at) c
trnh by trn hnh 3.5. Kt qu cho thy, t s bt i xng tng khi nng tp tng, c s thay
i v v tr cc nh v c bit v dng ph hunh quang lin quan n chuyn mc lng cc
in 5D0 7F2 l chuyn di chu nh hng mnh ca trng tinh th v mc ln xn xung
quang ion Eu3+ nh lu trn. Nu nh trong mu cha nng Eu3+ thp (0,5%) vch
ng vi chuyn di ny bao gm hai nh c cng xp x nhau ti bc sng ~ 611 nm v
615 nm, th khi tng nng Eu3+ cng nh 615 nm yu dn, cc i chim u th 611
nm v xut hin nh hunh quang mi ti 625 nm. Ngoi ra i vch n 5D0 7F0 c s dch
nh t 577,4 nm n 590 nm. Trc khi tm hiu nguyn nhn ca s thay i ny chng ta xt
ph kch thch hunh quang ca cc mu trn.
Nhng
_____________________________________________________________________________________
F0- D1
a
5
Cuong do (cps)
D 0- F 4
D 0- F 3
706.5
701.2
b
625.9
579.9
F0- D2
464.6
466.7
D 0- F 0
577.5
D 0- F 1
585.6
591.9
596.6
500000
F0- D3
394
654.7
Cuong do (cps)
D 0- F 2
611.9
615.4
1000000
d
4000000
532.8
c
525.6
361.2
b
a
560
600
640
680
720
Buoc song (nm)
350
400
450
500
550
Buoc song (nm)
Hnh 3.5. Ph hunh quang ca cc mu

Zn(Al1-xEux)2O4; T = 6000C
a- x = 0,005; b- x = 0,08
c- x = 0,15

ca mu Zn(Al1-xEux)2O4, T = 6000C
a- x = 0,005; b- x = 0,08;
c- x=1,5; em=611nm; d- x=1,5; em= 625 nm
Hnh 3.6 biu din cc ph kch thch hunh quang ly ti em = 611nm ca mu bt nano
ZnAl2O4:Eu3+ kt tinh tt ti nhit 6000C vi cc nng tp Eu3+ tng ng l 0,5:8:15 %
at. Ta thy hnh dng v v tr cc nh v c bn l nh nhau, ngoi tr di ng vi dch chuyn
7
5
F0
D2. i vi chuyn mc hp th ny trong mu nng Eu 3+ thp (0,5% at) ch tn ti
mt vch n ti 464,6 trong khi vi mu nng cao (15 % at) ngoi vch 464,6 nm cn
xut hin mt vch cng yu hn ti 466,7 nm. Cng vch ny s tng mnh khi ph
kch thch hunh quang o ti em = 625nm (ng d hnh 3.6).
610.8
8000000
200000
394
628
100000
Cuong do (nm)
622.3
466.7
464.6
b
4000000
533
579.9
705
592
Cuong do (cps)
0
550
600
650
700
750
Buoc song (nm)
Hnh 3.7. Ph hunh quang

a- Eu2O3
b- Zn(Al1-xEux)2O4 (x = 1,5); T = 6000C
350
400
450
500
550
Buoc song (nm)

a- Eu2O3
b- Zn(Al1-xEux)2O4 (x = 1,5); T = 6000C
Cn nhn mnh rng nhng nt c bit nu trn i vi ph hunh quang v kch thch
hunh quang trong cc mu nhit cao c cha nng tp Eu 3+ cao l mu khng n
pha. T kt qu nhiu x hnh 3.1 ta thy khi nhit t gi tr 6000C tr ln cc mu kt tinh
tt hn, nhng bn cnh pha spinel ZnAl2O4 cn xut hin thm pha Al2O3. So snh ph hunh
Advances
_____________________________________________________________________________________
quang v kch thch hunh quang ca bt Eu2O3 v ZnAl2O4: Eu3+ (15% at) trn hnh 3.7 v 3.8
cho thy dng ph ca chng kh ging nhau. iu ny cho php kt lun khi nng tp Eu 3+
thp (0,5% at) mu bt tng hp l n pha spinel nn cc tnh cht quang ca mu hon ton
lin quan n ion Eu3+ trong trng tinh th ZnAl2O4. Khi nng tp Eu3+ cao t gi tr 15 %
at bn cnh pha spinel tn ti pha Eu2O3, tnh cht quang ca mu ny quyt nh bi Eu3+ trong
tinh th Eu2O3. i vi trng hp trung gian khi nng tp t 8 % at, ion Eu 3+ trong c hai
tinh th ZnAl2O4 v Eu2O3 cng ng gp vo ph hunh quang ca mu tng hp.
Li cm n
Cng trnh ny c thc hin di s h tr kinh ph ca chng trnh nghin cu c bn
405506 thuc B Khoa hc v Cng ngh v ti c bit i hc Quc gia H Ni (QG 0705). Nhm tc gi xin chn thnh cm n PGS.TS. L Vn V v cc php o nhiu x tia X.
Ti liu tham kho
1. A.S.S. de Camargo, L.A.O. Nunes, J.F. Silva, A.C.F.M. Costa, B.S. Barros, J.E.C. Silva,
G.F. de S and S. Alves Jr, J. Phys. Condens. Matter. 19 (2007) 2462099
2. Vijay Singh, M.D. Masuqul Haque and Dong Kuk Kim, Bull. Korean Chem. Soc. (2007), 28,
No.12, pp 2477-2480.
3. Baochang Cheng, Shengchun Qu, Huiyng Zhou and Zhanguo Wang, Nanotechnology 17
(2006) 2982.
4. Trnh Th Loan, L Hng H, Nguyn Ngc Long, VNU Journal of Science, mathematicsphysics 23 (2007) 84-91.
5. Chih-Cheng Yang, San-Yuan Chen, Syh-Yuh Cheng, Powder technology 148 (2004) 3-6.
Nhng
_____________________________________________________________________________________
NGHIN CU CH TO MNG A LP GNG NNG TRUYN QUA QUANG

XC TC TiO2/Ti/Ag/Ti/TiO2 TRN THY TINH CORNING BNG PHNG
PHP PHN X MAGNETRON D.C
L Trn a, H Tn Ha b, Nguyn Hu Ch a, Trn Tun a
a)
Khoa Vt L-trng H Khoa Hc T Nhin - HQG Tp. HCM

b)
Trng THPT Nguyn Hu Cnh, Bin Ha, ng Nai
E-mail: ltran@phys.hcmuns.edu.vn
Tm tt: Mng gng nng truyn qua c tnh cht quan trng l truyn qua cao trong vng
kh kin v phn x cao trong vng hng ngoi. Mng TiO2/Ag/ TiO2 c ch to bng phng
php phn x phn ng magnetron d.c trn thy tinh Corning, ng vai tr nh mng gng
nng truyn qua. Ngoi ra, lp TiO2 trn cng cn c tnh cht quang xc tc. Tuy nhin, s ph
thuc ng k ca c tnh quang xc tc vo b dy mng ca lp TiO2 trn cng li l mt tr
ngi. Thc nghim cho thy dy tt nht mng c tnh quang xc tc tt thng t 330nm
tr ln. Trong bi tng trnh ny, chng ti tm ra c mi lin h gia cc b dy mng qua
tnh ton l thuyt v thc nghim kim chng. Mng to c va c tnh cht gng nng
truyn qua, truyn qua trn 70% trong vng kh kin v phn x trn 85% trong vng hng
ngoi, va c tnh quang xc tc tt, phn hy Methylene Blue (MB) ABS 0,15 .
1. Gii thiu
Ngy nay, nhu cu s dng nng lng ngy cng ln nhng ngun nng lng khng phi
l v tn. V vy, vn tit kim nng lng c quan tm hng u. Mt trong nhng ngun
tiu th nng lng ln khng ng c l nhu cu s dng my iu ha nhit trong cc ta
nh cao tng. Mt gii php ti u gii quyt vn ny l thay cc tm knh thng thng
bng nhng tm knh c ph mng phn x hng ngoi m vn trong sut l mng gng
nng truyn qua. Tnh cht quang hc ca mng gng nng truyn qua [1, 2, 3], l truyn qua
cao trong vng kh kin (380nm
760nm) v phn x cao trong vng hng ngoi
(
760nm) . Mng gng nng truyn qua c th ch to theo ba hng [4].
(a) Mng kim loi c phn x hng ngoi cao nh mng kim loi Ag, Au, Cu, .
(b) Mng vt liu bn dn c c tnh phn x hng ngoi cao nh ZnO; SiN; PbO; Bi 2O3 ;
SnO2; In2O3 hoc nhng cht bn dn pha tp nh SnO2:F; SnO2:Sb; AZO; GZO; ITO; ....
(c) Mng a lp in mi/kim loi hoc in mi/kim loi/in mi.
Tuy nhin, mng kim loi thng khng bn v c, nhit v ha hc. Mng bn dn phn x cao
vng bc sng >1200nm, rt xa so vi cc i ph bc x nng lng mt Tri. Mng a
lp c kh nng khc phc c nhc im ca mng bn dn pha tp l c vng bc sng
phn x rng >760nm nhng bn hn mng kim loi v c, nhit v ha hc. Mt s cng trnh
nghin cu mng a lp in mi/kim loi/in mi nh TiO2/Au/TiO2; TiO2/Ag/TiO2 [5];
SiO2/Al/SiO2 [6] CeO2/Cu/CeO2 [7]. Nhng lp kim loi gia vn cn nhc im v bn
nh ni trn v th lm tnh cht quang ca mng thay i theo thi gian. Mt gii php
khc phc nhc im trn ca mng a lp kim loi/in mi/kim loi l thay lp kim loi
bng lp TiN, c tnh cht quang hc tng t nh Au, phn x cao trong vng hng ngoi [9],
ng thi li bn v c, nhit v ha hc. Tuy nhin, mng TiO2/TiN/TiO2 [8] c truyn qua
trong vng kh kin thp, ch c 40%, nn ch ng dng thch hp cho vng kh hu nhit i.
tng truyn qua ca mng TiO2/TiN/TiO2, mt s tc gi thay lp TiN bng lp Ag.
Nhng lp Ag li khng bn v c nhit v ha hc nn tnh cht quang ca mng khng n
nh. khc phc iu ny, chng ti a ra mt gii php hon ton mi l to thm hai lp
m Ti, mi lp dy c 2nm, gia lp TiO2 v lp Ag, bo v lp Ag khi s oxi ha. Ngoi
ra, lp Ti cn c tc dng ngn s khuch tn ca O2 t cc lp TiO2, ng thi tng kh nng
Advances
_____________________________________________________________________________________
epitaxy v mng Ti pht trin trn mng TiO2 hp thc hn mng Ag. Mt khc, Ti v Ag c bn
knh nguyn t sai khc nhau khng ng k (3,4%, rAg=144pm; rTi=145pm) nn kh nng hp
mng ca Ti v Ag cao [10]. Trong cng trnh ny, chng ti nghin cu v ch to mng a lp
gng nng truyn qua TiO2/Ti/Ag/Ti/TiO2 trn thy tinh Corning bng phng php phn
x magnetron d.c. Tuy nhin, tnh quang xc tc cng nh tnh kh phn x ph thuc rt ln
vo dy mng [11, 12]. V vy, mc ch ca ti ny l da vo bi ton tng qut h mng
a lp c xy dng t l thuyt Fresnel v phng php ma trn [13], kt hp vi cc thng
s chit sut, h s tt ca Ag v TiO2 c kho st t thc nghim xy dng h mng a
lp l thuyt, v dng kt qu ny nh hng cho thc nghim i vi nhng trng hp c th.
2. Thc nghim
Mng a lp TiO2(5)/Ti(4)/Ag(3)/Ti(2)/TiO2(1) c ch to bng phng php phn x
magnetron d.c trn thy tinh Corning. Mng TiO2 c to t bia lm bng vt liu Titan c
tinh khit (99,6%) trong hn hp kh Argon nguyn cht (99,999%) v kh hot tnh l
Oxygen (99,99%) theo t l p(O2)/p(Ar)=8%, mng Ag c to t bia Bc c tinh khit
(99,995%). Hn hp kh c trn ln trong bnh thp khng r theo t l cho trc v a vo
bung chn khng bng h van kim. Khong cch gia bia Titan v bia Bc vi ln lt l
4,5cm v 6cm.
Lp TiO2(1) trong cng c ch to p sut 3.10-3Torr, nhit l 3000C b mt ca
mng mn, mng c cu trc tinh th do kh phn x tt, do chit sut ca mng cao. Lp
TiO2(5) ngoi cng c to p sut 13.10-3Torr b mt mng g gh v nh th mng to
c c tnh cht quang xc tc tt [10].
Tnh cht gng nng ca mng c xc nh qua ph truyn qua UV-Vis v ph phn x
hng ngoi. Tnh cht quang xc tc ca mng c xc nh bng phng php o s phn hy
ca Metylen Blue (MB) di iu kin nh sng Thy ngn (Hg). o truyn qua ca mu (
ngm trong dung dch MB nng 1mol/l/h) trc (To) v sau (T) khi chiu n Hg kh nng
phn hy MB, ABS=ln(T/To). B dy, chit sut mng TiO2 c xc nh bng phng php
Swanepoel [14], b dy, chit sut v h s tt lp Ag c xc nh bng phng php
Elippsometry, cu trc mng c xc nh bng ph nhiu x tia X, g gh b mt c xc
nh bng nh AFM.
3. Kt qu v bn lun
3.1 Tnh cht quang xc tc ca mng TiO2
Mng TiO2 c tnh cht quang xc tc rt tt, v ang c nhiu tc gi trong v ngoi
nc nghin cu. Ngy nay, ti ny vn cn nhiu vn mi l v hp dn i vi cc nh
khoa hc. Trong cng trnh [8], kho st tnh quang xc tc ca mng TiO2 theo b dy, kt
qu t c lp TiO2 vi b dy ngng c 360 nm, c to p sut 13.10-3Torr, cho tnh
cht quang xc tc tt nht. Trong cng trnh ny, chng ti tha k kt qu cng trnh [8], ch
to mng TiO2 hai lp TiO2(5)/TiO2(m)/thy tinh. Mc ch to mng hai lp ny trn lp Ti
nh cp trong phn gii thiu. Lp TiO2(m) c tc dng hn ch s oxy ha hon ton
lp Ti qu mng trong mi trng kh nhiu Oxi. y, lp Ti khng c qu dy, v kim loi
Ti c h s hp th ln, s lm gim truyn qua ca mng a lp. Do vy, chng ti to lp
TiO2(m) p sut 3.10-3Torr vi b dy c 70nm, dy hn ch s oxy ha lp Ti, m
khng nh hng nhiu n tnh cht quang xc tc ca mng TiO2, do cu trc tinh th thay i
khng ng k. S phn hy ca MB v g gh b mt (RMS) (hay cn gi l din tch hiu
dng b mt) theo b dy mng TiO2 c trnh by trong bng 1. Kt qu cho thy mu W34 c
b dy ngng c 330 nm, c phn hy MB cao nht, iu ny l do din tch hiu dng b
mt ln nht. T ph nhiu x tia X hnh (1) ta nhn thy tt c cc mu TiO2 u c cu trc
anatase vi gc 2 =24,6o (mt 101). Kt hp ph nhiu x tia X hnh (1) v hnh nh AFM hnh
Nhng
_____________________________________________________________________________________
Bng 1:S phn hy ca MB v g gh b mt theo b dy mng TiO 2.

Mu
W48
W34
W56
W55
dy (nm)
300
330
370
400
RMS
2.64
3.61
2.86
1.62
ABS
0.14
0.18
0.11
0.10
Cng nhiu x ca mt (101) (Au)

117
140
172
226
Mu W48: RMS=2.64
Mu W56: RMS=2.86
Hnh 1. Ph nhiu x tia X ca cc mng TiO2

theo b dy
Mu W34: RMS=3.61
Mu W55: RMS=1.62
Hnh 2. Hnh nh AFM ca cc mng TiO2

theo b dy
(2), cho thy s pht trin tinh th ca TiO2 l hp qui lut. Ring qui lut thay i ca din tch
hiu dng b mt c th gii thch nh sau: khi b dy mng cha ln, cu trc tinh th thp,
kch thc ht nh v u nhau dn n din tch hiu dng b mt nh. Khi mng t b dy
ngng (mu W34), mt s ht pht trin to ra v sp xp u xen ln vi cc ht c kch thc
b v to ra din tch hiu dng b mt ln nht. Khi mng vt qu b dy ngng, kch thc
ht to hn v sp xp u nhau, v th din tch hiu dng b mt gim.
3.2 Thng s quang ca mng TiO2
Ph truyn qua UV-Vis ca cc mng TiO2 c o bng my quang ph V350 ca phng
Vt l k thut cao trng i hc Khoa hc T nhin Tp.HCM. Da vo ph truyn qua, tnh
dy v chit sut ca mng bng phng php Swanapoe [14], t hiu chun chit sut ca
mng theo bc sng c dng Cosi nh hnh (3). Phng php tnh Swanepoel c lp trnh
bng ngn ng Matlab.
Hnh 3. Chit sut n ca mng TiO2 theo

bc sng
Hnh 4. Chit sut n, h s tt k ca mng Ag theo

bc sng
3.3 Tnh cht quang v cu trc ca mng Ag

dy d, chit sut n v h s tt k ca lp Ag c xc nh bng phng php
Ellipsometry. Kt qu c th hin trong hnh (4). R rng, Ag c chit sut thp v h s tt
cao nn c la chn lm lp kim loi trong mng in mi/kim loi/in mi. Da vo ph
nhiu x tia X hnh (5), ta thy mng Ag ch pht trin theo mt mt duy nht l mt (111) gc
Advances
_____________________________________________________________________________________
2 =37,65o. Hnh (6) cho thy mt (111) ca mng Ag hp mng vi mt (002) ca mng Ti [10].
Ch rng do mng Ag tinh th hn mng Ti nn ta ch thy mt (111) ca mng Ag. Chnh s
hp mng ny lm tng bn c hc cho mng v tng bm dnh gia cc lp mng vi
nhau.
Hnh 5. Ph nhiu x tia X ca mng Ag.
Hnh 6. Ph nhiu x tia X ca mng Ti/Ag/Ti.
3.4 M phng l thuyt ph truyn qua v phn x ca mng a lp TiO2/Ag/TiO2

T kt qu phn 3.2 v 3.3, tm c
chit sut n, h s tt k ca cc lp TiO2 trong,
lp Ag v lp TiO2 ngoi, bc sng 550nm
nh c trnh by trong bng 2. Da vo kt
qu thc nghim t bng 2 v s dng l thuyt
ma trn v h mng a lp [13] tm ra b dy
thch hp ca tng lp sao cho truyn qua cao
bc sng 550nm. Ngoi ra, vi mc tiu t ra
ban u, mng khng ch c tnh gng nng
m cn phi c tnh quang xc tc. V vy, kt
hp vi chng trnh my tnh khng ch b dy
Hnh 7. Mu H1 v A1 m phng t l thuyt
lp trong v lp ngoi ca mng TiO2. C th,
vi b dy cc lp trnh by bng 3
mng TiO2 c tnh quang xc tc tt vi b dy
c 330 nm, nn lp TiO2 ngoi cng c
khng ch vi chn di v chn trn ca b dy l 300 nm v 400 nm. Kt qu nhn c nh
trnh by bng 3, t m phng ph l thuyt truyn qua v phn x ca mng a lp theo
bc sng nh trnh by hnh (7). T hnh (7), ta thy mu A1 c nhiu nh giao thoa, l
do lp ngoi TiO2 dy. Mu H1 khng c nh giao thoa v lp TiO2 ngoi mng. Ph th hin
rt r tnh cht gng nng truyn qua. Ngha l, truyn qua cao trong vng kh kin (>90%),
phn x cao trong vng hng ngoi (>85%). Nh vy, mng TiO2/Ag/TiO2 thch hp ng dng
lm gng nng truyn qua quang xc tc.
2.5. Ph truyn qua v phn x ca mng a lp TiO2/Ti/Ag/Ti/TiO2 c to t thc nghim
T kt qu m phng phn 3.4, chng ti tin hnh thc nghim vi thng s nh mng A1,
nhng c thm hai lp m Ti dy c 2nm nhm bo v lp Ag khi b oxi ha nh trnh by
hnh (8). Tht vy, hnh (8a) v hnh (8b) l mng a lp TiO2(5)/Ti(4)/Ag(3)/Ti(2)/TiO2(1). Do lp
TiO2(5) c to trong mi trng kh hot tnh nhiu O2 (p sut ring phn ca O2 l 10-3Torr),
Hnh 8. a) Mng a lp vi lp Ti B oxy ha; b) Mng a lp khng c lp Ti

c) mng a lp vi lp Ag lm nhit cao
nn vi b dy lp Ti c 2nm khng che chn hon ton lp Ag khi b oxi ha, lp ny

khng ph dy hn v h s hp th ca n ln. Do vy, gii php c a ra l to lp TiO2(5)
hai ch p sut: lp u tin dy c 70nm, c to p sut ton phn c 3.10-3Torr (gm
Nhng
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92% Ar v 8% O2, p sut ring phn ca O2 l 0,8.10-3Torr), lp TiO2 sau cng dy c 260nm
p sut 13.10-3Torr nhm to din tch hiu dng b mt ln v nh th mng to c c tnh
cht quang xc tc tt. Ngoi ra lp Ag c to nhit phng, v nhit trn 1000C, Ag
s b kt t thnh m nh hnh (8c). Vy lp TiO2 ngoi cng c to hai ch p sut
khc nhau nh kt qu trnh by trong phn III.1. Tt c cc mng a lp to c u khng
thy du vt lp Ti hay lp Ag b oxy ha nh trnh by trong hnh (9). Mng a lp to c c
kt qu kh ph hp vi kt qu m phng t l thuyt. Kt qu ny c th hin r trong hnh
(10) v hnh (11). Hnh (10), trnh by kt qu thc nghim ca mng a lp TiO 2/Ti/Ag/Ti/TiO2
vi b dy nh sau 350nm/2nm/18nm/2nm/24nm (mu H73). Tuy nhin, mng c truyn qua
Hnh 9. Mng a lp TiO2(5)/TiO2(m)/Ti(4)/Ag(3)/Ti(2)/TiO2(1) c to trn Corning
Hnh 10. Mng a lp H73 TiO2/Ti/Ag/Ti/TiO2

to t thc nghim. Mng A1: TiO2/Ag/TiO2 m
phng t l thuyt
Hnh 11. Mng a lp H74 TiO2/Ti/Ag/Ti/TiO2

to t thc nghim. Mng A1: TiO2/Ag/TiO2 m
phng t l thuyt
Bng 4: phn hy MB ca mt s
mng a lp
Mu
ABS
H59
0.10
H74
0.15
H56
0.13
H73
0.12
Hnh 12. Ph nhiu x tia X ca cc mng a lp
trong vng kh kin khong t 70 80% thp hn so vi kt qu m phng t 10 15%. iu ny

c gii thch l do lp Ti hp th nh sng trong vng kh kin. Hnh (11) trnh by kt qu
thc nghim ca mng a lp TiO2/Ti/Ag/Ti/TiO2 vi b dy nh sau
350nm/2nm/22nm/2nm/24nm (mu H74), kt qu tng t mu H73, ch c phn x cao, trn
90%, t bc sng 800 nm tr i, l do lp bc dy ln. Cc mng to c khng ch c tnh
gng nng truyn qua m cn c tnh quang xc tc. Kt qu o phn hy Methylene Blue
c trnh by trong bng (4).
2.6 Cc thng s ca mt s mng a lp
Nhng mng a lp to c gm H56, H59, H73 v H74 va tha tnh cht gng nng
truyn qua nh trnh by trong hnh (10, 11), va c tnh quang xc tc tt vi kt qu phn hy
MB ghi trong bng (4) ph hp vi cu trc nhiu x tia X trnh by trong hnh (12).
Advances
_____________________________________________________________________________________
4. Kt lun
Qua nghin cu l thuyt v thc nghim v mng a lp gng nng truyn qua quang xc
tc, nhm tc gi thu c mt s kt qu ng k sau:
Mng TiO2 (k c lp m) c tnh quang xc tc tt b dy ngng c 330nm.
Xy dng c bi ton l thuyt ma trn i vi mng a lp, c th l 3 lp
TiO2/Ag/TiO2. T , m phng dng ph truyn qua v ph phn x ca mng gng nng
TiO2/Ag/TiO2.
Nghin cu ch to thnh cng mng a lp TiO2 /Ti/Ag/Ti/TiO2 tha mn tnh cht gng
nng truyn qua nh m phng t l thuyt, c th l truyn qua trn 70% trong vng kh
kin v phn x trn 85% trong vng bc sng t 800 nm tr i. Loi mng ny ng dng
lm ca knh cho cc ta cao c vng kh hu n i. ti ny ch mi c cc tc gi
trn th gii nghin cu mc ng dng lm gng nng. Chng ti nghin cu
thnh cng mng TiO2/Ti/Ag/Ti/TiO2 va c tnh cht gng nng va c tnh quang xc
tc tt. Vn quan trng nht ca loi mng ny l khc phc c s khuch tn oxy t
cc lp in mi vo trong mng Ag, v s oxy ha trc tip mng Ag t trong qu trnh to
mng, l nh lp Ti (dy 2nm) bo v.
Ti liu tham kho
1. H.K. Pulker, Coating on Glass, ELSEVIER, page 423, (1984).
2. Cheng - Chung Lee, Optical Monitoring of Silver - based Transparent Heat Mirrors,
Applied Optics, Vol. 35, No. 28, pages 5698 - 5703, October 1996.
3. R.J. Martin - Malma, Accurate determine of the optical constants of sputter - deposited Ag
and SnO2 for low emissivity coating, J.Vac.Sci. Technol. A,Vol. 16, No. 2, Mar/Apr, pages
409 - 412, (1998).
4. C.M. LAMPERT, Solar Energy Mater, page 319, (1979).
5. J.C.C. FAN and F.J. BACHNER, ibid, 15, 1012, (1976).
6. D.C. MARTIN and R. BELL, in Proceeding of Conference on Coatings for the Aerospace
Environment, Dayton, Ohio, WADD-TR-60-TB, (1960).
7. Journal of Material Science Letters 8 (1989), pages 391 - 394.
8. Hi Ngh Vt L Cht Rn Ton Quc Ln V, Mng Gng Nng Truyn Qua Quang Xc
Tc TiO2/TiN/TiO2, trang 476, (2007)
9. Trn Vn Phng, To Mng Bng Phng Php Phn X Phn ng Magnetron D.C, Hi
Ngh Vt L Cht Rn Ln V - 2007, (2007).
10. T.Tepper, D.Shechtman, D.Van Heerden, D. Hosell, fcc titanium in titanium/silver
multilayers, Material Letter 33 (1997), pages 181 - 184.
11. Akira Fujishima, Tata N. Rao, Donald A.Tryk, Titanium dioxide photocatalysis, Journal
of Photochemistry and Photobiology C: Photochemistry Reviews 1, pages 1 - 21, (2000).
12. Masato Tazawa, Masahisa Okada, Kazuki Yoshimura and Shunjiro Ikezawa, Solar Energy
Material & Solar Cells 84, pages 159 - 170, (2004).
13. O.S. Heaven, Optical Properties of Thin Solid Films, London Butterworths Scientific
Publications, ch. 4, (1955).
14. R. Swanepoel, Dertermination of The Thickness And Optical Constants of Amorphous
Silicono, J.Phys,E:Sci. Instrum, Vol. 16 , May, (1983).
Nhng
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TNH CHT PHT QUANG CA SrAl2O4 PHA TP ION T HIM CH TO BNG

PHNG PHP SOL-GEL
Nguyn Mnh Sna, L Th Tho Vinb, L Vn Khoa Boc,
Nguyn Ngc Trca, L Th Lin Phnga
a)
b)
Khoa Vt l, Trng i hc Khoa hc Hu

Khoa Vt l, i hc Qui Nhn, (c) Khoa T nhin, Trng i hc Duy Tn, Nng
Tm tt: Vt liu SrAl2O4 pha tp cc ion t him Eu v Dy uc iu ch v nghin cu.

Vt liu c tng hp bng phng php sol-gel i t phc citrat nung ti nhit 9500C trong
3 gi. Ph nhiu x tia X ch ra rng SrAl2O4: Eu3+, Dy3+ l n pha. Ph pht quang ca vt liu
gm cc vch hp c trng cho cc tm pht quang Eu3+, Dy3+ v mt di rng ca ion Eu2+. Cc
c trng ph ca vt liu uc kho st v tho lun.
1. M u
Trong nhng nm gn y, vt liu ln quang di v c chi cao trn nn aluminate kim
th pha tp cc ion t him (Eu2+ v RE3+) v ang c quan tm nghin cu, bi tnh u
vit ca vt liu ny so vi vt liu ln quang truyn thng ZnS [1, 2]. Nhiu nghin cu tp
trung vo vai tr ca ion Eu2+ trong cc nn aluminate kim th (MAl2O4, trong M: Sr, Ca,
Ba, ..) [3, 4, 7], mt s khc tp trung vo nghin cu nh hng ca ion t him ho tr 3 cng
kch hot [5]. Trong cc vt liu pht quang MAl2 O4: Eu2+, RE3+, cc ion t him thay th v tr
ca ion kim th M2+ trong mng, ph pht quang l mt di rng do ng gp ca chuyn di
in t 4f65d-4f7 ca ion Eu2+, ngha l ion Eu2+ ng vai tr tm pht quang m cc i bc x
c th thay i t bc sng 450 nm n 520 nm ph thuc vo ion kim th M2+ m n thay th
trong mng tinh th MAl2O4. Ngc li, bc x ca ion RE3+ ng kch hot khng xut hin
trong ph bc x. Nhiu kt qu thc nghim chng t rng, cc ion RE3+ ny ng vai tr l
cc by l trng, su by ph thuc vo loi ion RE3+ trong tng mng nn MAl2O4. Bo co
ny trnh by cc kt qu kho st quang ph ca vt liu pht quang SrAl2O4 pha tp cc ion t
him ho tr 3 c ch to bng phng php sol-gel v phng php n [6]. Vt liu c cu
trc n t, dng bt, cc ht nan c kch thc khong 80 nm. Ph bc x gm cc vch hp
c trng ca ion RE3+ v mt di rng pha sng ngn cng vi bc x c trng ca nn.
Kho st ng cong nhit pht quang tch phn ca cc vt liu ny cho thy, c s hnh thnh
cc by tng t nh trong vt liu ln quang.
2. Thc nghim
Vt liu aluminate strontium (SAO) c ch to t cc phi liu ban u gm: Sr(NO3)2,
Al(NO3)2.9H2O, Eu2O3, Dy2O3. Trc tin, cc oxide t him c ho tan trong dung dch
HNO3 to ra cc nitrate t him, cc nitrate kim loi cng c ho tan trong nc ct thu
c dung dch trong sut. Cc hn hp ny c trn theo mt t l thch hp trong dung dch
acid citric nhm to gel citrate. Tip n mt lng nc amonia b sung dn vo gel citrate to
mi trng c pH thch hp vo khong 6,5-7. Hn hp c sy kh nhit 1000C trong
2 gi, sau nung nhit 9500C trong 3 gi trong khng kh. Sn phm thu c c dng
bt, xp v c mu trng. Nhit nung c xc nh t vic kho st phn tch nhit DTA
thc hin trn h SETERAM nh trnh by trn hnh 1, y l khong nhit to pha n nh.
Mu cng c ch to bng phng php n nh c trnh by trong bo co trc y [6].
Cc kt qu phn tch nhiu x tia X bng thit b D8 Advance Brucker m t trn hnh 2 cho
thy, cc mu ch to l n pha, c cu trc n t. Cc hng s mng c phn tch bi
chng trnh Topas xc nh nh sau: a = 8.442 , b = 8.822 , c = 5.160 , = 93.415o.
Advances
_____________________________________________________________________________________
nh SEM ca mu ch to bng phng php sol-gel ch ra trn hnh 3. Vic phn tch nh
SEM cho thy: vt liu ch to bng c hai phng php sol-ugel v phng php n u cho
kt qu mu dng bt, c kch thc nan khong 80 nm, cc ht c kch thc khng ng.
60
40
80
60
20
40
-10
-20
dTG (%/min.)
100
Heatflow ( V)
TG (%)
120
20
0
-30
-20
-20
-40
-40
-60
-40
-80
-50
-100
-120
0
200
400
600
-60
800
-60
1000
Nhit ( C)
Hnh 1: Gin TG v DTA ca mu SrAl2O4 ch to theo phng php sol-gel

160
140
C- ng (vt)
120
100
80
60
(2 )
40
20
0
(1 )
-20
10
20
30
40
50
60
70
Hnh 2: Gin nhiu x tia X ca mu SrAl2O4: Eu (1%mol), Dy (2%mol)

ch to bng phng php n (1) v phng php sol-gel (2).
Hnh 3: nh SEM ca mu SrAl2O4: Eu (1%mol), Dy (2%mol)
Nhng
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3. Kt qu v tho lun
Ph bc x ca cc mu SAO pha tp cc ion Europium v Dysprosium vi nng khc
nhau c ch to bng hai phng php khc nhau, kch thch bi bc x 365 nm ch ra trn
hnh 4. Kt qu ph bc x ca cc mu ch to theo phng php n trn hnh 4(a) cho thy:
Ph ca vt liu nn SAO c mt di cc i khong 655 nm, c th do ng gp ca mng
nn. Trong vt liu SAO: Dy3+ quan st c cc vch hp c cc i cc bc sng 487 nm,
578 nm ng vi cc chuyn di 7F9/2 6H15/2, 13/2 c trng ca ion Dy3+. vt liu pht quang
SAO: Eu, ph bc x ngoi cc vch hp c trng cho ion Eu3+ ng vi cc bc sng 580 nm,
593 nm v 614 nm c trng cho cc chuyn di 5D0- 7F0, 1, 2 , c mt di rng c cc i
khong 487 nm, di bc x ny c kh nng l c trng cho bc x ca ion Eu2+ gy ra do
chuyn di in t t trng thi 4f65d1- 4f7 trong mng nn aluminate strontium ny nhng
dch v phia bc sng ngn hn so vi trong vt liu ln quang SAO: Eu2+, Dy3+ [6, 7]. Ph
pht quang ca vt liu SAO ng pha tp Eu v Dy trn hnh 4a (4) l t hp cc bc x ca ion
Eu (Eu3+ v Eu2+) v Dy3+.
Cc kt qu ny cng c lp li cc mu ch to bng phng php sol-gel nh trn hnh
4(b).
5.0
(1). SrAl2O4
(2). SrAl2O4:Eu(1%)
(3). SrAl2O4:Dy(1%)
(4). SrAl2O4:Eu(1%),Dy(1%)
4.0
C-ng (vt)
3.5
2.0
3.0
2.5
2.0
1.5
3
2
1.0
0.5
(1). SrAl2O4:Eu(2%)
(2). SrAl2O4:Dy(2%)
(3). SrAl2O4:Eu(2%),Dy(2%)
2.5
C-ng (vt)
4.5
1.5
1.0
2
0.5
4
0.0
0.0
400
450
500
1
-0.5
550
600
B-c sng (nm)
650
700
750
400
450
500
550
600
650
700
750
B-c sng (nm)
Hnh 4 : Ph bc x ca cc mu SrAl2O4 pha tp cc ion t him ch to bng phng

php n(a) v phng php sol-gel (b) kch thch bi bc x 365 nm.
Cc kt qu thc nghim v ph pht quang ca cc vt liu ny chng t rng, trong s cc

vt liu aluminate kim th pha tp cc ion t him Europium v Dysprosium ch to, s
pht quang l do ng gp ca ion Europium trng thi ho tr Eu2+ v Eu3+ khi mu trong
khng kh, trong khi bc x ca Dysprosium ch tn ti trng thi Dy3+. y cng l mt qui
lut thng gp trong cc vt liu pht quang cha ion Europium [5]. Bc x ca ion Eu2+ trong
cc vt liu ny l di rng c cc i 487 nm c th l do ng gp ca hiu ng ht kch
thc nan v nh hng ca tng tc gia cc ion Eu2+ vi cc ion t him ho tr 3+ trong
mng tnh th ny [7].
Tc ng ca cc ion t him trong mng tinh th cn c kho st bi hin tng nhit
pht quang. ng cong nhit pht quang tch phn ca cc vt liu SAO pha tp cc ion Eu v
Dy c chiu x bi bc x tia X trong thi gian 1 pht, tc nhit l 1 0C/s trnh by trn
hnh 5. Kt qu ny cho thy, s hnh thnh cc by trong vt liu khng pha tp c xut hin
tng ng vi nhit nh khong 800C nhng vi mt rt b, vi vt liu SAO: Dy3+ cn
xut hin thm nh nhit pht quang c nhit khong 1200C. Bn cnh , trong vt liu pht
quang SAO: Eu3+ trn ng cong nhit pht quang tch phn xut hin mt nh mnh nhit
khong 940C, y cng l bng chng chng t s tn ti cc by lin quan n ion Eu3+
trong mng ny. ng cong nhit pht quang ca mu SAO: Eu, Dy trn hnh 5a(2) chng
Advances
_____________________________________________________________________________________
1.0x10
(1): SrAl2O4: Eu (1%)

(2): SrAl2O4: Eu (1%), Dy (1%)
(3): SrAl2O4
(4): SrAl2O4: Dy (1%)
x10
5.0x10
2.0x10
1.5x10
1.0x10
5.0x10
SAO:Dy(2%)
SAO:Eu(1%),Dy(2%)
C- ng TL (nA)
Cuong do (nA)
1.5x10
(1)
x10
(2)
(3)
0.0
0.0
(4)
50
100
150
O
Nhiet do ( C)
200
250
50
100
150
o
Nhit ( C)
(a)
200
250
(b)
Hnh 5. ng cong nhit pht quang tch phn ca cc mu SrAl2O4:Eu, Dy ch to bng

phng php sol-gel (a), phng php n (b) c chiu x tia X, tc nhit l 10C/s
t s xut hin t hp cc nh trn v c s che ph ln nhau gia chng. Trn hnh 5b, ng
cong nhit pht quang ca cc mu ch to theo phng php n cng cho kt qu tng t.
4. Kt lun
Cc kt qu thc nghim thu c chng t vt liu pht quang SAO: Eu, Dy ch to bng
phng php sol-gel v phng php n c cu trc n pha- pha n t. l vt liu dng bt,
c kch thc nan.
S pht quang ca cc vt liu ny gm cc vch hp c trng cho ion Dy3+ v ion Eu3+.
Ngoi ra cn tn ti mt bc x di rng c trng cho chuyn di ca ion Eu2+ tn ti ng thi
trong mng tinh th SAO c pha tp ion Europium. S hnh thnh cc nh nhit pht quang c
th do cc sai hng ca tinh th cng vi s ng gp ca cc ion t him.
Li cm n
Bo co ny c s ti tr ca chng trnh nghin cu c bn ca B Khoa hc v Cng
ngh, m s 40 91 06.
Ti liu tham kho
1.
2.
3.
4.
5.
6.
7.
T. Matsuzawa, Y. Aoki, N. Takeuchi and Y. Murayama. J. Electrochem. Soc. 143 (1996), p.

2670.
E. Nakazawa, T. Mochida. J. Lumin. 72 (1997), p. 236
S. Mochida, H. Kubo, Y. Usui, H. Aizawa, T. Katsumata, S. Komuro and T. Morikawa.
SICE annual Conference in Sapporo, August 4-6, 2004, p. 2498.
Nguyn Mnh Sn, Journal of Science, Hue University. No 38, 4-2007, pp.85-93
Nguyn Mnh Sn, Nguyn Vn To, Nguyn Vn Su. Tuyn tp cc bo co Hi ngh
Vt l cht rn ton quc ln th V. Vng Tu 11/2207. Trang 454-456.
Nguyn Mnh Sn, L Th Tho Vin, Nguyn Ngc Trc. Synthesis of long afterglow
phosphors MAl2O4 (M: Ca, Sr, Ba) codoped with rare earth ions by combustion method and
their optical properties. Bo co ti Hi ngh Quang hc-Quang ph ton quc ln th V,
Nha Trang 9/2008.
Y. Lin, Z. Zhang, F. Zhang, Z. Tang and Q. Chen, Mater. Chem. Phys. 65 (2000), pp. 103
106.
Nhng
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C TRNG QUANG PH CA VT LIU NN HALOSULPHATE PHA TP

NGUYN T T HIM (RE)
L Vn Tut , Bi Tin t, Thi Ngc nh
Khoa Vt l, Trng H Khoa hc Hu.
Tm tt: Bo co trnh by cc kt qu kho st c trng quang ph ca vt liu nn
halosulphate (KMgSO4Cl) pha tp v ng pha tp cc nguyn t t him. y l ln u tin
quy trnh iu ch loi vt liu ny c tin hnh ti Khoa Vt l, Trng i Hc Khoa Hc
Hu, s dng c hai phng php: ho t v kt hp. Mt s kho st ban u v c trng ph
quang pht quang (PL) v nhit pht quang (TL) thay i theo quy trnh cng ngh ch to v
nng pha tp cng c trnh by v tho lun. Kt qu cho thy, s dng phng php kt
hp l la chn thch hp iu ch loi vt liu pht quang ny. ng thi, c trng ph PL
ca KMgSO4Cl:Dy, KMgSO4Cl:Eu do cc tm ion Dy3+ v Eu3+ quyt nh; bn cnh qu trnh
kch thch trc tip ln tm pht quang v mng ch cn c qa trnh truyn nng lng t tm
Ce3+ sang tm Dy3+ trong vt liu KMgSO4Cl:Ce,Dy; cng bc x PL mnh nht nng
ng pha tp 2.5%mol Dy3+, 10%mol Ce3+ v tng dn trong khong nng 0.05 0.55%mol tp
Eu3+. S pha tp, ng pha tp cc ion RE3+ dn n s xut hin nh TL khong 1670C i
vi vt liu KMgSO4Cl:Eu v 1970C i vi vt liu KMgSO4Cl:Ce(10%mol),Dy. Khc vi ph
PL, nng pha tp ti u cho hiu ng TL ca KMgSO4Cl:Eu l 0.35%mol Eu v ca
KMgSO4Cl:Ce,Dy l 10%mol Eu, 1.0%mol Dy.
1. Gii thiu
Vt liu pht quang v c ng dng su rng trong nhiu lnh vc khc nhau: k thut
chiu sng, k thut hin th v cnh bo (cc loi mn hnh), thng tin si quang, o liu bc x
ion ha, Tip tc tm kim vt liu pht quang mi, c c trng quang ph thch hp vi cc
i hi ng dng thc t, l cng vic thng xuyn ca nhiu nhm nghin cu khoa hc trn
khp th gii [1]. V vy, bn cnh nhng thnh cng c khng nh trong vic nghin cu
v pht trin ng dng nhm vt liu pht quang nn sulphate pha tp, ng pha tp, gn y mt
s nh khoa hc n (S.V. Moharil, S.C. Gedam, S.J. Dhoble, L.M. Nagpure, ) quan tm
nghin cu h vt liu nn halosulphate pha tp v ng pha tp cc nguyn t t him, m i
din tiu biu l vt liu KMgSO4Cl:RE. Theo
Dung dch xSO4 (x=Mg, Ca, )
nhm tc gi ny: do c mt s u th nh d ch
to, hiu sut quang pht quang cao, c trng
Dung dch yCl (y=K, Na,)
nhit pht quang kh thch hp cho ng dng o
liu bc x, vt liu nn halosulphate ha hn c
Dung dch RE2(SO4)3 (RE=Eu, Dy, )
nhiu ng dng.
Vt liu nn halosulphate pha tp cc ion t
him c iu ch bng phng php ho t
Dung dch yxSO4Cl:RE
(The wet chemical method) [2-6]. Quy trnh ca
Sy 800C, 8h
phng php c khi qut theo s trn hnh
Sy 1500C, 4h
v 1. Khi lng cc vt liu ban u c tnh
ton v cn theo t l xc nh sao cho thu c
Bt tinh th
khi lng sn phm v nng pha tp theo
yxSO
4Cl:RE
Nung,
mun. Ln lt ha tan tng phi liu vi lng

RE
nc ct hai ln va , phi trn thnh dung dch
Vt liu yxSO4Cl:RE
hn hp v chng ct, nung , cui cng thu c
RE
vt liu pht quang dng bt. T s ta thy, Hnh 1. Phng php ha t ch to vt liu
halosuphate pha tp ion t him.
thu c dung dch sulphate t him, trc ht
phi dng axit sunfuric (H2SO4) sunfat ha cc
Advances
_____________________________________________________________________________________
oxit t him, do vt liu ban u cha nguyn t

t him thng dng oxit (RE 2O3). Vic dng
axit sunfuric t nhiu s gy nhim mi trng.
ng thi, bc cui cng ca quy trnh cng
ging nh phng php tng tc pha rn truyn
thng, nung vt liu nhit cao hon tt
vic pha tp, n nh cu trc v c trng quang
ph ca vt liu.
Ta thy, c th ch to vt liu bng phng
php kt hp gia phng php ha t vi
phng php tng tc pha rn. Quy trnh ca
phng php c m t bng s trn hnh v
2. Dng phng php ny, c th va trnh gy
nhim mi trng va ci thin c hiu sut
pht quang ca vt liu. chnh l mc tiu
nghin cu ca chng ti mi c thc hin ti
B mn Quang Quang ph, Khoa Vt l,
HKH Hu v trnh by trong bo co ny.
Dung dch xSO4 (x=Mg, Ca, )

Dung dch yCl (y=K, Na,)
Sy 800C, 8h
Sy 1500C, 4h
Bt tinh th yxSO4Cl
Oxit t him, RE2O3
Nghin, trn v
nung
Vt liu yxSO4Cl:RE
Hnh 2. Phng php kt hp gia phng
php ha t v tng tc pha rn..
2. Thc nghim
Vt liu nn halosulphate pha tp v ng pha tp cc nguyn t t him c ch to theo
c hai phng php: ha t v kt hp. Cu trc vt liu c kim tra bng php o ph nhiu
x tia X, trn h o Siemens D5000.
Cc php o ph quang pht quang (PL) c o trn h o dng n sc k SPM2 vi cch
t 651vch/mm, bc x kch thch c bc sng =365nm ly t n thy ngn p sut thp, u
thu nhn quang in loi M12FQS51, h o c ghp ni v vn hnh bn t ng thng qua
my tnh c nhn. Php o nhit pht quang (TL) c o trn h o thng mi Harshaw TLD
3500, tc nhn kch thch l tia X ly t ngun YCP1 (Lin x c), i m cc Co, pht ch
20kV-1mA.
3. Kt qu v tho lun
3.1. Kho st phng php ch to vt liu
Trc tin cn la chn nhit nung thch hp cho c hai phng php ch to vt liu, v
vy chng ti kho st s thay i c trng ph PL ca vt liu KMgSO 4Cl v KMgSO4Cl:Eu
theo cc nhit nung. Nhit nung c thay i t 300 0C n 6000C, do khi t 7000C vt
liu c du hiu nng chy, chuyn sang pha thy tinh. Kt qu kho st trn hnh 3 cho thy,
bc x ca nn yu nht v cc bc x c trng ca tm Eu3+ mnh nht u ng vi nhit
nung khong 6000C. Nh vy, nhit nung thch hp cho c hai phng php pha tp ion
t him cho vt liu KMgSO4Cl l 6000C.
Sau khi ch to vt liu c kim tra bng php o nhiu x tia X. Hnh 4 l gin nhiu
x tia X ca vt liu ch to theo hai phng php ha t v kt hp. Kt qu xc nhn vt
liu nn thu c t hai phng php u ging nhau, c cu trc n pha, mang c trng
chung ca nhm cc tinh th khong vt Anhydrokainite v thuc nhm cu trc khng gian
C2/m. ng thi, ph hp vi l thuyt d on, vic pha tp tp ion RE vi nng nh khng
lm thay i cu trc ca mng ch.
Nhng
_____________________________________________________________________________________
(b)
(a)
o
2.0
400 C
C- ng PL (vt)
C- ng PL (vt)
0.8
0.6
o
700 C
0.4
o
600 C
0.2
600 C
1.5
1.0
o
500 C
o
400 C
0.5
500 C
o
300 C
0.0
300 C
0.0
500
550
600
650
560
700
600
640
680
B- c sng (nm)
B- c sng (nm)
Hnh 3. Ph PL ca KMgSO4Cl (a) v KMgSO4Cl:Eu (b) thay i theo nhit nung.
(a)
(b)
Hnh 4. Gin nhiu x tia X ca mu KMgSO4Cl:Eu iu ch bng phng php

ho t (a) phng php kt hp (b).
(b)
(a)
3.0
Ph- ng ph p kt h p
Ph- ng ph p ho - t
C- ng TL (nA)
C- ng PL (vt)
2.5
2.0
1.5
1.0
Ho - t
40000
20000
0.5
0.0
550
Kt h p
60000
575
600
B- c sng (nm)
625
650
100
200
300
Nhit ( C)
Hnh 5. Ph quang pht quang - PL (a) v ng nhit pht quang tch phn - TL (b) ca
KMgSO4Cl:Eu (0.15%mol) ch to theo hai phng php.
c c s nh gi phng php kt hp, chng ti thc hin so snh c trng ph PL v

ng cong nhit pht quang tch phn TL ca vt liu KMgSO4Cl:Eu (0.15%mol) ch to theo
hai phng php. Hnh 5 a ra kt qu cc php o .
Ta thy, c hai phng php u cho cng cc bc x PL c trng ca ion Eu 3+
khong 580 nm v 597 nm tng ng nhau, nhng bc x khong 618 nm c cng
mnh hn phng php kt hp, hnh 5a. Tng t, ng cong TL thu c u c nh
khong 1670C, nhng phng php kt hp cho cng nh ln hn, hnh 5b.
Nh vy, cng vi phng php ha t, chng ti thc hin c phng php kt hp
v hon ton c th dng phng php ny thay th cho phng php ha t iu ch vt
liu KMgSO4Cl:RE ni chung. Dng c hai phng php chng ti ch to c mt h
thng vt liu phc v cho cc nghin cu, kho st trong bo co ny.
Advances
_____________________________________________________________________________________
3.2. Kho st c trng quang pht quang

(PL) ca vt liu KMgSO4Cl:RE
KME55
C- ng PL (vt)
Hnh 6 trnh by kt qu o ph PL ca
6
vt liu KMgSO4Cl:Eu, ch to bng
KME45
phng php kt hp. Cng cc bc x
KME35
3+
KME25
3
c trng ca Eu tng ng vi cc
KME15
KME05
chuyn di 5D0 7Fj, c cc i cc bc
sng 1=580nm, 2=597nm v 3=618 nm
0
u tng dn khi nng pha tp (d kin)
500
550
600
650
B- c sng (nm)
thay i t (0.05 0.55%mol) v cha c du
hiu dp tt do nng . Nh vy, vic pha
Hnh 6. Ph PL ca KMgSO4Cl:Eu thay i
tp ion Eu3+ c thc hin kh d dng
theo nng pha tp Eu3+.
i vi vt liu nn KMgSO4Cl.
Kt qa a ra trn hnh 7 cho thy ion Ce3+ gi vai tr tm nhy sng v ion Dy3+ gi vai tr
tm pht quang trong vt liu ng pha tp Ce, Dy. Tc l tn ti qu trnh truyn nng lng t
tm Ce sang tm Dy, kt qu lm cho cng cc bc x c trng ca Dy3+ mnh ln rt
nhiu do s c mt tm Ce. ng thi, qu trnh truyn nng lng thay i theo nng tm
Dy3+ v t hiu qu nht gi tr pha tp 2.5%mol Dy3+ khi nng Ce3+ c nh 10%mol,
hnh 8.
(a)
10
KMCD10-2.5
KMCD10-2
(3)
(1) KMC10
(2) KMD0.5
(3) KMCD100.5
C- ng PL (vt)
C- ng PL (vt)
(b)
(2)
(1)
0
KMCD10-3
KMCD10-1.5
KMCD10-1.0
KMCD10-0.5
KMCD10-0.1
0
400
450
500
550
600
650
700
B- c sng (nm)
Hnh 7. Ph PL ca KMgSO4Cl:Ce,
KMgSO4Cl:Dy v KMgSO4Cl:Ce, Dy
400
500
600
700
B- c sng (nm)
Hnh 8. Ph PL ca KMgSO4Cl:
Ce(10%mo),Dy thay i theo nng Dy
T cc kt qu , chng ta a ra nhn nh: c ch qu trnh PL ca vt liu

KMgSO4Cl:RE l t hp ca hai qu trnh. Th nht, mng nn nhn nng lng kch thch sau
truyn cho cc tm pht quang RE; th hai, nng lng kch thch tc ng trc tip ln tm
pht quang RE. Hai qu trnh c m t theo s sau:
- h kt + Nn + RE (Nn) * + RE (Nn) + (RE)* (Nn) + RE + h PL
- h kt + RE (RE)* RE + h PL
i vi vt liu ng pha tp KMgSO4Cl:Ce,Dy, bn cnh hai qu trnh trn cn c qa trnh
truyn nng lng t tm Ce sang tm Dy, theo s :
- h kt + Ce + Dy Ce* + Dy Ce + (Dy) * Ce + Dy + h PL
3.3. Kho st c trng nhit pht quang TL ca vt liu KMgSO 4Cl:RE
Hnh 9 biu din kt qu o ng nhit pht quang tch phn (TL) ca vt liu
KMgSO4Cl:RE. Kt qu cho thy, vic pha tp Eu v ng pha tp Ce, Dy lm xut hin
cc by bt trong vng cm ca nn KMgSO4Cl, l nguyn nhn lm xut nh TL khong
1670C v 1970C tng ng vi hai trng hp. Khc vi ph PL, c mt gi tr nng pha tp
Eu3+ ti u, cho cng TL mnh nht ca KMgSO4Cl:Eu l 0.35%mol. Cn i vi Dy3+ l
khong 1.0%mol khi nng Ce3+ l 10%mol, tc l so vi ph PL (nng Dy3+ ti u l
2.5%mol) th nng ng pha tp ti u cho hiu ng TL thp hn. iu ny hon ton hp l
Nhng
_____________________________________________________________________________________
v c ch ca hai qu trnh hon ton khc nhau: qu trnh TL lin quan cht ch vi s hnh
thnh cc by bt do pha tp v mt ht ti b bt trn by sau kch thch cn qu trnh PL ch
lin quan nng pha tp RE.
(a)
0.35% mol
8.0x10
4.0x10
0.05%
0.45%
0.15%
0.25%
0.55%
0.0
C- ng TL (nA)
C- ng TL (nA)
1.2x10
(b)
mol
mol
mol
mol
mol
3.2x10
2.4x10
1.6x10
8.0x10
KMCD-10,1.0
KMCD-10,2.5
KMCD-10,2.0
KMCD-10,0.5
KMCD-10,1.5
KMCD-10,3.0
KMCD-10,0.1
0.0
0
100
200
300
50
100
150
200
250
300
350
Nhit ( C)
Nhit ( C)
Hnh 9. ng cong nhit pht quang tch phn ca vt liu KMgSO4Cl thay i theo nng pha tp
Eu3+ (a) v thay i theo nng Dy3+ khi nng Ce l 10%mol (b).
c th hng ti vic ng dng vt liu ny trong php o liu bc x da trn hiu ng

TL chng ti thc hin kho st s thay i cng TL ca vt liu KMgSO 4Cl:Eu theo thi
gian chiu x tia X. Bt KMgSO4Cl:Eu c p thnh vin nn, c ng knh c 3.0mm, dy
c 0.5mm v khi lng trung bnh c 7.0mg, chiu x tia X vi thi gian chiu thay i t
5 60s. Kt qu o TL, xc nh cng nh v dng ng p ng cng nh theo thi
gian chiu x c a ra trn hnh 10.
Ta thy ng thng dng c c h s hi quy tuyn tnh rt cao, R=0.9991. iu c
ngha l p ng TL ca vt liu l tuyn tnh trn mt khong gi tr liu chiu tng i rng.
ng thi, vin nn c to ra t vt liu bt khng dng cht kt dnh nn nhy TL khng
b nh hng; sau nhiu ln o lp li hnh dng, mu sc ca vin nn khng b thay i. Vi
cc c trng vic nghin cu ng dng vt liu KMgSO 4Cl:Eu lm liu k nhit pht
quang l hon ton kh thi.
(a)
60s
50s
Y = A + B*X
A = -313018.031
B = 743071.005
R = 0.9991
3.6x10
C- ng nh (nA)
C- ng TL (nA)
(b)
5x10
4.5x10
40s
2.7x10
30s
7
1.8x10
20s
6
9.0x10
10s
5s
4x10
3x10
2x10
1x10
0.0
0
100
200
0
300
Nhit ( C)
10
20
30
40
Thi gian chiu x (s)
50
60
Hnh 10. ng TL ca vt liu KMgSO4Cl: Eu(0.15%mol) (a) cng nh TL (b) thay i theo
thi gian chiu x.
4. Kt lun
Bn cnh phng php ho t chng ti thc hin c phng php kt hp iu
ch vt liu pht quang nn KMgSO4Cl pha tp v ng pha tp ion t him. Phng php kt
hp c u im l quy trnh n gin hn, nhit nung khng qu cao, gim thiu c yu t
gy nhim mi trng v cng cho vt liu c hiu sut quang pht quang - PL, v nhit pht
quang - TL ging nh phng php ho t.
Advances
_____________________________________________________________________________________
Ging nh nhiu loi vt liu khc, cc ion RE3+ gi vai tr tm PL, s hp th nng lng
kch thch cn xy ra trong mng ch hoc tm nhy sng trong trng hp ng pha tp. Cha
c du hiu dp tt nh sng pht quang do nng trong vt liu KMgSO4Cl:Eu trong khong
nng tp tng dn t 0.05 0.55%mol Eu3+. Vt liu KMgSO4Cl:Ce,Dy cho cng bc x
PL mnh nht nng tp tng ng l 10%mol Ce v 2.5%mol Dy.
Cc by bt hnh thnh do pha tp, ng pha tp cc ion RE3+, dn n s xut hin nh
TL khong 1670C i vi vt liu KMgSO4Cl:Eu v 1970C i vi vt liu
KMgSO4Cl:Ce(10%mol),Dy. Khc vi ph PL, nng pha tp ti u i vi hiu ng TL ca
KMgSO4Cl:Eu l 0.35%mol v ca KMgSO4Cl:Ce,Dy tng ng l 10%mol v 1.0%mol.
Ti liu tham kho
1. G.Blasse, B.C.Grabmaier. Luminescent Materials. Springer-Verlag, Berlin Heidelberg, 1994.
2. S.C. Gedam, S.J.Dhoble, S.V.Moharil. Eu2+ and Ce3+ emission in sulphate based phosphors
. Jounal of Luminescence 128, pp 1-6, 2008.
3. S.C. Gedam, S.J.Dhoble, S.V.Moharil. Dy3+ and Mn2+ emission in KMgSO4Cl phosphor.
Jounal of Luminescence 124, pp 120-126, 2007.
4. S.C. Gedam, S.J.Dhoble, S.V.Moharil. 5d 4f transision in halosulphate phosphor. Jounal
of Luminescence 126, pp 121-129, 2007.
5. S.C.Gedam, S.J.Dhoble, S.K.Omanwar, and S.V.Moharil. TL in halosulphate phosphors
prepared by wet chemical methode. Eur. Phys. J. Appl. Phys. 39, 39-24 (2007).
Nhng
_____________________________________________________________________________________
NH HNG CA NHIT N CU TRC V TNH CHT QUANG CA NANO

TINH TH ZnS PHA TP Mn
Nguyn Tr Tuna,c, Phm Thnh Huyb,c, Phm Vn Tunb, Trnh Xun Anhb,
Nguyn Trng Tuna, L Hng Hd, Nguyn Huyn Tnge
a
Khoa Khoa hc, i hc Cn Th, Qun Ninh Kiu - Cn Th (Email: trituan@ctu.edu.vn)

b
Vin Tin tin Khoa hc v Cng ngh (HAST), i hc Bch khoa H Ni
c
Vin o to Quc t v Khoa hc Vt liu (ITIMS), i hc Bch khoa H Ni
d
i hc Khoa hc T nhin, i hc Quc gia H Ni
e
Vin Vt l K thut, i hc Bch khoa H Ni
Tm tt: Cc ht nano ZnS pha tp Mn2+ c tng hp bng phng php ng kt ta. nh
hng ca nhit n cu trc v tnh cht quang ca cc nano tinh th ZnS pha tap Mn nhit
t 200 800oC trong mi trng kh nit. Kt qu phn tch gin nhiu x tia X, ph kch
thch hunh quang v quang hunh quang cho thy vic nhit khng ch lm thay i cu trc
v tnh cht quang ca nano tinh th m cn lm thay i rng vng cm ca cc nano tinh th.
T kha: ZnS:Mn; Nano tinh th; ng kt ta; nhit
1. Gii thiu
Cc ht nano bn dn c nghin cu nhiu trong sut hai thp k qua, do tnh cht mi v
kh nng ng dng trong nhiu lnh vc khc nhau nh l quang xc tc, pin mt tri, mn hnh
phng v cc linh kin mi khc [1]. Trong s , ZnS l mt trong nhng i tng c quan
tm nhiu nht do c vng cm rng, thng v c th pht x trong vng kh kin khi c pha
tp cc kim loi chuyn tip v t him thch hp. Rt nhiu cng trnh nghin cu c
cng b lin quan n vic tng hp v pha tp nano tinh th ZnS vi cc tp cht khc nhau [2].
Mn l mt trong nhng nguyn t pha tp trong mng nn ZnS c nghin cu nhiu nht.
Nano tinh th ZnS:Mn2+ vi hiu sut lng t cao t 20 n 40 % c cng b trong thi
gian gn y [3,4]. Tuy nhin, cc nghin cu trc y tp trung vo vic hiu r v gii quyt
cc vn lin quan n vai tr v nh hng ca cht pha tp. Cc nghin cu v s thay i
tnh cht cu trc khi cc ht nano c nhit trong cc mi trng khc nhau cn l vn
m v cn lm sng t thm.
Nh bit, ph quang hunh quang ca nano bn dn lin quan nhiu n cht lng ca
tinh th, vic tn ti cc tm donor v acceptor, cc tm ti hp v by, ng sut v sai hng... c
th lm nh hng nhiu n ph hunh quang c trng. ng thi qu trnh chuyn pha cu
trc, cng c th dn ti nhng thay i ng k ph pht x ca vt liu. i vi ZnS, cc cng
b gn y cho thy khi kch thc nano, qu trnh chuyn pha cu trc t lp phng gi km
sang lc gic c th din ra nhit 400-500oC, thp hn nhiu so vi nhit chuyn pha
tng ng vt liu khi [4].
Trong bi bo ny chng ti trnh by kt qu nghin cu nh hng ca qu trnh nhit ln
tnh cht quang ca nano tinh th ZnS pha tp Mn ch to bng phng php ng kt ta trong
nn polyme. S chuyn pha cu trc t mng lp phng sang mng lc gic nhit thp ~
500oC c quan st. S thay i ca c trng hunh quang ca mu cc nhit khc
nhau s c trnh by v tho lun chi tit.
Advances
_____________________________________________________________________________________
2. Thc nghim
2.1. Ch to mu
Bt nano tinh th ZnS:Mn c tng hp bng phng php ng kt ta trn nn
sodium polyphosphate (PP) - Na(PO3)n . Ban u 40,8 g cht to mi trng nn PP (Aldrich,
96%, n~10) c ho tan vo 320 ml nc kh ion. Sau khi PP tan hon ton trong nc, ta ly
40 ml Zn(CH3COO)2.2H2O 1M v 32 ml MnCl2 0,1M a vo bnh phn ng. Sau khi khuy
bng my khuy t trong thi gian khong 30 pht nhit phng, 40 ml dung dch Na2S
.9H2O 1M tip tc c cho nhanh vo bnh. Ton b hn hp c khy trong vng 12 gi
ng h. Sn phm thu c l mt hn hp dung dch mu trng c (dng huyn ph). Dng
my quay li tm tc cao (18000 vng/pht) tch chit mu ra khi dung dch, sau ra
mu thu c bng nc kh ion nhiu ln v ethanol 3 ln. Bt t thu c sau c ht
kh trong chn khng (10-2 10-3 Torr), sn phm nhn c cui cng l bt kh. Mu bt kh
thu c l cc ht nano ZnS:Mn c nng tp tng ng Mn 0.8%. Sau mu c nhit
trong mi trng kh nit t 200 800 0C.
2.2. Cc php o
Cc mu thu c sau khi tng hp c kho st tnh cht cu trc bng gin nhiu x tia
X (SIMEMS D 5000) ti Khoa Ha hc, Trng i hc Khoa hc T nhin, i hc Quc gia
H Ni. Tnh cht quang ca vt liu c o trn h hunh quang FL3-22 (JOBIN YVON
SPEX FL-3-22 fluorescence spectrophotometer) ti Khoa Vt l, Trng i hc Khoa hc T
nhin, i hc Quc gia H Ni.
3. Kt qu v tho lun
3.1. Tnh cht cu trc
Hnh 1 l gin nhiu x tia X ca bt nhn c sau qu trnh tng hp (ng a) v bt
sau khi c 200oC trong mi trng kh nit trong thi gian 1 gi (ng b). C th thy
trong hnh 1, gin nhiu x tia X c c trng bi 3 nh nhiu x c cng yu v
rng bn ph ln. V tr cc nh ny l hon ton tng ng vi nhiu x trn 3 mt (111), (220)
v (311) ca ZnS c cu trc lp phng gi
km. Kt qu ny khng nh bt nhn c
250
(111)C-ZB
1
ch-a nhit
t quy trnh tng hp ca chng ti l ZnS.
2
200 C-1g-N
Cng yu v rng bn ph ln ca
200
cc nh nhiu x cho thy cc tinh th nhn
c c kch thc nh v kt tinh thp.
(220)C-ZB
150
Khi nhit 200oC trong 1 gi trong mi
trng kh nit, cng cc nh nhiu x
(311)C-ZB
tng ln cho thy s kt tinh tt hn ca
100
mu.
o
Khi tip tc tng nhit ln 300, 400

v 500oC kt qu o nhiu x tia X, hnh 2,
cho thy, 5000C trong mu bt u xut
hin mt s nh nhiu x mi. Cc nh
ny c th c cho l tng ng vi ba
pha khc nhau l pha ZnS vi cu trc lp
phng gi km, pha ZnS vi cu trc lc
gic v pha ZnO vi cu trc lc gic.
2
50
0
20
30
40
50
2 theta
60
70
Hnh 1. Gin nhiu x tia X ca bt nano tinh th

ZnS:Mn cha nhit v nhit 200oC vi thi
gian 1gi trong mi trng kh
Nhng
_____________________________________________________________________________________
300
C- ng
250
: ZnS-lp phng gi k m a
: ZnS-lc gi c
b
: ZnO-lc gi c
350
1100
300 C-1g-N 2
1000
400 C-1g-N 2
500 C-1g-N 2
900
150
600 C-1g-N 2
700 C-1g-N 2
800 C-1g-N 2
o
o
: ZnS-lp ph-ng gi km
: ZnS-l cgic
: ZnO-l cgic
800
600
700
200
200 C-1g-N 2
500
400
d
c
100
50
200
100
300
30
40
50
60
70
2 theta
Hnh 2. Gin nhiu x tia X ca nano tinh th

ZnS:Mn c nhit ti nhit 200, 300, 400 v
500oC vi thi gian 1 gi trong mi trng nit
3
2
1
0
20
30
40
50
60
70
2 Theta
Hnh 3. Gin nhiu x tia X ca bt nano tinh

th ZnS:Mn c nhit 600, 700 v 800oC
vi thi gian 1 gi trong mi trng nit
Khi tip tc tng nhit mu ln 600, 700 v 8000C, kt qu o gin nhiu x tia X
hnh 3 cho thy, qu trnh chuyn pha din ra nhanh khi nhit tng t 600 ln 7000C. 7000C
pha ZnS cu trc lp phng gi km hu nh chuyn hon ton sang pha ZnS cu trc lc
gic. nhit 8000C, hai pha chnh quan st c trong mu l ZnS v ZnO c cu trc lc
gic.
T kt qu kho st ph nhiu x tia X c th khng nh c s chuyn pha cu trc ca
nano tinh th ZnS t lp phng gi km sang lc gic nhit ~ 5000C. Nhit chuyn pha
ny l thp hn nhiu so vi nhit chuyn pha tng ng trong vt liu khi 10200C. Tuy
nhin, gi tr ny li cao hn cht t so vi kt qu c cng b gn y i vi nano tinh th
ZnS:Mn nhit ~ 4000C [4]. S khc bit v nhit chuyn pha so vi kt qu cng b
trong ti liu tham kho 4 c th c gii thch l do: i) trong nghin cu ca chng ti cc
nano tinh th c trong mi trng kh nit khc vi ti liu tham kho 4 l cc nano tinh th
ZnS:Mn c trong mi trng chn khng cao; ii) s hnh thnh ng thi pha ZnO trong
mu ca chng ti khi c trong mi trng kh nit to ra s cnh tranh lm thay i nhit
chuyn pha. C th ni vic b xy ha v hnh thnh pha ZnO trong mu ca chng ti l
mt iu khng mong mun v nm ngoi d kin. Nguyn nhn y c th l do bn thn
lng xy hp th trong mu, do xy d tn ti trong l trc khi thi kh nit, hoc do s d
khng kh trong qu trnh nhit. S chuyn ha xy ra do phn ng trao i gia oxy v sulfua
c th c m t theo phng trnh:
2ZnS + 3O2 2ZnO + 2SO2
nh gi s b s thay
i kch thc ht khi c Bng 1. S thay i kch thc ht nano tinh th khi c
nhit, chng ti tin hnh nhit cc nhit khc nhau
tnh ton kch thc ht s
Mu
dc (nm)
dng cng thc Sherrer v kt
(radians)
(radians)
qu o gin nhiu x tia
200 0C
0.25032
0.05652
2.5
trn, kt qu nhn c c
0
300 C
0.25128
0.05233
2.7
trnh by trong bng 1. Tuy
0
400
C
0.25085
0.04884
2.9
nhin y cn lu l kt qu
0
500 C
0.24997
0.03785
3.8
bng 1 ch mang tnh cht tham
0
0
600 C
15.8
0.25006
0.16328
kho do nhit trn 500 C,
0
700 C
0.24893
0.00418
34.2
trong mu tn ti 3 pha tinh
0
800
C
0.24893
0.00314
45.5
th vi kch thc khc nhau.
Hnh 4 l ph hunh quang
Advances
_____________________________________________________________________________________
(PL) vi bc sng kch thch 320 nm v kch thch hunh quang (PLE) vi bc sng hunh
quang l 595 nm ca nano tinh th ZnS:Mn cha nhit. Ph PL nhn c bao gm hai vng
ph c trng vi cc i tng ng 428 v 595 nm. Vng ph ~ 430 nm thng quan st
c cc mu ZnS:Mn c kch thc nano v c gii thch l do cc sai hng ca mng nn,
hoc do cc trng thi b mt ca cc nano tinh th. nh 595 nm l c
3.2. Tnh cht quang
4000000
348
595
PLE-ZnS-Mn-27 C
o
PL-ZnS-Mn-27 C
20000000
344
16000000
3000000
C- ng
C- ng
3
2000000
320
1
1000000
1
2
Ch- a nhit
o
200 C-N2
300 C-N2
400 C-N2
500 C-N2
12000000
o
o
o
8000000
354
4000000
428
320
1
362
0
300
350
400
450
500
550
600
B- c sng (nm)
Hnh 4. Ph kch thch hunh quang (1) v hunh

quang (2) ca ht nano tinh th ZnS:Mn cha
nhit di bc sng kch thch 320 nm v bc
sng pht x 595 nm
300
330
360
390
420
450
B- c sng (nm)
Hnh 5. Ph kch thch hunh quang ca cc ht

nano tinh th ZnS:Mn c x l nhit ti cc
nhit 200, 300, 400, 500oC vi thi gian 1 gi
trong mi trng nit v mu cha nhit
trng hunh quang ca ion Mn2+ trong nn ZnS do chuyn mc 4T1-6A1. Ph kch thch hunh
quang ch c mt nh duy nht ~320 nm. nh ph ny l do chuyn mc gia vng dn v
vng ha tr ca ZnS. So vi ph kch thch hunh quang ca ZnS khi 342 nm, c mt dch
chuyn xanh (blue shift) ~ 22 nm trong ph kch thch hunh quang ca mu to c. iu ny
chng t c s thay i rng vng cm ca cc nano tinh th so vi mu khi. kho st
k hn vn ny, ph PLE ca cc mu c cc nhit khc nhau c kho st v
kt qu c trnh by trong hnh 5. rng vng cm tng ng tnh ton t ph PLE c lit
k trong bng 2.
Kt qu bng 2 cho thy khi cha nhit rng vng cm ca cc nano tinh th kch thc ~ 3
nm l c 3.88 eV, tng ln ~0.3 eV so vi rng vng cm ca ZnS khi. Khi mu c nhit
trong 1 gi 2000C, rng cng cm ca cc nano tinh th gim xung cn 3.62 eV, rt gn
vi gi tr ca ZnS khi. Vic tip tc gim rng vng cm ca cc nano tinh th ti gi tr
nh hn gi tr rng vng cm ca
Bng 2. S thay i nng lng vng cm ca cc ht
ZnS khi khi tip tc tng nhit
nano tinh th ZnS:Mn khi cc nhit khc nhau
mu l vn m chng ti cha th trong mi
gii thch. C th gi thit nh sau:
Mu nhit nh ph kch
Eg (eV)
Kch
khi mu c nhit nhit
0
trong nit
thch hunh
thc
400 C v cao hn, ngoi pha ZnS lp
quang
(nm)
ht
(nm)
phng gi km ban u, trong mu
0
27 C
2.5
bt u hnh thnh cc pha ZnS c
320
3.88
0
cu trc lc gic (Eg ~3,9 eV) v ZnO
200 C
2.7
343
3.62
(Eg~ 3.3 eV), ph PLE nhn c i
300 0C
2.9
vi cc mu ny s bao gm ng
348
3.57
gp ca c ba thnh phn ni trn nn
400 0C
3.8
354
3.51
vic xc nh rng vng cm t
500 0C
2.5
ph PLE khi khng cn chnh xc
362
3.43
na.
Nhng
_____________________________________________________________________________________
20000000
a
b
c
595
200 C-N2
o
300 C-N2
o
400 C-N2
496
3500000
a
b
c
d
T- A1
3000000
15000000
2500000
500 C-N2
o
600 C-N2
o
700 C-N2
o
800 C-N2
C- ng
C- ng
a
10000000
5000000
2000000
1500000
1000000
432
d
500000
b
c
450
500
550
600
650
700
400
B- c sng (nm)
Hnh 6. Ph hunh quang ca mu nano tinh th

ZnS:Mn khi c x l ti cc nhit 200, 300,
400 0C
0
400
595
450
500
550
600
650
700
B- c sng (nm)
Hnh 7. Ph hunh quang ca mu nano tinh th

ZnS:Mn khi c x l ti cc nhit 500, 600,
700, 800 0C
Hnh 6 v hnh 7 l ph hunh quang tng ng ca cc mu nano tinh th ZnS:Mn sau khi
nhit cc nhit t 200 8000C trong mi trng kh nit trong 1 gi. Cc php o c
thc hin nhit phng v mu c kch thch vi bc sng ex ~350 nm. T hnh 6 v hnh 7
c th nhn thy, cng ca c hai vng ph ~430 v 595 nm gim nhanh khi tng nhit
mu t 200 ln 5000C. Khi tip tc tng nhit ln 7000C mt vng ph mi xut hin vi
cc i nh ph ~ 496 nm. Cng ca nh ph mi xut hin ny tng rt nhanh khi tng
nhit mu ln v hon ton chim u th 8000C. nh ph 496 nm ny nhn c l do
pht x ca ZnO. Kt qu ny ph hp vi kt qu nhiu x tia X. iu ny cho thy tinh th
ZnO l thnh phn ch yu trong mu nhit 8000C.
4. Kt lun
Nano tinh th ZnS:Mn c ch to bng phng php ng kt ta trong nn polyme vi
kch thc tinh th nhn c ~ 3 nm. Cc kt qu phn tch gin nhiu x tia X cho thy, i
vi cc mu cha nhit v nhit t 200 n 4000C trong mi trng kh nit, nano tinh th
ZnS c cu trc pha lp phng gi km. Khi nhit nhit 500 v 6000C, trong mu tn ti
ba pha cu trc khc nhau l pha ZnS lp phng, pha ZnS lc gic v pha ZnO lc gic. nhit
cao hn cc pha chnh trong mu l ZnS v ZnO cu trc lc gic. c trng hunh quang
ca Mn2+ trong ZnS vi nh 595 nm quan st c vi cng rt mnh i vi mu
cha nhit, v gim nhanh khi tng nhit ln 5000C. Mt nh hunh quang mi vi cc
i ~ 496 nm quan st c trong mu khi tng nhit ln 6000C v hon ton chim u
th trong mu c nhit 8000C. S thay i c trng hunh quang ca cc nano tinh th
c gii thch l do c s chuyn pha ca mu t pha ZnS c cu trc lp phng, sang pha
ZnS c cu trc lc gic v do qu trnh xy ha ZnS thnh ZnO.
Li cm n: Nghin cu c thc hin vi s ti tr ca chng trnh Nghin cu Khoa hc
C bn.
Ti liu tham kho
1.
2.
3.
4.
J. Mu, D. Gu, Z. Xu, Material Research Bulletin 40 (2005) 2198.

W.Q. Peng_, S.C. Qu, G.W. Cong, Z.G. Wang, Journal of Crystal Growth 279 (2005) 454.
B. Bhattacharjee, D. Ganguli, S.Chaudhuri, A.K. Pal, Thin Solid Films 422 (2002) 98.
A. D. Dinsmore, D. S. Hsu, S. B. Qadri, J. O. Cross, T. A. Kennedy, H. F. Gray, and B. R.
Ratna, Journal of Applied Physics 88 (2006) 4985
Advances
_____________________________________________________________________________________
TNH CHT QUANG V IN HA CA MNG MNG La0.67-xLi3xTiO3 CH TO

BNG PHNG PHP BC BAY CHM TIA IN T
L nh Trnga, Xun Maib, L H Chib, Nguyn Nng nhc, Phm Duy Longb
a)
Khoa Vt l, i Hc s phm H ni 2 Xun Ha Vnh Phc, Vit nam

b)
Vin Khoa hc Vt liu, Vin Khoa hc v Cng ngh Vit nam
18 Hong Quc Vit, Cu Giy, H ni
c)
Trng i hc Cng ngh, i hc Quc gia H ni
E-mail: authorlongphd@ims.vast.ac.vn
Tm tt: Mng mng La0.67-xLi3xTiO3 (LLTO) c ch to thnh cng bng cng ngh bc
bay chm tia in t. Mng dng v nh hnh v gn nh trong sut trong vng kh kin,
truyn qua khong 80%, vi dn ion Li+ kh cao khong 3.5.10-5 Scm-1 ti nhit phng.
Ngoi ra cc tnh cht in sc ca h mng WO3 c hoc khng c ph lp mng LLTO cng
c kho st, cc kt qu ch ra rng mng La0.67-xLi3xTiO3 c th c s dng lm cht in ly
rn trong linh kin in sc ton rn.
1. M u
H vt liu LaLiTiO3 v ang c quan tm nghin cu nhiu trong thi gian gn y
bi chng l loi vt liu c kh nng dn ion (v d nh Li+, H+) rt tt ngay ti nhit phng,
dn ion Li+ ca chng c th t rt cao t 10-6 n 10-3 Scm-1 [1-3]. y c xem l cc vt
rn dn ion v c gi l cc superionic conductors, rt c trin vng trong lnh vc nghin
cu ch to cc loi pin ion rn, pin nhin liu, cc linh kin in sc, cc linh kin quang in
ha, cc loi senso .v.v [1-5]. Cc vt liu ny c th ng vai tr nh cht in ly rn khng c
hi, d bo qun, s dng v cho php d dng thit k ch to cc linh kin vi cc hnh nh
bt k m vi cc cht in ly lng khng th thc hin c. c bit, n ang c xem l cc
vt liu rt c trin vng trong vic nghin cu ch to cc loi pin ion siu nh, cc pin ion
mng mng vi dung lng cao, cc linh kin hin th in sc ton rn, cc ca s nng lng
hiu dng v.v.. Trong cc nghin cu trc y [4, 6] chng ti thnh cng trong vic ch to
vt liu La0.67-xLi3xTiO3 dng khi bng phng php phn ng pha rn vi dn ion Li+ ti
nhit phng xc nh c l vo khong 10-4 n 10-3 Scm-1. Cc kt qu nghin cu cho
thy vt liu La0.67-xLi3xTiO3 ch to c hon ton c th s dng lm cht in ly trong pin
ion ton rn.
Trong cng trnh ny trnh by cc kt qu nghin cu v ch to vt liu La0.67-xLi3xTiO3
di dng mng mng bng k thut bc bay chm tia in t cng nh kho st cc tnh cht
in v quang ca vt liu. Cc kt qu nghin cu hiu ng in sc trn h mng
ITO/WO3/LiLaTiO3 cng s c trnh by.
2. Thc nghim ch to mu
Hp cht La0.67-xLi3xTiO3 ban u c ch to bng phng php phn ng pha rn t cc
xit La2O3, TiO3 v mui Li2CO3 c sch cao. Hn hp cc vt liu ny c nghin trn
theo t l nht nh (trong trng hp ny x = 11) sau c nhit 8000C trc khi c
a vo nghin trn bng my nghin Frisch Model Pulverisette 6 trong thi gian 6 gi. Chi
tit ca qu trnh nh c ch ra trong [6]. Vt liu ny sau c dng lm ngun bc bay
to mng mng. Mng La0.67-xLi3xTiO3 vi chiu dy khong 300 nm c lng ng trn
thy tinh, thy tinh c ph mng dn in trong sut ITO (Indium Tin Oxide), thy
tinh/ITO/WO3 v Si/TiO2/Pt. kho st dn ion ca mng bng k thut ph tng tr mt
lp in cc Ag c bc bay to cu trc bnh kp ITO/LLTO/Ag v c kho st trn h
AutoLab Potensiostat PGS-30. Hiu ng in sc ca h mng ITO/WO3 v ITO/WO3/LLTO
Nhng
_____________________________________________________________________________________
c kho st trong dung dch 1M LiClO3 + PC (propylene cacbornate). S thay i tnh cht
quang trong hiu ng in sc c xc nh bng vic o ph truyn qua ca cc mng trong
qu trnh nhum v ty mu trn h UV VIS NEAR Carry - 5000.
3. Kt qu v tho lun
3.1. c im cu trc tinh th
Ph nhiu x tia X ca mng LLTO trn Si/TiO2/Pt theo cc nhit khc nhau c
ch ra trn hnh 1. C th nhn thy rng mng sau khi bc bay c dng v nh hnh trn hnh
1(a) ph nhiu x tia X chi thy xut hin mt nh sc nt ca Si v mt nh gc 2 =
40,010 tng ng vi mng Pt. Cu trc ca mng khng thay i thm ch khi nhit tng
ln n 6000C nh trn hnh 1 (b). Sau khi 7500C trong 2 gi xut hin qu trnh ti kt
tinh ca mng LLTO, trn ph tia X khi xut hin cc nh nhiu x c trng cho cu trc
tinh th ca La0,52Li0,45TiO3 vi s kt tinh u tin theo hng ca mt (110) v (111) ng vi
cc gc nhiu x 2 tng ng l 27.090 v 40,010. Chnh s xut hin ca nh ti 40,010 ca
mng LLTO trng vi nh ph ca mng Pt lm cho nh ph ti y tng ln r rt. Ngoi ra
chng ti cn nhn thy c s xut hin cc nh c trng cho cu trc ca LiTi2O4 vi vi v
tr ca cc nh nhiu x 2 = 18,900 v 28,700 nh ch ra trn hnh 1(c). Kt qu ny ph hp
vi cc kt qu nhn c khi ch to mng LLTO bng cng ngh bc bay xung laser trong
[1,7].
Experiment title
30
25
-Z'' / ohm
20
15
10
0
160
165
170
175
180
185
190
195
Z' / ohm
c:\user\lab-measurements\long's document\impedance\mang-ic\ito-ic-au3-03aug-05.pfr
Hnh 2. Ph tng tr ca mng LLTO
3.2. Tnh cht dn ion

c trng dn ion ca mng mng c ch to, phng php o ph tng tr xoay chiu
c thc hin trn h in ha Autolab Potensiostat PGS 30 vi tn s c th thay i t 1
MHz n 0.0001 mHz. Hnh 2 l ph tng tr ca mng c thc hin nhit phng vi di
tn s o t 1 MHz n 0.1 Hz. xc nh chnh xc c dn ion ca mng chng ti
tin hnh phn tch ph c trng trn c s s dng phng php trng kht ph l thuyt vi
thc nghim, chi tit nh c ch ra trong [8]. Trong trng hp ny dn ion ca mng
c xc nh c gi tr Li = 3,5.0-5 Scm-1. So vi dn khi ca vt liu ban u, dn ion
ca mng gim 5 bc. iu ny c gii thch bi s phn ly mt phn ca Li trong qu trnh
bc bay dn ti s thiu ht hm lng Li trong mng cng nh s bt ng nht trong thnh
phn pha ca vt liu mng nh c trnh by trn.
Advances
_____________________________________________________________________________________
3.3. Ph c trng C-V

Trn hnh 3 l ph c trng C-V ca h mng ITO/WO3 v ITO/WO3/LLIO c thc hin
trong dung dch 1M LiClO3 + PC. C th thy rng trong c hai h mng u c qu trnh tim
thot cc ion Li+. Tuy nhin trong cng mt khong th qut ( 1V) mt dng ion trao i
trong mng WO3 khng ph lp LLTO ln hn rt nhiu. iu ny c gii thch bi vic cc
ion Li+ c tim trc tip vo mng, trong khi h mng ITO/WO3/LLTO cc ion Li+ phi
khuych tn qua lp dn ion LLTO. Khi tng in th qut ln (t -1,2V n 2,5 V), ph c
trng C-V m rng hn v khi mt dng tim thot ion cng tng ln ng k (ng c).
Trong trng hp ny mng LLTO c xem nh l lp vt liu dn ion Li+, dn ion ca n
thp hn so vi dung dich cht in ly (10-5 Sm-1) dn n in p tim thot ion cng tng ln.
3.4. Tnh cht quang
Hnh 3. Ph C-V ca mng WO3(a); WO3/LLTO (b), (c)

100
80
60
100
1
2
Do truyen qua (%)
Do truyen qua (%)
(a)
40
20
0
400
600
800
Buoc song (nm)
1000
1200
(b)
80
60
40
20
0
400
600
800
1000
1200
Buoc song (nm)
Hnh 4. Ph truyn qua ca mng WO3/LLTO (a): (1) mng sau khi ch to, (2) mng sau khi ty mu
+1V; (3) nhum mu th -1V; (4) Nhum mu -1,2 V v ph truyn qua ca mng WO3 khng ph
lp LLTO (b): (1) mng sau khi ty mu +1V; (2) nhum mu -1V
c hai h mng u quan st rt r s thay i tnh cht quang trong hiu ng in sc.
Trn hnh 4 (a) v (b) l s thay truyn qua ca mng ITO/WO3/LLTO v ITO/WO3. h
mng ITO/WO3 s thay i ph truyn qua rt ln t khong 80% xung di 20% gia hai
trng thi ty v nhum mu trong vng nh sng nhn thy vi in th ty v nhum mu (
1V). i vi mng ITO/WO3/LLTO khi nhum mu in th -1 V truyn qua gim xung
Nhng
_____________________________________________________________________________________
khong 50 %, khi tip tc nhum mu th -1,2 V truyn qua tip tc gim mnh xung cn
khong 2030 % ng (3) v (4) trong hnh 4(a). Khi o chiu in trng qu trnh ty mu
c thc hin mng tr ln trong sut, ph truyn qua l ng (2). h mng ny ph truyn
qua khng tr v trng thi ban u nh i vi mng sau khi ch to ng (1). iu ny l do
s c mt ca lp mng dn ion LLTO ngn cn qu trnh tim v thot cc ion Li+ nh
trnh by khi kho st ph C-V. Tuy nhin vi h mng ny s thay i truyn qua l kh ln
gia hai trng thi nhum v ty mu, v qu trnh ny l thun nghch.
4. Kt lun
Bng k thut bc bay chm tia in t ch to thnh cng mng La0.67-xLi3xTiO3 c tnh
cht dn ion Li+. Mng nhn c dng v nh hnh, dn ion c gi tr Li = 3,5.10-5 Scm-1.
Cc kt qu kho st hiu ng in sc trn c hai h mng ITO/WO3 v ITO/WO3/LLTO cho
thy c th s dng mng LLTO lm cht in ly rn trong linh kin in sc ton rn sau ny.
Li cm n: Cng trnh ny c thc hin bi s h tr ti chnh t Vin Khoa hc vt liu
trong chng trnh NCKHCB.
Ti liu tham kho
1. Jun-Ku Ahn, Soon-Gi Yoon, Electrochimica Acta 50 (2004), pp. 371-374.
2. L.X. He, H.I. Yoo, Electrochimica Acta 48
(2003) 1357-1366.
3. Shin-ichi Furusawa, Hitoshi Tabuchi, Takahiko Sugiyama, Shanwen Tao, John T.S. Irvine,
Solid State Ionic, 176 (2005), pp. 553-558
4. Nguyen Nang Dinh, Pham Duy Long, Le Dinh Trong, Communication in Physics, Vol. 14,
No 2 (2004) pp. 90-94.
5. K. Kishida, N. Wada, H. Adachi, K, Tanaka, H. Inui, C. Yada, Y. Iriyama, Z. Ogumi, Acta
Materialia 55 (2007) 4713-4722.
6. L nh Trng, Phm Duy Long, Xun Mai, Nguyn Nng nh, Tuyn tp bo co hi
ngh Vt l cht rn ton Quc ln th V, Vng Tu 11/2007, 702-705.
7. Chi-Lin Li, Bin Zhang, Zheng-Wen Fu, Thin Solid Films Vol 515 Issue 45 (2006) 18861892.
8. L.D. Trong, P.D. Long, V.V. Hong, N.N. Dinh, AJSTD Vol 21 Isues 1&2 (2007) 35-40.
Advances
_____________________________________________________________________________________
MNG MNG Al2O3 VI CC L XP KCH THC NANO C TO

BNG PHNG PHP IN HA
Giang vn Phc a , L V Tun Hng b, Ng Th Kim Hab,
Trn Th Khnh Chib, Lm Quang Vinhb, L Vn Hiub, Hunh Thnh tb
a
i Hc An Giang, An Giang
i Hc KHTN, i Hc Quc Gia Tp HCM
Tm tt: Nhm oxide thng c ch to dng cho mc ch xc tc di dng gm s xp.

Trong cng ngh nano, mng mng v xp ca nhm oxide c th c dng lm khun mu cho
cc qu trnh lng ng si nano. Bi vit ny nhm gii thiu mt phng php gi thnh thp
to mng nhm oxide c cc l xp c nano. Mng c to bng phng php in ha v
c nghin cu bng cc phng php quang ph v nh AFM. Hn na, tnh xp ca mng
cn c th c dng to ra cm bin m .
T kha: Alumina, electrochemical.
1. Gii thiu
Vic to ra nhm oxit [1, 2] c th
thc hin c bng phng php in
ha anode nhm kim loi trong dung dch
axit mnh, dn n vic to ra mng mng
nhm oxit trn b mt ca n. Nhiu thc
nghim chng t mng ny c tnh xp,
v c bit l cc l xp xuyn sut b
dy ca n t mt ngoi n tn lp giao
tip oxit v kim loi . Thi gian in
ha cng di, lp giao tip ny tip tc b
oxi ha v mng tr nn xp nn mng
cng tip tc dy thm. Cc l xp thng
Hnh 1. S thay i in dung theo m ca mng
c dng ging hnh tr (hnh 3), phn b
nhm oxit theo [3]
kh u n theo dng t ong [6].
V dung dch in ha, nhiu tc gi pht trin cc qu trnh rt khc nhau s dng ch
yu l axit sulfuric, oxalic v phosphoric. Trc y, phng php ny ch c p dng i vi
nhm. Tuy nhin, trong thi gian gn y, mt s nhm nghin cu th p dng v
thnh cng trong vic to c mng nhm oxit trn tantalium, titanium v silicon.
Nhm tc gi Paul G. Miney [2] tin hnh to mng nhm oxit trn thy tinh. thy
tinh ca hnng c lm sch trong dung dch axit sulfuric v 30% hydrogen peroxide. Nhm
kim loi c ph ln mt lp dy 500nm bng phng php phn x magnetron DC. Qu
trnh oxi ha c tin hnh vi dung dch axit phosphoric 10%, nhit 298K v in p 80V.
Nhm tc gi Veronika Timar-Horvath [3] tin hnh to mng nhm oxit trn silicon
pha tp n. c ra sch bng dung dch 1:20 HF v c oxi ha bng lung kh O2 nhit
11000C. Lp SiO2 to thnh c dy vo c t 70 117nm, sau c ph chng mt lp
nhm kim loi 99.99% bng phng php bc bay. Vic oxi ha nhm c tin hnh vi dung
dch axit sulfuric 23% v mt dng in 5 20 mA/cm2. Sau , mt lp nhm kim loi khc
c ph chng ln v hai lp nhm kim loi c ni ra ngoi bi cc dy bng vng bng
phng php p nng. Lm nh vy cui cng thu c mt t in vi lp in mi xp s
c s dng lm cm bin m .
Nhm nghin cu ca chng ti thc hin to mng nhm oxit trn thy tinh v nhm
kim loi bng phng php in ha vi cch thc n gin hn. Mng to ra c nghin cu
Nhng
_____________________________________________________________________________________
bng cc phng php quang ph v nh AFM. Kt qu cho thy mng c cu trc xp c nano
v kim chng tnh xp bng cch ng dng to ra cm bin m vi chi ph kh thp.
2. Thc nghim
2.1.To mng Al2O3 bng phng php in ha:
Thc hin mng mng Al2O3 bng
phng php in ha mt bc nh hnh 02.
Dung dich in ha c th c dng l
sulfuric acid, oxalic acid, chromic acid v
phosphoric acid. C hai in cc c lm
bng nhm kim loi.
S to thnh mng Al2O3 din ra theo c
ch sau:
Anode: 2Al + 3H2O = Al2O3 + 6H+ + 6e
Cathod:
6H+ + 6e = 3H2
Hnh 2. S nguyn l to mng in ha
Ngoi ra, trong dung dch cn c s ti
hp mt phn: Al2O3 + 6H+ = 2Al3+ + 3H2O
Trong thc nghim c thc hin
trng i Hc An Giang, in cc l
nhm kim loi 99.9% dng tm c b dy
0.5mm v mng mng nhm kim loi trn
thy tinh c ph bng phng php bay hi
vt l c dy c 1 m. in cc c lm
sch bng sulfiric acide long 12.5% trong 5
pht. Dung dich in ha c th nghim l
sulfuric acid v oxalic acid, tuy nhin, chng Hnh 3. S to lp xp nhm oxide trn nhm
ti chn oxalic acid nng 0.1M/l, bi l
ha cht ny thn thin v t c hi i vi ngi dng. C hai in cc u dng nhm kim
loi. Khong cch gia hai in cc c c nh 40mm. Qu trnh in ha c tin hnh
vi cc mt dng v in p khc nhau t 5v 40v. Thi gian thc nghim thay i t 5 30
pht. Mng Al2O3 c to thnh trn anode. (hnh 4)
Mng to thnh c nhit qua cc nhit 4000C, 5000C v 6000C trong khng kh v sau
c kho st ng dng. Vic kho st da trn ph XRD, ph phn x hng ngoi v nh
chp AFM.
dy mng khng o c trc tip m c tnh tan thng qua in p v mt dng.
in p tng V ca h thng in ha c tnh:
V = Va + RS. Ia
Trong : Va l in p thc ri trn cc in cc v Rs, Ia l in tr v dng ca dung dch in
.L
Rs
phn. Vi
l in tr sut, L l khong cch gia hai in cc v S l din
S
tch in cc. Mt im kh l Va ph thuc vo dy hox ca mng ang tng trng.
n. hox .Va
hox . Va
Va b.hox
v
b
2
2
n. hox
hox
Do dy mng lin h vi hng s Faraday nn sau mt s tnh ton thch hp, ta thu c:
hox (t )
J .M
F .n.d
Advances
_____________________________________________________________________________________
Trong : hox l tc to mng, d l mt

nhm oxide, thay i t 3 3.6 g/cm3 v
thng c chn tt nht l 3.3 g/cm3, J l
mt dng, F l s Faraday, M l khi lng
mol ca Al2O3: 101.94 g/mol, n l bc oxi
ha, i vi nhm oxide l n = 3.
Mng to thnh c xp rt ln v phn
b tng i u n trn b mt. Cc l xp
ny c kch thc thay i t 50 200nm ty
theo iu kin thc nghim.
Hnh 5. Ph XRD ca mng cha , bng

ph biu hin mng v nh hnh, cc nh
cao l ca nhm kim loi
Mng
Al2O3
Al
Hnh 4.Mng Al2O3 xp trn nhm kim loi
Hnh 6. Ph ATR ca mng cha x l

nhit
S dng cc phng php quang ph v nh chp AFM nghin cu mng. Kt qu XRD

(hnh 5 v 6) kt hp vi cc php o hng ngoi cho thy mng cha c cu trc v nh hnh
v c cha gc nhm oxalate. Sau khi nhit 5000C trong 30 pht, cu trc ca mng vn biu
hin dng v nh hnh nhng gc oxalate b loi b phn ln, do dc dng l thy tinh
v nhm kim loi nn cc th nghim nhit cao hn 600 0C cha tin
hnh c. Cc kt qu o ph hp thu hng ngoi phn x tt dn (ATR) cho thy mng c
thnh phn ha hc l Al2O3, khi cha c cha gc oxalate. Gc ny b nhit phn sau khi
li thnh phn mng Al2O3 v nh hnh v mt phn pha .
3. Kt qu v bn lun
3.1. Kho st bng ph hng ngoi
Quan st ph phn x hng ngoi ca mng cha x l nhit, ta tht r hai nh 1566 cm-1 v
1471 cm-1 l ca gc oxalate. nh 435 cm-1 l ca pha v nh hnh cn bng rng
948 cm-1 nghi ng l ca pha , tuy nhin do cn gc oxalate nn cha kt lun c. iu ny
khp vi cng b [1] hnh 8 ph ATR ca mng cha x l nhit. Ch rng trong hnh 6, 7
v 8 cc th ph c cc trc c chn hi khc nhau l do c th ca thit b o.
Sau khi tin hnh nhit gc oxalate b nhit phn phn ln. Quan st ph phn x hng
ngoi ca mng x l nhit, ta tht r hai nh 435 cm-1 v 898 cm-1 l ca pha . (hnh 9),
hai bng rng biu hin ca pha v nh hnh. Song song , ph ATR ca mng trn thy
Nhng
_____________________________________________________________________________________
Hnh 7. ph ATR ca mng trn nhm kim loi

x l nhit 5000C trong 30 pht
Hnh 8. ATR ca mng cha x l nhit [1]
tinh sau nhit cho thng tin r rt hn. (hnh 8). Cc nh 534 cm-1, 825 cm-1 biu hin pha ,
nh 416 cm-1 l ca pha v nh hnh. Cc nh ph c tham kho theo [7, 8, 9].
Kho st nh AFM ca mng do nhm chng ti thc hin ta thy mng c cc l xp tng
i u n. Tuy nhin, cc l ny c kch thc kh ln c 100 x 200 nm. (hnh 10)
3.2. ng dng thc hin cm bin m dng hiu ng in dung.
ng dng tnh xp ca mng, nhm chng ti ch
to cm bin m in dung vi lp in mi cm bin l
Al2O3 xp. Cm bin gm mt nhm kim loi c to
mng Al2O3 bng phng php nu trn vi dy tnh
ton c c 2 m. Mt lp nhm kim loi c ph
chng ln v cui cng l mt lp ng ni linh kin
vi cc mch in khc. (hnh 10)
Kho st s thay i in dung ca ca cm bin trn
chng ti nhn thy: mt nhit xc nh, in dung
ca cm bin thay i ng bin tuyn tnh vi m mi
trng. mt m xc nh, in dung ca cm bin
thay i ng bin tuyn tnh vi nhit mi trng. S
ph thuc ny l do s thay i hng s in mi khi mng
tch m, lm gia tng in dung ca t in, c th c
hnh dung nh sau [3]:
n
Hnh 9. nh AFM ca mng trn

nhm kim loi
Cw
w
Cd
d
Trong Cw v Cd l in dung khi m v kh, w v d
l hng s in mi trong trng thi tch m v gii m. n l
s m ph thuc vo hnh thi mng in mi. C gi tr
ca n c xc nh t thc nghim. Khi tch m, cc l
xp ht cc phn t nc v lm gia tng hng s in mi
ca lp cch in Al2O3 ko theo s gia tng in dung ca
Hnh 10. Cm bin m
cm bin.
Hnh 11 cho thy s ph thuc ca in dung vo m nhit 27 0C, p sut 1atm ca
mt mu cm bin c ch to. Do s ph thuc ny c i chng bi mt m k c sai s
0.01 nn ng cong hi th. Tuy nhin cc gi tr in dung o c c sai s n c 0.001 nn
kh nng phn gii ca cm bin s cao hn.
Advances
_____________________________________________________________________________________
4. Kt lun
Mng Al2O3 thc hin bng phng php in ha
mt bc c cch in cao v xp. dy mng
tnh ton c c 2 m. Cc l xp c dng ging vi
kch c trung bnh khong 100 x 200nm phn b cch
nhau cng c 200nm. Tnh xp ny c th ng
dng c thc hin mt cm bin m vi gi
thnh rt thp trong nc. p ng ca cm bin
c kho st trong khong 40 70% cho thy in
dung ca mu bin thin tng trong khong
0.1 0.2 F.
V kh nng m rng nghin cu, chng ti ang
tip tc vic thc hin mt s x l trung gian v in
ha thm mt ln na ci thin tnh xp v
phn b. Lc ny mng c th sn sng lm khun
mu cho cc ng dng lng ng si nano ca cc vt
liu khc.
Hnh 11. th s ph thuc

ca in dung vo m
Ti liu tham kho

1. M.E. Mata-Zamora and J.M. Saniger, Thermal evolution of porous anodic aluminas: a
comparative study, Apartado Postal 70-186, Mexico, 04510 D.F., Recibido el 23 de mayo
de 2005; aceptado el 7 de julio de 2005
2. Paul G. Miney, Paula E. Colavita, Maria V. Schiza, Ryan J. Priore, Frederick G. Haibach,
and Michael L. Myrickz, Growth and Characterization of a Porous Aluminum Oxide Film
Formed on an Electrically Insulating Support, Department of Chemistry and Biochemistry,
University of South Carolina, Columbia, South Carolina 29208, USA 2003.
3. Veronika Timar-Horvath, Laszlo Juhasz, Andras Vass-Varnai, Gergely Perlaky, Usage Of
Porous Al2o3 Layers For Rh Sensing, Budapest University of Technology and Economics
(BUTE), Department of Electron Devices,Budapest, Hungary Stresa, Italy, 25-27 April 2007
4. Serebrennikova, P. Vanysekf and V. I. Birss* , Characterization of porous aluminum oxide
films by metal electrodeposition, Department of Chemistry, DeKalb, IL 60115-2862, U.S.A.
(Received 23 January 1996; in revised form 29 April 1996)
5. MARJAM KARLSSON, Nano-porous Alumina, a Potential Bone Implant Coating, ACTA
UNIVERSITATIS UPSALIENSIS UPPSALA 2004
6. Guorong Xu*a,b, Fenglian Rena, Shihui Sia, Qingfeng Yib, Porous anodic alumina
electrode modifi ed with a thin film of Prussian blue: Application to amperometric
detection of hydrogenPeroxide, aCollege of Chemistry and Chemical Engineering, Hunan
University of Science and Technology, Xiangtan, 411201,P.R. China.Received: March 14,
2006
7. Quang ph hng ngoi ca thy tinh v tinh th (1972), Nxb Chemie (Ting Nga),trang
110 121.
8. A.Contreras, Satoshi Sugita, Esthela Ramos, Leticia M.Torres and Juan Serrato; A New
Production Method of Submicron Alumina Powders; http://www.azom.com/oars.asp; 2006.
9. Lung-Teng Cheng, Mong-Yen Tsai, Wenjea J.Tseng, Hsing-I.Hsiang, Fu-su Yen; Boehmite
coating Al2O3 particles via a Sol gel route; Department of Materials Engineering,
National Chung Hsing University, Taiwan; 2006.
Nhng
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XC NH BN CHT MT VI DCH CHUYN BC X TRONG BT PHT

QUANG ZnO C CH TO BNG PHNG PHP SOL-GEL
V PHNG PHP GM
Bi Hng Vn, Phm Vn Bn, Phng Th Ho
Khoa Vt l, Trng i hc Khoa hc T nhin, i hc Quc gia H Ni
Tm tt: Cc bt pht quang ZnO c ch to bng phng php sol-gel v phng php gm
vi nhit , thi gian nung khc nhau. Khi kch thch bng bc x ca laser He-Cd vi bc
sng 325 nm, trong ph pht quang ca ZnO 300 K xut hin cc m 382 nm, 510 - 550 nm,
mt s m vng da cam-vng v vng . Bn cht ca s dch chuyn bc x ng vi cc
m pht quang ny c gii thch da vo s ph thuc ph pht quang ca ZnO vo nng
Cu, Co pha tp, mt cng sut kch thch v ph pht quang phn gii theo thi gian.
1. M u
ZnO l hp cht bn dn vng cm rng (Eg = 3.37 eV 300 K), c chuyn di in t
thng, nng lng lin kt exciton ln (khong 60 meV), l mt vt liu dng ch to cc
dng c quang in t nh diode pht quang, random laser... lm vic vng ph t ngoi v
nhit phng [1,2]. Ph pht quang ca ZnO 300 K gm hai m c cc i 380 - 410 nm
(m tm), 500 - 530 nm (m xanh l cy), mt s m vng da cam - vng v vng . m
tm c trng cho s ti hp bc x ca exciton t do. m xanh l cy c th c trng cho cc
nt khuyt ca oxy di dng tm F+ (tm tch in dng in ho mt ln) hoc chuyn di bc
x ca cc in t ca cc ion Cu2+ thay th cc ion Zn2+ trong ZnO. Cc m vng da cam vng c th c trng cho s ti hp bc x ca cc cp donor - acceptor, trong donor l cc
nguyn t oxy nm l lng gia cc nt mng, cc acceptor l cc nt khuyt ca Zn, cn m
vng c trng cho cc tp cht nh Li, Fe c trong tinh th ZnO [1,2,3]. Tuy nhin, s
xut hin cc m pht quang trong ZnO v bn cht bc x ca chng ph thuc vo cc iu
kin ch to mu. Nhm lm sng t thm bn cht ca mt vi dch chuyn bc x trong bt
pht quang ZnO, chng ti kho st s thay i ph pht quang ca ZnO vo nng ca Cu,
Co pha tp, mt cng sut kch thch v ph pht quang phn gii theo thi gian.
2. Mu nghin cu v thit b thc nghim
2. 1. Quy trnh ch to cc bt pht quang ZnO, Zn1-xCuxO, Zn1-xCoxO
Cc bt pht quang ZnO, Zn1-xCuxO (1.10-3 x 6.10-3), Zn1-xCoxO (2.10-2 x 2.5.10-1)
c ch to bng phng php sol-gel v phng php gm. Trong phng php sol-gel, ZnO
c ch to t km acetate dihydrate Zn(CH3COO)2.2H2O, dung mi etylenglycol C2H6O2 v
glycerol C3H8O3 theo quy trnh nh hnh 1a. c Zn1-xCuxO ngoi cc cht trn, chng ti
dng thm Cu(CH3COO)2.2H2O. Trong phng php gm ZnO, Zn1-xCoxO c ch to t bt
ZnO, CoO theo quy trnh nh hnh 1b. Cc ha cht dng ch to bt pht quang l ca hng
Merck c tinh khit cao, nng ca cc tp cht u nh hn hoc bng 10-5.
2.2. Thit b thc nghim
Cu trc tinh th ca ZnO, Zn1-xCuxO, Zn1-xCoxO c kho st bng gin nhiu x tia X
(XRD) trn thit b XD8 Advance Bukerding dng bc x CuK ( = 1.5046 Ao , 2 = 10o
70o). Hnh thi b mt, nng ca Zn, O, Cu, Co v mt s tp cht trong ZnO c th hin
qua nh SEM v ph tn sc nng lng (EDS) chp trn knh hin vi in t qut JEO L5410VL. Ph pht quang, ph pht quang phn gii theo thi gian v ph kch thch hunh quang ca
chng 300 K c kch thch bng bc x ca cc laser He-Cd, N2, He-Ne, n xenon cc
Advances
_____________________________________________________________________________________
bc sng tng ng 325 nm, 337 nm, 632.8 nm, 300- 450 nm v c ghi trn h o OrielSpec MS-257, GDM-1000 dng k thut Boxca v FL3-22
3. Kt qu v bin lun
3.1. Cu trc tinh th ca ZnO, Zn1-xCuxO, Zn1-xCoxO
a
C2H6O2
Zn(CH3COO)2.6H2O
2500C
C3H8O3
ZnO
ZnO
un nng
Nung hn hp
T = 7500C, t = 1.5h
b
Nghin, trn
trong 8h
p vin
CoO
t hn hp
T = 3700C
Khuy t
Sol
Gel
175 C
Sy hn hp T = 8000C, t = 20h
Nung hn hp ln 1:T = 900 oC, t = 6 h

Nung hn hp ln 2:T =1290 oC, t = 12 h
Tc tng nhit 9o/pht
Zn1-xCoxO
Hnh 1: Quy trnh ch to ZnO, Zn1-xCuxO bng phng php sol-gel (a)
v ZnO, Zn1-xCoxO bng phng php gm (b)
Hnh 2:Ph XRD ca ZnO (a)

v Zn1-xCuxO (x=3.10-3) (b) ch to
bng phng php sol-gel
Hnh 3: nh SEM ca ZnO ch to bng phng php

sol-gel (a) v phng php gm (b)
Hnh 2a l ph XRD ca ZnO ch to bng phng php sol-gel nung trong khng kh
nhit 7500C v thi gian 1.5 h. T ph XRD cho thy ZnO kt tinh dng a tinh th, c cu
trc lc gic thuc nhm khng gian P63mc vi cc mt phn x chnh l [100], [002], [101],
[102] v c cc hng s mng: a
b
3.2508 A0, c
5.2044 A0. Khi a Cu vo ZnO vi
-3
nng x = 3.10 th v tr cc mt phn x chnh v cc hng s mng hu nh khng thay i
m ch thay i t s cng gia cc mt phn x (hnh 2b). Cc kt qu ny cng ph hp
vi ZnO v Zn1-xCoxO c ch to bng phng php gm.
T nh SEM ca ZnO ch to bng hai phng php sol-gel v gm (hnh 3a, 3b) cho thy
cu trc ca chng c dng gn lc gic, cc ht phn b kh ng u vi kch thc ht
khong t 2 m n 3 m. Trong ph EDS ca ZnO ch yu xut hin cc nh c trng cho
cc nguyn t Zn, O v mt s tp cht khc c nng rt nh. i vi Zn1-xCuxO, Zn1-xCoxO,
ngoi cc nh c trng trn cn xut hin cc nh c trng cho Cu, Co.
3.2. Xc nh bn cht mt vi dch chuyn bc x trong bt pht quang ca ZnO
Nhng
_____________________________________________________________________________________
a. S ph thuc ph pht quang ca ZnO vo nng Cu, Co
Hnh 4: Ph pht quang ca ZnO 300 K

ch to bng phng php sol-gel (a,b) v
phng php gm (c) khi kch thch bng
bc sng 325 nm ca laser He-Cd
Hnh 5: Ph kch thch hunh quang m

510 nm ca ZnO 300 K ch to bng
phng php sol-gel
Hnh 4 l ph pht quang ca ZnO 300 K khi kch thch bng bc sng 325 nm ca laser
He-Cd. Vi ZnO ch to bng phng php sol-gel tip xc t vi khng kh, trong ph pht
quang ca n xut hin mt m tm 382 nm c cng nh, m 510 nm c cng ln
v m da cam vng, m 625 nm, 691 nm c cng yu hn (hnh 4a). Vi mu ZnO
ch to bng phng php sol-gel tip xc nhiu vi khng kh v phng php gm th m tm
b dp tt hon ton, cc m xanh l cy 510 nm, m da cam-vng, m u c cng
gim, chng ha vo nhau thnh mt m rt rng c cc i tng ng khong 574 nm, 553 nm
(hnh 4b,c). S gim cng m xanh l cy 510 nm i vi ZnO tip xc nhiu vi khng
kh so vi ZnO tip xc t vi khng kh cho thy m ny phi lin quan n nt khuyt ca oxy
m khng lin quan n Cu. m tm c trng cho s ti hp bc x ca t hp exciton t do
vi s tham gia ca nhiu phonon quang dc LO [2]. m da cam - vng c trng cho s ti
hp bc x cc cp donor - acceptor lin quan n cc nt khuyt ca Zn (VZn) v cc nguyn t
oxy nm l lng gia cc nt mng, cn m c th lin quan n mt s tp cht nh Li, Fe,
Mg, Sn c trong ZnO [1,2,3]. Kho st ph kch thch hunh quang m 510 nm ca ZnO ch
to bng phng php sol-gel chng ti thy ph ny tri ra trong vng t 300 nm n 380 nm
nhng lc la tt nht 367 nm (hnh 5). m ny c trng cho chuyn di hp th vng
vng trong ZnO [2].
lm sng t thm bn cht chuyn di bc x ng vi cc m pht quang ca ZnO
chng ti ch ng pha tp Cu, Co vo trong n. Vi cc mu Zn1-xCuxS
ch to bng
phng php sol-gel tip xc nhiu vi khng kh, khi a Cu vo ZnO nng x = 1.10 -3 ,
cc m trong ph pht quang ca ZnO hu nh b dp tt, trong ph ch xut hin mt m
128 nm) (hnh 6a). Khi tng nng ca Cu, v
550 nm c dng i xng v rng ln (
tr ca m ny hu nh khng thay i, cn cng ca n tng v t cc i x = 3.10-3
(hnh 6b,c). iu ny chng t cc ion Cu2+ thay th cc v tr ca cc ion Zn2+ v cc nt
khuyt ca chng trong ZnO v to nn m pht quang 550 nm. Khi tip tc tng nng ca
Cu t x = 4.10-3 n x =5.10-3 th cng ca m ny b gim nhng v tr ca n vn khng
thay i (hnh 6d,e). Khi nng ca Cu l x = 6.10-3 th cng ca m 550 nm gim mnh,
n ho vi cc m vng da cam vng, thnh mt m rt rng v c cc i dch v pha
bc sng di (hnh 6f). S gim cng m 550 nm khi tng nng ca Cu l do s tng
tc gia cc ion Cu2+ vi cc ion ca mng tinh th v gia cc ion Cu2+ vi nhau [1,2,3]. Vi
nhng c im trn, chng ti cho rng m pht quang 550 nm phi c trng cho s chuyn
di bc x trong lp v in t 3d9 ca cc ion Cu2+ trong ZnO [1,2].
Advances
_____________________________________________________________________________________
Hnh 6: Ph pht quang ca

Zn1-xCuxO (1.10-3 x 6.10-3) 300 K ch to
bng phng php sol-gel khi kch thch bng
Hnh 7: Ph pht quang ca Zn1-xCoxO

(0.02 x 0.25) 300 K khi kch bng
bc sng 632.8 nm ca laser He-Ne
Vi phng php gm, khi kch thch Zn1-xCoxO (x = 0.02) bng bc sng 325 nm ca laser
He-Cd, trong ph pht quang ca n 300 K ch xut hin mt m c cc i khong 510
nm. Khi tng dn nng ca Co, cng ca m ny gim dn v n
x = 0.25 th cng
ca m ny gn nh bng khng. Cn khi kch thch Zn1-xCoxO (x = 0.02) bng bc sng
632.8 nm ca laser He-Ne, trong ph pht quang ca n ch xut hin mt m 693 nm c
cng ln v dng i xng Khi nng Co tng dn, cng ca m ny cng tng v
t cc i nng x = 0.1, sau n b gim dn khi tip tc tng nng Co (hnh 7). iu
ny chng t cc ion Co 2+ thay th cc ion Zn2+ v nt khuyt ca chng. Cc ion Co 2+ to ra
4
m pht quang 693 nm 4T1
A2 lm dp tt cc m pht quang lin quan n cc nt
khuyt ca oxy, Zn v cc tp cht c trong ZnO [4]. Khi tip tc tng nng Co c th xy ra
s tng tc gia cc ion Co 2+ vi cc ion ca mng tinh th v gia cc ion Co2+ vi nhau v th
cng ca m b gim i.
b. S ph thuc ph pht quang ca ZnO vo mt cng sut kch thch v ph pht quang
phn gii theo thi gian
Kho st s ph thuc ph pht quang ca ZnO ch to bng phng php sol-gel theo mt
cng sut kch thch, chng ti thy vi mu tip xc t vi khng kh khi tng mt cng
sut kch thch ca laser He-Cd t 18 W/cm2 n 57 W/cm2 th v tr ca m tm 382 nm v
m xanh l cy 510 nm hu nh khng thay i (hnh 8), cn cng ca cc m ny tng
theo quy lut Ihq = A Inkt vi cc h s tng ng n1 1.1, n2 1.0. Vi mu ZnO tip xc nhiu
vi khng kh khi tng mt cng sut kch thch ca laser He-Cd t 0.6 W/cm2 n 3.0 W/cm2
v tr ca m 573 nm hu nh khng thay i v cng ca n cng tng vi h s n3 1.2.
Vi mu ZnO ch to bng phng php gm khi tng mt cng sut kch thch t 0.4 W/cm2
n 3.3.102 W/cm2 th v tr ca m xanh l cy 553 nm cng hu nh khng thay i v
cng pht quang ca n tng vi h s
n4 1.1 (hnh 9). Chng ti cho rng cc h s n1,
n2, n3, n4 c gi tr cng bc (n 1) v kch thch ZnO vi mt cng sut trn l kch thch yu.
S khng thay i v tr ca cc m ny chng t s tng mt cng sut kch thch trong
khong trn vn cha lm thay i ng k nhit ca mu, do rng vng cm ca ZnO
khng thay i.
Nhng
_____________________________________________________________________________________
Hnh 8: S ph thuc ph pht quang ca ZnO Hnh 9: S ph thuc ph pht quang ca

300 K ch to bng phng php sol-gel vo mt ZnO 300 K ch to bng phng php gm
cng sut kch thch khi s dng bc sng
vo mt cng sut kch thch khi s dng
325 nm ca laser He-Cd
Hnh 10 : Ph pht quang phn gii theo thi

gian m 382 nm ca ZnO 300 K
ch to bng phng php sol-gel khi kch
thch bng bc sng 337 nm ca laser N2
Hnh 11: ng cong tt pht quang m

382 nm ca ZnO 300 K ch to bng
phng php sol-gel khi kch thch bng
bc sng 337 nm ca laser N2
Kho st ph phn gii theo thi gian ca ZnO chng ti thy: khi tng thi gian tr t 10 ns
n 20 ns, v tr m tm 382 nm hu nh khng thay i nhng cng ca n b gim dn
(khong 1.8 ln) (hnh 10). T nhng kho st trn, chng ti cho rng m tm 382 nm l do
ti hp bc x ca t hp cc exciton t do. Thi gian sng ca cc exciton t do khong 72 ns
c suy t ng cong tt pht quang theo thi gian m ca 382 nm khi kch thch bng bc
sng 337 nm ca laser N2 vi rng xung l 6 ns, tn s lp li l 10Hz (hnh 11). m xanh l
cy 510 nm c trng cho s chuyn di bc x ca cc in t t do t vng dn xung mc
F+ c trng cho nt khuyt ca oxy tch in dng mt ln. m vng da cam vng c
trng cho s ti hp bc x ca cc cp donor-acceptor, trong donor l cc nguyn t oxy
nm l lng gia cc nt mng, cn acceptor l cc nt khuyt ca Zn. m c th lin quan
n mt s tp cht nh Mg, Sn, Fe c trong tinh th ZnO. Theo kt qu ca phn tch quang
ph pht x, nng ca cc tp ny trong ZnO nh hn hoc bng 10 -5.
4. Kt lun
Da vo s ph thuc ph pht quang ca ZnO vo nng ca Cu, Co v iu kin ch to
mu (cho mu tip xc t vi khng kh hoc tip xc nhiu vi khng kh) v ph pht quang
phn gii theo thi gian ca ZnO, chng ti lm sng t thm bn cht ca mt vi dch
chuyn bc x trong bt pht quang ZnO c bit l m tm 382 nm v m xanh l cy 510
nm. m tm 382 nm c trng cho s ti hp bc x ca t hp cc exciton t do vi thi
Advances
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gian sng khong 72 ns. m xanh l cy 510 nm c trng cho s chuyn di bc x ca in

t t do t vng dn xung mc F+ lin quan n cc nt khuyt ca oxy ion ho mt ln. m
vng da cam - vng v m c trng cho s ti hp bc x ca cc cp donor - acceptor v
mt s cht nh Mg, Sn, Fe c trong ZnO, trong donor l cc nguyn t oxy nm l lng
cc nt mng v acceptor l cc nt khuyt ca Zn.
Li cm n: Chng ti xin chn thnh cm n ti: QG.07.45 h tr kinh ph hon
thnh bi bo ny
Ti liu tham kho
1. ..e, .., ,
(1987)
2. .., . , . ,
(1984)
3. M.Koyano, Phung Quoc Bao, Le Thi Thanh Binh, Phys. Stat. Sol(a),Vol.193, No.1, (2002),
pp 125 - 128.
4. B. Martiner, F,Sandiumenge,L. Balcell, J. Fontcuberta, F.Sibieude, C.Monty, J.M.M.M,
No.290 - 291(2005), pp 1012 - 1015.
5. David C Look, Semicond.Sci. Technol.20(2005), S55-S61
6. HoJung Chang, Chang-sik son, Journal of the Korean Physical Society, Vol.45, No.4,
(2004), pp 959-962
Nhng
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NH HNG CA Co V Cu LN TNH CHT QUANG V T

CA MNG MNG ZnO
Nguyn nh Lm, Phm Vn Hi, ng Th Huyn Trang, Nguyn Vn Hng,
Phm Chung, Nguyn Th Khi v Lc Huy Hong
Khoa Vt l, Trng i hc S phm H ni
136, Xun Thy, Cu Giy, H Ni
E-mail: Lamnd2005@yahoo.com
Tm tt: Mng mng ZnO pha Co, Cu trn thy tinh c ch to bng phng php spincoating. Cc tnh cht ca mng c kho st bng php o nhiu x tia X, ph hp th
quang hc v ng cong t ha. T gin nhiu x tia X, cc mng l a tinh th vi cu trc
wurtzite v u tin nh hng theo phng vung gc vi mt . Cc chuyn di hp th
in t gia cc mc nng lng ca Co2+ trong trng t din c th hin rt r trn ph hp
th khi nng pha tp ca Co l 5% v Cu l 1%. Vi nng Co l 5% th s thay th Co cho
Zn trong tinh th l tt nht. Cc mng ZnO:Co,Cu u th hin tnh cht st t nhit phng.
Tnh cht t ca cc mu ZnO:5%Co,Cu chu nh hng ca nng Cu pha tp. Lc khng t
ca mu ZnO:5%Co, 1%Cu t n 70 Oe v t bo ha l 3,7.10-5 emu/cm2 (??).
1. M u
ZnO l hp cht bn dn thuc nhm AIIBVI c nhiu u im nh: b rng di cm ln (3,4
eV nhit phng), chuyn mc vng cm thng v nng lng lin kt exciton c 60 meV.
c bit l khi ZnO c pha tp thm kim loi chuyn tip th n c th c tnh st t nhit
phng (vt liu bn dn pha t long (DMS)).
Trong s cc kim loi chuyn tip nh Fe, Co, Ni th Co c t ha kh cao, ha tr n
nh v bn knh ion Co2+ gn bng vi bn knh ion ca Zn2+. V vy, trong mng tinh th ca
ZnO, ion Zn2+ c th c thay th tng i d dng bi ion Co2+. Mt s cng b gn y
cho thy, cu trc wurtzite ca mng ZnO khng thay i khi nng pha tp Co di 25% v
mng thng nh hng theo phng u tin (002) [1]. cc mng ZnO khi pha tp Co xut
hin di hp th ti 500 n 700nm v b hp th dch v pha bc sng ngn[2].
Nguyn nhn gy ra tnh st t trong vt liu ZnO:Co c gii thch bng nhiu gi
thuyt khc nhau. Mt gi thuyt cho l do tng tc trao i kp gia cc ion Co2+ thng qua
in t dn (c gii thch bng l thuyt RKKY). Mt gi thuyt khc c a ra l c kh
nng cc pha CoO hoc s t m ca Co l nguyn nhn gy nn hiu ng st t trong mu. V
vy, xc nh bn cht t tnh ca vt liu, mng mng ZnO:Co c pha thm Cu vi
mc ch lm tng mt in t dn. Khi pha mt lng Cu vo mu, th t ca mu tng
ln ng k. T t gi tr ln nht khi nng Cu pha tp l 1%. Nu nng pha tp Cu
tng ln th t li gim [3].
Trong bo co ny, chng ti tin hnh ch to mng mng ZnO pha Co, Cu vi cc nng
khc nhau bng phng php spin-coating. Cu trc tinh th, hnh thi b mt, tnh cht
quang v t ca cc mu cng c nghin cu v tho lun thng qua cc php o ph
nhiu x tia X, nh SEM, ph hp th v ng cong t ha.
2. Thc nghim
Cc mng mng ZnO pha tp Co v Cu c ch to bng phng php spin coating. Quy
trnh to mu c th c chia lm hai bc:
+ Bc 1: to sol
Cc ha cht ban u l: Zn(CH3COO)2.4H2O, Cu(CH3COO)2.H2O, Co(CH3COO)2.4H2O,
C2H5OH v Ethandamine(DEA) vi sch phn tch. Cc mui axetat u dng bt c cn
Advances
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theo hp phn, ha vo dung mi gm C2H5OH v DEA to sol. Qu trnh kho st cho thy
st nng cc mui trong dung dch tt nht khi nng ca dung dch mui kim loi
Zn(CH3COO)2 l 0,5M; Co(CH3COO)2 l 0,05M v Cu(CH3COO)2 l 0,05M. Cc dung dch
mui c khuy nhit khong 70 oC trong thi gian 2h. Sau khuy khng nhit trong
5h vi tc 500 vng/pht thu c sol trong sut, ng u, khng b lng ng, nht
cao. Cc sol thu c c mu c trng cho tng loi mui axetat: Zn2+ mu trng trong sut,
Cu2+ mu xanh, Co2+ mu hng.
+ Bc 2: to mng
Cc mu ch to c kho st tnh cht cu trc thng qua php o nhiu x tia X trn
my SIEMENS D-5005 Trng i hc Khoa hc t nhin i hc Quc gia H Ni. Ngun
bc x l Cu-K c bc sng 1,5406 , gc qut 2 ca my c t t 15 60. Ph hp
th ca mng ZnO pha Co v Cu c nghin cu trn my hp th JASCO V-670 thuc B
mn Vt l Cht rn-in t, Khoa Vt l Trng i hc S phm H ni, trong khong bc
sng t 300800 nm. Php o t k mu rung c thc hin trn my VMS-8800 ti Trng
i hc Khoa hc t nhin, i hc Quc gia H ni.
Quy trnh to mng c thc hin theo s sau:
Dung dch coban
axetat 0,05 M (B)
Dung dch km
axetat 0,5 M (A)
19ml A
10ml B
18.6ml A
14ml B
18ml A
20ml B
18,8ml A
10ml B
2ml C
Dung dch ng
axetat 0,05 M (C)
18,6ml A 18,4ml A
10ml B
10ml B
4ml C
6ml C
SPIN - COATING
Mng ZnO Mng ZnO Mng ZnO Mng ZnO
7% Co
10% Co
5% Co
Mng ZnO Mng ZnO Mng ZnO

5%Co
5%Co
5%Co
1%Cu
2%Cu
3%Cu
X L NHIT: TI 500 oC TRONG MI TRNG KHNG KH
S 1: Quy trnh ch to mng mng ZnO:Co,Cu bng phng php spin-coating
Nhng
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3. Kt qu v tho lun
3.1. Cu trc v trng thi b mt ca mng ZnO
Hnh 1. Gin nhiu x tia X ca mng mng Zn1xCoxO (x=0; 0,05; 0,07; 0,1)
Hnh 2. nh SEM ca mu mng mng ZnO ch

to bng phng php Spin-Coating
Gin nhiu x tia X ca cc mu Zn1-xCoxO (x = 0 ; 0,05 ; 0,07 v 0,1) c trnh by trn

hnh 1. Nm nh nhiu x xut hin ti cc v tr c 2 l: 31,85 o ; 34,53 o ; 36,42 o ; 47,69 o v
56,73o tng ng vi cc ch s (hkl): (100) ; (002) ; (101) ; (102) v (110). Trong , nh
(002) c cng mnh nht. Cc nh ny u thuc v cu trc wurtzite ca pha ZnO. Ngoi
ra, chng ta cn nhn thy khng c s tn ti ca cc pha l trong mu. iu chng t mu
kt tinh theo cu trc wurtzite, n pha v c u th nh hng theo phng (002).
T gin nhiu x tia X, ta xc nh c cc hng s mng ca mu l a = b = 3,26 ,
c = 5,19 . Co pha tp thay th tng i tt cho Zn trong mng ZnO.
nh (SEM) ca mng mng ZnO cho thy, b mt mng c dng xp, cc ht c xp xp
tng i ng u v c kch thc vo c 50 nm (hnh 2).
3.2. Tnh cht quang ca mng ZnO v ZnO:Co
1.0
0.04
a)
ZnO
b)
5% Co
7% Co
10% Co
5% Co
7% Co
10% Co
0.002
0.06
0.03
0.8
0.000
0.04
0.03
0.4
0.02
475
500
525
550
575
600
0.02
hp th (a.u)
0.6
hp th
hp th (a.u)
hp th
0.05
-0.002
-0.004
-0.006
0.01
-0.008
450
Bc sng (nm)
500
550
600
650
700
750
Bc sng (nm)
0.00
0.2
0.0
400
500
600
Bc sng (nm)
700
800
-0.01
300
400
500
600
700
800
Bc sng (nm)
Hnh 3. Ph hp th ca mu mng Zn1-xCoxO (a: x = 0; b. x = 0,05; 0,07; 0,1)
Hnh 3a trnh by ph hp th ca mu mng ZnO ch to bng phng php spin-coating.

Trn ph, ch thy mt b hp th duy nht ca ZnO c dng thng v dc ti v tr ng vi
bc sng 370nm, tng ng vi nng lng vng cm l 3.34 eV (trong khi mu khi l 3.4
Advances
_____________________________________________________________________________________
eV). Kt qu ny l mt bng chng c th khng nh mt ln na mu ch to c l n

pha vi cu trc wurtzite.
Cc mu ZnO :Co vi nng 5, 7 v 10% xut hin b hp th ti 330nm. B hp th ca
mu b dch chuyn v pha bc sng ngn so vi mu khi c gii thch l do s giam gi
lng t [2]. Ngoi ra, ta cn quan st thy di hp th ca Co trong khong t 500 n 700nm
(hnh 3b). Di ny c ngun gc t s chuyn di gia trng thi c bn 4A2 v trng thi kch
thch 4T1(P) ca ion Co2+ trong trng t din[4]. Nh vy, ion Co2+ thay th ion Zn2+ trong
mng tinh th ca ZnO. S thay th l tt nht khi nng Co pha tp l 5%.
3.3. Tnh cht t ca mng ZnO:Co,Cu
0.03
a)
% 5 Co
0.04
b)
% 5 Co, 1% Cu
0.02
0.02
memu/cm
0.00
-0.01
0.00
0.00
0.01
-0.02
memu/cm
memu/cm
memu/cm
0.01
-0.02
0.00
-0.01
-0.03
-400
T tr-ng ngoi (Oe)
-0.04
-250
250
T tr-ng ngoi (Oe)
-0.04
-6000
-4000
-2000
2000
4000
6000
-6000
T tr-ng ngoi (Oe)
-4000
-2000
2000
4000
6000
T tr-ng ngoi (Oe)

0.04
0.04
c)
d)
% 5 Co v 2 % Cu
0.02
%5 Co, 3% Cu
memu/cm
0.00
0.01
0.00
0.01
0.00
memu/cm
-0.02
memu/cm
memu/cm
0.02
0.00
-0.02
-120
-60
60
120
-0.01
180
T tr-ng ngoi (Oe)

-200
-100
T tr-ng ngoi (Oe)
-0.04
-6000
-4000
-2000
2000
4000
T tr-ng ngoi (O e)
600
-0.04
-6000
-4000
-2000
2000
4000
600
T tr-ng ngoi (Oe)
Hnh 4. ng cong t ha ca mu mng Zn0,95-yCo0,05CuyO
(a: y = 0,0;b: y = 0,01; c: y = 0,02; d: y = 0,03)

ng cong t ha nhit phng ca cc mu mng ZnO:Co,Cu vi nng Co l 5%
v Cu l 0, 1, 2, 3% c trnh by trn hnh 4 v 5. Cc mng ZnO pha tp Co v Cu u th
hin tnh cht st t nhit phng vi t bo ha t c 1250 Oe.
Cc thng s c bn thu c t ng cong t ho ca bn mu trn c trnh by trong
Bng 1.
Bng 1. Cc gi tr t bo ho, t d v t trng bo ha thu c t ng cong t ho
ca cc mu ZnO pha tp Co v Cu
Vt liu
T bo ha
Bbh (memu/cm2)
t d
Br(memu/cm2)
T trng
Hbh(Oe)
Tch s
B.H
Zn0,94Co0,05Cu0,01O
0,037
0,0152
1250
46
Zn0,93Co0,05Cu0,02O
0,035
0,0142
1250
44
Zn0,92Co0,05Cu0,03O
0,036
0,0147
1250
45
Zn0,95Co0,05O
0,030
0,0092
1250
38
Nhng
_____________________________________________________________________________________
0.04
0.02
memu/cm
Bng 1 cho thy, mng ZnO pha Co 5%

c t bo ha Bbh(0,03 memu/cm2), t
d Br(0,0092 memu/cm2). Khi c pha thm
Cu, t bo ha v t d tng ln ng
k. Ti nng pha tp 1% Cu , t bo ho
ca mng l vi Bbh(0,037 memu/cm2), t
d Br(0,0152 memu/cm2) v lc khng t 70
Oe (hnh 5). Tuy nhin, t bo ho gim khi
tip tc tng nng pha tp Cu ln 2%. T
bo ho t gi tr ln nht trong mu
Zn0,94Co0,05Cu0,01O. iu ny c th c gii
thch rng, vic pha thm Cu vo mng
Zn0,95Co0,05O lm tng mt in t dn,
tng tc RKKY c tng cng, v vy t
bo ha ca mu tng. Tuy nhin, khi nng
Cu pha vo ln hn mt ngng no ,
trong mu s hnh thnh pha th hai CuO, lm
mt ht dn gim i v t ha cng
gim mnh.
0.00
-0.02
5% Co
5% Co, 1% Cu
5% Co, 2% Cu
5% Co, 3% Cu
-0.04
-6000
-4000
-2000
2000
4000
6000
T trng ngoi (Oe)
Hnh 5. ng cong t ha ca mu mng

Zn0,95-yCo0,05CuyO
(y = 0; 0,01; 0,02; 0,03)
4. Kt lun
Mng mng Zn1-xCoxO (x=0.05, 0.07, 0.10) v Zn1-(0,05+y)Co0.05CuyO (x=0.01, 0.02, 0.03)
c ch to thnh cng bng phng php spin-coating. Cc mng to c l n pha, c cu
trc wurtzite v c xu hng kt tinh nh hng theo phng (002) (???). B mt ca mng c
dng xp, cc ht xp xp tng i ng u, vi kch thc ht trung bnh l 50nm. Cc mng
ZnO:Co c b hp th ti 330nm v mt di hp th ca Co t 500nm 700nm. Cng ca
cc di ny gim dn khi nng pha tp Co tng ln. Mu ch to c c t tnh tt nht khi
pha tp 5%Co v 1%Cu.
Li cm n : Cc tc gi chn thnh cm n s h tr kinh ph ca Trung tm H tr Nghin
cu Chu & Qu gio dc Cao hc Hn quc v ti nghin cu khoa hc m s SPHN-08184 cp Trng i hc S phm H Ni.
Ti liu tham kho
1. C. Roy, S. Byrne, E. McGlynn, J.-P. Mosiner, E. De Posada, D. OMahony, J.G. Lunney,
M.O. Henry, B. Ryan, A.A. Cafolla. Thin Soid Film 436 (2003) 273-276.
2. P.Lommens and et al, Photoluminescence properties of Co2+-doped ZnO nanocrystals,
Journal of Luminescence 118 (2006) 245-250.
3. Hung-Ta Lin, Show-Hau Lin, Rong-Tan Huang, Enhancement of ferromagnetic properties in
Zn1-xCoxO by additional Cu doping. Appl.Phys.Lett.Vol 85, No.4 (2004)
4. H.A Weakliem, Optical spectra of Ni2+, Co2+ and Cu2+in Tetrahedral sites in Crystals,
J.Chem.Phys 36 (1962), 2117 2140.
Advances
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STRUCTURAL ANALYSIS ALGINIC ACID FRACTION EXTRACTED FROM

BROWN SEAWEEDS BY USING FT-IR SPECTROSCOPY
Tran Thi Thanh Van, Nguyen Quoc Cuong, Vo Mai Nhu Hieu,
Cao Thi Thuy Hang and Bui Minh Ly
Nhatrang Institute of Technology Research and application
Abtract: Sodium alginates, obtained by alkaline extraction of Turbinaria ornata, S. mcclurei,
S.polycystum from central Vietnam, were partially hydrolized with HCl (acide hidrocloric). Each
of them gave three fractions that were analyzed using FT-IR spectroscopy. Results compared with
solution 1H and 13C NMR spectroscopic studies show that fraction solubled in 0,3M HCl, fraction
solubled at pH=2,8, and fraction insolubled at pH=2,85 were heteropolymeric block,
homopolymannuronic acid blocks, and homopolyguluronic acid blocks, correspondingly .Two
dimensional spectra confirmed the fine structure of hetero and homo polymeric fractions
1. M u
Axit alginic l thnh phn polysacarit ch yu c trong rong Nu (Phaeophyta). Chng l
polyme mch thng c to thnh bi cc gc (1-4) -D-mannopyranuronic axit (M) v (1-4)
-L-gulopyranuronic axit (G) (hnh 1). S sp xp cc gc M v G trong mch polyme khng
theo qui lut m ph thuc vo tng loi rong v chu trnh sinh trng ca chng 1 . T l M/G
nh hng n tnh cht ha l cng nh hot tnh sinh hc ca axit alginic. Nu s gc G ln
hn s gc M th axit alginic c kh nng to gel cao, nu t l M/G ln hn 1,8 v trng lng
phn t ca axit alginic nh hn 30.000 DA th chng c kh nng khng khi u, khng vim
nhim, khng ng t mu 2,3 . V vy khi bit c t l M/G v qui lut sp xp ca chng
th chng ta c th d bo c tnh cht ha l v sinh hc ca axit alginic.
c nhiu cng trnh nghin cu cu trc ca axit alginic v xc nh c t l M/G 3,4 ,
Tuy nhin nhng cng trnh trn hu nh cha a ra c kiu sp xp gia cc gc M v G
trong cc mu nghin cu.
Trong bi bo ny chng ti nghin cu cu trc tinh vi ca 03 axit alginic chit t 03 loi
rong Nu sinh trng ti vng bin Khnh Ha bng phng php ph Hng ngoi (IR) v c
kim tra li bng ph Cng hng t ht nhn (NMR) v bc u a ra t l cc kiu lin kt
ca cc gc M v G trong 03 mu nghin cu.
2. Phn thc nghim
2.1. Chit Natri alginat t rong Nu Vit Nam
Cc mu rong c thu thp vo thng 5 nm 2006 ti b bin Khnh Ha. Mu rong bin
sau khi thu v ra sch nc bin, rc v ct bng nc ngt em phi kh ri chit theo qui
trnh 1 thu c natri alginic.
2.2 Tch phn an natri alginat
Thy phn 0,5 g natri alginat trong 50 ml dung dch HCl (0,085 M) trong 03 gi. Dung dch
sau khi thy phn em ly tm. Phn dung dch c trung ha bng NaOH (1M) n pH=7, c
thm tch loi mui v ta bng cn ethanol thu c phn on 1 (F1). Phn cn khng tan
tip tc c thu phn ln 2 trong dung dch HCl (0,3 M) trong 02 gi. Dung dch sau thy
phn c trung ha n pH=2,85 v c ly tm ln 2. Phn dung dch em thm tch loi
mui ri ta bng cn ethanol thu c phn an 2 (F2). Phn cn khng tan c ha tan bng
dung dch NaOH pH=8, sau thm tch loi mui v ta bng cn ethanol thu c phn
an 3 (F3).
Nhng
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* Ph Hng ngoi (IR) ca natri alginat v cc phn on c ghi trn my Bruker IFS trong
vng 4000-400 cm-1.
* Ph cng hng t ht nhn (NMR) ca natri alginat v cc phn on c o trn my
Bruker 500 MHz trong dung mi D2O nhit 800C.
3. Kt qu v tho lun
Bng 1. Hiu sut tch phn an ca cc mu Natri alginat
Natri alginat
Turbinaria
ornata
Sargassum
mcclurei
Sargassum
polycystum
Phn on
F1
F2
F3
F1
F2
F3
F1
F2
F3
Hiu sut (%)

4,0
38,1
49,2
9,7
48,2
15,7
8,7
41,5
21,9
Kt qu bng 1. cho thy rng hiu sut tch phn on t 75 % trong phn an F1 cha
hm lng nh nht. xc nh s c mt cc monome M hay G trong cc mu alginat v cc
phn on chng ti tin hnh o ph IR ca chng. T ph IR ca mu alginat chit t
Turbinaria ornata (hnh 1.a) v cc gii hp th chnh trn ph IR chng ti c nhn xt sau.
Trong vng s sng t 4000 400 cm-1 trn ph IR xut hin cc vn ph 3427 , 2927, 1615,
1415, 1301, 1125, 1095 v 1035 cm-1 chng t s c mt cc lin kt O-H, C-H, O-C-O, C-OH,
C-C-H, O-C-H, C-O, C-C trong vng pyranose 5 ca cc monome M v G. c bit s c mt
nhng vn ph trong vng ( 950 -750 cm-1 ) hay cn gi l vng vn tay ca cc gc anome.
Tuy nhin trn kt qutrn ph IR, chng ti ch thy cc vn ph 948, 888, 820 cm-1 tng ng
vi dao ng ha tr ca lin kt C-O trong axit uronic, dao ng bin dng ca lin kt C1-H
ca -mannuronic axit v dao ng c trng ca -mannuronic axit 4 m khng thy xut
hin cc vn ph chng t s c mt ca monome G. gii quyt vn ny chng ti o ph
IR vi phn 02 ln (second derivative FT-IR) ca cc mu alginat (hnh 1.b).
Phng php ny c s dng rng ri trong vic nghin cu ph dao ng ca cc
polycarit sinh hc 6 . Trn hnh 1b, xut hin nhiu vn ph hn ph IR thng thng (hnh
1a). l s xut hin thm cc vn ph 994 cm-1 thuc v dao ng ha tr ca lin kt C-O, CC v vn ph 902,4 cm-1 thuc v dao ng bin dng ca lin kt C1-H ca gc -L guluronic
axit (G), vn ph 781 c cng mnh hn ph IR thng thng rt nhiu. T kt qu so snh
cc vn ph trn 02 ph, chng ti a ra bng dao ng c trng ca nhm nguyn t trong
cc monome M v G (bng 2).
Advances
_____________________________________________________________________________________
Hnh 1. Ph hng ngoi ca alginat tch chit t loi rong Turbinaria ornata
A. Ph FTIR
B. Ph hng ngoi vi phn 02 ln ( The second derivative FT-IR)
Bng 2. Mt s dao ng c trng ca gc M v G
S sng
cm-1
Dao ng ha tr ca lin kt C-O 948
trong axit uronic
Dao ng bin dng ca lin kt C1- 888
H trong gc mannuronic axit (M)
Dao ng c trng ca gc M
820
Dao ng bin dng ca lin kt C1- 902
H trong gc guluronic axit (G)
Dao ng c trng ca gc G
781
Dao ng bin dng ca lin kt
815
C-O-C trong polyme d th
Dao ng bin dng ca lin kt
812
COH v CCH ca gc G
IR* : Ph second derivative FT-IR.
Loi dao ng
Cng
IR
IR*
TB
Mnh
Ti liu
4
TB
Yu
TB
TB
Mnh
TB
8
7
Yu
Yu
Mnh
Yu
7
7
Mnh
Nhng
_____________________________________________________________________________________
Bng 3. Mt s vn ph chnh trn ph hng ngoi ca cc phn on

Natri alginat trong vng vn tay
Mu
Turbinaria
Ornata
S.mcclurei
S.polycystum
Phn
on
F1
F2
F3
F1
F2
F3
F1
F2
F3
948
964
946
951*
936*
947
962
946
951*
937*
947
960
948
951*
937*
947
888
889
883
890
885
890
888
S sng (cm-1)
820
902
781
910
774*
820
824*
902
910
779*
776*
781*
903
912
781
820
823*
823*
820
823*
815
815*
812
813
813
815
812
815
781*
903
781
813
Kt qu o ph cc phn on F1, F2 v F3 c ch ra trn bng 3. So snh cc vn ph

chnh trong cc phn on F1, F2 v F3 vi cc vn ph c trng ca cc gc M v G (bng 2)
d dng nhn thy rng ph IR ca cc phn on F3 u c cc vn ph 947, 903, 812 v 781
cm-1 l nhng dao ng c trng ca gc G v nh vy c th khng nh rng phn on F3 l
polyme ng th v chng c cu to t cc gc guluronic axit (G). Ph hng ngoi ca cc
phn on F2 c cc dao ng chnh sau: 946, 883, 820, cm-1 l cc dao ng c trng ca
gc
mannuronic axit (M). Tuy nhin trn ph vi phn 02 ln ca cc phn an F2 chit t
loi rong S.mcclurei v S. polycystum cn xut hin vn ph 781 cm-1 thuc v dao ng ca gc
G. iu ny c gii thch l do vn c lng nh cc gc G c mt trong cc phn an ny .
Chng ti cho rng phn an F2 ca mu Turbinaria ornata l cc polyme ng th c to
thnh bi cc gc
mannuronic axit (M) cn cc phn an F2 ca cc mu S.mcclurei v S.
polycystum c thnh phn chnh l cc monome M v c lng nh cc gc G. Ph IR ca cc
phn an F1 phc tp hn so ph IR ca cc phn on F3 v F2 . Trn ph dao ng ca
chng xut hin c 02 loi dao ng c trng ca c 02 gc M v G v hn th na trn ph ca
chng cn xut hin vn ph 815 c trng cho dao ng ca lin kt glycozit trong mch
polyme d th. Nh vy phn on F1 l polyme d th c to thnh bi cc gc M v G.
xc nh mc tin cy ca phng php ph hng ngoi chng ti tin hnh o ph
cng hng t ht nhn (NMR) ca cc phn on F1, F2, F3 ca cc mu nghin cu kt qu
c dn ra bng 4.
Theo ngn hng d liu ph 3 th cc 06 tn hiu 102,1; 71,7; 72,7; 78,5; 77,2; 176,4 tng
ng vi dch chuyn ca 06 nguyn t Cac bon trong gc anome guluronic axit ca polyme
d th v cc tn hiu 100,5; 65,8; 70,3; 80,8; 68,5; 176,4 tng ng vi dch chuyn ca 06
nguyn t Cac bon trong gc anome mannuronic axit ca polyme d th. So snh s liu ny
vi kt qa thu c trn bng 4, chng ti thu c kt qu hon ton tng t nh kt qu
nhn c khi phn tch cc phn on bng ph hng ngoi. l phn on F1 l polyme d
th c to bi 02 anome M v G, phn an F2 v F3 l polyme ng th c to thnh bi
cc anome M v G tng ng. Phn an F2 chit t rong S.mcclurei v S. polycystum trn ph
hng ngoi cn c lng nh anome G, tuy nhin trn ph NMR khng thy cc tn hiu tng
ng vi cc anome ny iu ny c th gii thch do nhy ca ph 13C NMR khng c
th ghi tn hiu ca lng nh cc anome ny.
Advances
_____________________________________________________________________________________
Bng 4. dch chuyn ha hc ( ppm) ca 13C trong cc phn an F1, F2 v F3
Mu
Turbinaria
Ornata
S.mcclurei
Phn
an
F1
F2
F3
F1
F2
F3
S.polycystum F1
F2
F3
C1
102,13
100,52
100,85
101,95
102,13
100,52
100,83
101,40
102,10
100,52
100,85
101,92
dch chuyn ha hoc (ppm) ca cac bon

C2
C3
C4
C5
71,70
72,70
78,59
77,18
65,82
70,40
80,90
68,70
70,9
72,21
78,79
76,92
66,0
70,10
80,72
68,27
71,69
72,68
78,56
77,18
65,84
70,40
80,89
68,70
70,73
72,18
78,81
76,89
65,97
69,97
80,69
68,18
71,65
72,69
78,60
77,15
65,83
70,38
80,85
68,59
70,87
72,23
78,85
76,93
66,04
70,05
80,70
68,22
C6
176,39
176.40
175,70
175,82
176,50
176,52
175,65
175,85
176,35
176,35
175,60
175,77
T s liu trn bng 1. cho thy trong 03 mu rong nghin cu th alginat chit t loi rong
Turbinaria ornata c hm lng axit guluronic l ln nht v tng quan gia M/G l nh nht
Theo cng trnh 9 th kh nng to gel ca alginat chit t loi rong ny c kh nng to gel tt
nht trong 03 loi rong k trn.
4. Kt lun
Axit alginic chit t rong Nu c 03 dng cu trc c tch phn an thy phn c 03
dang cu trc chnh sau:
Phn an F1 thy phn trong 0,085 M v tan trong nc l l polyme d th c to bi 02
anome M v G
Phn an F2, F3 l polyme ng th c to thnh bi cc anome M v G tng ng.
Li cm n
Chng ti xin chn thnh cm n Chng trnh Ngh nh th Vit Nam Lin bang Nga
h tr kinh ph thc hin ti ny.
Ti liu tham kho
1. Painter, T. Alga Polyssaccharides. In The polysaccharides, Aspinall, G. O. Ed Academic
Press, Orlando,II,196-285, 1983
2. Panikkar R, Brasch D. J.,Carbohydr. Res. 293, 119-132, 1996
3. Heyraud A, Grey C. Leonard C. Rochas C, G Carbohydr. Res. 289, 11-23, 1996
4. Chandia N. P, Matsuhiro B, Vasque A. E, Carbohydr. Polym, 46, 81-87, 2001.
5. Silverstein, R. M, Clayton Bassier G, Morrill T. C. , Spectrometric identification of organic
Compound, Wiley, Newyork, 1991.
6. Michel A. J, Carbohydr. Res. 173, 185-195, 1990
7. Chandia N. P, Matsuhiro B Mejias E, Moenne A, J. Appl. Phycol. , 6, 127-133, 2004
8. Mathlouthi M, Koenig J. L, Adv. Carbohydr. Chem. Biochem. 44, 7-66, 1986
9. Grant G, Morris E. A, Ress D. A, Smith, J.C, Thom D, FEBS Lett. 32, 195-198, 1973.
Nhng
_____________________________________________________________________________________
TNG HP VT LIU SiO2-SnO2 BNG PHNG PHP SOL - GEL

V KHO ST CC TNH CHT CA SiO2-SnO2
Bi Thanh S, L Vn Hiu, Lm Quang Vinh,
Nguyn c Ho
, Trn Th Thanh Vn.
Khoa Vt l, i hc Khoa hc T nhin Tp.HCM.
in thoi: 0918.464.237 E-mail: sibuithanh@yahoo.com.vn
Tm tt: Tng hp vt liu SiO2-SnO2 l bc tin to vt liu SiO2-SnO2 pha tp
Ytterbium (Yb). Vt liu SiO2-SnO2/Yb dng ch to laser hng ngoi cng sut ln nhm
ng dng trong lnh vc truyn thng tin bng si quang. Trong cng trnh ny, chng ti tng
hp SiO2-SnO2 bng phng php Sol-Gel. y, tetraethylorsillicate (TOES) ng vai tr l
tin cht ca Silic v SnCl2.2H2O l tin cht ca Thic. Sau khi x l nhit, thnh phn v kch
thc ht nano SnO2 trong vt liu SiO2-SnO2 c kho st bng cch s dng ph Raman v
ph hp th UV/Vis.
T kha: Sol-gel, vt liu SiO2-SnO.
1. Gii thiu
H thng vin thng ngy cng ng vai tr quan trng trong x hi, do nhu cu cn tng
thm dung lng truyn thng tin nh internet, hnh nh, m thanh v.v l l do v sao ngy
nay vic truyn thng tin cn thit s dng nh sng quang hc, v vy cn nhng thit b mi
nh b ghp tch
sng quang x l tt c nhng tn hiu. B ghp tch sng quang
hc cn c ch to nh nhng vt liu c tnh cht quang phi tuyn cao. V vy vic pha tp
nano bn dn trong thy tinh nhm n to mt vt liu c tnh cht quang phi tuyn cao, do ht
mang in tch b gii hn bi khng gian 3 chiu trong cu trc nano dn ti cc mc nng
lng b gin an trong vng dn v vng ha tr ng thi lm tng nng lng vng cm Eg,
l nh hng c trin vng trong ch to nhng vt liu dng trong cng ngh thng tin.
Trong cng trnh nghin cu ny, chng ti ch to vt liu khi SiO2 bng phng php
Sol-Gel v pha tp nano SnO2 vo trong nn SiO2 nhm thu c vt liu c tnh cht quang phi
tuyn cao v to mch dn sng ng dng trong photonic. Trc ht, chng ti thc hin vic
ch to vt liu SiO2, l vt liu c tinh khit, ng u cao v mi trng tng hp vt liu
nhit thp rt d dng iu khin c cc thnh phn trong qu trnh ch to vt liu. C th
l chng ta c th pha tp vo trong nn SiO2 vi mt nng pha tp kh ln nhng vn m
bo tnh trong sut ca vt liu nn.
Tip theo , sn phm vt liu khi SiO2-SnO2 thu c c trong sut v ng nht cao
l yu cu cn t c. Kt qu cho thy ph hp th ca vt liu khi SiO2-SnO2 c s dch
chuyn b hp th v bc sng di khi t l phn trm thnh phn pha tp tng. iu ny rt
ph hp vi l thuyt v hiu ng suy gim cp in t l trng trong ht nano bn dn da vo
phng trnh ca Kayanuma[2].
2. Thc nghim ch to vt liu
Dung dch sol c iu ch t nhng ha cht c bn: TOES (Tetraethoxysilane), Tin

(II)chloride dihydrate, DMF(Dimethylformamide), ru tylic C2H5OH, axit clohydric (MERK,
c).
Advances
_____________________________________________________________________________________
2.2. Chun b dung dch Sol SiO2

Dung dch SiO2 c chun b theo hng alkoxide ca phng php Sol-Gel. Tin cht silic l
TOES (Tetraethoxysilane), dung mi ca qu trnh ch to C2H5OH v DMF c s dng nh
l cht sy kh to gel khi. S tin hnh tng hp dung dch sol SiO2 c trnh by c
th nh s 1. Dung dch TOES-DMF trn vi C2H5OH theo t l 1:1:2, TOES c thy
phn nhit phng vi s trn ln dung dch C 2H5OH v H2O (gm 0.15 M HCl) vi t l
1:1. Sau khi khuy 1 gi, dung dch ng nht v cho dung dch C2H5OH v H2O (gm 0.15 M
HCl) vi t l 1:4 tip tc qu trnh thy phn TOES. Khuy 1 gi na, dung dch sau cng
chit vo cc l bi nh ng knh 2,5 cm, y kn np v gi 2 tun to hnh vt liu.
2.3.Qui trnh tng hp dung dch sol x%SnO2-(100-x)%SiO2
Vt liu x%SnO2-(100-x)%SiO2 ch to theo hng sol gel thng qua cc cht ban u to
SiO2 v SnO2 l TOES v SnCl2.2H2O. Dung dch TOES-DMF trn chung vi C2H5OH theo t
l 1:1:2, TOES c thy phn nhit phng vi s trn ln dung dch C 2H5OH v H2O (
gm 0.15 M HCl) vi t l 1:1. Sau khi khuy 1 gi, nh git dung dch SnCl2.2H 2O ha tan
trong 1 mol C2H5OH theo t l ca qui trnh vo dung dch ban u v khuy 1 gi cho dung
dch ng nht. Tip tc cho thm dung dch C2H5 OH v H2O (gm 0.15 M HCl) vi t l 1:4
hon thnh qu trnh thy phn TOES[3]. Khuy 1 gi na, dung dch sau cng c chit vo
cc l bi nh ng knh 2.5 cm, y kn np v gi 2 tun to hnh vt liu.
2.4. Qu trnh gel ha, sy v x l nhit
Cc mu sau khi 2 tun nhit phng, gel t c nhit 400C thnh gel v
tng nh nhit t 40 ti 600C gi 2 ngy. Tng nh nhit t 60 ti 800C gi 2 ngy tng
nh nhit t 80 ti 1500 C gi 1 ngy sy kh gel[4].
Cc gel c sy kh nung vi tc nhit 600C/gi ln n 3000C, 5000C v 7000C gi 2
gi. Qu trnh x l nhit ca vt liu xy ra trong khng kh[5].
phn tch cu trc vt liu khi SiO2 v vt liu khi xSnO2(100-x)SiO2, chng ti s
dng my quang ph Micro-Raman vi bc sng ngun laser kch thch l 632.81nm t ti
PTN. Cng ngh N
kho st bng my Jasco UV-Vis 530 ti PTN.Vt liu K thut Cao, Trng i hc Khoa hc
T nhin.
Bng 1: Kt qu kho st t l mol khc nhau ca cc cht.
Kt qu (s mu khng b)
TOES C2H5OH
H2O
DMF
HCl (37%)
Sy 1500C Nung 3000C
Nung 5000C
0.01
4/5
3/5
0.01
4/5
1/5
10
0.01
5/5
12
0.01
5/5
0.01
4/5
3/5
nt
0.01
4/5
4/5
4/5
0.01
2/5
1/5
0.01
1/5
1/5
Nhng
_____________________________________________________________________________________
3. Kt qu v bn lun
3.1.
Vi t l mol sau khi kho st

TOES:C2H5OH:H2O:DMF:HCl = 1:4:5:1:001 sau
khi khuy xong theo quy trnh trn, dung dch
c nh hnh sau 4 ngy nhit phng.
2
c
800
: H2
2H5
0
300 C,
v cc
thnh phn hu c cng nh nhm -OH chy do
Hnh 1: Mu khi SiO2 nhit 800C
Hnh 2: Mu khi SiO2 5000C v 7000C
Hnh 3: Mu khi SiO2 nhit 300 oC
vy vt liu chuyn sang mu en. nhit trn 5000C, mu dn dn tr nn trong sut do cc

thnh phn hu c chy ht v bay ra khi mu. y l giai on cc nhm -OH gim rt
nhiu hnh thnh cc lin kt ca Si-O. iu ny th hin r qua cc ph Raman ( Hnh 1,2,3).
3.2. Ph Raman
Ph Raman ca vt liu khi SiO2 x l nhit cc nhit khc nhau th hin qua cc
hnh: 4,5 v cc vng ph Raman thu c th hin qua bng 1.
Qua cc hnh trn, ta c th thy r s nh hng nhit . C th cc mu nhit 7000C,
cng hp th ng vi cc tn s dao ng ca vng gc t do -OH khng cn xut hin. Ch
1200
488.701
200
1000
150
800
Intensity
Intensity
483.026
100
977.651
50
174.714
SiO2-500 C
805.525
692.036
600
400
200
173.768
979.542
803.634
604.082
SiO2 - 700 C
0
-200
-50
500
1000
1500
2000
-1
wavenumber (cm )
Hnh 4: Ph Raman ca mu SiO2 nhit 5000C
500
1000
1500
2000
-1
wavenumber (cm )
Hnh 5: Ph Raman ca mu SiO2 nhit 7000C
Advances
_____________________________________________________________________________________
cn xut hin dao ng 977.651 cm-1 ca Si-OH trn b mt vt liu do qu trnh hp th H2 O

trong thi gian h nhit trong qu trnh nung mu v nhit phng v thi gian ch o mu.
Thm vo , khi nhit tng c s dch chuyn peak v pha tn s thp do tng tnh trt t
ca cu trc vt liu so vi xut hin tn s dao ng gc O-Si-O ca mch vng rt c trng
cho to vt liu khi SiO2 .
3.3.
khi SiO2
SiO2 - 700 C
40
30
T (%)
Kt qu ph truyn qua ca vt liu khi

SiO2 nhit 1500C, 5000C v 7000C
c biu din hnh 6 v 7, cho thy
truyn qua ca vt liu khi SiO2 trong vng
kh kin khong 50 65%.S d truyn
qua ca vt liu thp l do:
S tn x ca nh sng do b mt
mu khng phng (mu sau khi
nung cha c x l b mt).
dy ca mu ln (4-5 mm).
50
20
10
0
-10
200
400
600
800
1000
1200
wavelength (nm)
70
SiO2 - 500 C
65
60
T (%)
55
50
45
40
35
200
400
600
800
1000
1200
wavelength (nm)
Hnh 6: Ph truyn qua ca mu SiO2 150 0C
Hnh 7: Ph truyn qua ca mu SiO2 500 0C
3.4. Ph Raman ca vt liu khi 7%SnO2 93%SiO2
1463.05
1282.04
1320.35
1113.49
1145.09
976.536
661.453
468.954
530.247
Intensity
883.369
Vi vt liu khi 7%SnO2-93%SiO2 1500C c tt c cc dao ng vi cng peak dao

ng c trong vt liu u c cng rt thp. So vi SiO2 nhit 5000C v 7000C, nhit
ny vt liu khng c cc peak dao ng vng 3, 4 ca O-Si-O (692.036 cm-1 ) v dao ng
bin dng Si-O-Si (805.525 cm-1) ch
300
xut hin dao ng O-Si-O (468.954
cm-1 ) ca mch vng nhng vi cng
250
rt thp. nhit 1500C, cc cht
hu c cha chy v thot ra khi th
200
hin qua dao ng ni i =CH2
150
(883.639 cm-1 )[5] ng thi cn thm
cc peak dao ng ko bt i xng
100
SiOSi (1113.49 cm-1, 1145.09 cm-1)
50
v peak dao ng n SiO (1320.35
-1
-1
cm , 1320.35 cm ). Khi pha tap
0
SnCl2.2H2O, nhit ny hnh
-50
thnh c lin kt thng qua dao
400
600
800
1000
1200
1400
1600
ng OSnO (530.247 cm-1 v
wavelength (cm-1)
661.453 cm-1) cho thy trong nn SiO2
Hnh 8: Ph Raman: 7%SnO -93%SiO 1500C
2
Nhng
_____________________________________________________________________________________
c mt ca SnO2, iu ny cho thy r rng hn khi chng ta kho st ph hp th ca vt

liu.
Da vo hnh ph hp th ca vt liu xSnO2(100-x)SiO2 x l nhit 1500C qua 2 ngy
trong khng kh cho ta thy b hp th dch chuyn v pha b nng lng thp khi nng % x
pha tp SnO2 tng. Trong khi vt liu khi SnO 2 trong t nhin c gi tr rng vng cm
khong t 3.59 eV[14]. Hn th na, thng qua ph dao ng Raman cho thy s hin din cc
lin kt ca OSnO (530.247 cm-1 v 661.453 cm-1) cho thy trong nn SiO2 c cc ht bn
dn SnO2. Da theo phng trnh ca Kayanuma, phng trnh ch dn ra hiu ng suy gim cp
electron l trng trong ht bn dn, ph hp th c s dch chuyn b hp th v bc sng di
khi t l phn trm thnh phn pha tp tng.
Bng 2 : Bng tng quan gia cc dao ng v s sng
7%SnO2-93%SiO2
Sy 1500C
469 cm-1
976 cm-1
530 cm-1
661 cm-1
884 cm-1
1113 cm-1
1145 cm-1
1282 cm-1
1320 cm-1
1463 cm-1
SiO2
Dao ng
Nung 500 C Nung 7000C
483 cm-1
489 cm-1 Dao ng gc O-Si-O ca mch vng[10]
-1
692 cm
604 cm-1 Dao ng vng 3, 4 ca O-Si-O
805 cm-1
803 cm-1
978 cm-1
979 cm-1 Dao ng ha tr Si-OH trn b mt.
Dao ng OSnO[11]
Dao ng OSnO
Dao ng ni i =CH2[12]
Dao ng ko bt i xng SiOSi
Dao ng ko bt i xng SiOSi
Dao ng n SiO[13]
Dao ng n SiO
Dao ng ni ba CH.
0
khi xSnO2(100-x)SiO2
3.5
Bng 3: rng vng cm vi cc thnh phn SnO2

khc nhau.B
1 2 34
1: SiO2
2: 3SnO2-97SiO2
3: 5SnO2-95SiO2
4: 7SnO2-93SiO2
xSnO2-(100-x)SiO2
Eg (eV)
Abs
5.17 4.38
3.97 3.75
Da vo hnh ph hp th ca vt liu xSnO2

(100-x)SiO2 x l nhit 1500C qua 2 ngy trong
khng kh cho ta thy b hp th dch chuyn v pha
b nng lng thp khi nng % x pha tp SnO2
tng. Trong khi vt liu khi SnO2 trong t nhin c
wavelength (nm)
gi tr rng vng cm khong t 3.59 eV[14]. Hn
th na, thng qua ph dao ng Raman cho thy s
Hnh 9: Ph hp th mu SiO2 v
hin din cc lin kt ca OSnO (530.247 cm-1 v
cc mu xSnO2(100-x)SiO2 1500C
661.453 cm-1) cho thy trong nn SiO2 c cc ht
bn dn SnO2. Da theo phng trnh ca Kayanuma, phng trnh ch dn ra hiu ng suy gim
cp electron l trng trong ht bn dn, ph hp th c s dch chuyn b hp th v bc sng
di khi t l phn trm thnh phn pha tp tng.
2
200
400
600
800
1000
1200
4. Kt lun
Trong cng trnh ny, chng ti tin hnh tng hp vt liu khi SiO2 v vt liu khi
xSnO2(100-x)SiO2 bng phng php sol-gel t precursor TOES v SnCl2.2H2O.
Advances
_____________________________________________________________________________________
T kt qu v phn tch ph Raman, truyn qua v hp th ca mu, chng ti thu c cc

kt qu sau:
1. a ra qui trnh ch to vt liu khi SiO2 theo t l mol gia cc cht
TOES:C2H5OH:H2O:DMF:HCl=1:4:5:1:0.01, sn phm khi SiO2 tng hp c c tinh
khit cao v truyn qua ca vt liu trong vng kh kin l t 50 - 60 %.
2. ng thi, bc u a ra c qui trnh tng hp vt liu khi xSnO2(100-x)SiO2. ng
thi cho thy, khi thnh phn pha tp SnO2 trong nn SiO2 tng t 0 7% th rng cng cm
Eg ca vt liu gim.
Cm n: Nhm tc gi chn thnh cm n CN. Phm Duy Phong v ThS. L Thy Thanh Giang
cng tc ti Phng th nghim Vt liu K thut cao - Trng i hc Khoa hc T nhin TP.
HCM gip chng ti trong qu trnh nung mu v o ph hp th cng ph truyn qua
UV/Vis.
Ti liu tham kho
1. Lm Quang Vinh , Ch to v nghin cu tnh cht tnh cht quang ca mng mng TiO2
pha tp nano bn dn CdS ng dng trong photonic, ti cp b.
1. Tomokatsu Hayakawa, Masayuki Nogami, High luminescence quantum efficiency of Eu
doped SnO2SiO2 glasses crystals due to excitation energy transfer from nano-sized SnO2,
Science and Technology of Advanced Materials 6 (2005) 6670.
2. Tomokatsu Hayakawa, Takehiro Enomoto, and Masayuki Nogami, Nanocrystalline SnO2
particles and twofold-coordinated Sn defect centers in sol-gel-derived SnO2 - SiO2 glasses, J.
Mater. Res., Vol. 17, No. 6, Jun 2002.
3. S. Fujihara, T. Kato, T. Kimura, Influence of solution composition on the formation of
SiO2/LaF3 composites in the sol-gel process, Journal of materials science (2000) 2763
2767.
4. Te-Yu Wei, Shih-Yuan Lu, Yu-Cheng Chang, Rich photoluminescence emission of SnO2
SiO2 composite aerogels prepared with a co-fed precursor solgel process, Journal of the
Chinese Institute of Chemical Engineers 38 (2007) 477481.
5. Te-Yu Wei, Shih-Yuan Lu, Yu-Cheng Chang, Rich photoluminescence emission of SnO2
SiO2 composite aerogels prepared with a co-fed precursor solgel process, Journal of the
Chinese Institute of Chemical Engineers 38 (2007) 477481.
6. I.K. Battisha, H.H. Afify, Structural and Photoluminescence Behaviors of Nano-Structure
Thin Film and Bulk Silica Gel Derived Glasses, Journal of Sol-Gel Science and Technology
25, 515, 2002.
7. O. Majerus, L. Cormier, D.R. Neuville, L. Galoisy, G. Calas, The structure of SiO2GeO2
glasses: A spectroscopic study, Journal of Non-Crystalline Solids 354 (2008) 20042009
8. [9] K. Dahamouche, C. Bovier, J Dumas, J. Serughetti, Densification of acid catalysed silica
xerogels, Journal of materials science 30(1995) 4149-4151.
9. I.K. Battisha and H.H Afify, Structural and Photoluminescence Behaviors of Nano-Structure
Thin Film and Bulk Silica Gel Derived Glasses, Journal of Sol-Gel Science and Technology
25, 515, 2002.
10. William S. Cardoso, Maria Suzana P. Francisco, Alzira M.S. Lucho, Yoshitaka Gushikem,
Synthesis and acidic properties of the SiO2/SnO2 mixed oxides obtained by the solgel
process. Evaluation of immobilized copper hexacyanoferrate as an electrochemical probe,
Solid State Ionics 167 (2004) 165173.
11. Nguyn Vn n, Cc phng php nghin cu bng Quang ph hng ngoi, Trng i
hc Khoa hc T nhin, TP.HCM, (2002).
12. M. Langlet and C. Vautey, Elaboration at 80C of SiO2 Layers Deposited by Aerosol-Gel
Process, Journal of Sol-Gel Science and Technology 13, 743747 (1998).
13. J. Robertson, J. Phys. C: Solid State Phys. 12, 4767 (1979).
Nhng
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NH HNG CA NNG TP ANTIMONY LN CC TNH CHT

QUANG V IN CA MNG DN IN TRONG SUT SnO2: Sb
L Vn Ngc a, Nguyn c Thnh a, Nguyn Th Kim Thn a,
Trn Tun a, Hunh Thnh t b
a)
Khoa Vt L, i Hc Khoa Hc T Nhin, Tp. H Ch Minh.

b)
i Hc Quc Gia Thnh Ph H Ch Minh.
Tm tt: Mng SnO2: Sb ch to bng phng php phn x phn ng magnetron dc t bia hp
kim Sn:Sb trong mi trng hn hp kh Ar + O2. Cc bia hp kim c t l phn trm antimony
theo khi lng ln lc l 4%, 5%, 6%, 8% v 10%. Trong qu trnh to mng c gi
nhit khng i, v trong cc ln to mng khc nhau th nhit thay i t nhit
phng n 4000C. Cu trc v tnh cht in ca mng c kho st tng ng bng gin
XRD v phng php o Hall. Bn cnh mt s tnh cht v quang cng c kho st.
T kho: SnO2, Sb, in tr sut, nng ht ti, linh ng.
1. M u
Nhiu cng trnh nghin cu cho thy mng SnO2: Sb c in tr sut thp ~ 10-3 cm v
c truyn qua cao trong vng kh kin ~ 80% [2]. Bn cnh mng SnO2:Sb li c tnh
phn x cao trong vng hng ngoi, bn c hc v ho hc cao, c bit l rt bn vi mi
trng, v d ch to [2]. V nhng u im ny mng SnO2:Sb v ang c nhiu phng th
nghim trong v ngoi nc trin khai nghin cu, vi hi vng trong tng lai c th s dng
mng ny thay th phn no cho mng ITO, FTO ng vai tr lm in cc dn in trong sut
trong cc thit b quang in t.
Trong cng trnh ny mng SnO2: Sb c to ra bng phng php phn x phn ng
magnetron dc trong hn hp kh (Ar + O2) t bia hp kim Sn:Sb. Phng php to mng ny c
Nhiu u im ni bc, chng ta c th iu chnh d dng hp thc ca mng bng cch
thay i t l p sut ring phn O2: Ar trong hn hp kh phn ng, hoc thay i cng sut
phn, v mng to ra c ng u cao, c kh nng trin khai cho mng c din tch ln
[1]. T nhng mng to c chng ti s tin hnh kho st cc c trng ca mng theo cc
iu kin to ch to, i su nghin cu nh hng ca nng pha tp ln tnh cht quang v
tnh cht in.
2. Thc nghim
to ra mng SnO2:Sb, chng ti s dng bia hp kim Sn:Sb c ng knh 90 cm, c
nu luyn t kim loi thit v antimon c tinh khit l 99.95%. Cc bia c nng tp
antimon theo khi lng ln lt l 4%, 5%, 6%, 8% v 10%.
H phn x c ht bng bm khuch tn, c chn khng ban u l 10-4 torr. Kh Ar v O2
s dng trong qu trnh phn x c tinh khit l 99.999%.
dng to mng l loi thu tinh chu c nhit cao. Trong qu trnh to mng nhit
c gi mt nhit khng i, c khong dao ng 15 oC.
dy ca mng c o bng thit b stylus, tnh cht in c o bng phng php bn
mi d v hiu ng Hall. Tnh cht quang c xc nh bng thng qua ph UV Vis. Cu trc
tinh th ca mng c kho st bng gin nhiu x tia X.
Advances
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3. Kt qu v bn lun
T bng 1 ta thy rng in tr sut ca mng SnO2: Sb gim mt bc (~ 10 ln) so vi
mng SnO2 khng pha tp. iu ny l do cc cation Sb5+ v Sn4+ c bn knh ion gn bng
nhau (0.71 A0 v 0.65 A0) [6], nn cc cation Sb5+ d dng chn vo nt mng thay th cho
cation Sn4+. Khi vo c mng, cc cation Sb5+ ny lm tng mc donor ln 35 meV y
vng dn [5;6], kt qu l tng cng tnh dn in ca mng pha tp.
Bng 1: in tr sut, nng ht ti v linh ng ca cc mu theo nng
tp c to mng nhit lng ng 3000C
Nng Sb
(%)
in tr
sut(cm)
Nng ht
ti N (cm-3)
linh ng
(cm2V-1s-1)
12.10-2
4,8.10-3
2,03.1020
6,03
7,5.10-3
1,92.1020
4,3
7,8.10-3
1,92.1020
4,24
7,85.10-3
1.,9.1020
4,16
10
8,16.10-3
1,89.1020
4,05
i vi cc mu pha tp, khi nng pha tp Sb tng trn 4% in tr sut ca mng tng.
Theo [5], nng tp vt gi tr ngng in tr sut ca mng s tng. Trng hp pha tp
antimon, do nguyn t ny c hai trng thi ion vi oxi (Sb5+ v Sb3+),nn khi nng pha tp
gi tr ngng Sb5+ chuyn thnh Sb3+. Cc cation Sb3+ ny ng vai tr l tm acceptor, to ra
cc l trng bt in t lm gim dn in ca mng [6].
Theo nhiu ti liu nghin cu [4; 5; 6 ], gi tr ngng ca tp antimon khong 5% 7%.Trong cng trnh ny in tr sut ca mng tng khi nng tp antimon bia hp kim
Sn:Sb ln hn 4% khc [4; 5; 6 ], t suy ra nng tp ca mng c th khc vi nng
tp ca bia. Do nhng nh hng ban u cha c chun xc nn cng trnh ny cha tm ra
gi tr ngng ca nng pha tp.
Khi nng pha tp chuyn t gi tr 4% ln 5%, nng ht ti gim t 2.03 1020 cm-3
xung 1.92. 1020 cm-3 gim khng nhiu, linh ng gim t 6.03 cm2V-1s-1 xung 4.3 cm2V1 -1
s tng i gim ng k, in tr sut tng t 4.8.10-3 cm ln 7.8. 10-3 cm. Vy in tr
sut tng ch l do gim linh ng ca ht ti, v khi tng lng tp antimon qua gi tr
ngng s lm gim th nng bin ht v tng tn x bin, kt qu l gim linh ng ca in
t v tng in tr sut ca mng [4].
Nhng
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Nng tp Sb (%)
Hnh 1: S bin i ca in tr sut, nng ht ti theo nng pha tp
4%
5%
6%
8%
10%
Bc sng (nm)
Hnh 2: Ph truyn qua ca cc mu pha tp 4%, 5%, 6%, 8%,10%
T hnh 2, ta thy i vi mng c nng pha tp trn 8%, truyn qua ca mng gim,
cc nh giao thoa thp. Quan st bng mt, mng c mu hi xm v ng sang xm. Theo [6],
khi nng tp vt gi tr ngng cc cation Sb5+ bin ht s cm ng cc in tch b mt,
tng cng kh nng hp th oxi b mt, to nn nhng m Sb2O5 nm ri rc trong mng
cng c th l to nn dng dung dch rn Sb2O5 SnO2. Chnh dung dch rn v nhng m
Sb2O5 lm gim truyn qua v tng h s hp th ca mng.
Tuy nhin t hnh 2 ta kh pht hin c s thay i ca hp th v mng ca chng ta
khng dy lm. Nhng khi quan st bng s liu 2 ta thy h s hp thu tng khi tng nng
pha tp, ph hp vi [4; 5; 6].
Advances
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Nhn vo gin XRD hnh

3, ta thy mng to ra c cu trc
a tinh th vi ba mt mng u tin
(110), (101) v (211). Khi nhit
to mng tng c ba mt mng cng
pht trin, trong mt (211) l
c u tin hn c.
i vi cc mu c to mng
t bia hp kim 4% Sb, nhit
khng nh hng nhiu n tnh
cht quang ca mng, cc mng
to ra u c truyn qua cao
trn 85%. Theo chiu tng ca
nhit , nng ht ti v linh
ng u tng, dn n in tr
sut gim, iu ny ph hp vi
nhiu cng trnh nghin cu trc
y [2; 4; 5; 6].
400 oC
300 oC
200 oC
100 oC
2
Hnh 3: Ph XRD ca cc mu SnO2:Sb 4% Sb theo
nhit lng ng
Bng 2: H s hp thu, chit sut, nng lng vng cm ca cc mu theo nng tp
dy d (nm)
H s hp thu
Chit sut n
Nng lng vng cm
400
0,75.10-4
1,84
3,61
450
1.10-4
1,88
3,64
470
1,49.10-4
1,89
3,64
550
2,18.10-4
1,82
3,7
530
4,34.10-4
1,78
3,6
Nhit lng ng tng t 2000C ln 300 0C, in tr sut gim t 4.7 .10-2 cm xung 5.1.
10 cm, nng ht ti tng t 3. 1019 cm-3 ln 2.03. 1020 cm-3, linh ng tng t 4.4
cm2V-1 s-1 ln 6 cm2V-1 s-1, ta thy in tr sut gim i mt bc, nng ht ti tng ln mt
bc. Da vo ph XRD bc nhy vt ny c th c gii thch nh sau. Khi nhit lng
ng chuyn t 2000C ln 3000C bc tinh th ca mng tng ln, mng chuyn sang trng thi
kt tinh tt hn [3; 4], ng thi cc cation Sb5+ c chn vo mng nhiu hn, nng mc
donor tng ln dn n nng ht ti tng ln ng k, lm gim mnh in tr sut ca mng
[4].
Qua bng 2, ta thy chit sut v nng lng vng cm ca mng khng ph thuc nhiu vo
nng pha tp.
i vi cc mu c to mng t bia hp kim 4% Sb, nhit khng nh hng nhiu n
tnh cht quang ca mng, cc mng to ra u c truyn qua cao trn 85%. Theo chiu tng
ca nhit , nng ht ti v linh ng u tng, dn n in tr sut gim, iu ny ph
hp vi nhiu cng trnh nghin cu trc y [2; 4; 5; 6].
-3
Nhng
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Bng 3: in tr sut, nng ht ti, linh ng ca cc mu c to t bia hp kim 4% Sn theo

cc nhit lng ng khc nhau
Nhit
(oC)
in tr sut
(cm)
Nng ht ti
100
13,3.10-2
2.1019
2.4
200
4,7.10-2
3.1019
4,4
300
5,1.10-3
2,03.1020
400
3,9.10-3
2,1.1020
7,63
Nhit lng ng tng t

2000C ln 3000C, in tr sut
gim t 4.7 .10-2 cm xung 5.1.
10-3 cm, nng ht ti tng t
3. 1019 cm-3 ln 2.03. 1020 cm-3,
linh ng tng t 4.4 cm2V-1 s-1 ln
6 cm2V-1 s-1, ta thy in tr sut
gim i mt bc, nng ht ti
tng ln mt bc. Da vo ph
XRD bc nhy vt ny c th
c gii thch nh sau. Khi nhit
lng ng chuyn t 2000C ln
3000C bc tinh th ca mng tng
ln, mng chuyn sang trng thi
kt tinh tt hn [3; 4], ng thi
cc cation Sb5+ c chn vo
mng nhiu hn, nng mc
donor tng ln dn n nng ht
ti tng ln ng k, lm gim mnh
in tr sut ca mng [4].
-3
(cm )
linh ng
(cm2V-1s-1)
Hnh 4: S nh hng ca nhit ln in tr

sut,nng ht ti v linh ng ca mng c to
t bia hp kim 4% Sb
4. Kt lun
Trong cng trnh ny chng ti to c cc mng dn in trong sut SnO2: Sb t cc bia
hp kim Sn: Sb c nng tp Sb trong bia ln lt l 4%, 5%, 6%, 8% v 10%. To c mng c
in tr sut thp ~ 3.9. 10-3 cm vi truyn qua trung bnh trong vng kh kin t 88%,
ng vi mng c to t bia hp kim 4% Sb v nhit lng ng l 4000C.
Qua cng trnh ny c th d on rng gi tr in tr sut ny cn c th tip tc gim v
khi nng pha tp trn 4% th in tr sut ca mng tng, v nhit lng ng tng th in
tr sut vn ang tip tc gim. ng vi iu kin to mng c tin hnh th in tr sut
ca mng s t gi tr ti u khi nng pha tp ca bia nh hn 4% v nhit lng ng ln
hn 4000C.
Advances
_____________________________________________________________________________________
Ti liu tham kho

1
2
3
4
5
6
L Vn Ngc, Bo co chuyn III, chng trnh nghin cu sinh, Vt l Quang hc

Quang ph, Trng H KHTN Tp. HCM. (2008).
Phm Th Hin, Ch to mng SnO2 v SnO2:Sb lm in cc trong sut bng phng php
phn x magnetron dc, Lun vn Thc s Vt l Quang hc, Trng H KHTN Tp. HCM,
(2008).
Nguyn Th Kim Thn, Kho st nh hng ca nng pha tp antimony v nhit
ln tnh cht mng dn in trong sutSnO2:Sb, Lun vn C nhn Vt l ng dng, Trng
H KHTN Tp. HCM, (2008).
H L Hartnagel, A L Dawar, A K Jain, C Jagadish, Semiconducting Transparent Thin films,
Institute of Physics Publishing, Bristol and Philadelphia, (1995).
K L Chopra, S Major and D K Pandya, Transparet conductors A status review, Thin solid
films, 102, (1983).
Terho Kololuoma, Preparation of multifunctional coating materials and their applications,
VTT publications 499, Expoo 2003.
Nhng
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SO SNH CC TNH CHT CA MNG MNG Al2O3 C TO

BNG PHNG PHP PHN X MAGNETRON RF V SOL GEL
Giang vn Phc a , L V Tun Hng b, Ng Th Kim Hab,
Trn Th Khnh Chib, Lm Quang Vinhb, L Vn Hiub, Hunh Thnh tb
a)
b)
i Hc An Giang, An Giang
i Hc KHTN, i Hc Quc Gia Tp HCM
Tm tt: Nhm xt thng c ch to dng cho mc ch xc tc di dng gm s xp. N

cng c th c ch to bng phng php phn x magnetron rf hoc phng php solgel.
Mc tiu ca cng trnh ny nhm so snh cc c trng ca Al2O3 trn iu ch t hai phng
php nu c th s dng chng vo cc mc ch khc nhau. Vic nghin cu c tin
hnh trn cc php o quang ph v nh chp AFM. Cc kt qu nghin cu bao gm cc so snh
v tnh cht quang, cu trc, s chuyn pha v hnh thi b mt ca mu.
T kha: Alumina, sol gel process, RF magnetron sputtering.
1. M u
Hp cht Al2O3 c nghin cu nhiu vo cc thp nin 50 60 v t c quan tm trong
thi gian tip theo. Gn y, k t nm 2000, hp cht ny bt u c quan tm nhiu v s
lng nghin cu phm vi nano tng cao, nht l t nm 2005. Xem cc cng b v Al2O3, a
s cc bi bo u nghin cu Al2O3 iu ch dng khi rn hoc dng ht nano, rt t cng b
thng tin v dng mng mng.
Mng Al2O3 (corundum, alumina) c quan tm nghin cu bi cc ng dng ht sc hu
ch ca n. Tiu biu nh lp ph cch in va chu tc ng c hc va chu tc ng ha hc
cho cc cm bin du vn tay ang v s c ng dng rng ri. Do vy Al2O3 ng c quan
tm nghin cu. to mng c nhiu phng php nh phn x phn ng, lng ng t phn
x bng chm laser (PLD), ngng t dung dch (sol gel), trong , k thut phn x v solgel
c p dng rng ri nh vo kh nng to c rt nhiu loi mng. c bit l to mng rn
Al2O3.
Bi vit ny trnh by v cng ngh ch to mng alumina bng phng php phn x
magnetron rf v Solgel. Qua , so snh cc c trng ca mng mng Al2O3 ch to bng c
hai phng php trn c th nh hng chn la trong cc ng dng tip theo. C hai loi
mng u c ch to trng i hc Khoa hc T nhin thnh ph H Ch Minh. Vt liu
c chn l thy tinh v Si, nhm c th o c c sn phm bng c phng php
truyn qua kh kin t ngoi ( thy tinh) v hp th hng ngoi ( Si). Nghin cu chuyn
pha c thc hin trn Si bng phng php nhit trong dy nhit t 5000C n 12000C.
kho st mng, cc phng php c s dng l ph dao ng v gin nhiu x tia X
(XRD) xc nh thnh phn, cu trc tinh th ca mng Al2O3 qua mi giai on chuyn pha
v kho st hnh thi b mt ca n bng nh chp AFM. Ph hng ngoi c o phng th
nghim k thut cao trng i hc Khoa hc T nhin thnh ph H Ch Minh. Gin XRD
c o Vin Ha Du Vit Nam thnh ph H Ch Minh v nh AFM c chp Phng th
nghim nano thuc i hc Quc gia thnh ph H Ch Minh.
2. Thc nghim
To mng bng phng php phn x magnetron rf
H phn x c dng l my Univex 450. Mng Al2O3 c phn x t bia nhm kim loi.
iu kin tin hnh c tnh ton trc bng phng php m phng dng thut tan Monte
Carlo (MC) v m hnh c trnh by trong [2]. Theo , qu trnh phn x tin hnh trong mi
Advances
_____________________________________________________________________________________
trng kh lm vic Argon v kh phn ng

Oxygen vi t l O:Ar l 1:10. Cng sut thay
i trong khong t 100 250W, p sut thay
i trong khong 0.1 0.5 Pa. khng gia
nhit.
Bng 2: Chit sut mng Al2O3 vi cc phng
php to mng khc nhau
Phng php
Chit sut 550 nm
Bng 1: Chit sut mng thc hin bng phn x rf

dy
mng ( 30 nm)
864 nm
Chit sut trung bnh

( 550nm)
1.69 0.02
595 nm
1.67 0.02
404 nm
1.66 0.02
Phng php
Chit sut 550 nm
Bc bay
1.5
Phn x chm ion
1.65
Phn x phn ng
(trong bi vit ny)
Hai chm tia ion
1.62
K thut FCVA
1.68 1.69
Bc bay phn ng
1.63
To khi (Bulk)
1.755 1.77
1.68
Mng to ra trn thy tinh (microscope slide) ca hng Marielfeld c truyn qua rt
cao c 93%, chit sut gn bng chit sut thy tinh. y chnh l u im quang hc ca
mng trong cc ng dng ph lp bo v quang hc cho cc quang c chu tc ng c hc, ha
hc v nht l cc quang c hot ng vi bc x laser t ngoi. Song song , mng cng c
ph trn Silicon Wafer loi p (111) o ph hp thu hng ngoi v phc v cho qu trnh
nhit chuyn pha.
S dng ph truyn qua UVVIS ca mng thu c, x l bng phn mm Jasco version
1.53.00 ( hnh 3), dy v chit sut c tnh theo l thuyt Swanepoel bng phng php
gii tch s ng thi c so snh vi kt qu tnh c bng phn mm m phng do nhm
nghin cu ca chng ti bin son. Phn mm ny c son tho trong mi trng Matlab 6.5
nhm thit lp ph truyn qua UVVIS l thuyt ri so snh vi nh ph truyn qua thc nghim
gii an cc tham s quang ca mng (hnh 9).
Kt qu cho thy cc mu c dy khc nhau th c chit sut khc nhau cht t. Trong
phm v dy nh hn 1000 nm, chit sut c khuynh hng tng theo dy. Chit sut trung
bnh ca hu ht cc mu vo c n 1.67.
So snh vi chit sut mng mng thc hin vi cc phng php khc ta thy c s ph hp
tt. Chit sut mng cao hn mng bc bay phn ng v thp hn cc phng php
FCVA(Filtered Cathodic Vacuum Arc) Technique v Bulk (bng 2).
So snh ph hng ngoi (hnh 1) ca Al2O3 dng bt rn ng vin KBr c cu trc tinh th
Al2O3. v ca mng Al2O3 ( th di) phn x t bia nhm kim loi trong mi trng hn
hp Ar v O2 ta thy mng Al2O3 c hnh thnh. Ph ca mng phc tp hn, kt hp vi
cc kho st trn ph IR v XRD ca mng chng t cu trc ca mng thu c l v nh hnh.
Mng thc hin trn Si cng c nghin cu bng ph hng ngoi cho thy ni chung
mng l v nh hnh tuy c s khc bit nh so vi mng to trn thy tinh. S khc bit ch
yu ca mng ny l c cha + Al2O3.
Xem xt gin XRD (hnh 2a) ca mng trn Si cho thy mng c thm mt phn nh
cu trc a tinh th ca pha v , l do cc lp lng ng u tin k tha cu trc tinh th
ca Si, sau pht trin dn thnh cu trc v nh hnh. Kt qu ny ph hp vi cc cng
b ca cc tc gi khc [3]
V hnh thi b mt mng, nh AFM ca mng Al2O3 trn Si 5000C c ghi ti Phng th
nghim Nano thuc i hc Quc gia thnh ph H Ch Minh v c x l bng phn mm
WSxM version 4.0. Xem xt nh cho thy kch thc ht kh th, c 300 nm. Mng c ng
u trung bnh. (hnh 02b)
Nhng
_____________________________________________________________________________________
Hnh 1: Ph hp thu hng ngoi IR ca Al2O3 bt rn trong vin nn KBr (trn)

v Al2O3 dng mng mng trn thy tinh (di)
Hnh 2 a: Ph XRD ca mng phn x trn

Si (111)
Hnh 2 b: AFM ca mng Al2O3

thc hin bng phn x rf
To mng bng phng php solgel

Bng 3: Chit sut mng thc hin bng solgel
dy
mng ( 30
nm)
113 nm.
724 nm
Chit sut trung

bnh
( 550nm)
1.61 0.02
1.74 0.02
Hnh 3: S to Sol.
Tin cht (Precursor) [13,14,15] c s dng to sol bao gm Aluminum Sec-Butoxide

(ASB) Al(OC4H9)3. M = 246.33 g/mol; d = 0.96 g/cm3; C% = 98%. (Merck c), Nitric acid
v nc vi cc hm lng thnh phn nh sau: 450ml H2O+1mlHNO3+100gASB+4 ml HNO3.
Ban u dung dch ASB trong sut, ngay sau khi cho vo chuyn sang mu trng c. Trong
sut qu trnh khuy nhit 900C, do s bay hi s lm gim trung bnh mt na lng H2O.
Sau khi cho HNO3 vo th dung dch chuyn sang trong nhng vn cn hi c. Lng HNO3
thm vo c tc dng lm sch dung dch v lm tng lng cht cha Al ti im ho gel. ASB
d dng tham gia phn ng thy phn [6]
bi v cc phn t nc c nhiu thn hch hn nhm alkoxyl. Tc l phn t nc d kt thn
vi cc v tr thiu in t (v tr Al3+) hn nhm alkoxyl. V vy d dng xy ra cc phn ng
Advances
_____________________________________________________________________________________
thn hch hnh thnh AlO(OH).H2O. Tri

li, nhm alkoxyl thu nhn cc proton hnh
thnh ru. Phn ng thy phn trong mi
trng xc tc axt 900C lm tng s hnh
thnh ht nano boehmite.
Vic ph mng c tin hnh bng
phng php dip coating. My dip coating
t ti phng th nghim Quang Quang ph,
b mn Vt l ng dng, trng H KHTN
TpHCM.
Phn ng xy ra trong qu trnh to Sol:
Al (OC 4 H 9 ) 3 + (n + 2) H 2 O AlO(OH ).n( H 2 O) + 3C 4 H 9 OH
Tng t nh trn, chng ti s dng 2 loi
: thy tinh, Si(111). Qu trnh chuyn pha
Hnh 4: AFM ca mng Al2O3 thc hin bng
ca Alumina xy ra nhit cao (t 500
solgel
12000C) nn chng ti s dng Si thay cho
thu tinh kho st. Bn cnh , chng ti
cng thc hin mt s mu trn thch anh
so snh i chiu kt qu nhit.
Trong qu trnh thc nghim chng ti nhn
thy tc dip coating tt nht l 25
mm/pht. V nht ca sol kh ln nn vi
vn tc ny mng thu c kh ng u nht.
Mng c ph 1 lp c dy rt mng
khong 100 110 nm 5000C v dy tip
tc gim khi nng nhit ln cao hn.
Kt qu ph truyn qua UVVIS ca mng
Hnh 5: ph phn x IR ca mng sol gel
sau khi nhit phn 5000C.
Al2O3 cho thy truyn qua ca mng l
khong 91%.
nh AFM ca mng Al2O3 trn Si c
x l bng phn mm WSxM version 4.0. Kt
qu cho thy mng km ng u hn so vi
mng phn x. (hnh 04)
Thnh phn mng c kho st bng ph
XRD v ph phn x hng ngoi. Kt qu o
XRD cho thy mng c dng v nh hnh
pht trin t pha Boehmite (AlO(OH)). iu
ny c minh ha thm bi ph phn x IR
(hnh 05) ca mng sol gel sau khi nhit
phn 5000C.
Ph hng ngoi ca mng sol gel v mng
phn x c dng rt tng ng. Cc nh
540, 553 v 815 cm1 nhit phng gn
ging vi kt qu ca nhm tc gi Lung- Hnh 6: Ph hng ngoi ca mng solgel trn Si
Teng Cheng [6] v c kt lun l dng Boehmite (AlO(OH)). nhit 5000C, vn cn nh
546 v 815 cm1 nhng cng c xut hin thm nh 412 cm1 thuc pha v nh hnh [7].
Nh vy, 5000C dng Boehmite pht trin thnh pha v nh hnh.
Mng sol gel cng c thc hin trn Si (p111), Ph hng ngoi (hnh 06) cho thy
mng cng c dng v nh hnh bi cc nh 432, 721 cm1.
Nhng
_____________________________________________________________________________________
Tuy nhin, cng cn ghi nhn thm cc nh 547, 815 cm-1 ca pha gamma v 447, 607, 617,
669, 972 cm-1 ca pha alpha.
Nh vy, khc vi mng phn x, mng sol gel trn Si bt u c cu trc ca nhiu pha
tinh th khc nhau trn nn v nh hnh. Ngoi ra, c mt nh 1081 cm-1 rt mnh. nh ny
khng xut hin khi mng ph trn thy tinh v khng mt i khi x l nhit. Tham kho ti
liu [4], [5] chng ta c th kt lun nh 1081 tng ng vi dao ng ha tr bt i xng ca
lin kt SiAlO.
So snh s chuyn pha
Tin hnh nghin cu bng cch
o ph IR ca mng Al2O3 ph trn
Si trc v sau nhit qua cc nhit
tri di t 600 11000C vi bc
tng 500C. Trong khong nhit
800 9000C c kho st chi tit
vi bc tng nhit 200C. Thi gian
nhit chung cho tt c mu l tng
nhit trong 6 gi, lu nhit 1 gi
nhit v gim t nhin v nhit
phng.
Kho st qu trnh chuyn pha
bng nhit trong khng kh, t ph
IR ta thy cc nt chnh sau: Cu trc
mng bt u thay i t 7000C. Cu
Hnh 7: Ph XRD chuyn pha ca mng phn x trn
trc thay i mt cch phong ph
Si(111)
trong min 800-9000C, 8800C cu
trc a tinh th r nt.
T 900 10000C mng chuyn
dn sang cu trc n tinh th
corundum (nh 1049 v 1087 cm1).
Trong khi , so snh ph XRD ca
cc pha trung gian v ph XRD ca
mng Al2O3 ph trn Silic nhit
n 12000C (hnh 07), ta thy cu to
ca mng chuyn dn sang pha
Al2O3 nhng cha han ton do vn
cn tn ti cc pha trung gian v
ng vi 2 = 310 v 2 =33.50
Xem xt ph XRD chuyn pha ca
Hnh 8: Ph XRD chuyn pha ca mng solgel
mng solgel trn Si(111) qua cc
trn Si(111)
nhit 50012000C. Hnh 8 tt c
cc nhit u c xut hin nh vi 2 = 28.330 l c trng ca Si(111). bc nhit u
tin, do s vt tri hon ton ca nh Si(111) nn t tm thy thng tin ca mng Al2O3. Ta
thy hnh 8 nhit ny thy xut hin 2 nh c cng yu tng ng vi pha v . Nu
kt hp vi kt qu ph IR c th kt lun 5000C l pha . Khi tng nhit ln 9000C, c th
thy rng nh 66.91 ng vi pha 5000C pht trin thnh nh 66.41 ng vi pha v nh
ny tip tc pht trin mnh giai on nhit tip theo l 10000C. Ngoi ra, 10000C cn
xut hin thm 2 nh 32.779 v 31.487 tng ng vi . Nh vy 10000C, pha pht trin
mnh nhng vn c tn ti pha . Kt lun tng t i vi nhit l 11000C. Cui cng, khi
ln n 12000C th pha bin mt, tt c cc nh ph hon ton l ca pha .
Advances
_____________________________________________________________________________________
3. Kt qu v bn lun
Nh vy, qua so snh ta c th rt ra mt s nt chnh sau:
Mng Al2O3 phn x rf
Mng Al2O3 solgel
Chit sut 550 nm: n 1.67

truyn qua c 93%
B mt mng tng i ng u
Mng trn thy tinh l v nh hnh
Mng trn Si l v nh hnh v mt t
pha ,
Trong qu trnh chuyn pha, cc pha trung
gian r rt v bin i mnh 8000C
12000C cha chuyn ha hon ton sang
pha
Gi thnh mu cao
Chit sut 550 nm: n 1.7

truyn qua c 91%
B mt mng km ng u hn
Mng trn thy tinh l v nh hnh
Mng trn Si l v nh hnh v mt t pha
,
Trong qu trnh chuyn pha, cc pha trung
gian r rt v bin i mnh 9000C
12000C chuyn ha hon ton sang
pha
Gi thnh mu thp hn
c bit, cu trc tinh th ca mng trn Si 12000C y pht trin mnh mt (300),
khc vi mng lm bng phng php phn x magnetron RF cng iu kin ti liu [1] pht
trin mnh mt (002). Nh vy, i vi tng yu cu vt liu khc nhau ta c th chn phng
php ph mng cho thch hp.
4. Kt lun
Tm li, chng ti hon thnh vic so snh mt s c trng ca mng Al2O3 thc hin
bng phn x rf v solgel. Kt qu so snh cho thy c hai phng php c mt s im tng
ng v d bit. Nh c th chn la phng php v vt liu ty theo yu cu s dng ca
mng. Trong cc trng hp thng thng, phng php solgel t ra hp dn hn nh gi thnh
r v chuyn pha sang pha trit hn.
Ti liu tham kho
1. Giang Vn Phc; Chuyn mng mng; 2008
2. Giang Vn Phc , L V Tun Hng, Nguyn Vn n, Hunh Thnh t , M Hnh Ha v
M Phng Qu Trnh To Mng Al2O3 bng Phn X Magnetron ,Tp Ch Pht Trin Khoa
Hc v Cng Ngh i hc Quc gia TP. H Ch Minh vol.10 thng 03 nm 2007.
3. Sawada, Kazuaki; Ishida, Makoto; Nakamura, Tetsuro; Ohtake, Norio Metalorganic
molecular beam epitaxy of gamma-Al2O3 films on Si at low growth temperatures Applied
Physics Letters (ISSN 0003-6951), vol. 52, May 16, 1988, p. 1672-1674.
4. S. S. Rayalu, J. S. Udhoji, S. U. Meshram, R. R. Naidu and S. Devotta; Estimation of
crystallinity in flyash-based zeolite-A using XRD and IR spectroscopy; Environmental
Materials Unit, National Environmental Engineering Research Institute, Nagpur 440 020,
India; 2005.
5. S.Tanriverdi, B.Mavis2, G.Gunduz, U.Colak; Electrospinning and characterization of
alumina borosilicate ceramic nanofibres; Ortadou Teknik niversitesi, Ankara 06531,
Turkey; 2007.
6. Lung-Teng Cheng, Mong-Yen Tsai, Wenjea J.Tseng, Hsing-I.Hsiang, Fu-su Yen; Boehmite
coating Al2O3 particles via a Solgel route; National Chung Hsing University, Taiwan;
2006.
Nhng
_____________________________________________________________________________________
M HNH HM IN MI CHO PH QUANG HC

CA MNG MNG ZnO PHA TP GA
Trn Cao Vinh, Cao Th M Dung, T Th Kiu Hnh
Phng Th Nghim Vt liu K Thut Cao, i hc Khoa hc T nhin, HQG TP. HCM
E-mail: tcvinh@hcmuns.edu.vn
Tm tt:Ph truyn qua ca mng mng ZnO pha tp Ga ch to bng phng php phn x
magnetron rf c xy dng bng chng trnh my tnh da trn m hnh hm in mi. Hm
in mi c ng gp t 3 s hng. Dch chuyn ni vng ca in t t do c m t bi m
hnh Drude v c m rng bng cch a thm vo s ph thuc ca tn s va chm in t
vo tn s m t chnh xc hn c tnh ph trong vng kh kin v hng ngoi gn. M hnh
dao ng Lorentz c a ra m t dch chuyn vng-vng ca in t lin kt t vng ha
tr ln vng dn. Mt hng s in mi nn c gi s c t ng gp ca tt c cc s hng
phn cc ngoi tr ng gp ca in t t do v in t lin kt. Ph tnh ton c khp vi
ph thc nghim rt ra thng s vt l cn thit nh linh ng ph thuc vo tn s, dy
mng, rng vng cm v chit sut. Khi lng hiu dng ca in t trong vng dn ph
thuc vo iu kin ch to v c c tnh c 0.32 0.34 khi lng in t t do.
1. Gii thiu
Ph quang hc c nhiu tc gi nghin cu kho st cc tnh cht ca mng mng
dn in trong sut (TCO). Brehme [1] s dng ph phn x hng ngoi xc nh nng
v linh ng ca in t trong mng ZnO-Al ch to bng phn x phn ng theo l thuyt
Drude. Tng t, vic s dng ph phn x vi l thuyt Drude cng c Hamberg p dng
cho ITO ch to bng bay hi chm in t [2]; Brewer s dng ph phn x FTIR cho ITO v FSnO2 [3]. Vi l thuyt Drude, Weijtens [4] rt ra hm in mi trong vng 1.6 eV - 5.6 eV ca
ITO ch to bng phn x dc magnetron t phng php o phn cc nh sng phn x
(ellipsometry). Nhng nm gn y, vi s tr gip ca my tnh v cc phn mm chuyn dng,
vic tnh ton cc hm in mi cho phn tch cc tnh cht t quang ph tr nn rt hu hiu.
Cc tc gi Mergel [5], Solieman [6], Lai [7] p dng cc m hnh in mi khc nhau kho
st tnh cht ca mng ITO c ch to ln lt bi cc phng php phn x rf it, phng
php spin v phn x dc magnetron. Qiao [8] p dng cc m hnh tng t Mergel cho ZnOAl ch to bng phn x rf magnetron. Kt qu cho thy cc tnh cht quang hc thu c ph
thuc rt ln vo phng php v iu kin ch to. V hm in mi, c th thy l thuyt
Drude c s dng trong tt c cc m hnh v ch yu dng m t tnh cht quang hc ca
mng mng TCO trong vng hng ngoi v d trong cc ng dng phn x nhit, ca s pht x
thp. Tuy nhin, tnh cht quang hc trong vng kh kin v gn b hp th li t c quan tm
hn. Mergel v Qiao l hai tc gi quan tm n tnh cht quang hc trong vng kh kin v
b hp th ca TCO. Mergel kho st s thay i ca chit sut, rng vng cm ca ITO theo
nng in t t 3 x 1019 cm-3 n 1.5 x 1021 cm-3 c ch to bng phn x trong iu kin
dng xi khc nhau [5]. Trong khi Qiao kho st tnh cht tng t i vi mng ZnO-Al c
ch to bng phn x t cc bia ZnO+Al2O3 c nng pha tp Al2O3 ln lt l 0.5, 1 v 2%
khi lng [8]. m t tnh cht quang hc ca cc mng TCO th ngoi m hnh Drude hai tc
gi Mergel v Qiao s dng m hnh OJL [9] m t ng gp ca vng hp th vo hm
in mi ca ITO v AZO. Tuy nhin, khi p dng cc m hnh in mi cho cng mt ph thc
nghim ca mng ZnO pha tp Ga (GZO) so snh th m hnh Lorentz cho thy l thch hp
hn so vi m hnh OJL.
Advances
_____________________________________________________________________________________
2. Thc nghim
Mng mng GZO c ch to bng phng php phn x magnetron rf trong h Leybold
Univex 450 t bia gm t ch to. M t chi tit v to mng c trnh by trong cc bo co
khc [10,11]. Trong bo co ny, cc tnh cht quang v in ca mng GZO c kho st vi
iu kin cng sut phn x 180W, nhit thay i t nhit phng n 3500C. in tr
sut thp nht ca mng t c 3x10-4 cm vi nng v linh ng ca in t ln lt l
7.2 x1020 cm-3 v 28 cm2V-1s-1 c xc nh bng php o hiu ng Hall trn my HMS 3000.
Ph truyn qua UV-Vis-NIR c ghi nhn trong vng bc sng t 0.25 n 1.8 m trn my
Jasco V-530 v Bruker Equinox 55. Qu trnh tnh ton ph truyn qua t hm in mi v khp
vi ph thc nghim c thc hin bng phn mm Scout [12].
M hnh hm in mi
Trong bo co ny, ph truyn qua cho mng mng GZO c tnh ton da trn hm in
mi , c ng gp t 3 s hng:
2
1. S hng Drude:
N
fe
do trong vng dn [13]. Trong ,
, biu din ng gp vo hm in mi ca in t t
Ne 2
* l biu thc ca tn s Drude, N l nng in
om
t t do, m* l khi lng hiu dng ca in t trong vng dn, o v e l in thm chn
khng v in tch in t. l tn s va chm, c trng cho s tn x ca in t t do trong
trong vng dn. i vi cc bn dn pha tp ln, nh tnh v mt l thuyt cho thy tn s va
chm ca in t ph thuc vo tn s kch thch ca trng in t. biu din s ph
thuc ny Theiss [12] a ra biu thc:
L
arctan
Cross
(1)
l biu thc ton hc, tr gip biu din mt cch trn v lin tc s gim ca vo tn s. Gi
tr ca thay i t L tn s thp n H tn s cao, qua mt vng chuyn tip c nh
ngha bi tn s cross v
, ln lt nh du tm v rng ca vng chuyn tip. Khi nh
( << cross) th L, khi tng th s gim v khi rt ln ( >> cross) th H . Tn
s cross tng ng vi tn s bng ( L + H)/2 v th hin tn s m c s thay i
ln ca .
th hin mc thay i nhanh hay chm ca trong vng chuyn tip. Theo
Theiss, ngha vt l ca biu thc (1) l: tn s cao, chiu tc ng ca in trng thay i
qu nhanh nn chuyn ng ca in t b hn ch. Do khi tn s kch thch vt qua mt
gi tr ngng ( y l cross) th tn s va chm ca in t s gim nhanh. Vi 4 thng s L,
c th thay i, biu thc (1) m t tt ph thc nghim ca ITO [5] v AZO [8].
H, cross,
2
2. S hng Lorentz:
Nc
ve
t lin kt trong vng ha tr
2
c
, biu din ng gp vo hm in mi ca in
c
[14]
. Trong ,
Nc
Nce2
*
* , Nc l mt in t lin kt v mv
m
o
v
l khi lng hiu dng ca in t lin kt trong vng ha tr. c l gi tr ca tn s cng

hng v c l m rng vch ti c. Hai gi tr ny cho php c tnh c gi tr v dng ca
b hp th ca GZO.
3. Li in mi: , l hng s thc, biu din ng gp vo hm in mi ca tt c in
tch li bn trong ca vt liu, bao gm gi tr 1 ca chn khng. y gi s trong vng
Nhng
_____________________________________________________________________________________
tn s kho st UV-Vis-NIR, trng in t khng tc ng n cc in tch bn trong. ng

gp vo hm in mi ca dao ng mng ch nm trong vng hng ngoi xa.
Nh vy hm in mi cho m t tnh cht quang hc ca mng GZO l:
fe
ve
3. Kt qu & bn lun
u tin hm in mi ca thy tinh cn c xc nh. c s dng l loi thy tinh
kim (soda-lime) nhn hiu Marienfeld (c). Hm in mi ca thy tinh c rt ra t ph
truyn qua trong vng t 0.25 m n 1.8 m bng m hnh Lorentz. So snh ph tnh ton vi
ph o v b tr php o c th hin trn Hnh 1. C th quan st thy s trng khp rt tt
gia hai ph. Thc nghim cho thy i
vi cc cht in mi trong sut, cng
thc Cauchy hoc Sellmeier thng c
s dng m t c trng tn sc ca cc
vt liu ny trong vng kh kin. V bn
cht cc cng thc ny u c th suy ra t
m hnh Lorentz trong vng tn s xa b
hp th. Nn trong trng hp y, vic
s dng m hnh Lorentz l hp l bi tnh
tng qut hn ca n khi vng ph kho
st ko di n vng hp th mnh. Gi tr
tnh ton ca phn thc v phn o ca
hm in mi, chit sut v h s tt ca
thy tinh c trnh by trong Hnh 2.
Cu trc ca h mng- trong tnh
ton ph quang hc v so snh gia ph
tnh ton v ph o c trnh by trn
Hnh 1. Ph o v ph tnh ton ca thy tinh
Hnh 3 cho mu c tnh cht tt nht. Quan
cng vi b tr php o truyn qua.
st cho thy m hnh Drude m rng v
Lorentz m t tt ph truyn qua ca mng
GZO trn thy tinh. Trong bo co ny,
quan h gia tn s Drude N v tn s L
( << cross) c xc nh theo biu thc:
2
N
eN dc
dc
L
L
dc
(2)
linh ng lin h vi tn s va
chm theo biu thc:
e
dc
*
c
m L
Biu thc (2) c s dng gim bt
mt thng s trong m hnh Drude m rng
khi in tr sut dc c xc nh bng
php o 4 mi d hoc van der Pauw. Hnh
Hnh 2. Hm in mi, chit sut v h s tt ca
4 biu din s ph thuc ca tn s v thy tinh Marienfeld c xc nh t ph truyn qua
linh ng theo bc sng c tnh t biu
e
thc (1) v
.
Da trn Hnh 4 c th thy vng bc sng di khng ph
m*c
thuc nhiu vo bc sng. Thc vy trong vng ny, chu k dao ng ca sng in t l ln
Advances
_____________________________________________________________________________________
Hnh 4. S ph thuc ca tn s va chm in

t v linh ng in t theo bc sng
photon kch thch
Hnh 3. Ph o v ph tnh ton truyn qua

ca mng GZO trn thy tinh thu c t m
hnh Drude m rng + Lorentz
hn nhiu ln so vi thi gian va chm trung bnh ca in t trong vng dn.

Vi dc ~ 28 cm2V-1s-1 ng vi L ~ 1000 cm-1, khong thi gian trung bnh va chm ca in t
c th tnh mt cch n gin t biu thc :
*
dc m c
0
e
Gi tr c tnh ca 0 ~ 10-14 s. Nh vy khi > 10 m, chu k sng >> 0, linh ng
khng ph thuc vo bc sng. S gim nhanh tn s va chm xy ra bc sng ~1 m.
Php o hiu ng Hall cho kt qu mng GZO c nng ht ti N dc l 7.2 x 1020 cm-3. Nu gi
s N ~ Ndc , ngha l ton b in t tham gia vo qu trnh dn u tham gia vo qu trnh kch
thch quang hc, th t biu thc tn s Drude c th xc nh khi lng hiu dng ca in t
m *c
N dc (cm-3 )
~
~ 0.33 .
trong vng dn:
m e 1.12 1013 2N (cm-1 )
i vi ZnO dng khi khng pha tp gi tr ny l 0.28me [15] hoc 0.29me [16]. Mt s gi tr
khc nhau ca khi lng hiu dng i vi ZnO pha tp Al t mt s tc gi c tham kho
nh Chen [17] l 0.4me, Manivannan l 0.67me [17], Qiao l 0.6me [8], Brehme l 0.5me [1] v Jin l
1.02me [18]. C th thy cc kt qu l rt khc nhau do trong mi trng hp mng c ch to
vi phng php v cc iu kin khc nhau.
T kt qu tnh ton hm in mi, chit sut v h s tt c tnh bi cc biu thc:
1
2
2
r
2
i
1
2
2
r
2
i
Hnh 5 trnh by kt qu tnh chit sut v h s tt ca cc mng GZO ph cc nhit

khc nhau. Chit sut mng 0.55 m l 1.86. Trong vng kh kin ~ 0 th hin tnh trong
sut ca vt liu GZO. Quan st v tr ca tn s plasma p ti n = cho thy p dch chuyn
v bc sng ngn khi nng in t tng v nh nht nhit 150 0C. Khi > p th >>
n nn GZO th hin tnh phn x mnh trong vng hng ngoi. T tr s ca , c th tnh h s
4
hp th ca mng GZO theo biu thc:
(3)
Nhng
_____________________________________________________________________________________
Hnh 5. Chit sut v h s tt ca cc mng

GZO vi nhit khc nhau khi ph mng
Hnh 6. Dch chuyn b hp th ca cc

mng GZO khi c ch to vi nhit
khc nhau
Bng 1. Tnh cht quang ca mng GZO ch to cc nhit khc nhau

R
(3 m)
( m)
0.82
0.83
1.42
100
0.82
0.83
150
0.84
250
TS
(oC)
50
n0.55
mc*/me
(cm )
Eg
(eV)
1.88
475
4.06
3.62
0.32
1.42
1.87
927
4.05
3.48
0.33
0.84
1.42
1.85
234
4.10
3.49
0.33
0.84
0.83
1.47
1.85
590
4.00
3.51
0.34
300
0.83
0.81
1.53
1.86
538
4.03
3.46
0.33
350
0.84
0.77
1.67
1.86
183
3.92
3.49
0.32
0.55
-1
Hnh 6 th hin s thay i ca bnh phng h s hp th theo nng lng photon c tnh
ton t biu thc biu thc (3). Vi ZnO c dch chuyn thng cho php, rng vng cm c
tnh t ngoi suy t vng tuyn tnh ca ng cong 2 nh trn Hnh 6. Gi tr vng cm c bn
Eg ca xt ZnO khng pha tp l 3.38 eV [15]. Gi tr b hp th ca GZO cao hn so vi gi tr
Eg ca xt ZnO l ch yu do dch chuyn Burstein-Moss. i vi ZnO pha tp nng, l cc bn
dn loi n c nng in t ln hn nhiu so vi nng ti hn Mott (2.2 x 10 19 cm-3 i vi
ZnO [19]) do xy ra dch chuyn bn dn kim loi, cc trng thi in t y vng dn
b lp y, mc Fermi c xc nh bi trng thi b chim cao nht v bn dn tr nn suy
bin. Do dch chuyn quang hc vng vng s chu tc ng ca nng ht ti t do. Biu
thc dch chuyn Burstein-Moss c dng [2]:
2
2k F
Eg
(4)
2m cv
Trong biu thc khi lng hiu dng rt gn:
(4) :
E g (eV) 0.363 10
14
1
m *cv
1
m *c
1
*
*
* , ta lun c mcv < mc , nn t
mv
N 2 / 3 (cm 3 )
. Vi gi tr ca n ~ 7.2 x 1020 cm-3 v mc* ~ 0.33me
m *c / m e
Advances
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cho GZO, th Eg > 0.9 eV. Thc t gi tr ca Eg thu c ~ 0.7 eV nh hn gi tr c tnh do

c s thu hp b hp th bi s tn x ca in t. dch c th ln n 0.5 eV vi ZnO pha
tp Al c nng in t 5 x 1020 cm-3 [15]. Trong bo co ny, b hp th ln nht l ~ 4.1 eV
nhit 150oC v cng l iu kin c in tr sut thp nht ~ 3 x 10 -4 .cm trong cc
mng GZO c ch to. Hn na truyn qua trong vng kh kin 84% v phn x hng
ngoi 84% cng l nhng gi tr tt nht t c i vi mng ZnO pha tp. Bng 1 tng hp
cc thng s quang hc c bn ca mng GZO thu c t tnh ton da trn hm in mi
Drude m rng v Lorentz trong kho st theo nhit . Trong bo co, gi tr ca
thay
i trong khong t 3.5 n 3.6 trong khi gi tr ca ZnO khi khng pha tp l 3.85 [15]. Khi
lng hiu dng thay i trong khong 0.32 0.34 me.
4. Kt lun
M hnh Drude m rng v Lorentz c p dng xy dng hm in mi cho phn tch
tnh cht quang hc ca mng GZO. Cc thng s vt l cn thit nh linh ng ph thuc
vo tn s, dy mng, rng vng cm v chit sut c rt ra. Khi lng hiu dng ca
in t trong vng dn c c tnh v ph thuc vo iu kin ch to.
Ti liu tham kho
1. Brehme S. (1999), Thin Solid Films 342, pp. 167 173
2. Hamberg I., (1986), J. Appl. Phys. 60(11), pp. R123 R159
3. Brewer S. H. (2002), Journal of Alloys and Compounds 338, pp. 73 79
4. Weijtens C. H. L. (1991), Thin Solid Films 196, pp. l 10
5. Mergel D. (2002), J. Phys. D: Appl. Phys. 35, pp. 794 801
6. Solieman A. (2006), Thin Solid Films 502, pp. 205 211
7. Lai F. (2007), Thin Solid Films 515, pp. 73877392
8. Qiao Z. (2006), Thin Solid Films 496, pp. 520 525
9. OLeary S. K., Johnson S. R., Lim P. K. (1997), J. Appl. Phys., 82(7), pp. 3334 3340
10. Trn Cao Vinh, Nguyn Hu Ch (2005), Tp ch Pht trin KH v CN - HQG Tp. HCM,
Tp 8, S 3, trang 5-10
11. Cao Th M Dung, Trn Cao Vinh, Nguyn Hu Ch (2007), Tp ch Pht trin KH v CN HQG Tp. HCM, Tp 10, S 3, 2007, trang 37 40.
12. Theiss W., Scout 98, Germany, www.mtheiss.com
13. Edwards P. (2004), Dalton Trans., The Royal Society of Chemistry UK, pp. 2995 3002
14. Reitz J. R. (1993), Foundation of electromagnetic theory, 4th Ed., Addison-Wesley, USA
15. Sernelius B. E. (1986), Physical Review B 37, pp. 10244-10248
16. Baer W. S. (1967), Physical Review 154, pp. 785 789
17. Chen M. (2000), J. Phys. D: Appl. Phys. 33, pp. 2538 2548
18. Jin Z. C., Hamberg I., Granqvist C. G (1988), J. Appl. Phys. 64(10), pp. 5117 5131
19. Roth A. P. (1982), Physical Review B 25, pp. 7836 7839
Nhng
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TNG HP FORSTERITE MG2SIO4 PHA MANGAN, VANADI

SYNTHESIS OF FORSTERITE MG2SIO4 DOPED MANGANESE, VANADIUM
Phm Gia Ng a, Phm Vn Lm a, Phm c Hiu b,
L Th Ct Tng c, Phan Th Bch Ho c
a)
Vin Ho Hc Vin Khoa hc v Cng ngh Vit Nam;

b)
Khoa Vt l trng i hc S phm H Ni 2;
c)
Vin Khoa hc vt liu-Vin Khoa hc v Cng ngh Vit Nam
Abstract: In this work, Mn-doped Mg2SiO4 and V-doped Mg2SiO4 were synthesized by sol gel
method, using TEOS, MgCl2.6H2O, MnCl2.4H2O and TEOS, MgCl2.6H2O, NH4VO3 ( Mn and V
0,1% in weight) in presence of NH4OH (pH=11-12), resulting to gel mixture of silicic acid,
magnesium hydroxide and Mn(OH)2 or V(OH)5. The gel mixture was filtered, washed and then
thermal treated at high temperature. The decomposition of gel precursor mixture and formation of
Mn - doped Mg2SiO4 or V - doped Mg2SiO4 depend strongly on thermal treatment. Thermal
gravimetry analysis (TGA) and differential thermal analysis (DTA) and X-Ray diffraction (XRD)
indicate the thermal decomposition of mixture until 7500C and the formation of phase Mn-doped
Mg2SiO4 or phase V-doped Mg2SiO4 at 9000C. During the process, Mn-doping or V- doping
dispersed uniformly into Mg2SiO4. The luminescence of Mn in Mn doped Mg2SiO4 or of V in
V doped Mg2SiO4 was observed at room temperature.
1. M u
Trong h MgO-SiO2, Forsterite t lu c nhiu ng dng lm vt liu chu nhit v cch
nhit [1]. Gn y, Mg2SiO4 dng tinh th, c pha tp c dng lm vt liu quang hc [2,3].
dng bt mn, Mg2SiO4 l thnh phn quan trng trong cc gm sinh hc do c bn ho hc
cao, khng c hi, khng b c th o thi Theo phng php truyn thng, Forsterite c th
c iu ch bng phn ng pha rn [4]. Vi phng php ny qu trnh tng hp phi thc
hin trong thi gian di nhit 14000C n 15000C v cc cht u v sn phm u trng
thi rn, tc phn ng b gii hn bi qu trnh khuch tn trong pha rn. khc phc nhng
nhc im trn, nhiu tc gi s dng phng php kt ta ng thi v phng php Solgel ch to Forsterite ni ring v vt liu gm ni chung [5-11]. u im ca cc phng
php ny l to ra vt liu c sch v ng nht cao trong thi gian ngn nhit thp.
Bn cht ca phng php ny l to ra cc hp cht trung gian trng thi phn b ng nht
v c nhit phn hu thp, to iu kin thun li cho phn ng pha rn [9].
Trong bi ny, tip theo nhng nghin cu trc [10,11] chng ti nghin cu ch to
Forsterite Mg2SiO4 c pha tp mangan (Mn) hoc vanadi (V) lm nguyn liu cho vt liu
laser v quang hc. Cc phng php phn tch nhit (TGA, DTA), nhiu x tia X (XRD),
Raman v hunh quang c s dng nghin cu qu trnh hnh thnh pha v a tp vo
tinh th.
2. Thc nghim
2.1. Ho cht
tng hp Forsterite Mg2SiO4 pha Mn cc ho cht Si(C2H5O)4 (TEOS, Aldrich),
MgCl2.6H2O, MnCl2.4H2O v NH4OH (Trung quc) c sch P.A c s dng.
Cn tng hp Forsterite Mg2SiO4 pha V cc ho cht Si(C2H5O)4 (TEOS, Aldrich),
MgCl2.6H2O, NH4VO3 v NH4OH (Trung quc) c sch P.A c dng.
Advances
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2.2. Qu trnh tng hp

Cc ho cht MgCl2.6H2O v Si(C2H5O)4 c tnh ton theo hp thc ca Mg2SiO4.
Lng MnCl2.4H2O hoc NH4VO3 c tnh ton sao cho thnh phn Mn (hay V) trong sn
phm bng 0,1% khi lng. Pha 100ml dung dch hn hp cha 0,67 mol/l v 0,71mol/l MgCl2.
Hn hp dung dch mui MgCl2.6H2O, MnCl2.4H2O (hoc mui MgCl2.6H2O, NH4VO3)
chun b nh trn c un nng trn my khuy t nhit c 700C 800C. Lng TEOS
c nh git t t vo dung dch, ng thi s dng NH4OH 10% iu chnh pH lun
khong trong 10-11. Phn ng to ra dung dch huyn ph mu trng sa. Sau khi dng ht
TEOS, tip tc khuy v un nng dung dch huyn ph 900C-1000C khong 60 pht. Tin
hnh lc, ra huyn ph bng nc ct loi ht cc sn phm ph. Sy kt ta nho, trng mn
thu c 1000C khong 48 gi.
xc nh hnh vi nhit ca hn hp gel sau khi sy chng ti s dng phng php phn
tch nhit (TGA v DTA ) trn thit b Shimadzu TA-50 (Nht Bn) vi tc tng nhit tuyn
tnh 100C/pht t nhit phng n 9000C.
xc nh nhit nung hp l, tin hnh nung hn hp gel theo hai ch :
- Nung n 5000C, tc tng nhit tuyn tnh 100C/pht, lu mu 5000C trong khong
thi gian 30 pht.
- Nung n 9000C, tc tng nhit tuyn tnh 100C/pht, lu mu 9000C trong khong
thi gian 90 pht.
Cc sn phm thu c sau khi nung c o nhiu x tia X trn thit b Siemens D5000
(CHLB c), ph hunh quang c o nhit phng trn my MicroSpec 2300i (M) dng
laser Kimmon-Nht Bn v o Raman trn my LABRAM1B.
3. Kt qu v bn lun
S thu phn trc tip ca TEOS
trong hn hp dung dch MgCl2 v
MnCl2 (hoc NH4VO3) khong
pH=10-11 to thnh hn hp gel
ng nht gia H2SiO3, Mg(OH)2 v
Mn(OH)2 hoc V(OH)5. y
NH4OH ng vai tr kim yu, y
nhanh qu trnh to thnh gel H2SiO3
ng thi vi gel Mg(OH)2 v
Mn(OH)2 hoc V(OH)5. Vic tip tc
khuy nhit 90-1000C sau khi
phn ng kt thc c tc dng lm
Hnh 1. Gin phn tch nhit TGA ca hn hp
bn ho hn hp gel, ng thi
gel H2SiO3-Mg(OH)2
chuyn mt phn gel H2SiO3,
Mg(OH)2 v Mn(OH)2 hoc V(OH)5) thnh SiO2..H2O, MgO.H2O, Mg3Si4O10(OH)12, Vic
lm bn ho hn hp gel c tc dng ngn nga s ho tan ca chng trong qu trnh lc, ra
tip theo.
Gin phn tch nhit TGA v DrTGA ca hn hp gel H2SiO3-Mg(OH)2 c mt ca
Mn(OH)2 (hnh 1) cho thy qu trnh hao ht khi lng xy ra theo ba bc r rt ng vi cc
vng nhit 100-1250C, 236-3300C v 451-5000C. Ti vng 100-1250C ngoi vic gim khi
lng do s mt nc m trong mu, bt u xy ra qu trnh dehydrat cc gel H2SiO3 v gel
Mg(OH)2 thnh SiO2 v MgO. Vic mt nc kt tinh ca hn hp gel xy ra ng vi cc nh
2360C, 2900C, 4510C c th ko di n 7500C.
Nhng
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Trong giai on ny ng thi vi qu trnh dehydrat, qu trnh phn ng to thnh pha mi

Forsterite Mg2SiO4 gia SiO2 v MgO (va mi to thnh trng thi ng nht) cng bt u.
a
Hnh 2. Gin nhiu x tia X ca mu Mg2SiO4 pha Mn nung :

a) 5000C, b) Nung 9000C
Hnh 3. a) Gin nhiu x tia X ca mu Mg2SiO4 pha V 500oC

b) Mu nung 9000 C trong 90 pht
Hnh 4. Ph Raman ca mu Mg2SiO4 pha Mn nung 9000C trong 90 pht
n nhit 9000C c th coi qu trnh phn ng kt thc hon ton. iu ny cng th hin
trn gin nhiu x tia X (hnh 2).
Gin nhiu x tia X ca mu sau khi nung n 5000C (hnh 2a) cho thy pha Forsterite
Mg2SiO4 hnh thnh tng i r rng nhit ny. Tinh th tip tc hon thin khi nung
n nhit cao hn, 9000C tinh th hon chnh hn th hin trn gin XRD (hnh 2b) vi
cc nh sc nt v nhn hn. D liu XRD cng cho thy vic pha tp Mangan vi hm lng
nh nh vy khng lm nh hng n cu trc ca Forsterite. Kt qu cng tng t khi
Forsterite Mg2SiO4 pha Vanadi 0,1% trng lng (hnh 3a, 3b).
khng nh thm s n pha ca Forsterite, mu c o ph Raman. Hnh 4 l ph
Raman ca mu vi cc vch c trng ca Forsterite.
Mangan v Vanadi c a vo mng tinh th ca Forsterite vi vai tr lm tm pht hunh
quang cho vt liu. V vy xc nh s c mt ca mangan, vanadi trong pha tinh th ca
Forsterite, chng ti s dng ph hunh quang.
Advances
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Hnh 5. Ph hunh quang ca cc mu Mg2SiO4
a) Mg2SiO4 khng pha tp, b) Mg2SiO4 pha tp mangan, c) Mg2SiO4 pha tp vanadi
Vi mu khng pha tp chng ti nhn c ph hunh quang nh 658 nm (hnh 5a), cn
vi mu pha tp (Mn bng 0,1% khi lng) th nhn c ph hunh quang nhng vi nh 662
nm (hnh 5b). Lm li nhiu ln chng ti u nhn c kt qu nh nhau, cc kt qu th
nghim hon ton lp li. iu chng t rng Mn vo mng tinh th v lm dch chuyn
vch hunh quang. Bn cht ca hin tng ny l g chng ti cn ang nghin cu. Nhng
nhn mnh rng kt qu thc nghim l tin cy v lp li. Vi mu pha vanadi th ph hunh
quang nhn c 559 nm rt rng v mnh (hnh 5c).
Theo R. Zhu Vin Vt l cht rn, Vin Hn lm khoa hc Trung Quc [12] v Murase N.
[13] th c l nh 662 nm ng vi chuyn mc 4T1 6A1 ca ion Mn2+, cn nh yu hn 451
nm ng vi tm khuyt tt c th l l trng oxy hay cc khuyt tt b mt khc.
4. Kt lun
S dng phng php Sol-gel tng hp thnh cng a tinh th Forsterite Mg2SiO4 n
pha c pha tp Mn v V. Phng php tng hp c thc hin nhit thp (9000C) so vi
phng php tng hp pha rn truyn thng (14000C 15000C).
y l nhng kt qu nh hng cho vic nghin cu ch to nguyn liu ca vt liu laser
trn nn a tinh th Forsterite Mg2SiO4 n pha.
Vic xc nh hm lng Mn, V cng nh trng thi ca chng trong a tinh th Forsterite
Mg2SiO4 ang c tip tc nghin cu.
Li cm n: Cng trnh ny c s gip ti chnh ca chng trnh NCCB v ho hc giai
on 2006-2008. Cc tc gi xin trn trng cm n Ban ch nhim chng trnh NCCB, chn
thnh cm n PGS. Phan Vnh Phc, PGS. Nguyn Xun Ngha, TS. Phm Hng Dng, TS.
o Quc Hng, Th.S Nguyn Thanh Ngn gip trong vic ch to, o XRD, Raman v
ph hunh quang.
Ti liu tham kho
1. Iler., R. K., The Chemistry of silica, Vol.1, Winley, NewYork. (1979)
2. D.Elwell, Man_made Gemstones Center for Materials Research Stanford University.
3. V.F. Lebedev, I.D. Ryabob, A.V. Gaister, E.V. Zharikov Russian Solid state Physics 2005,
Vol.47 No 8 (1447-1449).
4. G.W. Brindley, R.Hayami, Phil. Mag. 12 (1965), 505
5. Kazakos, S. Komarneni, R. Roy, mater. Lett. 9 (1990), 405.
6. B.E. Yoldas, J. Mater.Sci.,12 (1977), 1203.
7. B.D. Mitchell, D. Jackson, P.F. James, Journal of Non-Crystalline Solid 225 (1998), 125.
8. A. Douy, Journal of Sol-Gel Science and technology 24 (2002), 221.
9. C.J. Brinker and G.W.Scherer, Academic Press, San Diego, (1990)
Nhng
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10. o Quc Hng, Phm Gia Ng, Advances in Optics Photonics Spec. and App. Viet Nam
Academic Press 2007 tr 90-93 Cn Th, Vit Nam August 15-19, 2006.
11. Phm Gia Ng, o Quc Hng, Phm Vn Lm, Tp ch Ho Hc T.45, 6A, 2007 tr. 710.
12. R.Zhu, X.S. Peng, S. H Sun, Y. Lin, L.D.Zhang. Photoluminescence properties of forsterite
(Mg2SiO4) nanobelts synthesized from Mg and SiO2 powders (Institute of Solid State
Academy
of
Sciences,
Hefei
230031,
P.R.China;
Physics,
Chinese
http://arxiv.org/abs/physics/0310114).
13. Murase, N.; Jagannathan, R.;Kanemastu, Y.; Watanabe, M.; Kurita, A.; Hirata, K.; Yazawa,
T.; Kushida, T. J. Phys. Chem. B 103, (1999), 754.
Advances
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KHO ST S NH HNG CA PHA TP Ga LN CU TRC IN T V TNH

CHT QUANG CA ZnO BNG THUYT HM MT
inh Son Thach a, Tran Nguyen Quynh Nhu b
a
University of Natural Sciences-VNU-HCM

(b)
Thalmann High school
227, Nguyen Van Cu St., Dist.5, HCMC
E-mail: trannhu_phys@yahoo.com
Tm tt: S nh hng ca pha tp Ga ln cu trc in t v tnh cht quang ca ZnO c

nghin cu bng phng php gi th sng phng da trn thuyt hm mt (DFT) vi hm
hiu chnh gradient Perdew-Wang 91 (GGA-PW91). Cc kt qu tnh ton pht hin ra rng do s
pha tp electron, c nhiu ht ti in y vng dn v mc Fermi dch chuyn vo trong vng
dn. ng thi, mt trng thi (DOS) cng dch chuyn v pha nng lng thp v khe nng
lng quang hc c m rng. Mt cng hng nhn c quy cho orbital Ga 4s xut hin ngay
pha di mc thp nht ca nhng vng ha tr Zn 3d. B rng ca nh ny tr nn rng hn
khi s lng tp cht Ga tng, phn nh s tng tng tc vi orbital 2p ca nhng nguyn t O
xung quanh. Kt qu tnh ton cng m phng r rt s dch chuyn Burstein- Moss v s co li
ca khe vng c bn khi pha tp tng. Hn na, s tng hm lng Ga cng khin cho th tch
ca n v b m rng. Tnh cht quang bao gm hm in mi, chit sut, h s tt, h s hp
thu, h s phn x v tn s plasma cng c kho st t m. Phn mm Materials Studio 3.2
c s dng tnh ton trong ti ny.
Key words: density functional theory, ZnO, Ga- doping, electronic structure, optical properties
1. Gii thiu
Mng TCO c ng dng rng ri trong cc dng c quang in v in tr sut thp v
truyn qua cao trong vng kh kin. Hu ht nhng kho st trc y trn mng TCO u tp
trung vo ITO hoc SnO2, nhng nhng nm gn y ZnO thu ht c nhiu ch nh mt
ng c vin c th thay th cho ITO. Bn cnh nhng u im ni tri nh nhit lng ng
kh thp, tnh cht bn vng tt trong plasma trong sut qu trnh lng ng, ZnO cn l vt
liu c gi thnh r, ngun phong ph v khng c hi.
ZnO l hp cht bn dn c vng cm rng. Khi tinh th cu trc wurtzite, ZnO l trong
sut trong vng kh kin v vng cm ln vo khong 3.3eV. Bng cch phun ht ti in cng
vi a vo nhng tp cht, ta c th iu khin c nng electron t do trong ZnO v to
nn nhng dng c quang in. Do , vic nghin cu cn k s nh hung ca pha tp ln
nhng tnh cht ca vt liu ch ZnO rt c ngha i vi nhng ng dng ca n. Nhng
nghin cu thc nghim pht hin ra rng khe nng lung quang hc s c m rng hn
khi pha tp Al, Ga, hoc In v dn in tng m khng lm suy gim s chuyn mc quang
hc [14,15]. c bit, tp cht Ga trong s nhng nguyn t nhm III l tp cht rt c hiu lc
trong vic tng cung tnh dn v gy ra s gim ng k nng lng Madelung [16]. V vy,
ZnO pha tp Ga tr thnh mt vt liu c cc nh khoa hc quan tm v nghin cu rng
ri.
2. Phng php tnh ton
Vic tnh ton c thc hin bng phn mm Accelrys, module CASTEP, da trn thuyt
phim hm mt (DFT), s dng phng php gi th m t tng tc gia electron vi li
v s khai trin sng phng vi hm sng. S ng gp ca tng quan trao i vo nng lng
ton phn c b sung qua vic s dng phng php gn ng mt cc b (LDA) vi hm
cc b CA-PZ (Ceperley v Alder, 1980; Perdew v Zunger, 1981) trong tnh ton nng lng
Nhng
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v phng php hiu chnh gradient (GGA) vi hm hiu chnh gradient PBE (Perdew et al,
1996) trong ti u ho cu trc.
3. Kt qu v bn lun
3.1. Cu trc in t
Sau khi xy dng m hnh tinh th wurtzite-ZnO v tin hnh ti u ha cu trc, chng ti
thu uc cc thng s mng nh sau: a = b = 3.257 Ao, c = 5.259 Ao, c/a = 1.614, u = 0.377. Tt
c cc thng s u ph hp tt vi kt qu thc nghim cng nh kt qu ca nhng tnh ton
trc [1,2]. iu ny chng t phng php tnh ton ca chng ti l hp l, kt qu thu
uc hon ton c cn c v ng tin cy.
Hnh 1: M hnh cu trc tinh th ca siu mng wurtzite ZnO

a) Nhn t trn xung ca siu mng ZnO; b) ZnO sch; c) Ga0.0625Zn0.9375O
Cu trc vng nng lng ca tinh

th w- ZnO c tnh ton trn m hnh
2x2x2 supercells (hnh 1). Kim tra v
mc tin cy ca tnh ton, ta thy b
rng vng ca nhng trng thi ha tr
kh ph hp vi cc kt qu thu
Ef
c. Hn na, vic tnh ton cu trc
vng xung quanh gi tr cc i ca
vng ha tr v cc tiu ca vng dn ti
im G cng ph hp tt vi thc
nghim nhng kt qu trc [3]
Hnh 2 ch ra rng ZnO vi cu trc
wurtzite c vng cm thng gia nh
vng ha tr v y vng dn ti im G.
Hnh 2: cu trc vng nng lng
v mt
trng
Vng ha tr c ng gp
ch
yuthi
t ca cu trc w- ZnO
1.0eV, mc nng lng trong vng ny
c cho rng c s tng tc nh vi nhng vng ha tr khc. Nhng trng thi ha tr tn ti
y gm hai nhm chnh: nhng mc t -6 n -4eV phn ln l nhn c t orbital 3d ca
Zn v c in y hon ton. Vng ha tr cao hn -4eV ch yu do mc 2p ca O, so vi
vng dn th vng ny phng hn nhiu, kt qu l khi lng hiu dng nng hn i vi l
trng vng ha tr. S chnh lch ln gia khi lng hiu dng ca electron v l trng l mt
trong nhng nguyn nhn chnh gy kh khn cho vic ch to ZnO nh nhng vt liu c tnh
dn in cao loi p.
Vng dn l mt rng nhng trng tri di t 1eV n 7eV, ch yu l do s ng gp ca
nhng obital 4s v 4p ca Zn cng vi mt lng khng ng k ca O 2p. Mt trng thi
ton phn v thnh phn (DOS v PDOS) c biu din hnh 3. Ta c th thy nh PDOS
tng ng vi O 2p tng i nhn do s chen ln nh vi cc orbital khc. iu ny cng
chng t nhng electron O 2p lin kt cht ch vi cc nguyn t Oxi v ngn cm s ng gp
vo y vng dn. S mu t cu trc vng ca cu trc w- ZnO ph hp tt vi nhng quan st
Advances
_____________________________________________________________________________________
Hnh 3: DOS ca ZnO

sch v ZnO pha tp Ga
Hnh 4: cu trc vng nng lng ca ZnO pha tp

Ga theo m hnh 2x2x2
thc nghim. Tuy th, rng vng cm thu c t kt qu tnh ton l 0,97 eV, nh hn nhiu
so vi gi tr thc nghim 3,3eV [4] nhng li ph hp tt vi cc kt qu tnh ton trc
[5,6]. S c tnh thp ny c bit nh mt im c trng ca phng php DFT, ch yu
xy ra khi p dng vi cht bn dn v cht cch in.
m phng s nh hng ca nhng lng pha tp Ga khc nhau vo ZnO, chng ti kho
st 4 m hnh tng ng vi t l pha tp l 6.25%, 12.5%, 18.75% v 25%. Vic pha tp Ga vo
m hnh c thc hin bng cch thay th nguyn t Ga vo v tr ca Zn v thc hin vng lp
ti u ha thu c cu trc n nh. Sau , thc hin cc tnh ton da trn m hnh ti
u ha (hnh1(c)).
Mt trng thi i vi nhng nng pha tp khc nhau c hin th hnh 3. C mt s
di ra ca electrron ti y vng dn, iu c ngha l electron t nguyn t tp cht Ga c
tr vng dn ca mng ch ZnO v tham gia vo tnh dn in, kt qu l ZnO tr thnh bn
dn loi n khi pha tp Ga. Hnh dng ca vng ha tr trong nhng hnh ny v c bn ging nh
trng hp khng pha tp hnh 2. Tuy nhin, do pha tp Ga a ht ti in loi n vo h nn
mc Fermi dch chuyn vo trong vng dn (VBs). Chnh s thay th kim loi Ga ha tr 3 vo
v tr Zn ha tr 2 thnh lp nhng mc donor nng bn trong vng dn gy nn s dch
chuyn mc Fermi.
So vi hnh 3(a) ta thy mt trng thi thnh phn (PDOS) cng dch chuyn ng k v
pha nng lng thp khi nng pha tp Ga tng. Thm vo , PDOS ca ZnO pha tp cng
c s thay i ln: gia vng ha tr thp hn v cao hn xut hin hai nh mi. Mt nh di
vng ha tr thp hn ch yu l do s ng gp ca nhng trng thi Zn 3d v mt nh hp rt
nhn khc xut hin ngay pha di trng thi Zn 3d. nh ny c nhn din do orbital 4s ca
tp cht Ga. B rng ca nh tr nn rng hn khi nng pha tp tng, chng t rng s tng
tc lin kt gia orbital 4s ca Ga v obital 2p ca nhng nguyn t O gn tp cht s mnh ln.
Kt qu ca s lin kt ny chc chn gp phn vo tnh n nh ca ZnO pha tp Ga khi nng
tp cht tng. S tn ti ca nh ny cng c bo co trong nhng nghin cu trc
[7].
kho st s nh hng ca tp cht Ga ln vng dn, s phn ly orbital DOS ca nguyn
t Ga gn mc Fermi cng c tnh ton. ng gp to ln n mt trng thi ca vng dn
gn mc Fermi l do nhng orbital s v tr Ga. Cng ca thnh phn ny tng t t khi s
lng tp cht tng. Hn na, mt trng thi ca thnh phn s trong ion Ga ln hn ng k
so vi ca nguyn t Zn, iu c ngha l Ga ng vai tr ch yu trong tnh dn ca ZnO pha
tp.
Hnh 4 biu th cu trc vng nng lng ca ZnO pha tp theo m hnh 2x2x2 supercells
ng vi 6.25%Ga. Nh ni trc , pha di trng thi ha tr 3d ca Zn xut hin vng 4s
Nhng
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Bng 2: Cc gi tr tnh ton i vi ZnO sch, ZnO pha tp Ga trong m hnh I IV bao gm dch
chuyn Burntein- Moss (EBM), hp khe vng (W), th tch ca n v () v nng ht ti t do n
ZnO sch
EBM (eV)
W (eV)
(10-24 cm3)
n (1021 cm-3)
Eg (eV)
0
0
55,78
0
0,97
M hnh III
(6,25% Ga)
1,64
0,47
56,24
2,22
2,14
M hnh IV
(12,5% Ga)
2,60
0,5
56,68
4,41
3,10
ca Ga vi b rng khong 0,1eV. Chng ta cng thy c s m rng ca khe nng lng do
s chim ng nhng trng thi thp nht ca vng dn vn trng bi cc electron c thm
vo v do s h thp ca khe nng lng c bn. Quan st hnh 4 ta thy khe nng lng tng
khi nng ht ti in t do tng. Hai c ch tc ng n rng vng cm trong bn dn c
tp cht l: hiu ng vng in
y Burstein- Moss [8, 9] v s thay
i cng tng tc gia tp cht Ga v mng tinh th ch ZnO [10].
Hiu ng Burstein- Moss gy ra s dch chuyn v tr EBM ca nh hp th quang hc,
s dch chuyn ny t l xp x vi n2/3, n l nng ht ti t do.
S tng tc electron- electron v tn x tp cht lm cho khe vng hp li khi mt
electron tng ln.
V vy, nng lng vng cm c tnh nh sau: Eg = Ego + EBM - W
Trong W l co khe vng so vi trc pha tp
Cc kt qu tnh ton ca EBM v W c trnh by trong bng 2. thy c mi quan
h nh lng ca nng lng vng cm v nng ht dn, ta cng lit k trong bng 2 th tch
ca n v v mt electron t do n t tp cht Ga. y, ta xem nh mi ion Ga ng gp
mt electron t do cho mng tinh th ch v b qua s ng gp t nhng sai hng mng ca
ZnO nh ch khuyt O hay k h Zn.
T cc kt qu tnh ton, ta c th nhn thy rng khi nng pha tp Ga tng th s dch
chuyn Burstein- Moss EBM tng v khe vng b hp li c ngha l co W tng. Tuy nhin,
khi nng ht ti in t do tng, s ng gp ca EBM ng k hn nhiu so vi cc s hng
tn x nn n nh hng ln n s dch chuyn khe nng lng. iu cng c ngha l nng
lng vng cm Eg c m rng khi nng ht dn tng hay cng c th ni nh hp th
dch chuyn v pha nng lng cao.
Ngoi ra, ta cng d dng nhn thy rng khi s lng tp cht Ga tng th th tch cng tng.
Nhng theo tnh ton th chiu di gia lin kt Ga- O l 1,909 Ao nh hn so vi chiu di lin
kt Zn- O (1,981 Ao). Hin tng ny c th c gii thch l do khi s lng Ga tng, lc y
pht sinh t nhng ht dng thm vo ca cation Ga cng tng lm cho th tch c m rng.
Ta cng nhn c kt qu tng th tch tng t khi pha tp Sn vo In2O3 [11].
3.2. Tnh cht quang
V c bn, tt c ph quang hc vi m ca vt liu u nhn c t hm in mi ().
Hm in mi () thc cht l s m t hin tng phn ng tuyn tnh ca h vi bc x in
t. Phn o ca n 2() c th thu c bng cch tnh ton nhng phn t ma trn xung lng
gia nhng hm sng in y v khng in y trong gii hn ca quy tc chn lc. Phn thc
1() c th thu c t phn o 2() bng php bin i Kramer- Kronig. Tt c nhng tnh
cht quang khc bao gm chit sut n(), h s hp th (), h s tt k(), h s phn x R()
v ph mt mt nng lng electron L() u c suy ra t 1() v 2() [12]
Ph phn o hm in mi 2() ca ZnO v Zn1-xGaxO c hin th hnh 5. ZnO sch
(hnh 5(a)), ph phn o 2() c 3 nh chnh ti 2.4, 6.9 v 10 eV. nh ti v tr 2.4 eV tng
ng vi s chuyn mc quang hc gia nhng trng thi O 2p trong vng ha tr cao nht v
nhng trng thi Zn 4s trong vng dn thp nht. nh xung quanh 6.9 eV ch yu do s chuyn
Advances
_____________________________________________________________________________________
Hnh 5: Hm in mi
mc gia nhng trng thi Zn 3d v O 2p, cn nh nhn

ti v tr 10 eV tng ng vi s chuyn trng thi t
nhng orbital Zn 3d v O 2s. Hai nh ny rt gn vi
nhng tnh ton khc [5]. i vi hp cht
Ga0.0625Zn0.9375O hnh 5(b), ta thy qu trnh chuyn
mc quang hc gia nhng trng thi O 2p v Zn 4s b
tc ng bi s hp nht Ga. Khi pha tp Ga, gi tr ca
Hnh 6: cc hng s quang ca
ZnO v Ga0.0625Zn0.9375O
2() dch chuyn v pha nng lng thp hn, iu
c ngha l s hp th nh sng b dch chuyn . S
thay i trong hp th nh sng ny hon ton ph hp vi s thay i trong cu trc in t.
Cng phi ni thm rng, s dch chuyn ca chuyn mc quang hc v pha nng lng thp
mt ln na khng nh khe nng lng gim khi nng Ga tng, ph hp tt vi kt qu mt
trng thi (DOS). Bn cnh , vi nng Ga tng, ta cng d dng quan st c nh ti
v tr 10 eV tng nh v dch chuyn quang hc gia nhng trng thi Zn 3d v O 2p ti 6.9 eV
b dch chuyn v pha nng lng thp nguyn nhn l do tnh nh x ca trng thi Zn 3d.
Ngoi ra, cn c mt vi nh xut hin di v tr 2.4 eV c quy cho s chuyn mc gia
vng ha tr v nhng mc nng lng tp cht hoc gia nhng mc tp cht v vng dn. So
vi DOS trong hnh 3, khong cch gia nhng mc nng lng tp cht v vng ha tr hoc
vng dn th rt nh, v vy electron trong nhng mc tp cht ny ch cn c kch thch bi
mt nng lng photon nh v tt nhin h s hp th l rt ln trong vng nh sng nhn thy.
Trong thc nghim, iu ny c th c s dng ci tin tnh cht quang xc tc ca ZnO
di nhng bc x kh kin.
Hnh 6 biu din cc hng s quang ca ZnO v Zn1-xGaxO trong vng nng lng t 0 n
20 eV. Nhng hng s quang chng hn nh dn quang hc, hm mt mt nng lng, ch s
khc x v phn x... rt quan trng i vi vt liu quang v nhng ng dng lin quan. Nhn
chung, cc thng s quang khng i trong vng nng lng cao hn 15eV v c s thay i nh
trong vng nng lng thp. Chng hn nh s nh hng ln dn quang bi s hp nht Ga
khng quan st c trong vng nng lng ln hn 10eV nhng li c s gim nhn pha
trn vng 12 eV, tng ng vi s thay i ca 2(). Mt kt qu tng t cng thu c i
vi ph hm mt mt nng lng L() hnh 6(b). nh ti v tr 15 eV trong hm mt mt nng
lng l nh cng hng plasma, chng ch ra im chuyn t tnh kim loi sang tnh in mi.
S hp nht ca tp cht Ga gy ra s dch chuyn ca nh 15 eV vi s tng nh trong ph
mt mt.
Chit sut hnh 6(c) v h s phn x hnh 6(d) ca ZnGaO tng trong vng nng lng
thp, iu ng ngha vi s gim khe nng lng quang hc. Theo kt qu tnh ton, gi tr
Nhng
_____________________________________________________________________________________
cc i ca chit sut ca ZnO sch trong vng nng lng thp vo khong 2.1 khp hon ton
vi d liu thc nghim [13].
4. Kt lun
Tm li, phng php lng t c s dng nh gi tnh cht in t v tnh cht quang
ca h Zn1-xGaxO trong cc cu hnh khc nhau. Do s pha tp electron, mc Fermi dch chuyn
vo trong vng dn v h th hin nhng c im ca bn dn suy bin loi n. So vi mt
trng thi ca ZnO sch, trong vng ha tr ca ZnO pha tp Ga xut hin mt nh nhn ca
trng thi Ga 4s. Nng pha tp cng tng th nh ny cng m rng, chng t s tng tng
tc gia Ga 4s v nhng orbital 2p ca nhng nguyn t O xung quanh. Kt qu tnh ton cng
m phng r rt s dch chuyn Burstein- Moss v s co li ca khe vng c bn khi pha tp
tng. Ngoi ra, s tng nng Ga cn dn n s m rng th tch ca mng tinh th. Cui
cng, nhng tnh cht quang bao gm hm in mi, chit sut, h s tt, h s hp thu, h s
phn x v tn s plasma cng c kho st t m. Tt c thng s quang c gi khng i
trong vng nng lng cao hn 15 eV, ngc li trong vng nng lng thp, nng pha tp
li nh hng mnh m n cc thng s quang. Khi nng pha tp tng, s chuyn mc
quang hc gia vng ho tr cao nht v vng dn thp nht dch chuyn v pha nng lng thp
v cc hng s quang nh chit sut, h s phn x c khuynh hng tng nh. Nhng kt qu
ny c th xem nh mt im khi u tt cho nhng nghin cu trong tng lai v s nh
hng ca pha tp ln nhiu h phc tp bao gm c nhng khuyt tt bn trong.
Ti liu tham kho
1. F. Decremps, F. Datchi, A.M. Saita, A. Polian, S. Pascarelli, A. DiCicco, J.P. Iti, and F.
Baudelet, Phys. Rev. B68, 104101 (2003)
2. J.Serano, A.H. Romero, F.J. Manjn, R. Lauck, M. Cardona, and A. Rubio, Phys.Rev.B69,
094306 (2004)
3. Y. Mi, H. Odaka and S. Iwata. Jpn. J. Appl. Phys. 38 (1999), p.3453
4. K.H.Hellwedge, O. Madelung (Eds), Numerial Data and Functional Relationship in Science
and Technology, Landolt-Bnstein, New Series, Group III, Vol. 17, Part a, Springer, Berlin,
1982
5. A.Ohtomo, M. Kawasaki, I. Ohkubo, H. Koinuma, T. Yasuda and Y. Segawa, Structure and
optical properties of ZnO/Mg0.2Zn0.8O superlattices, Appl. Phys. Lett. 75, 980-982 (1999)
6. Chen kun, Fan Guang- Han, Zhang Yong, Ding Shao- Feng, First- principle Calculation of
Nitrogen-doped p-type ZnO, Acta Phys. Chim.Sin., 2008 24 (01): 61-66
7. T.Yamamoto and H.K. Yoshida. Jpn. J. Appl. Phys. 38 (1999), p. L166
8. E. Burstein. Phys. Rev. 93 (1954), p. 632
9. T.S. Moss. Proc. Phys. Soc. London Sect. B 55 (1954), p. 775
10. A.P. Roth, J.B. Webb and D.F. Williams. Phys. Rev. B 25 (1982), p. 7836
11. G.B. Gonzalez, J.B. Cohen, J.H. Hwang, T.O. Mason, J.P. Hodges and J.D. Jorgensen. J.
Appl. Phys. 89 (2001), p. 2550.
12. S. Saha and T.P. Sinha. Phys. Rev. B 62 (2000), p. 8828
13. H. Yoshikawa and S. Adachi, J. Appl. Phys., Part 1 36 (1997), p. 6237
14. Z.Y. Ning, S.H. Cheng, S.B. Ge, Y. Chao, Z.Q. Gang, Y.X. Zhang and Z.G. Liuet. Thin Solid
Films 307 (1997), p. 50
15. H. Hiramatsu, K. Imaeda, H. Horio and M. Nawata. J. Vac. Sci. Technol. A 16 (1998), p.
669.
16. T. Yamamoto and H.K. Yoshida. Jpn. J. Appl. Phys. 38 (1999), p. L166
Advances
_____________________________________________________________________________________
NH HNG CA CH CNG NGH TI CC TNH CHT CU TRC

V TNH CHT T CA H ZNO PHA TP MN.
Ng Thu Hng, Nguyn Th Thc Hin
Khoa Vt l, Trng i hc Khoa hc T nhin, HQG H ni.
Tm tt: H ZnO pha tp Mn c ch to bng c hai phng php gm v phng php bc
bay nhit. Trong bi bo ny, chng ti trnh by nh hng ca ch cng ngh ti cc tnh
cht cu trc v tnh cht t ca h vt liu ny. Ph nhiu x tia X v s liu EDS cho thy
chng c cu trc Wurtzite. Cc dy nano ca h c kch thc t 20 n 80 nm. H vt liu c
tnh cht st t yu c ch ra t cc php o tnh cht t.
1. M u
Mt loi vt liu c c tnh cht ca vt liu t v ca vt liu bn dn c gi l vt liu
bn dn t pha long (DMS) c nghin cu v ng dng rt nhiu. Trong thi gian gn y,
rt nhiu nhm nghin cu tp trung vo nghin cu tnh cht cu trc cng nh tnh cht t
ca loi vt liu ny. Trong lnh vc ny, hng lot cc cu hi cn gii p nh ti sao khi pha
tp mt nguyn t khng t li lm tng tnh cht t ca vt liu? Ti sao kt qu li ph thuc
rt nhiu vo iu kin cng ngh ch to vt liu cng nh thnh phn pha tp [1-4]? Theo mt
s tc gi, trong trng hp kho st vt liu khi th mu li khng c tnh cht t trong khi vt
liu mng li c t tnh. Vic nghin cu vt liu bn dn t pha long l kh l th.
Trong bi bo ny, chng ti trnh by nh hng ca ch cng ngh ti cc tnh cht cu
trc cng nh tnh cht t ca c hai loi vt liu mng v khi Zn1-xMnxO (0,0 x 0,15).
2. Thc nghim
H vt liu Zn1-xMnxO (0,0 x 0,15) c ch to t cc hn hp oxit ZnO (c sch
99,95%) v MnO2 (c sch 99,99 %) bng c hai phng php gm v phng php bc bay
nhit trong mi trng kh Ar. H vt liu khi c ch to theo cc bc ca ch to mu gm
truyn thng. Qu trnh nung s b c thc hin 2000C, gi nhit trong 10 gi sau c
lm lnh chm n nhit phng. Qu trnh to phn ng pha rn ca cc mu c thc hin
trong qu trnh nhit ti cc nhit 400, 550, 650 v 8000C. Cc mu mng ZnO pha tp Mn
c ch to bng phng php bc bay nhit trong mi trng kh Ar. Hn hp cc oxit theo
hp phn c trn thm vi 2% khi lng cacbon. Bt sau khi trn c t trong thuyn s
v t trong l c nhit 11000C, thi gian gi nhit 60 pht sau lm lnh n nhit
phng. Cc Si [111] c t trong khong nhit t 5500C n 6500C. Php o nh nhiu x
tia X c thc hin trn thit b D5005. nh SEM v ph EDS c thc hin trn knh hin vi
in t qut JEOL JSM-5410 LV. Cc php o t tr v t ca h mu c thc hin trn h
PPMS 6000.
3. Kt qu v bin lun
Ph nhiu x tia X ca c hai loi vt liu khi v vt liu mng u c kho st. i vi
h mu khi, khi nhit thp ph nhiu x ca cc mu vn xut hin cc nh khng phi
ca ZnO. Khi nhit cao, cc mu l n pha. Hnh 1 ch ra ph nhiu x tia X ca cc mu
khi h Zn1-xMnxO c nhit 6500C. Hng s mng a v c ca cc mu c tnh bng
phng php Riveld vi cc gi tr ln lt l 3,252 A0 v 5,210 A0.
Nhng
_____________________________________________________________________________________
Intensity (arb. units)
x = 0.15
(110)
(102)
(101)
500
(002)
600
(100)
Zn1xMnxO
x = 0.12
400
x = 0.09
300
x = 0.06
200
x = 0.03
100
x= 0.00
0
20
30
40
50
60
Hnh 1: nh nhiu x tia X ca cc mu khi Zn1-xMnxO 6500C.
Hnh 2 l nh SEM ca cc mu khi h Zn1-xMnxO khi 650 oC. Hu ht tt c cc mu

u c mt ht thp (x = 0,00; 0,06; 0,09 and 0,12) khi nhit thiu kt thp. Kch thc
trung bnh ca ht c 200 nm tr mu c thnh phn x = 0,03. Khi nhit cc mu tng th
kch thc ca cc ht cng tng ln.
Khi nghin cu h mu mng, cu trc ca cc mu hon ton khc vi h mu khi. Hnh 3
l nh SEM ca mu mng ZnO khng pha tp vi cc phng i khc nhau. Chng c cu
trc dng hnh ng, que c mc t v kch thc cng tng khi u ng. S to thnh ng
bt u xut hin t cc git hi ban u. Qu trnh bc bay ko di th kch thc ca ng cng
pht trin nn c s khc nhau v kch thc ti vng st vi vng xa . Theo [5], nhit
cao, cacbon kh ZnO to thnh hi Zn v ZnOx. Cc hi ny ngng t trn ti vng nhit
thp to thnh cc git lng trn ng vai tr nh cc mm. Cc mm ny ln ln t bin gii
git lng v to thnh khong trng gia. Chng c pht trin theo hng u tin ca cu
trc Wurize v hnh thnh nn cc ng nh xut hin trn hnh 3.
a) x = 0,00
b) x = 0,03
c) x = 0,06
d) x = 0,09
e) x = 0,12
f) x = 0,15
Hnh 2: nh SEM ca cc mu khi Zn1-xMnxO 6500C
Advances
_____________________________________________________________________________________
Hnh 3 : nh SEM ca mu mng ZnO
a) x = 0,06
b) x = 0,09
c) x = 0,12
d) x = 0,15
Hnh 4: nh SEM ca h mu mng Zn1-xMnxO
Hnh 4 l nh SEM ca cc mu mng ZnO pha tp Mn vi cc thnh phn khc nhau: 0,06;
0,09; 0,12 v 0,15. Hnh 4a l nh SEM ca mu 6% Mn. Cc dy nano mnh vi kch thc c
100 150 nm. u dy ta thy cc hnh l c hnh thnh.
Khi thnh phn Mn pha tp tng ln 9%, cu trc kh l c bit (hnh 4b). Mt u mc ln
gia cc khi hnh thoi, u cn li li mc ra cc dy nano thng. Kch thc ca cc thanh
ny l kh ln v c dng tetraport.
i vi mu pha 12% Mn (hnh 4c), cc thanh c xu hng mc theo phng song song.
Mt s v tr c dng cu trc ci rng lc. Ti cc u thanh, cu trc lc gic vi kch thc
Nhng
_____________________________________________________________________________________
Zn0.94Mn0.06O - MH 300K
0.016
0.08
0.06
400oC
0.014
0.012
550oC
0.04
650oC
1:
2:
3:
4:
0.02
0.010
M (emu/g)
Moment (emu/g)
800oC
0
-0.02
-0.04
2
0.008
1
0.006
0.004
-0.06
-0.08
-1.5 104
Zn0.94Mn0.06O
Zn0.91Mn0.09O
Zn0.88Mn0.12O
Zn0.85Mn0.15O
0.002
-1 104
-5000
0
5000
Magnetic Field (Oe)
1 104
1.5 104
100
200
300
400
T (K)
Hnh 5: T ph thuc vo t trng

300K i vi mu Zn0.94Mn0.06O ti cc nhit
khc nhau.
Hnh 6: ng ph thuc nhit ca cc mu

mn Zn1-xMnxO 6500C c o t trng
500 Gauss.
v mt kh u nhau ti cc v tr trn . Khi iu kin cng ngh vn gi nguyn th cc kt

qu thu c c tnh lp li kh cao.
Khi thnh phn Mn rt ln ln n 15% (hnh 4d) th cu trc dng chy lc gic xut hin
rt u.
Khi cc mu c ch to cng mt iu kin nh nhau nhng cu trc ca chng li ph
thuc rt nhiu vo nng Mn pha tp. Vi cng mt thnh phn mu, hai iu kin ch to
mu khc nhau: phng php gm v phng php bc bay nhit th kt qu thu c kh l l
th v chng c cu trc hon ton khc nhau. V th iu kin cng ngh nh hng rt nhiu
n s hnh thnh cc tnh cht ca h vt liu.
Khi nghin cu tnh cht t ca c hai loi vt liu mng v vt liu khi th kt qu ca h
vt liu khi tt hn. V vy y chng ti a ra cc kt qu t tnh ca h mu mng Zn1xMnxO.
Hnh 5 l th ca t ph thuc vo t trng 300K i vi mu mng Zn0.94Mn0.06O
ti cc nhit khc nhau. T c ch ra l c tnh thun t hoc st t yu nhit
phng. Gi tr cao nht ca t t 0.07 emu/g vi mu c 8000C. Ti gi tr cc i ca
t trng nhng gi tr t vn cha t bo ho chng t chng mang tnh thun t.
Cc ng t ph thuc vo nhit M(T) c o t trng 500 Gauss vi cc mu
c nhit 6500C ca h mu mng Zn1-xMnxO c a ra trn hnh 6. vng nhit
thp, t c xu hng gim kh mnh khi nhit tng. Khi tng nng Mn pha tp, cc
ng M(T) dch dn v pha vng c nhit cao hn. iu cho thy nhit Curie ca cc
mu s tng khi thnh phn Mn tng. Bng cch xc nh thng thng, nhit Curie ca cc
mu tng t 77 K n 102 K khi x tng.
4. Kt lun
H vt liu bn dn t pha long ZnO pha tp Mn c ch to thnh cng c hai dng
khi v mng. iu kin cng ngh cng nh nng pha tp Mn nh hng rt nhiu n tnh
cht cu trc v tnh cht t ca chng. Vi h mu khi, cu trc ht kch thc kh ln c
micromet c hnh thnh. Vi h mu mng, cc dng ng, dy, rng lc cng nh dng chy
c kch thc c hng trm nanomet c to ra. Cc tnh cht t ca h mu cho thy t bo
ho, t d, lc khng t tng theo nhit . Tt c cc mu pha tp Mn u c tnh cht thun
t v st t yu.
Advances
_____________________________________________________________________________________
Li cm n : Cc tc gi chn thnh cm n ti 406306 v ti 405506 h tr kinh ph

thc hin nghin cu ny.
Ti liu tham kho
1. A. I. Savchuk, V. I. Fediv, S. A. Savchuk, A. Perrone, Superlattices and Microstructures 38
(2005) 421.
2. H. Schmidt, M. Diaconu, H. Hochmuth, M. Lorenz, A. Setzer, P. Esquinazi, A.Poppl, D.
Spemann, K. W. Nielsen, R. Gross, G. Wagner, M. Grundmann, Superlattices and
Microstructures 39 (2006) 334.
3. A. K. Pradhan, D. Hunter, Kai Zhang, J. B. Dadson, S. Mohanty, T. M. Williams, K. Lord, R.
R. Rakhimov, U. N. Roy, Y. Cui, A. Burger, Jun Zhang, D. J. Sellmyer, Applied Surface
Science 252 (2005) 1628.
4. A. Che Mofor, A. El-Shaer, A. Bakin, H. H. Wehmann, H. Ahlers, U. Siegner, S. Sievers, M.
Albrecht, W. Schoch, N. Izyumskaya, V. Avrutin, J. Stoemenos, A. Waag, Superlattices and
Microstructures 39 (2006) 381.
5. J. Zhang, R. Skomski, D. J. Sellmyer, J. Appl. Phys. 97 (2005) 10D303.
Nhng
_____________________________________________________________________________________
THE SYNTHESES BY CHEMICAL PROCESS AND THE OPTICAL PROPERTY OF

THE POLYMER-CAPPED CU DOPED ZNS NANOCRYSTALLINE THIN FILMS
Tran Minh Thi a, Nguyen Minh Vuong b,
Le Thi Thu Huyen c, Pham Van Hai a, Vu Quoc Trung d
a)
Faculty of Physics, Hanoi University of Education, Vietnam

b)
Quynhon University, Vietnam
c)
Faculty of Physics, Le Quy Don Technical University, Vietnam
d)
Faculty of Chemistry, Hanoi University of Education, Vietnam
E-mail: tranminhthivl@gmail.com
Abstract: The polyvinylacohol (PVA)-capped Cu doped ZnS nanocrystalline thin films with Cu
concentration of 0.2 at% synthesised by wet chemical process and dip-coating method. The PVA
concentration changed from 1g to 4 g /100 ml of zinc acetat and mangan acetat solution.
Transmission electron microscopic image shown nanometer size particles about 5 nm within the
polymer matrix. The X ray spectra showed PVA doesnt affected to the microstructure of
nanomaterials ZnS. The optical propertiers of samples were studied by measuring the absorption
and photoluminescence spectra in the wavelength range from 300 nm to 900 nm at room
temperature. The direct band gap of PVA-capped Cu doped ZnS nanocrystalline thin films
were calculated for different PVA concentration in the samples. The values of direct band gap
achieved to 3.75 eV. The influence of PVA concentration on the optical property of this sample
systems is also discussed in the paper.
Keyword: PVA-capped Cu doped ZnS nanocrystalline thin films, dip-coating.
1. M u
ZnS l vt liu bn dn vng cm thng c rng vng cm ln ( Eg = 3,6 eV nhit
300K i vi mu khi) trong cc hp cht bn dn thuc nhm AIIBIV.
Trong nhng nm gn y, vic nghin cu bn dn c kch thc nano thu ht c s
quan tm ln ca cc nh khoa hc. i vi vt liu nano tinh th ZnS, cc kt qu nghin cu
ch ra nhiu tnh cht quang mi l v c tng cng khi pha tp kim loi chuyn tip. Khi
cc tp cht ny v t hp ca chng vi cc sai hng ring ca mng tinh th hnh thnh cc
tm pht quang khc nhau trong tinh th ZnS. S pht quang ca mu khi ZnS:Cu c th quan
st c 5 vng bc x t vng t ngoi (UV) n vng hng ngoi (IR) 1. Theo cc nghin cu
gn y ca nhm tc gi 2 th ngoi bc x xanh lc, ngi ta cn quan st c bc x ca
ZnS:Cu. Gii thch qu trnh bc x theo s chuyn mc nng lng ca ZnS:Cu ca nhm
tc gi 3. Bc x xanh lc ng vi qu trnh ti hp ca 1 electron b by mc donor nh x
nng vi mt l trng mc tp cht ca Cu. Ngun gc ca bc x c gii thch ph hp
vi nhiu cng b khc 45. Ngoi ra, cu trc v tnh cht quang ca mu ZnS cn chu nhiu
nh hng bi dung mi 6.
Trong bi bo ny chng ti trnh by cc kt qu nghin cu v cu trc, kch thc ht,
tnh cht quang ca mu bt v mu mng ZnS:Cu2+-0.2% bc ph Polymer PVA (Polyvinuyn
alcohol) vi cc hm lng khc nhau trn thy tinh. Vai tr v nh hng ca PVA ti cc
tnh cht ca nano tinh th ZnS:Cu c a ra
2. Thc nghim
2.1.
Ch to h mu bt nano ZnS:Cu
Bt nano ZnS:Cu c ch to bng phng php ha t. Cc dung dch ha cht tinh khit
cao c s dng trong qu trnh ch to: 0,1M dung dch I Zn(CH3COO)2.2H2O, 0,1M dung
Advances
_____________________________________________________________________________________
dch II Cu(CH3COO)2.H2O, 0,1M dung dch III Na2S.9H2O vi dung mi c dng cho dung
dch l H2O. u tin pha dung dch I v II vi t l thch hp nhm to ra cc vt liu ZnS:Cu
vi t l s mol Cu thay th cho Zn l 0,1%; 0,15%; 0,2%; 0,3% v 0,4%.
Cc tnh ton l thuyt cho thy rng c th chn pH = 3.6 to kt ZnS:Cu2+ trong
hn hp dung dch nhng khng to thnh kt ta Zn(OH)2.
Nh t t tng git dung dch III vo hn hp dung dch I v II. Thi gian phn ng ht
dung dch khong 60 pht. Khi cc phn ng s xy ra nh sau:
Zn(CH3COO)2+Na2S = ZnS+2CH3COONa
Cu(CH3COO)2+Na2S = CuS+2CH3COONa
Kt ta thu c ZnS v CuS kt tinh ngay t trong dung dch. Cc kt ta ny c lc
ra bng quay li tm vi tc 2500 vng/pht ri em sy chn khng 80C. Cc sn phm
thu c l h mu bt ZnS:Cu 0,1%; 0,15%; 0,2%; 0,3% v 0,4%.
2.2.
Ch to mu bt ZnS:Cu2+ 0.2% bc ph cc hm lng PVA khc nhau.
Sau khi ch to, h mu bt ZnS:Cu 0,1%; 0,15%; 0,2%; 0,3% v 0,4% c o hunh
quang 300 K trn my ph k HP 340-LP370 dng ngun laser c bc sng 325 nm. Chng
ti nhn thy mu ZnS:Cu 0,2% c cng hunh quang ln nht. d dng nghin cu nh
hng ca hm lng PVA ti hunh quang ca cc ht nano ZnS:Cu, chng ti ch to h mu
ZnS:Cu 0.2% bc ph PVA vi cc hm lng khc nhau
Trc tin trn cc dung dch I v II vi t l thch hp nhm to ra cc ht nano ZnS:Cu
0.2% vi quy trnh ging nh trn. Ha tan ln lt 1g, 2g, 4g PVA vo 100 ml hn hp dung
dch I v II. Gia nhit hn hp trn n khong 80oC cho lng PVA tan ht. Nh t t tng
git dung dch III vo hn hp dung dch I v II. Thi gian phn ng ht dung dch khong 60
pht.
Cc kt ta c lc ra bng my quay li tm vi tc 2500 vng/pht ri em sy chn
khng 80C thu c h mu bt bc ph PVA vi hm lng khc nhau: B-ZnS:Cu-0.2%PVA1, B-ZnS:Cu-0.2%-PVA2, B-ZnS:Cu-0.2%-PVA3, B-ZnS:Cu-0.2%-PVA4.
2.3.
Ch to mu mng ZnS:Cu2+ 0.2% bc ph cc hm lng PVA khc nhau.
Cuong do huynh quang (d.v.t.y)
Quy trnh to hn hp c PVA ging nh trn. Sau , cc mng mng M-ZnS-Cu-0.2%PVA1, M-ZnS-Cu-0.2%-PVA2, M-ZnS-Cu-0.2%-PVA3, M-ZnS-Cu-0.2%-PVA4 c ch to
bng phng php nhng ph thng thng trn thy tinh vi kch thc 22220,25mm3 .
nghin cu nh hng ca PVA ti tnh cht hunh quang v cu trc vi m ca cc
mng mng nano tinh th ZnS:Cu, cc h mu
50000
bt nano ZnS:Cu 0,1%; 0,15%; 0,2%; 0,3%,
45000
B3
0,4%, bt nano B-ZnS:Cu 0.2% bc ph PVA
B2
40000
v cc mu mng M-ZnS:Cu 0.2%-PVA c
B4
35000
o ph hunh quang 300K bng ph k HP
30000
B5
340-LP370 dng bc x ca lazer He-Cd vi
25000
20000
bc sng 325nm, o ph hp th
B1
15000
ULTRAVIOLET SPECTRUM JASCO -V670
10000
cho cc mu mng, phn tch nhiu x
5000
Ronghen (my XD8 Advance Bukerding dng
0
bc x CuK vi = 1,5406 ) v chp nh
-5000
300
400
500
600
700
800
900
hin vi in t truyn qua. T cc ph hp th
Buoc song (nm)
ca cc mng mng, cho php tnh c b
Hnh 1: ph hunh quang ca h mu bt
rng vng cm v kch thc ca cc ht nano
B1, B2, B3, B4, B5 tng ng vi cc mu
trong nn matrix PVA ca cc mu mng
ZnS:Cu c thnh phn 0,1%; 0,15%; 0,2%;
MZnS:Cu-0.2%-PVA.
0,3%, 0,4%
Nhng
_____________________________________________________________________________________
3. Kt qu v tho lun
3.1.
H mu bt nano ZnS:Cu 0,1%; 0,15%; 0,2%; 0,3%, 0,4%
Hnh 1 cho thy ph hunh quang ca h mu B1, B2, B3, B4, B5 tng ng vi cc mu
bt nano ZnS:Cu c cc thnh phn Cu l 0,1%; 0,15%; 0,2%; 0,3%, 0,4% c ch to bng
phng php ho t. Kt qu o hunh quang cho thy mu B3 (ZnS:Cu-0.2%) c cng
hunh quang mnh nht. Cc ph hunh quang trong hnh 1 c dng ging ht cc ph hunh
quang ca cc mu bc ph PVA trong hnh 4. Ph hunh quang ca cc mu c phn tch
bng phng php Gaussian cho thy c cc vch 486 nm v 555 nm. Vch 486 nm c quy
cho s chuyn di ca cc donor nng b by ngay di vng dn xung mc e. Cn vch 555
nm c quy cho s chuyn di mc nng lng t mc donor su xung mc t2 ca Cu2+. Cc
mc by donor ny c hnh thnh do cc khuyt tt, sai hng mng khi pha tp Cu. Hnh 1
cho thy khng c s dch cc nh hunh quang khi tng hm lng Cu
3.2.
Mu bt nano ZnS:Cu-0.2% bc ph hm lng PVA khc nhau.

1000
Theo kt qu o hunh quang trn hnh 1,

chng ti chn hm lng pha tp Cu 0.2%
ch to bt nano bc ph cc hm lng PVA
khc nhau.
Tn Mu
B-ZnS:Cu-0.2%
B-ZnS:Cu-0.2%-PVA2
B-ZnS:Cu-0.2%-PVA4
800
c-ng t-ng i
Bng 1: Kch thc ht tnh

Sherrer
theo cng thc
D (nm)
2.7
2.9
3.2
a B-ZnS:Cu-0.2%
b B-ZnS:Cu-0.2%-PVA2
c B-ZnS:Cu-0.2%-PVA4
900
700
c
600
500
400
300
200
100
20
30
40
50
60
70
2 theta
Hnh 2: Ph nhiu x tia X ca bt tinh th nano BZnS:Cu-0.2%, B-ZnS:Cu-0.2%-PVA2, B-ZnS:Cu0.2%-PVA4

30000
M-ZnS:Cu 0.2%-PVA4
25000
20000
15000
M-ZnS:Cu 0.2%-PVA2
10000
5000
M-ZnS:Cu 0.2%
0
300
400
500
600
700
800
900
1000
Buoc song (nm)
Hnh 3. nh TEM ca mng M-ZnS:Cu0.2%PVA2
Hnh 4: Ph hunh quang ca mng nano MZnS:Cu-0.2%-PVA2, M-ZnS:Cu-0.2%-PVA4, MZnS:Cu-0.2%
Cc mu bt B-ZnS:Cu-0.2%, B-ZnS:Cu-0.2%-PVA2, B-ZnS:Cu-0.2%-PVA4 c phn

tch nhiu x Ronghen nh trong hnh 2
So snh ph Ronghen ca cc mu B-ZnS:Cu-0.2%, B-ZnS:Cu-0.2%-PVA2, B-ZnS:Cu-0.2%PVA4 c th nhn thy rng PVA khng nh hng ti cu trc tinh th ca vt liu nano
ZnS:Cu. Cc mu ch to c kt tinh n pha, ng nht theo cu trc lc gic Wurtzite. y
l mt trong nhng cu trc c trng ca bn dn ZnS.
Kt qu tnh kch thc ht theo cng thc Scherrer nh trong bng 1.
Advances
_____________________________________________________________________________________
Hnh 5: Ph hunh quang ca mng M-ZnS:Cu0.2%-PVA2 phn tch bng phng php Gaussian
Hnh 6: Ph hp th ca mu M-ZnS:Cu-0.2%
bc ph cc PVA theo cc t l khc nhau
Hnh 3 m t cc ht nano c kch thc di 5 nm trong nn polymer ca mu mng MZnS:Cu 0.2%-PVA2. Kt qu tnh kch thc ht t ph Ronghen l kh ph hp vi nh TEM
trong hnh 3
Hnh 4 trnh by ph hunh quang ca cc mu mng tiu biu M-ZnS:Cu-0.2%-PVA2, MZnS:Cu-0.2%-PVA4 v M-ZnS:Cu-0.2% vi hm lng PVA 2g, 4g
Ch rng cc mng c b dy khc nhau do c ch to bng phng php nhng ph
trn thu tinh, do khng so snh c cng hunh quang ca cc mu. Nhng khi
phn tch ph ca cc mu M-ZnS:Cu-0.2%-PVA2 v M-ZnS:Cu-0.2% bng phng php
Gaussian, c th thy rng ph hunh quang ca cc mu u c chng cht ca hai di pht
x chnh c cc nh ti 486 nm, 555 nm v cc di pht x cng yu ti 660nm, 407 nm nh
hnh 5. T gin cc mc nng lng ca tp Cu trong mng tinh th ZnS [3], nh hunh
quang 486 nm c quy bi s chuyn di ca cc mc donor nng di vng dn xung mc
e, cn nh hunh quang 555 nm c quy bi cc chuyn di ca cc mc donor su xung
mc t2 [2] [4]. Cc mc by donor ny c hnh thnh do cc trng thi khuyt tt, sai hng
mng khi pha tp Cu. Cc vch hunh quang 407 nm v 660 nm c gn cho cc chuyn mc
gia cc trang thi b mt hoc mc donor su (c th lin quan n mc khuyt S2-) v mc tp
cht ca Cu2+.
T cc kt qu trn c th thy rng hm lng bc ph PVA khng lm thay i v tr cc
vch hunh quang ca cc ht nano ZnS:Cu-0.2% v cu trc tinh th ca chng
Hnh 6 trnh by ph hp th ca cc mu M-ZnS:Cu-0.2%-PVA1, M-ZnS:Cu-0.2%-PVA2,
M-ZnS:Cu-0.2%-PVA3, M-ZnS:Cu-0.2%-PVA4. Cc ph hp th a v b trong hnh 6 cho thy
b rng b hp th ca cc mu M-ZnS:Cu-0.2%-PVA1 v M-ZnS:Cu-0.2%-PVA2 tng ln so
vi mu khi. Nhng b hp th ca cc mu M-ZnS:Cu-0.2%-PVA3, M-ZnS:Cu-0.2%-PVA4
(ng c v d) c xu hng gim i khi tng hm lng PVA
T hnh 6 c th suy ra cc th biu din s ph thuc ca ( Ah ) 2 vo h cho cc mu
nh sau:
Mi trng vt cht hp th nh sng tun theo nh lut Beer-Lambert:
(1)
I ( ) = .I 0 ( ).e ( ) d
Trong : I 0 ( ) , I ( ) ln lt l cng ca chm tia sng ti v tia sng sau khi i qua
mi trng, ( ) l h s hp th ca vt liu i vi photon c nng lng h , d l dy
ca mu.
Ngi ta thng bin i cng thc (1) thnh dng logarit c s 10 nh sau:
Nhng
_____________________________________________________________________________________
I 0 ( )
I ( )
= ln 10. lg 0
= 2,3. A
(2)
I ( )
I ( )
I ( )
Trong : A = lg 0
c gi l hp th.
I ( )
Hnh 6 cho thy th biu din s ph thuc ca
h s hp th (hay hp th A ) theo bc
sng ca chm nh sng i qua vt cht.
Mi quan h gia h s hp th vi nng
lng ca photon ti c biu din bi phng
trnh sau [7] [8]:
n
K (h Eg ) 2
(3)
=
Hnh 7: S ph thuc ca (Ah)2 vo
h
h ca mu mng M-ZnS:Cu-0.2% bc
Trong K l hng s, E g l nng lng di
ph PVA theo hm lng khc nhau
cm v n l hng s (bng 1) i vi vt liu c
vng cm thng.
T phng trnh (2) v (3) suy ra i vi vt liu c b rng vng cm thng, ta c phng
trnh:
Kd 2
2
( Ah ) =
(h Eg )
(4)
2,3
Hnh 7 biu din s ph thuc ca ( Ah ) 2 vo h ca cc mu M-ZnS:Cu-0.2%-PVA1, MZnS:Cu-0.2%-PVA2, M-ZnS:Cu-0.2%-PVA3, M-ZnS:Cu-0.2%-PVA4. T th ta c th xc
nh nng lng di cm ca cc bn dn c vng cm thng bng cch ngoi suy ng thng
ct trc nng lng ( h ), im ct chnh l gi tr nng lng di cm cn tm. Hnh 7 cho
thy s thay i b rng di cm (Eg) ca mu theo hm lng Polymer PVA khc nhau. B rng
di cm ca cc mu mng M-ZnS:Cu-2% bc ph cc hm lng PVA khc nhau c tnh
nh trong bng 2.
Bn knh ht tinh th trong mng mng ZnS:Mn bc ph PVA c th c tnh thng qua
thay i b rng vng cm ca mu mng i vi bn dn khi ZnS [7] [8] theo mi quan h nh
1,8e 2
h2
E g = E g ( film) E g (bulk ) =
sau:
(5)
r
8r 2
( ).d = ln
me*mh*
Trong : Eg (bulk) = 3.6 (eV), = *
vi me* = 0,34mo , mh* = 0,24mo , mo l khi
*
me + mh
lng electron t do.. Cc kt qu tnh ton bn knh r ca cc ht nano trong cc mng mng c
cc hm lng polyme khc nhau nh trong bng 2
Bng 2: B rng vng cm v kch thc ht nano i vi cc mu mng
Mu
M-ZnS:Cu-0.2%-PVA1
M-ZnS:Cu-0.2%-PVA2
M-ZnS:Cu-0.2%-PVA3
M-ZnS:Cu-0.2%-PVA4
Eg(eV)
3.75
3.72
3.61
3.57
Kch thc ht r(nm)

4.3
4.8
16.5
Nhn xt: Cc mu mng M-ZnS:Cu-0.2%-PVA1, M-ZnS:Cu-0.2%-PVA2 c b rng vng

cm ln hn hn b rng vng cm ca bn dn khi ZnS. Nhng hm lng PVA cng tng th
b rng vng cm cng gim v km theo s tng ln ca kch thc ht ZnS trong nn PVA.
Nguyn nhn ca iu ny c gii thch nh sau: khi tng hm lng PVA trong qu trnh ch
to, nht ca hn hp dung dch c PVA tng ln, gy nn nh hng s khuch tn cc ht
nano ZnS:Cu vo nn PVA, lm tng cng s to m v lin kt cc ht. Do vy kch thc
Advances
_____________________________________________________________________________________
cc ht tng ln. hn ch s tng kch thc ht, cn phi la chn ch rung siu m v
phng php thch hp to mng mng.
4.
Kt lun
Chng ti ch to thnh cng h mu bt tinh th nano ZnS:Cu theo nng tp Cu khc

nhau v chn ra c nng Cu ti u 0.2% ch to thnh cng h mu bt ZnS:Cu-0.2%
bc ph PVA bng phng php ha t. Cc mu c cu trc Wurtzite v kch thc ht ca
cc mu khong 5nm. T chng ti a ra quy trnh ch to h mu mng nano MZnS:Cu-0.2% bc ph cc hm lng PVA khc nhau trn thy tinh. Cc kt qu nghin cu
tnh cht hunh quang, vi cu trc, ph hp th cho thy polymer PVA c tc dng l lp bo v,
che chn cho cc ht nano ZnS:Cu nhng khng nh hng ti cu trc tinh th ca vt liu v
bc sng pht x ca cc ht . Cc tnh cht hunh quang, nh hng ca b rng vng cm
v kch thc ht nano ca h mu mng M-ZnS:Cu-0.2%-PVA cng c kho st. Cc kt qu
nghin cu cho thy tim nng ng dng ca h vt liu ny trong cc thit b pht quang
Li cm n : Bi bo c hon thnh c s h tr ca ti cp nghin cu khoa hc v cng

ngh cp B m s 17TC-08-12
Ti liu tham kho
1. Ageeth A. Bol, Joke Ferwerda, Jaap A. Bergweff, Anderies Meijerink, Luminescennce of
nanocrytaline ZnS:Cu2+, Jounal of Luminescence 99 (2000) 325-334.
2. Atsushi Ishizumi, C.W.White, Yoshihiko Kanemitsu, Space-resolved photoluminescence of ZnS: Cu,
Al nanocrytals fabricated by sequential ion imlantaion, Applied physics Letters, V. 84, N. 13, 2004.
3. P. Peka, H. J. Schulz, Empirical one-electron model of optical transition in Cu-doped ZnS and CdS,
Physica B (1994) 57-65.
4. Ping Yang, Mengkai Lu, Dong Xu, Mei Pan, Guangjun Zhou, The photoluCuiescence characteristics
of ZnS nano crytal doped with M3+ (M=In, Ga, Al), Materials Research Bulletin 36 (2001), 13011306.
5. Mingwen Wang, Kingdong Sun, Xuefeng Fu, Chunsheng Liao Chinhua Yan, Synthesis and optical
properties of ZnS: Cu(II) nanoparticles, Solid State Communication 115 (2000) 492-496.
6. Sangwook Lee, Daegwon Song, Dongjin Kim, Jongwon Lee, Seotai Kim, In Yong Park,
Yong Dae Choi, Effects of synthesis temperature on patricle size/shape and photoluminescence
charateristcs of ZnS: Cu nanocrystals, (2003), 343-345.
7. P.K. Ghosh, S. Jana, S. Nandy, K.K. Chattopadhyay, Size-dependent optical and dielectric
properties of nanocrystalline ZnS thin films synthesizes via rf-magnetron sputtering
technique, Matterials Research Bulletin 42 (2007) 505-514.
8. R.Maity, U.N. Maiti, M.K. Mitra, K.K. Chattopadhyay, Synthesis and optical
characterization of polymer-capped nanocrystalline ZnS thin films by chemical process,
Physica E33(2006)104109.
Nhng
_____________________________________________________________________________________
CH TO MNG ZnO:Ti NNG CAO DN IN CA MNG

H Vn Bnh, L V Tun Hng, Nguyn Th Ngc Nhin, Hunh Thnh t,
Dng i Phng, L Vn Hiu.
Trng H KH T nhin, HQG Tp.HCM.
E-mail: lthung@phys.hcmuns.edu.vn
Tm tt: Mng ZnO:Ti c ch to trn thy tinh t cc bia gm ZnO pha tp vi nng
Ti khc nhau v bng phng php phn x magnetron DC. Kt qu thc nghim cho thy y l
cc mng trong sut dn in vi truyn qua kh cao. Vi nng pha tp Ti thch hp
(~1.5% Ti), ta c th lm gia tng dn in ca mng. truyn qua ca mng v rng
vng cm Eg ca mng c th xc nh bng phng php o truyn qua UV-Vis, cu trc mng
c xc nh bng nhiu x tia X, dn in ca mng c xc nh bng phng php 4 u
d, v mp m b mt ca mng uc xc nh bng phng php o AFM.
1. Gii thiu
Mng ZnO loi n c xem l loi mng oxide dn in trong sut (TCO) v thng c
dng thay th mng ITO. Mng ZnO c rng vng cm ln khong 3.3 eV, in tr ca
mng kh thp khong 10-6m, h s hp th ca mng trong vng kh kin khong 5x103 cm-1
[1]. Tuy vy, mng ZnO pha tp vn cn l lnh vc nghin cu mi m v cn ang tip tc
pht trin. Cc mng pha tp thng tp trung vo cc nguyn t pha tp nhm IIIA nh l Al,
Ga, In, v cc nguyn t nhm IA nh Li, Ni.
Trong bo co ny chng ti ch trng vo nguyn t pha tp Ti. Do khi pha tp Ti vo
mng ZnO, ion Ti4+ s thay th cho ion Zn2+ dn n lm gia tng nng ht ti t do trong
mng v tnh cht dn in ca mng c ci thin nhiu hn. Ngoi ra, mng ZnO:Ti c to
trn thu tinh c nhiu ng dng trong t bo quang in, cht ln quang xanh, cc loi cm
bin kh, mng hnh hin th phng
2. Thc nghim
Bia gm c ch to t bt ZnO v TiO2, trn vi cc t l khc nhau, sau nghin trong
4 h vi nc ct, v c p trong khun vung cnh 8,5cm vi p lc 400 kg/cm2. Mu p
c nung nhit 13500C nhit trong 3 gi, thiu kt li v cho sn phm bia gm ZnO
TiO2 (ZnO:Ti). Mu bia thu c c nn cht kh tt khong 91% t yu cu ch to
mng ( nn cht ca bia l t s gia khi lng ring ca bia vi khi lng ring ca vt
liu khi).
thu tinh c x l bng axit HF 10% loi b cc cht bn, sau c ra qua vi
axeton v nc ct, sy kh vi khng kh. X l b mt bng plasma phng in kh.
Chng ti to cc mng ZnO:Ti trn thy tinh bng phng php phn x magnetron d.c
t bia gm ZnO:Ti, vi cng cc thng s ch to ti u. Tnh cht quang ca mng c kho
st bng phng php o UV-VIS, cu trc mng c xc nh bng nhiu x X-Ray, mp
m b mt (RMS) xc nh bng phng php AFM, dn in ca mng c xc nh bng
phng php bn u d, b dy ca mng c o bng phng php stylus.
3. Kt qu v bn lun
3.1. Kho st tnh cht quang ca mng
Cc mng ZnO:Ti c ch to vi cc thng s nh nhau. p sut lm vic P =10-3 torr;
dng phn x: I = 0.2A; khong cch gia bia v : h = 5cm; kh Ar =100%, thi gian phn x t
= 21pht; hiu in th U = 310-350 V, nhit TS = 1700C.
Advances
_____________________________________________________________________________________
3%Ti
100
1.5%Ti
ZnO
80
Do truyen qua(%)
2.5%Ti
2%Ti
60
1%Ti
40
20
-20
200
400
600
800
1000
1200
Buoc song(nm)
Hnh 1: Ph truyn qua ca cc mng ZnO:Ti vi nng pha tp 1% wt TiO2, 1.5% wt TiO2,
2% wt TiO2, 2.5% wt TiO2, 3% wt TiO2.
Hnh 1 l ph truyn qua ca cc mng kh cao gn 90% trong vng kh kin v hng ngoi
gn. Cc mng c ch to u trong sut.
Chng ti dng phng php o b dy Stylus xc nh b dy ca cc mng, ng
thi dng phng php Swanepole xc nh chit sut cng nh b dy ca chng nh trnh
by trong bng 1.
Bng 1: dy, chit sut v rng vng cm ca cc mng ZnO:Ti
ZnO
ZnO:Ti
ZnO:Ti
ZnO:Ti
0%Ti
1%Ti
1.5%Ti
2%Ti
2.5%
3%Ti
dy mng d(nm)
700
750
740
700
720
600
Chit sut mng (n)
1.79
1.81
1.89
1.85
1.87
1.78
Nng lng vng cm Eg(eV)
3.34
3.33
3.30
3.31
3.34
3.40
Mu
ZnO:Ti ZnO:Ti
T bng 1, ta nhn thy rng vng cm ca mng ZnO:Ti (1.5%) l nh nht, hin tng
ny cc nh khoa hc gi l dch chuyn . Theo tc gi Jeng-Lin Chung [8], do s khc bit v
cu hnh in t gia Ti [Ar]3d24s2 v Zn [Ar]3d104s2, nguyn t Ti thay th Zn trong mng tinh
th, lm cho cc in t lin kt yu vi nguyn t, lm gia tng mt electron t do, dn n
vng nng lng b pha tp v m rng ra, tin ti b vng dn.
3.2. Kho st cu trc mng ZnO:Ti
Chng ti tin hnh chp nhiu x tia X cc mu to ra trn, kt qu c trnh by
trong hnh 2.
Nhng
_____________________________________________________________________________________
Qua ph nhiu x tia X trn hnh 2, ta nhn thy cu trc tt c cc mng u nh hng
theo mt mng (002) v c cu trc hexagonal wurtzite v khng xut hin nh ph ca TiO2
hay Zn2TiO4 . iu ny chng t nguyn t Ti c thay th hon ton nguyn t Zn trong
mng nguyn t. Tuy vy nu nng Ti trong mng qu cao, c th lm gim cu trc ca
mng. Kt qu thu c cng ph hp vi cc kt qu nghin cu ca tc gi J.J.Lu [17].
Ta c th nhn thy s thay i cu trc mng mt cch trc quan hn qua php o mp
m b mt AFM nh trong hnh 3 v hnh 4:
Hnh 2: Ph nhiu x tia X ca mng ZnO v cc mng ZnO:Ti, phn x cng iu kin trn
Hnh 3: nh AFM ca mng ZnO - mp m b

mt khong 9.7 nm
Hnh 4: nh AFM ca mng ZnO: Ti (3%) -

mp m b mt khong 4.5 nm.
T cc hnh 3 v hnh 4, ta nhn thy mp m b mt cng nh kch thc ht ca mng pha

tp (3%) gim r rt khi so vi mng ZnO khng pha tp. iu ny cng kh ph hp vi kt
qu chp nhiu x tia X trnh by trn.
3.3. Kho st dn in ca mng hp cht ZnO:Ti
Vi cc mng ZnO v ZnO:Ti ch to trn, chng ti kho st in tr sut ca chng bng
phng php 4 u d, kt qu thu c trnh by trong bng 2 di y:
Bng 2: Bng s liu in tr sut v dy cc mng ch to
Mu
dy (nm)
in tr sut cmx10-3
ZnO
0%Ti
700
10.04
ZnO:Ti
1%
750
8.03
ZnO:Ti
1.5%
740
3.15
ZnO:Ti
2%
700
5.88
ZnO:Ti
2.5%
720
7.3
ZnO:Ti
3%
600
30.35
Kt qu trong bng 2 cho thy in tr sut ca mng ZnO:Ti nh nht khi nng pha tp
Ti l 1,5%, do nguyn t Ti thay th v tr nguyn t Zn trong cu trc mng lm gia tng s
electron t do v do dn in ca mng c ci thin. Tuy nhin vi nng pha tp Ti
cao hn 1,5% th in tr sut ca mng li c khuynh hng gia tng ( dn in gim) do s
nguyn t Ti d tha (khng kt mng) gy cn tr s pht trin tinh th v dn in.
Advances
_____________________________________________________________________________________
Kt qu ny cng kh ph hp vi k qu ca cc tc gi khc, chng hn nh tc gi YangMing Lu [9], khi ch to mng ZnO:Ti bng phng php phn x magnetron ng thi (cosputtering), mng dn in tt nht khi Ti pha tp 2.5% l 3.78x10-2 cm. Hay tc gi J.J. Lu
[25], ch to bng phng php phn x r.f v d.c, kt qu thu c l mng dn in tt nht l
3.82x10-3cm vi nng Ti pha tp l 1.3%.
4. Kt lun
Sau qu trnh thc nghim ch to mng ZnO:Ti dn in trong sut t bia gm t to, chng
ti nhn thy:
- Cc mng ZnO:Ti u trong sut, c truyn qua kh cao trong vng kh kin v hng
ngoi gn khong 90%. Vi nng pha tp Ti l 1.5%, rng vng cm ca mng gim
xung cn 3.3 eV.
- Cc mng u c cu trc hexagonal wurtzite, nh hng mnh (002). Khi nng tp Ti gia
tng, cu trc tinh th s gim dn.
- Do s thay th Ti4+ cho Zn2+ trong mng lm gia tng cc ht ti t do, cc mng pha tp c
nng thch hp ci thin ng k tnh cht dn in ca mng. C th trong nghin cu
ny, mng ZnO:Ti vi nng Ti l 1.5% l thch hp nht.
Cc kt qu thu c kh ph hp vi cc cng trnh nghin cu nc ngoi, n c th lm
c s chng ti tip tc nghin cu cc tnh cht dn in ca mng ZnO pha tap bn dn loi
n v loi p.
Ti liu tham kho
1. S. Goldsmith, 2006, Filtered vacuum are deposition of undoped and doped ZnO thin films:
Electrical, optical, and structural properties, Surface and Coatings Technology 201, pp
3993-3999.
3. Da Young Yang, 2008, Properties of MgxZn1-xO thin films sputtered in different gases,
Applied Surface Sience 254, 2146-2149.
4. Wen Chen, 2007, Influence of doping concentration on the properties of ZnO:Mn thin films
by sol-gel method, Vacuum 81, p.894-898.
5. Hu Jie-Jin, 2004, Unidirectional variation of lattice constants of Al-n codoped ZnO films
by RF magnetron sputtering, Applied Surface Science 254, p.2207-2210.
6. L. El Mir, 2007, Preparation and characterization of n type conductive (Al, Co) co-doped
ZnO thin films deposited by sputtering from aerogel nanopowders, Applied Surface Science
254, p.570-573.
7. A. Mtsui, 2004, Thermal stability of electrical resistance of
(ZnO:Ga,Y)/(ZnO:Ga)/(ZnO:Ga,Y) multilayers for electrically heated windows, Vacuum
74, p.747-751.
8. Loren Wellington Rieth, 2001, Sputter deposition of ZnO thin films, lun vn tin s
trng i Hc Florida.
9. Jeng-Lin Chung, 2008, The influence of titanium on the properties of zinc oxide films
deposited by radio frequency magnetron sputtering, Applied Surface Science 254, pp 26152620.
10. Yang-Ming Lu, 2004, Improving the conductance of ZnO thin films by doping with Ti,
Thin Solid Films 447-448, pp 56-60.
11. H. Takikawa, K. Kimura, R. Miyano, 2000, Thin Solid Films 377-378, pp 74
12. R. Miyano, K. Kimura, K. Izumi, H. Takikawa, 2000, Vacuum 59, 159.
13. X.L. Xu, S.P. Lau, J.S.Chen, G.Y. Chen, B.K. Tay, 2001, Growth 223, 201.
14. Y.G. Wang, S.P. Lau, H.W. Lee, S.F. Yu, B.K. Tay, X.H. Zhang, K.Y. Tse, H.H. Hng, 2001,
J. Appl. Phys. 94 1597.
15. T. David, S. Goldsmith, R.L. Boxman, 2004, Thin Solid Films 447448, pp 61.
Nhng
_____________________________________________________________________________________
16. H.W. Lee, S.P. Lau, Y.G.Wang, B.K. Tay, H.H. Hng, 2004, Thin Solid Films 458, pp 15.
17. T. David, S. Goldsmith, R.L. Boxman, J. Phys. D: Appl. Phys. 38 (2005), pp 2407.
18. J.J Lu, 2007, Conductivity enhancement and semiconductor metal transition in Ti-doped
ZnO films, Optical Materials 29, pp 1548-1552
19. Su-Shia Lin, 2005, The effect of thickness on the properties of Ti-doped ZnO films by
simultaneous r.f. and d.c. magnetron sputtering, Surface and Coatings Technology, 190, pp
372-377.
Advances
_____________________________________________________________________________________
CH TO V TNH CHT QUANG CA TINH TH PHOTONIC KIU OPAL

Phm Thi Cng a, Phm Thu Linh b, Phm Thu Nga b, Nguyn Nh t c
C. Barthou d, C.Vion d, P.Benalloul d, A. Matr ed
a)
Trng i hc S phm, i hc Thi Nguyn, Vit Nam

Vin Khoa hc vt liu, Vin Khoa hc v Cng ngh Vit Nam, H Ni, Vit Nam
c)
Vin Vt l, Vin Khoa hc v Cng ngh Vit Nam, H Ni, Vit Nam
Institut des Nanosciences de Paris, UMR-CNRS 7588, Universits Pierre et Marie Curie
et Denis Diderot, F-75015 Paris, France
b)
d)
E-mail: ptcuong_phys@yahoo.com
Tm tt:Trong bo co ny, chng ti trnh by kt qu ch to cc tinh th photonic ba chiu
(3D) t cc ht cu silica (SiO2), gi l tinh th opal, bng phng php i lu t tp hp v tnh
cht quang ca chng. Chng ti kho st cc thng s (nng cc ht cu silica trong dung
mi, nhit bay hi dung mi) nh hng n dy v cht lng tinh th, nh hng ca x
l nhit n c trng cu trc v tnh cht quang ca tinh th. K thut chp nh knh hin vi
in t qut (SEM) v php o ph phn x phn gii theo gc (t 5o, 20o n 70o) c s dng
kho st c trng cu trc v tnh cht quang ca tinh th.
T kho: Tinh th photonic, opal, ht cu silica, tnh cht quang.
1. M u
Tinh th photonic (PC) l mt cu trc khng gian tun hon ca cc lp vt liu vi hng
s in mi khc nhau sp xp lun phin nhau, c chit sut thay i tun hon trn mt thang
chiu di c th so snh c vi bc sng trong vng hot ng ca n. Trong PC tn ti mt
vng cm quang (PBG), do c th kim sot s lan truyn nh sng trong n[1]. Cc tinh th
photonic kiu opal c ch to bng phng php t tp hp t cc ht cu n phn tn
(monodisperse) c coi l c nhiu trin vng ng dng trong s cc PC 3D[2] Tuy nhin,
phng php ny c hn ch c bn v tt yu l trong qu trnh to tinh th thng xut hin cc
kiu khuyt tt khc nhau [3]. Gim nng khuyt tt xut hin trong qu trnh to tinh th opal
khi ch cc thng s nh hng n cht lng kt tinh ca tinh th l hng quan tm ca nhiu
nhm nghin cu trn th gii [4],[5]. X l nhit c th lm thay i cc thng s cu trc v
tnh cht quang ca tinh th opal. V d nh, lm dch chuyn cc cc i phn x v pha bc
sng ngn khi tinh th c nung nhit cao, dn n s dch chuyn PBG[6].
Trong bi ny, chng ti s dng phng php i lu t tp hp ch to tinh th
opal t dung dch th huyn ph ca cc ht cu silica [7]. Chng ti kho st nh hng ca nng
cc ht cu silica trong dung dch n dy ca tinh th, nhit bay hi dung mi n cht
lng kt tinh ca cc ht cu silica. Chng ti cng bo co nh hng ca x l nhit (t 300 oC
n 1000 oC) n c trng cu trc v tnh cht quang ca opal. K thut SEM v php o ph
phn x c s dng nghin cu c trng cu trc v tnh cht quang ca tinh th opal.
2. Thc nghim
Cc mu opal c to t cc ht cu silica n phn tn c ng knh khong 300 nm (
lch chun so vi gi tr trung bnh c lng qua nh SEM khong 2%), trn thu tinh. Cc
v dng c thu tinh c lm sch bng cch ngm trong dung dch axt chromic-sulfuric khong
3 gi, sau ra sch bng nc ct nhiu ln, ri rung siu m trong cn nguyn cht v lm kh
trong khng kh.
Hnh 1 l b tr thc nghim phng php i lu t tp hp, thu tinh c t nghing
gc 20o so vi phng thng ng trong mt cc nh cha cc ht cu silica trong cn nguyn
Nhng
_____________________________________________________________________________________
cht (dung dch th huyn ph). To mt gradient nhit dc theo chiu thng ng trong dung
dch th huyn ph. Hnh 2 m t nguyn l i lu t tp hp, cc ht cu c chuyn v pha
mt trc bng mt dng chy i lu, s bay hi ca dung mi, tc dng ca cc lc mao dn v
lc cng b mt lm cho cc ht cu kt tinh to nn mt cu trc trt t 3D. kho st dy
ca mu opal (s lp tinh th) ph thuc vo nng cc ht cu silica trong dung dch, chng ti
to cc mu opal vi nng cc ht cu silica (tnh theo trng lng, wt.-%) ln lt l 0.1,
0.2, 0.5, 1.0, 2.0, 4.0, ..., 12.0 v 15.0 wt.-%.
Th vn
Cc lc mao dn
S bay hi
thu tinh
Th vn
Hnh 1. B tr thc nghim phng php i

lu t tp hp
Hnh 2. M t nguyn l i lu t tp hp
kho st nh hng ca nhit bay hi dung mi n cht lng kt tinh ca cc ht cu

silica, chng ti to 3 lot mu c k hiu l OPS1, OPS2 v OPS3. C 3 lot mu ny u c to
vi cng nng cc ht cu silica l 10.0wt.-%, m tng i ca mi trng xung quanh l
70%, lng dung dch th huyn ph nh nhau cha trong cng mt loi cc. Tuy nhin, gradient
nhit l khc nhau. Nhit ti y v trn mt thong dung dch i vi cc mu OPS1, OPS2 v
OPS3 ln lt l 80 oC - 65 oC, 40 oC - 30 oC v 70 oC - 60 oC. Tc bay hi trung bnh ca dung
mi i vi 3 lot mu ln lt l 2.08.10-3 ml.s-1, 0.29.10-3 ml.s-1 v 1.52.10-3 ml.s-1.
Vi mi lot mu trn, chng ti u t 3 thu tinh nghing gc 20o so vi phng thng
ng trong cng mt cc ng dung dch th vn to c ng thi cc mu opal trn c
cht lng tng i nh nhau. Cc mu opal c lm kh bng cch gim nhit bay hi ca
dung mi t t t n nhit v m mi trng xung quanh, sau c lm kh t nhin
trong khng kh khong 5 ngy. Tuy nhin, trong qu trnh lm kh mu, xut hin cc vt rn
nt song song vi hai mp bn ca . Cc vt rn nt l do dung mi (cn) trong khe h gia cc
ht cu bay hi lm xut hin ng sut, c vai tr nh lc mao dn trong qu trnh hnh thnh
mng, ko co mng tinh th. Cc mu opal tip tc c lm kh nhit 150 oC trong mt
ngy, khi cc mnh tinh th nh b bong khi . Chng ti s dng cc mnh tinh th bong
khi c din tch b mt ln hn khong 3 x 10 mm2 (trn cc mnh tinh th ny khng c vt
rn nt) nhit trong mi trng khng kh cc nhit khc nhau (300 oC, 400 oC, ..., 900
o
C, 1000 oC trong 3 gi, tc nng nhit l 1 oC/pht). Cu trc thc ca cc mu opal c
quan st v chp nh bng knh hin vi in t qut TM-1000 Hitachi, Nht. Ph phn x di
nh sng trng c ghi theo cc gc ti khc nhau ca chm tia ti trn mt (111) ca mu (xem
hnh 3). Cc gc ti v phn x thay i t 20 ti 70 c thc hin trn thit b o vi n
wonfram. Khi gc ti = 0, vt sng trn ca chm tia ti mt mu c ng knh 2 mm. Khi
gc ti > 0, vt sng ca chm tia ti mt mu c dng elip v khi = 70, cc ng knh
ca elip l d1 = 2 mm v d2 = 5 mm. Tt c cc ph u c chun vi ph n. Ph phn x
cng c o trn my quang ph UV-VIS-NIR V-670 Jasco, Nht, nhng ch vi gc ti c nh
= 5. Thit b phn x gng SLM-736 ca V-670 c thit k o h s phn x tng i
ca mu khi s dng nh sng phn x t gng phng c trng mt mng nhm mng tc dng
nh mt vt so snh. Chm tia ti mu l chm song song, vt sng ca chm ti trn mt mu c
dng hnh ch nht vi din tch ~ 3 x 5 mm2. Ph phn x thu c trn mu cn o l ph
c chun vi ph ca v vt so snh.
Advances
_____________________________________________________________________________________
180
dy ca mu (m)
160
Thc nghim
Kh p tuyn tnh d liu
140
120
100
80
60
40
20
0
10
12
14
16
Nng c c ht cu silica (wt.-%)
Hnh 3. Nguyn tc o
ph phn x.
Hnh 4. nh SEM mt s mu opal c

dy khc nhau.
Hnh 5. dy mu
ph thuc nng cc
ht cu silica.
3. Kt qu v tho lun
Hnh 4 l nh SEM mt s mu opal c dy khc nhau. Hnh 5 l th biu din dy
mu (s lp tinh th) ph thuc vo nng cc ht cu silica trong dung dch, cc hnh vung
mu en l gi tr thc nghim dy mu tng ng vi cc gi tr khc nhau ca nng cc
ht cu silica. dy ca mu ph thuc gn nh tuyn tnh vo nng cc ht cu silica trong
dung dch. V vy, c th to c cc mng opal c dy khc nhau khi thay i nng cc
ht cu silica. Tuy nhin, kim sot hon ton chnh xc dy ca mu l rt kh.
Hnh 6 l ph phn x (cng chun ho) ca cc mu opal ban u v ti cc nhit khc
nhau, c o ti gc ti 5o cho thy cc i phn x dch chuyn v pha bc sng ngn khi nhit
tng. c trng quan trng nht ca cc tinh th opal l tn ti PBG Egap tng ng vi
rng ti na cc i (FWHM) E ca di phn x [8]. Gi tr E ca opal OPS2 v OPS3 ti cc
nhit khc nhau c xc nh t ph phn x ca chng khi s dng phn mm LabSpec3
(xem bng 1) cho thy FWHM gim khi nhit tng, chng t cu trc tinh th tr nn trt t
hn.
588
(a)
(b)
opal OPS1
opal OPS2
595
594
(c)
589
800 C
o
700 C
592
1000 C
614
614
633
600 C
651
400 C
677
300 C
900 C
o
800 C
o
700 C
o
600 C
o
500 C
o
400 C
600
600
606
610
621
635
645
500
B- c sng (nm)
601
800 C
602
700 C
619
600 C
634
500 C
650
400 C
300 C
o
30 C
30 C
450 500 550 600 650 700 750 800
600
900 C
300 C
30 C
598
1000 C
C- ng chun ho
C- ng chun ho
C- ng chun ho
1000 C
900 C
opal OPS3
594
598
550 600 650

B- c sng (nm)
700
500
550
600
650
700
750
B- c sng (nm)
Hnh 6. Ph phn x (cng chun ho) ti gc ti 5o ca cc mu opal ban u v

nung ti cc nhit khc nhau: (a) OPS1, (b) OPS2 v (c) OPS3.
Bng 1. FWHM E (meV) ca di phn x ca opal OPS2 v OPS3.
Mu opal
OPS2
OPS3
30 C
224
195
300 C
205
188
Nhit nung (oC)

400 C 500oC 600oC 700oC
204
204
203
199
180
183
185
186
o
800oC 900oC 1000oC

197
190
184
183
169
168
Do vng cm quang ca tinh th opal l khng ton ton, nh sng c php truyn theo
mt s hng nht nh v b cm truyn i vi mt s hng khc. Tht vy, chm nh sng
ti mt (111) ca tinh th opal s b phn x trn h mt phng (111) ca mng fcc tng ng
vi nh lut phn x Bragg:
Nhng
_____________________________________________________________________________________
ma x
2 2
2
= 2 D neff
sin 2
3
(1)
trong D l ng knh ca cc ht cu silica, l gc ti so vi php tuyn ca mt (111) v

neff l chit sut hiu dng ca opal c xc nh theo cng thc:
neff = f sphere + (1 f ) air
(2)
v f l h s lp y (f = 0.74 i vi cu trc xp cht).
(a) 3.0
70
5.0
(b) 4.5
OPS1 Ban u
2.0
o
60
1.5
o
50
1.0
40
0.5
0.0
400
(c)
OPS1 nung t i 1000 C
70
4.0
Hs phn x (%)
Hs phn x (%)
2.5
30
20
450
500
550
600
650
B- c sng (nm)
700
750
800
3.5
3.0
2.5
60
2.0
o
40 30
20
50
1.5
1.0
0.5
0.0
400
450
500
550
600
650
B- c sng (nm)
700
750
800
Hnh 7. Ph phn x phn gii theo gc ca opal OPS1: (a) opal ban u v (b) nhit 1000 oC. (c)
th khp thc nghim vi nh lut Bragg ca opal nhit ti 1000 oC, D = 260 nm v neff = 1.387.
Hnh 7 (a, b) l ph phn x phn gii theo gc ca opal OPS1 ban u v ti 1000 oC. Hnh
7 (c) l th khp cc gi tr thc nghim max vi nh lut Bragg (1) ca opal OPS1 nhit ti
1000 oC, cho thy s ph hp gia cc kt qu thc nghim vi nh lut Bragg. Kt qu khp cc
gi tr thc nghim vi nh lut Bragg ca tng mu opal OPS1 ti cc nhit khc nhau cho
php suy ra c ng knh trung bnh D ca cc ht cu silica v chit sut hiu dng neff ca
opal tng ng. S dng biu thc (2) tnh c chit sut ca silica. Gi tr ng knh cc ht
cu silica D, chit sut hiu dng ca opal neff, chit sut ca silica nsilica c thng k trong bng
2. ng knh cc ht cu silica gim, chit sut hiu dng ca opal v chit sut silica tng khi
nhit nung tng. Cc ht cu silica xp l do c to nn t cc ht nano silic dioxit (-SiO2
nanoparticles) [6]. Nguyn nhn s gim ng knh cc ht cu v tng chit sut silica khi x l
nhit cao l do cc ht -SiO2 thm nhp vo nhau chim cc khong trng khng kh gia
chng.
Hnh 6 cho thy ph phn x ca cc opal ban u ( nhit phng ~ 30 oC) c dng bt i xng,
ph phn x ca opal OPS3 s bt i xng t hn. iu ny chng t c s a kt tinh khi hnh thnh
mng tinh th v t l sai hng sp xp cc ht cu l ln [10],[11]. Ngoi ra, v mt l thuyt, cc ht cu
rn dng khng tng tc lun lun c xu hng kt tinh to nn cu trc c dng xp cht fcc. Tuy
nhin, do s khc nhau v nng lng t do gia cu trc xp cht fcc v cu trc xp cht hcp cho mi ht
cu ch vo khong 10-3 kB, nn vn c v tr cc ht cu kt tinh to nn cu trc kiu mng lc gic xp
cht hcp [12,13]. Hnh 8 (a, c v e) l nh SEM mt (111) ca 3 mu opal ban u cho thy r iu ny. Tuy
nhin, nng khuyt tt ca hai loi mu sau gim ng k, trong opal OPS3 ban u c cu trc trt t
tng i tt hn. C th kt lun thng s ch to mu opal OPS3 l ph hp to c tinh th opal c
cu trc kiu mng fcc tng i trt t, nng khuyt tt thp. Vi iu kin nh vy s duy tr tc
bay hi ca dung mi n nh vo khong 1.52.10-3 ml.s-1. T , c th hy vng gn t c cn bng
gia s lng ng cc ht cu v s chuyn ng i lu ca dng dung dch, a cc ht cu silica n
vng mt khum gia dung dch v vi nng n nh. Khi , cc ht cu silica s bm trn mt to
thnh tng lp tinh th c cu trc kiu mng fcc tng i trt t.
T kt qu nh SEM v ph phn x c th nh gi c cht lng ba lot mu ch to v
nh hng ca x l nhit n c trng cu trc v tnh cht quang ca tinh th opal.
Vi c ba lot mu nhit 800 oC ph phn x ca chng (xem hnh 6) u tr nn c dng
i xng hn. Hnh 8 (b, d v f) l nh SEM ca cc mu nhit ti 800 oC cho thy cu trc ca
cc opal tr nn trt t v t khuyt tt hn so vi opal ban u, nht l i vi mu OPS3 trn
mt din tch b mt khong 15 x 18 m2 ch c mt vi khuyt tt. iu ny c th l do nhit
Advances
_____________________________________________________________________________________
Bng 2. ng knh cc ht cu silica, chit sut hiu dng ca opal v chit sut ca silica ti cc nhit
khc nhau
Nhit nung
D (nm)
neff
nsilica
30oC 300oC 400oC 600oC

299
298
295
280
1.326 1.326 1.325 1.347
1,423 1,423 1,422 1,449
(a)
(c)
(b)
(d)
700oC 800oC 900oC

279
271
270
1.349 1.357 1.370
1,452 1,462 1,478
1000oC
260
1.387
1,499
(e)
(f)
Hnh 8. nh SEM mt (111) cc mu opal: (a) OPS1 ban u, (b) OPS1 nhit ti 800 oC, (c)
OPS2 ban u, (d) OPS2 nhit ti 800 oC, (e) OPS3 ban u v (f) OPS3 nhit ti 800 oC.
cao s lin kt gia cc ht cu lin k nhau tr nn yu hn, nng lng lin kt gia chng
c th t ti cc tiu v cc ht cu c th thc hin nhng dch chuyn nh. S dch chuyn
ny c th lm cc ht cu sp xp st nhau hn, iu chnh li cc v tr sp xp "lch lc", cu
trc mng tr nn trt t hn. Mt khc, cc ht cu b co li khi c lm ngui t t cng c
th lm chng x dch st li nhau hn, gp phn gim cc khong trng khuyt tt im, khuyt
tt ng trong cu trc mng. C th kt lun cc mu opal khi c nhit cao ( 800
o
C) cht lng kt tinh ca chng tr nn trt t hn v nng cc khuyt tt gim, bn c
hc tt hn.
4. Kt lun
Cc thng s ch to tinh th opal OPS3 l ph hp to c cc tinh th opal c cht
lng tng i tt: nghing 20o, m tng i ca mi trng xung quanh khong 70%,
gradient nhit gia y v mt thong ca dung dch l 70 oC - 60 oC. Cc mu opal khi c
nhit nhit cao 800 oC s tr nn c cu trc trt t v nng cc khuyt tt thp hn
so vi cc opal ban u. ng knh cc ht cu gim, chit sut hiu dng ca opal v chit
sut silica tng khi nhit tng. Cc i phn x Bragg dch chuyn v pha bc sng ngn,
FWHM gim khi nhit tng.
Ti liu tham kho
1. J. D. Joannopoulos, R. D. Meade, and J. N. Winn, photonic crystals: Molding the Flow of
Light (princeton, NJ: princeton University press), (1995).
2. D. J. Norris, and Y. A. Vlasov, adv. mater. 13 371 (2001).
Nhng
_____________________________________________________________________________________
3.
Y. A. Vlasov, V. N. Astratov, A. V. Baryshev, A. A. Kaplyanskii, O. Z. Karimov, and M. F.

Limonov, Phys. Rev. E 61 5784 (2000).
4. A. A. Chabanov, Y. Jun and D. J. Norris, Appl. Phys. lett. 84 (18) 3573 (2004).
5. S. L. Kuai, X. F. Hu, A. Hache, V. V. Truong, Journal of Crystal Growth 267 317 (2004).
6. G. M. Gajiev, D. A. Kurdyukov, and V. V. Travnikov, Nanotechnology 17 5349 (2006).
7. P. Jiang, J. F. Bertone, K. S. Hwang, and V. L. Colvin, Chem. Mater. 11 2132 (1999).
8. M. S. Thijssen, R. Sprik, J. E. G. Wijnhoven, M. Megens, T. Narayanan, A.
Lagendijk and W. Vos, Phys. Rev. Lett 83, 2730 (1999).
9. Y. Xia, B. Gates and S. H. Park, J. Lightwave Tech. 17 1956 (1999); S. H. Park and Y. Xia,
Langmui 15 266 (1999).
10. N. D. Denkov, O. D. Velev, P. A. Kralchevsky, I. B. Ivanov, H. Yoshimura and K.
Nagayama, Nature 361 26 (1993).
11. A. S. Dimitrov and K. Nagayama, Langmuir 12 1303 (1996).
12. L. V. Woodcock, Nature 385 141 (1997); 388 236 (1997).
13. S. C. Mau and D. A. Huse, Phys. Rev. E 59 4396 (1999).
Advances
_____________________________________________________________________________________
CH TO MNG PHN X NH SNG TRN C S CC VT LIU

XT BN DN
Quang Trunga,b , Bi Vn Hob,c , Trn Ngc Khimb , Phm Thnh Huyb,d,
Trnh Xun Anhd, Nguyn Th Thanh Ngne, Phm Hng Dnge
a)
b)
Khoa C bn, Trng i hc Cng nghip Qung Ninh, Tnh Qung Ninh
Vin o to quc t v Khoa hc vt liu (ITIMS), Trng i hc Bch Khoa H Ni
c)
Khoa Vt l k thut, Trng i hc Quy Nhn
d)
Vin Tin tin khoa hc v cng ngh (HAST), Trng i hc Bch khoa H Ni
e)
Vin Khoa hc vt liu, Vin Khoa hc v cng ngh Vit Nam
E-mail: quangtrung2004_qn@yahoo.com
Tm tt: Bo co trnh by phng php ch to mng phn x nh sng v mng phn x ngc
trn c s s dng cc vt liu xt bn dn (TiO2, SiO2) v mui (BaSO4). Cc vt liu ban u
to mng phn x nh sng TiO2, BaSO4 v polymer c phn tn trong dung mi to thnh
dung dch ng nht. Dung dch ng nht sau c to mng trn thy tinh bng phng
php nhng ph. Cc mng phn x ngc c to ra bi mt lp bi cu SiO2 trn mt lp
phn x. H s phn x v hnh thi b mt ca mng phn x nh sng c kho st bng
phng php cu tch phn v hin vi in t qut (SEM). Cu trc b mt c quan st bng
knh hin vi quang hc. H o phn b phn x theo gc c xy dng theo s giao thoa k
Michelson. Cc mng phn x nh sng thu c c h s phn x trong vng nh sng nhn thy
trn 88%.
1. Gii thiu
Cng vi s pht trin ca cc ngnh quang hc, quang in t hc, vic nghin cu ch to
cc vt liu, cc mng, cc lp ph phn x hay chng phn x nh sng trn cc thit b quang
hc nhm hn ch ti a cc mt mt quang hc, gia tng kh nng truyn qua hoc kh nng
hp th nng lng v ang l mt trong nhng vn c quan tm nghin cu trong v
ngoi nc. Cho n nay, rt nhiu sn phm s dng hiu ng phn x ngc c a vo
cuc sng nh sn phn quang, gng, mng, vi, bng phn quang. Hu ht cc vt liu phn
quang c ch to trn c s cc kim loi (Al, Ag, Au) v cc xt bn dn (TiO2, SiO2, ZnO,
SnO2...). Cc xt bn dn c cu trc micro, nano, dng ht, dng mng mng c nghin
cu, ch to v kho st bng nhiu phng php khc nhau ng thi m ra kh nng pht trin
cc cu trc vt liu mi vi tim nng ng dng thc tin cao.
Vt liu BaSO4 l bt mu trng thng c s dng nh mt cht cm quang trong cc
php chun on bng tia X [1]. Bt BaSO4 c trng rt cao trong vng nh sng nhn thy v
thng c ph to thnh lp phn x tn x cao trong mt s thit b quang hc nhm trnh
cc tn hao nng lng quang v c s dng lm bt n cho sn trng [2]. Bt TiO2 ngoi
cc tnh cht nh: xc tc quang ha, tnh cht nhy kh, cn c kh nng tn x nng lng tt
v cho trng cao trong vng nh sng nhn thy. TiO2 c chit sut: 2,8 i vi rutile v 2,55
i vi anatase [3]. Mng phn x nh sng c ch to da trn cc vt liu BaSO4, TiO2 v
cc polymer cho h s phn x nh sng cao trong vng nh sng nhn thy c cng b
trong thi gian gn y. Mt s cc sng ch lin quan n cu trc v cng ngh ch to mng
phn x nh sng trn c s vt liu xt bn dn cng c ng k bn quyn sng ch cng
ngh [4]. Vi mc tiu nhm nghin cu v hng ti ch to th nghim mng phn x nh
sng v mng phn x ngc (retroreflection) [5], trong thi gian gn y chng ti trin khai
nghin cu ch to mng phn x nh sng da trn c s xt TiO2 v mui BaSO4 trong cc
mng nn khc nhau. ng thi cc mng phn x c nh hng (mng phn x ngc) cng
c nghin cu ch to s dng cc bi cu SiO2 c kch thc t vi chc m n ~ mm. Cc
Nhng
_____________________________________________________________________________________
kt qu nghin cu ch to, xy dng h o kho st v nh gi cc tnh cht ca cc mng ch

to c s c trnh by chi tit trong bi bo ny.
2. Thc nghim
2.1 Quy trnh ch to mng phn x nh sng
Mng phn x nh sng (light reflecting film) c hiu l mng c trng cao, khc vi b
mt phn x gng do vt liu kim loi to ra ( y nh sng chiu vo b mt s tn x theo
mi hng, nhng khng hp th nh sng). Mt c tnh m mng phn x nh sng phi c l
mng phi che lp ht , dy ti thiu che lp ht gi l dy v cc. dy v cc
ca mng cng nh th vic s dng cng d dng. V d, mng kem chng nng dng bt
TiO2 v bt Al2O3 phn x ht tia t ngoi (UV B) trong nh nng mt tri, lp kem bi phi c
dy khong 1 m, v kch thc bt c 30 nm. Mng kim loi c dy v cc thp (100
nm), do h s phn x ln (do c s tn ti ca m my plasma in t t do), nhng h s
phn x ca mng nhm cng ch t ti 92% trn gng, v 60% nu dng sn nh nhm.
Nguyn l c phn x tn x cao l cc ht bt phi c kch thc nm trong vng
nanomet, khng hp th v xp cht trong mng. Chng ti nghin cu quy trnh thc nghim
ch to mng phn x nh sng c phn x cao, s dng vt liu TiO2, BaSO4 lm bt n,
PPMA v monome acrylic lm mng keo (hnh 1).
Dung mi
(Toluen)
Polyme
(PMMA)
Monome
(Acrylic)
TiO2, BaSO4
Dung mi
(H2O)
H2O+HBM
Khuy, gia nhit (800C)
TiO2, BaSO4
Trn u
Dung dch
ng nht
Nghin bi
To mng
Hnh 1a : Quy trnh ch to mng phn x

nh sng s dng PMMA
Dung dch
ng nht
To mng
Hnh 1b: Quy trnh ch to mng phn x

nh sng s dng monome acrylic
Trong quy trnh m t trn hnh 1a, PMMA c ha tan trong dung mi toluen, v c gia
nhit nhit ~ 80 0C. Bt BaSO4 v TiO2 thng mi c trn u v cho vo dung dch
cha PMMA ha tan v tip tc khuy trong 2 gi to ra dung dch ng nht. Mng c
to bng phng php nhng ph. Trong quy trnh m t trong hnh 1b, BaSO4, TiO2 c ha
tan trong dung mi nc v cht hot ng b mt, sau c trn vi dung dch cha acrylic.
Hn hp nhn c c trn bng my nghin bi trong 4h thu c dung dch ng nht.
Tng t nh trn, cc mng c to bng phng php nhng ph trn (lam knh) trong
dung dch ng nht ny.
Advances
_____________________________________________________________________________________
2.2 Quy trnh ch to mng phn x ngc

Mng phn x ngc c c tnh l phn x tia sng tr li pha ngun sng. Mng cht
lng cao phi c gc m nh, phn x cao, to nn h s khuch i ln. Cu trc v quy
trnh ch to ca mng phn x ngc c m t trn hnh 2.
Polyme + Dung mi
BaSO4, TiO2
To lp phn x
Polyme
To lp bm dnh
Bi cu SiO2
Ph bi cu
Hnh 2: Quy trnh ch to mng phn x ngc s dng cc bi cu SiO2
Theo quy trnh ch to hnh 2, trc tin lp phn x c ch to s dng mng TiO2,
BaSO4 hoc mng nhm (Al) thng mi, tip mt lp polyme mng c ph trn lp
phn x ny, cui cng n lp bi cu SiO2 c tri u trn lp polyme. y cn lu , cc
bi cu cn phi m bo c tri u v n lp, cng nh phi c tri sao cho lp polyme
khng bao ph ht ton b bi cu.
2.3 Xy dng h o phn b phn x theo gc
D
x1
BS
S
D: Detector
L: Ngun Laser
BS: Knh tch tia

S: Mu
Hnh 3: S h o phn b phn x theo gc
H o phn b phn x theo gc c xy

dng da trn m hnh giao thoa k ca
Michelson. S h o c b tr nh hnh
3. Detector c th dch chuyn theo phng
ngang, knh tch tia c t nghing gc 450
so vi phng thng ng.
Tia laser ti c phn x qua tm knh
tch tia ti b mt mu, sau khi ti b mt
mu, chm sng phn x ngc tr li qua
knh tch tia v n detector. Detector c th
di chuyn theo phng nm ngang ghi li
cng sng ti cc v tr x1, x2, x3 tng
ng vi cc gc 1, 2,3 c cng sng
tng ng ti l I1, I2, I3
xi
l
l

Trn c s s liu nhn c, s dng phn mm Origin hoc Microsoft Office Excel, ta
nhn c ph phn b phn x theo gc ca mng phn x ngc. ng thi h s khuch i
ca mng phn x ngc cng c th c nh gi bng cch so snh kt qu nhn c vi
ph phn b ca mng khi khng c lp bi cu.
Gc phn x c tnh theo cng thc:
tg i =
xi
suy ra
i = arctg
Nhng
_____________________________________________________________________________________
3. Kt qu v tho lun
Hnh thi b mt ca mng phn x nh sng nhn bng phng php nhng ph c
kho st bng knh hin vi in t qut (SEM). Kt qu quan st nh SEM, hnh 4, cho thy sau
qu trnh ph v bay hi dung mi mng phn x nhn c c cu trc bao gm cc ht TiO2 v
BaSO4, cc ht ny c phn tn kh ng u trong mng nn PMMA. Cc ht phn tn c
kch thc trung bnh t 100-150 nm (TiO2) v 200-500 nm (BaSO4) v phn b kch thc ht
tng i ng u.
Hnh 4 : nh SEM hnh thi mt mng phn x nh sng c ch to vi t l TiO2:BaSO4 50:50 trong
mng nn PMMA (t l 6:1)
100
100
100
80
80
40
20
0
300
80
pigment : resin = 6:1

BaSO4 : TiO2 = 7:3
Reflectance (%)
Reflectance (%)
Reflectance (%)

BaSO4 : TiO2 = 9:1
60
60
40
20
400
500
600
700
800
400
500
Wavelength (nm)
600
700
800
300
400
500
600
700
800
900
Wavel engt h (nm)
100
100
80
80

BaSO4 : TiO2= 5:5
Reflectance (%)
Reflectance (%)
900
Wavelength (nm)
60
40
Pigment:resin= 6:1
TiO2
60
40
20
20
0
300
40
20
0
300
900
Pigment/resin = 6:1
BaSO44/TiO2 = 6:4
60
0
400
500
600
700
800
300
900
400
500
600
700
800
900
Wavelength (nm)
Wavelength (nm)
Hnh 5: Ph phn x ca mng phn x nh sng vi t l bt mu (pigment):cht nn (resin) = 6:1 v

t l BaSO4:TiO2 tng ng 9:1 (a) ; 7:3 (b) ; 6:4 (c); 5:5 (d) v 100% TiO2 (e)
Hnh 5 l ph phn x ca mng phn x nh sng s dng mng nn PMMA vi t l bt

mu/cht nn l 6:1 v t l BaSO4:TiO2 tng ng 9:1; 7:3; 6:4; 5:5 v 100% TiO2.
T ph phn x hnh 5 v bng tng kt phn x nh sng ti cc bc sng 450 nm, 550
nm, 650 nm (bng 1) ta thy cc mng c t l thnh phn bt mu khc nhau nhng u cho h
s phn x cao trong vng nh sng nhn thy (>88%). Kt qu nhn c l khng thay i
ng k i vi cc mu c ch to vi cc t l bt mu (pigment):cht nn (resin) khc
nhau. H s phn x tt nht t c i vi mu c t l BaSO4:TiO2 l 6:4. Kt qu ny l
tng i ph hp vi cc kt qu cng b trc y ca mng phn x nh sng trn c s
vt liu BaSO4 v TiO2.
Advances
_____________________________________________________________________________________
Bng 1: H s phn x ca mng phn x nh sng vi t l bt mu (pigment):cht nn (resin)= 6:1
T l BaSO4: TiO2
trong hn hp
BaSO4
TiO2
9
7
6
5
0
1
3
4
5
10
H s phn x (%)
450 nm
95,9
100
96,4
98,6
92,8
550 nm
96,9
99,1
99,6
97,3
91,3
650 nm
97,5
98,3
99,4
97,1
88,7
Khi thay i mng nn PMMA bng monome acrylic v vi cc t l pigment: resin khc
nhau chng ti cng nhn c kt qu tng t vi h s phn x trn 88%.
Hnh 6 v 7 l nh hin vi quang hc ca mng phn x ngc thng mi (hnh 6) v mng
c ch to s dng bi cu SiO2 (hnh 7) trong nghin cu ca chng ti. C th d dng nhn
thy t tng phn ca nh, cc bi cu dc s dng trong mng thng mi phn x (c nh
hng) tt hn so vi cc bi cu trong mng chng ti ch to c. iu ny c th c gii
thch do i) kch thc cc bi cu s dng ch to mu ca chng ti l ln hn dn ti xp
cht (phn b) trong mng km hn so vi mng thng mi. Do , khi c chiu sng, mt
phn nh sng ti b tn x bi lp phn x (khng phi l bi cu). ii) chit sut bi cu SiO2
chng ti s dng l kh thp ~1.5 so vi cc bi cu thng mi c chit xut > 1.9 dn ti kh
nng hi t v phn x ngc nh sng ca bi cu SiO2 yu hn so vi bi cu thng mi.
Hnh 6: nh hin vi quang hc ca mng phn

quang thng mi
Hnh 7: nh hin vi quang hc ca mng phn ch

to s dng bi cu SiO2 trn BaSO4:TiO2
C- ng I (Lux) (b)
C- ng I (Lux)
(a) Mng trng

(b) Mng thng mai
(c) Bi cu SiO2 trn BaSO4:TiO2
1.5
1.5
(b)
(a) Mng trng

(b) Mng thng mai
(c) Mu bi cu trn Al
1.0
1.0
0.5
0.5
(c)
0.0
-15
-10
-5
(a)
(c)
(a)
0.0
10
15
Gc q
Hnh 8: Ph phn b phn x theo gc ca cc

mu mng trng (a), mng thng mi(b) v
mng bi cu SiO2 trn nhm (c)
-15
-10
-5
10
15
Gc q
Hnh 9: Ph phn b phn x theo gc ca mu

mu mng trng (a), mng thng mi(b) v mng bi
cu trn BaSO4:TiO2 (c)
Nhng
_____________________________________________________________________________________
Kt qu o ph phn b phn x cho thy i vi mng trng th h s phn x hu nh

khng ph thuc vo gc (cng phn x ln nht l 0,04 Lux). Vi mng thng mi, gc
phn b phn x nhn c l hp khong 200 vi cng ln v nh ph nhn. Cc mu ch
to s dng bi cu SiO2 trn nhm (hnh 8) v trn BaSO4:TiO2 (hnh 9), ph nhn c c
cng thp v phn b gc tng i rng i vi mng s dng nhm (~ 300) v phn b
hp hn i vi mng trn BaSO4:TiO2 (~ 250). Cng phn x ln nht ca mu thng
mi l 16,3 Lux, mng trn nhm c cng ln nht 0,3 Lux v mng trn BaSO4:TiO2
c cng ln nht l 0,17 Lux.
4. Kt kun
Mng phn x nh sng v mng phn x ngc c ch to v kho st bng cc
phng php cu tch phn v o phn b phn x theo gc s dng s giao thoa k
Michelson. Kt qu thu c cho thy cc mng phn x nh sng trn c s vt liu BaSO4,
TiO2 trong cc mng nn PMMA v monome acrylic u c kh nng phn x trong vng nh
sng nhn thy trn 88% gn vi gi tr ng dng ca loi mng ny trong thc t. Mng phn x
ngc s dng bi cu SiO2 trn hai loi khc nhau l nhm v BaSO4:TiO2 bc u cho hiu
ng phn x nh hng theo gc tuy cn yu so vi cc mng thng mi. Vic la chn cc bi
cu vi chit sut v kch thc ph hp s l cc yu t quyt nh kh nng phn x ngc ca
mng.
Li cm n: Nghin cu c thc hin trong khun kh ti KHCN cp B B2007-01-103.
Ti liu tham kho
1. http://en.wikipedia.org/wiki/Barium_sulfate
2. G. Buxbaum, G Pfaff, Industrial Inorganic Pigments, WILEY-VCH Verlag GmbH & Co.
KGaA, Weinheim ISBN 3-527-30363-4, Third Edition (2005).
3. Zeno W. Wicks, Jr. Frank N. Jones, S. Peter Pappas, Douglas A. Wicks, ORGANIC
COATING Science and Technology Third Edition, John Wiley & Sons, Inc. All rights
reserved (2007).
4. Nigel I. Anderson, Morgenzicht, RETRO-REFLECTIVE MATERIALS,United States
Patent, Number 971692, July 27, 1976.
5. Syuji Kohta et al, Light reflecting Material, United States Patent, Number 5991080,
No.23, 1999.
Advances
_____________________________________________________________________________________
KHO STCU TRC CA MNG MNG WO3 PHT TRIN

TRN ITO/THY TINH BNG PH RAMAN V XRD
L Vn Ngc a, Trn Cao Vinh a, Nguyn c Thnh a, Hunh Thnh t b,
Trn Tun a, Dng i Phng a
a
i hc Khoa hc T nhin, i hc Quc gia Tp. H Ch Minh

b
i hc Quc gia Tp. H Ch Minh
Tm tt:Mng Vnfram oxt c ph trn ITO/thu tinh bng phng php phn x
manetron RF t bia gm WO3. Qu trnh to mng xy ra trong plasma ca hn hp kh O2 +
Ar. S nh hng ca iu kin to mng ln cu trc ca mng Vnfram oxt c kho st
bng phng php chp ph Raman v nhiu x tia X (XRD). Trong cng trnh ny chng ti
nhn thy rng dy ca lp ITO trong khong 150nm n 350nm nh hng rt r rt ln
ph Raman v ph XRD ca mng WO3..
1. Gii thiu
Mng WO3 v ang c nghin cu rng ri nh nhng tnh nng c bit ca n cng
nh kh nng ng dng l th ca n trong nhiu lnh vc. Mt trong nhng ng dng c
quan tm nhiu nht ca mng WO3 l dng lm thnh phn chnh trong thit b in sc, tnh
cht quang ca mng bin i thun nghch theo hiu in th t vo [1-3]. Gn y mng
Vnfram oxt c nghin cu ch to cc sensor kh c nh NOx, H2S, NH3, v CO hay mt
s kh khc nh H2, O2, O3, Cl2, SO2, CH4, [4-6]. Cc ng dng trn i vi mng Vnfram oxt
l da vo s khuch tn ca cc ht vo ra dc theo cc knh rng ca mng perovskit WO3 mt
cch thun nghch. Nh vy cu trc ca mng WO3 vi cc knh rng c nh hng v c kch
thc ln s nh hng rt thun li n cc tnh cht trn. Vic ch to mng Vnfram oxt
cng v ang c nhiu nhm tc gi thc hin vi nhiu phng php khc nhau nh:
phn x [7-10], Solgel [11], phun nhit [12-13], in ha [14], nhit bay hi [14-20].
Cng vi vic nghin cu cc tnh cht quang v cc tnh cht in ca mng WO3, cu trc
ca chng cng c nhiu tc gi nghin cu da trn ph XRD v ph Raman. Cc kho
st trn ph XRD hu ht u tp trung vo vng 200 250 ca cc gc nhiu x. Cc kho st
trn ph Raman ch yu tp trung trong vng s sng t 200 cm-1 1000 cm-1.
Trong cng trnh ny, mng WO3 c ph trn trn lp ITO/thy tinh vi dy ca ca
lp ITO ln lt thay i t 150 n 350nm. Cu trc tinh th ca mng c kho st thng qua
ph nhiu x tia X. Mng WO3 c cu trc tinh th v cu trc ny cn ph thuc vo dy ca
lp ITO. T s thay i ca cu trc WO3 nh trn, cng trnh ny cng tin hnh kho st ph
Raman ca chng. Cc nh ph Raman rng trong vng 600cm-1 1000 cm-1 c tch thnh
nhiu nh nh theo cc mode dao ng c bn. Vi s ch c bit vo cc nh ph Raman
ln cn 680 cm-1 v 950 cm-1 khng cho thy s nh hng ca pha nano tinh th ca Vnfram
oxt. Vic tm ra ngun gc ca nh ph trn cng c gii quyt trong bi bo ny.
2. Thc nghim
Trong cng trnh ny, cc mng ITO, WO3 c ch to bng phng php phn x
magnetron trong hn hp kh (Ar + O2). Cc kh thnh phn O2 v Ar c tinh khit l
99,999%. H chn khng to mng c th t c chn khng ban u l 10-7 Torr nh bm
phn t c hc, lp ITO c lng ng trn thy tinh bng phng php phn x magnetron
DC vi cc dy ln lt l xp x 150, 200, 250, 300, 350 nm. Mng WO3 c ph trn lp
ITO bng phng php phn x magnetron RF vi cng sut phn x l 100 W, thi gian phn
x l 30 pht.
Nhng
_____________________________________________________________________________________
Sau khi lng ng, h mng c nhit trong khng kh 4000C trong 4 gi. Cu trc
mng c kho st da trn ph XRD v ph Raman. Bc x c dng trong o ph XRD l
Cu - K c bc sng 1,5406. nh sng kch thch o ph Raman l laser He Ne c bc
sng l 0,6328m. Cc nh ph rng do s chng chp ca nhiu nh cng c phn tch
thnh cc nh c trng dng Gaussian cho cc mode dao ng bng phn mm Origin 7.5. c
bit i vi cc ph Raman ca cc mng WO3 c nhng ht tinh th a cu trc. Vic tch nh
ph l nh gi s tn ti ca nhiu dng cu trc tinh th trong mng.
3. Kt qu v bn lun
3.1. nh hng ca dy ITO ln cc nh ph XRD ca mng WO3
i vi cc mng WO3 c ch to nh trnh by trn, tt c cc mng u trong sut,
truyn qua trong vng kh kin ~90%. nh gi trng thi tinh th ca chng, chng ti
tin hnh ghi ph XRD ca mu bt WO3 nh hnh 1. Ba nh c cng mnh l (001), (020)
v (200) ng vi cc gc nhiu x l 2 = 23,290; 23,770; 24,510 tng ng vi cc khong cch
mng l d = 0,382 nm; 0,374 nm; 0,363 nm. Cc s liu ny cho thy mu bt WO3 m chng ti
s dng c cu trc tinh th dng monoclinic (m-WO3) vi cc kch thc cc gc v cnh l:
= = 900, = 90,150, a = 0,7285 nm, b = 0,7517 nm, c = 0,3835 nm. Cc nh XRD mnh (Cu =
1,5406) l (001) v (200) (theo International JCPDC database, JCPDC 5-363).[21]
3000
(020)
(001)
(200)
cuong do (cps)
2500
W O 3 M AU BO T
2000
(400)
1500
1000
500
0
20
30
40
50
2 Theta (deg)
Hnh 1: Ph XRD ca mu bt
Hnh 2: Ph XRD ca cc mng

WO3 trn cc lp ITO c dy khc nhau.
Trn hnh 2 l ph XRD ca cc mng trn cc dy lp m ITO khc nhau, cc nh

XRD phn b trong mt phm vi gc qu hp ca gc nhiu x 2 t ln cn 230 250 nn
chng ta khng th bit chnh xc l mng c cu trc tinh th dng n t monoclinic m-WO3
(vi cc thng s gc = = 900, = 90,150, v cc cnh a = 0,7285 nm, b = 0,7517 nm, c =
0,3835 nm) hay l dng trc giao orthorhombic o-WO3 (vi = = = 900, a = 0,7341 nm, b =
0,7570 nm, c = 0,3877 nm) do cc kch thc c s ca chng kh gn nhau.
T hnh 2 cho thy vi lp ITO khong 150 nm, ph XRD WO3 cho nh (200) rt mnh v
mt nh nh (001). Gia hai nh ny l nh (020) khng xut hin r rng m np vo chn
ca nh (200). Vi dy tng dn ca lp ITO khong 200, 250, 300, 350 (nm), ph XRD
WO3 cho thy s gim dn cng ca nh (200) v ng thi nh (001) tng dn. C bit l
nh (020) ch th hin kh r dy ITO l 250 nm. Vi lp ITO khong 300nm s pht trin
mng WO3 c s bt thng v tnh nh hng so vi cc mng khc do c s xut hin ca
mt s nh vng gc nhiu x ln. Vi lp ITO khong 350 nm s pht trin mng hu nh l
n hng theo mt mng (001) nhng vi khong cch mt mng kh ln 0,4001 nm. Gi tr
ny gn vi khong cch cc mt WO3 (001) ca dng cu trc WO3-tetragonal (t-WO3) lm
chng ta suy on rng mng ny c cu trc tinh th dng t-WO3 vi cc gc = = = 900 v
cc cnh a = b = 0,525 nm; c = 0,392 nm. Vi cu trc ny knh rng c to thnh dc theo
trc c nh hn nhiu so vi cu trc tinh th dng m-WO3 hoc o-WO3. Tuy nhin cu trc ca
Advances
_____________________________________________________________________________________
mng WO3 pht trin theo hng u tin (001) hay (200) th u cho chng ta thng tin rng
trong mng tn ti cc knh rng c phng vung gc vi b mt mng. V vi s pht trin
nh hng theo mt (200) ca o-WO3, mng s cho cc knh rng c kch thc ln nht trong
cu trc WO3 - perovskit.
30000
7 9 9 .4 2 9
8000
25000
W O 3 / IT O _ 1 5 0 n m
20000
a)
15000
2 6 5 .6
7 0 3 .7 7 1
2 7 .7 7 1
10000
Cuong do (cps)
cuong do
(2 0 0 )
W O 3/ IT O _ 1 5 0 n m
3 2 0 .1 1 4
5000
6000
4000
2000
(0 0 1 )
0
200
400
600
s o s o n g (c m
-1
800
20
1000
W O 3 / IT O _ 2 0 0 n m
10000
7 0 7 .8 8 6
2 6 8 .6 8 6
3 0 .8 5 7
(2 0 0 )
6000
b)
W O 3 / IT O _ 2 0 0 n m
5000
cuong do (cps)
Cuong do
50
7000
8 0 2 .5 1 4
5000
40
2 T h e ta (d e g )
20000
15000
30
3 2 3 .2
4000
3000
2000
(0 0 1 )
1000
0
0
200
400
600
s o s o n g (c m
800
_1
20
1000
30
40
50
2 T h e ta (d e g )
2000
6000
8 0 3 .5 4 3
W O 3 / IT O _ 2 5 0 n m
c)
1800
7 0 9 .9 4 3
2 6 9 .7 1 4
1 3 0 .8 5 7
2000
3 2 3 .2
1000
(0 2 0 )
800
600
400
0
200
400
600
800
1000
S o s o n g (c m -1 )
16000
8 0 2 .3
2 6 2 .9 2 5
12000
7 0 9 .2
1 2 7 .3 2 3
d)
8000
3 2 4 .6 5 5
6000
20
30
40
50
2 T h e ta (d e g )
W O 3 m u bt
14000
Cuong do
W O 3 / IT O _ 2 5 0 n m
1200
200
1000
10000
(2 0 0 )
1400
4000
3000
(0 0 1 )
1600
Cuong do (cps)
Cuong do
5000
1 7 8 .9 3 3
4000
Hnh 3: ph Raman v ph XRD

ca cc mng WO3 trn cc dy
lp ITO khc nhau v ca mu bt:
a) 150 nm ITO;
b) 200 nm ITO;
c) 250 nm ITO;
d) mu bt WO3.
2000
200
400
600
S o s o n g (c m
800
-1
1000
3.2. Ph Raman ca mng WO3

T s thay i cu trc mng WO3 theo dy ca lp mng ph ITO, chng ti tin hnh
kho st s nh hng ln ph Raman ca mng WO3. S nh hng ny s c xt trong
hai min dy ca lp ITO. l 150 nm 250 nm v 300 350 nm.
3.2.1. Ph Raman ca mng WO3 trn lp ph ITO t 150 nm n 250 nm.
Trn hnh 3 l ph XRD v ph Raman ca cc mng WO3 trn lp ph c dy 150 nm
n 250 nm ITO v ca mu bt. Nhn chung cc mng c t s vch XRD I(200)/I(001) ln hn
so vi mu bt. Trn ph Raman ca chng xut hin cc v tr 266 270 cm-1 ; 704 710 cm-1
Nhng
_____________________________________________________________________________________
v 800 803 cm-1. Cc nh ny c cho l c trng ca trng thi kt tinh ca WO3 . nh

265,6 cm-1 c trng cho dao ng bin dng ca lin kt (O-W-O) v vng 600 900 cm-1 lin
quan n dao ng ha tr ca lin kt (W-O) [23]. nh 950 cm-1 c trng cho lin kt (W=O)
v tr bin ht hu nh khng xut hin. iu ny cho thy t l din tch b mt so vi th tch
cc khi tinh th trong mng l khng ng k.
Mt khc ba nh ph Raman c trng cho trng thi kt tinh ca mng WO3 ln cn cc
v tr 263 cm-1; 709 cm-1; 802 cm-1 hu nh khng th hin r s khc bit v dng cu trc tinh
th so vi mu bt. iu ny cng c th nhn thy khong cch gia ba nh Raman c
trng trong c ba mng nu trn l ging nhau: khong cch gia hai nh xa nht l 534 cm-1,
khong cch gia 2 nh gn nhau nht l khong 90cm-1. Kt qu kho st ny khng cho thy
c s khc bit v dng cu trc tinh th gia cc mng WO3/ITO trn v mu bt. Tuy nhin
cng khng th ph nhn chng c th c cu trc tinh th dng orthorhombic do kch thc cc
cnh v cc gc ca c s ca chng rt gn nhau.
3.2.2. Ph Raman ca mng WO3 trn lp ph ITO 300 nm v 350 nm.
50000
1000
Cuong do
8 0 2 .5 1 4
(0 0 1 )
a)
30000
20000
2 6 7 .6 5 7
7 0 1 .7 1 4
3 0 .8 5 7
10000
800
Cuong do (cps)
W O 3 / IT O _ 3 0 0 n m
40000
W O 3 / IT O _ 3 0 0 n m
(2 0 0 )
600
400
200
0
200
400
600
800
1000
20
S o s o n g (c m -1 )
24000
W O 3 / IT O _ 3 5 0 n m
22000
b)
6 8 8 .3 4 3
18000
16000
14000
12000
W O
50
(0 0 1 )
W O 3 / IT O _ 3 5 0 n m
2500
2000
1500
1000
500
10000
0
200
400
600
800
1000
S o s o n g (c m -1 )
16000
8 0 2 .3
2 6 2 .9 2 5
12000
7 0 9 .2
c)
1 2 7 .3 2 3
8000
3 2 4 .6 5 5
6000
20
30
40
50
2 T h e ta (d e g )
W O 3 m u bt
14000
Cuong do
40
3000
Cuong do (cps)
Cuong do
3500
7 9 9 .4 2 9
2 5 3 .2 5 7
20000
10000
30
2 T h e ta (d e g )
1 7 8 .9 3 3
Hnh 4: ph Raman v ph XRD ca

cc mng WO3 trn cc dy lp
ITO khc nhau v ca mu bt:
a) 300 nm ITO;
b) 350 nm ITO;
c) mu bt WO3.
4000
2000
200
400
600
800
1000
S o s o n g (c m -1 )
Trn hnh 4 l ph XRD v ph Raman ca cc mng WO3 trn cc lp ITO 300nm, ITO
350nm v ca mu bt. T ph XRD cho thy mng WO3 trn lp ITO 300 nm c nh XRD
(001) vt tri so vi nh (200).
So snh gia cc ph XRD ca cc mng v mu bt, ta khng kt lun c v s khc bit
ca dng cu trc tinh th hc ca chng. Tuy nhin, ph Raman ca mng WO3/ITO 300 nm
(hnh 4a) cho thy ngoi hai nh c trng cho trng thi tinh th ca mng WO3 268 cm-1
ng vi dao ng bin dng v 802 cm-1 ng vi dao ng ha tr ca lin kt (W-O). nh
cn li ca mng 709 cm-1 c dng khc bit so vi mu bt do c s chng chp thm ca mt
nh ph mi gn v tr 680 cm-1 ng vi pha nano tinh th ca WO3.
Advances
_____________________________________________________________________________________
-1
701,7cm
802,5cm-1
803cm-1
688cm-1
-1
645cm
703cm-1
797cm-1
Hnh 5: Ph Raman ca mng WO3/ITO_300nm/thy tinh.
Tuy nhin, cng ging nh cc mu ng vi ph Raman trn hnh 3a, 3b v 3c, trong ph
Raman trn hnh 4a cng khng thy c s xut hin ca nh 950 cm-1 ng vi lin kt (W=O)
bin ht tinh th. iu ny cng cho thy t s gia din tch b mt v th tch ca cc ht
tinh th l khng ng k. Tnh ton t cc ph XRD cng cho thy c s tng ng v kch
thc ca cc ht tinh th trong tt c cc mng l vo khong 30 nm 35 nm. S so snh tng
quan v mc tn ti ca pha nano tinh th ny cng cho thy rng pha nano tinh th khng
gy nn nh c trng 680 cm-1 trong cc ph Raman trn hnh 3 th mng WO3/ITO 300nm
n cng khng hon ton gy nn nh Raman mnh c trng cho pha ny ln cn 680 cm-1.
Nh vy ngun gc ca nh ph ln cn 680 cm-1 ny cn do mt nguyn nhn khc.
hiu r thm vn trn, chng ti kho st ph XRD v ph Raman ca mng WO3 trn
lp ITO 350 nm. Kt hp vi s dng phn mm Origin 7.5 phn tch nh ph 709 cm-1 ca
mng WO3 trn lp ITO 300 nm.
Ph XRD ca mng WO3 trn lp ITO 350 nm cho thy mng ch pht trin theo mt mng
(001). Cc nh (020), (200) ch cn l dng ng phng di chn nh ph (001). Mng kt
tinh kh tt v trn nh ph Raman ca mng cng xut hin cc nh ph c trng, cho trng
thi kt tinh ca mng ngoi nh ph 799 cm-1. Hai nh cn li c s dch mnh v vng s
sng thp. nh c trng cho dao ng bin dng (O-W-O) c v tr 253 cm-1; nh cn li xut
hin 688 cm-1. Chng ti chn v tr 688 cm-1 ny lm c s cho vic phn tch nh ph
Raman 709 cm-1 ca mu WO3/ITO300 nm/thy tinh.
Tin hnh phn tch ph ca mng WO3 trn ITO 300 nm (hnh 5), ta nhn c nh c
cng yu 645 cm-1 ng vi mt dao ng ca WO3 H2O. Hai nh cn li ng vi cc
nh ph thnh phn l 708 cm-1 v 688 cm-1. Chng ti ch nhn c ng fit tt nht khi
nh 802cm-1 cng c tch thnh hai nh c v tr tng ng l 803 cm-1 v 797 cm-1 nh trn
hnh 5. Trong cc nghin cu trc y ca nhiu tc gi khc nhau cng lun xc nh ch c
hai nh Raman trong vng 600 900 cm-1 c trng cho dao ng ha tr ca lin kt (W-O).
Nh vy s tn ti ng thi bn nh 803 cm-1; 797 cm-1; 708 cm-1 v 688 cm-1 cho thy trong
mng ny to thnh ng thi hai dng cu trc tinh th ng vi hai cp nh (803 cm-1;
708cm-1) v; (797cm-1; 688 cm-1). iu ny cng cho thy rng mng WO3/ITO300 nm. Mng
khng nhng cho s pht trin tng cng mt (001) m cn c s chuyn i dng cu trc tinh
th t h n t (monochinic) m-WO3 hoc h trc giao (orthorhombic) o-WO3 sang dng khc.
Vi khang cch mng WO3(001) tnh t ph XRD ca mng WO3/ITO350 nm l 0,4 nm v t
bng d liu JCPDS [24], cu trc tinh th dng t phng (Tetragonal) t-WO3 c khong cch
gia cc mt (001) vung gc trc c l ln nht (0,393 nm). Nh vy chng ti cho rng lp
m ITO c dy ln cn 300 nm tr ln, mng WO3 bt u thnh lp dng cu trc tinh th
Nhng
_____________________________________________________________________________________
khc v t kt qu kho st ny chng ti cho l h t phng t-WO3 vi cc cnh a = 0,525

nm; b = 0,525 nm; c = 0, 392 nm; = = = 900.
4. Kt lun
Cng trnh ny to mng WO3 trn lp ITO/thy tinh bng phng php phn x
magnetron kt hp nhit trong khng kh. Vi lp ITO 150nm mng WO3 c cu trc tinh th
vi hng pht trin ch yu theo mt (200). Vi lp ITO c dy ln hn S pht trin ca
mng WO3 theo hng mt (200) gim ng thi theo hng (001) c tng cng.
Kt qu kho st ph Raman cho thy dng cu trc tinh th mng WO3 lng ng trn lp
ITO c dy di 250 nm c cu trc tinh th dng n t m-WO3 hoc trc giao o-WO3 vi
cc nh ph Raman ng vi cc dao ng c trng nm trong cc vng cc vng 262,6 cm-1
269,7 cm-1; 703,8 cm-1 709,9 cm-1; 800 cm-1 - 803,5 cm-1. Khi dy lp ITO ln hn 350 nm,
s pht trin ca mng WO3 c cu trc tinh th dng khc v chng ti cho l dng t phng
t-WO3 vi cc nh ph Raman ng vi cc mt dao ng c trng ln cn cc v tr 253cm-1;
688 cm-1 ; 797 cm-1.
Ti liu tham kho
1. C.G Granqvist, E.Alvendamo, A.Zeus Thin Solid Film 442,201 (2003).
2. Vu Thi Bich, Nguyen Thanh Binh, Nguyen Thi Bich Ngoc, A.Hugot-Le Goff. Proc.
IWOS2000, Hanoi, Vietnam, p.477-480.
3. Pham Duy Long, M.C. Bernard, Nguyen Thi Tu Oanh, A.Hugot-Le Goff, Nguyen Nang
Dinh. Proc. IWOS2000, Hanoi, Vietnam, p.473-476.
4. K.H. Lee, Y.K.Fang, W.J.Lee, J.J.Ho, K.H.Chen, K.S.Liao, Sens. Actuators B69,96 (2000).
5. E. Llobet, G.Molas, P.Molinas, J.Calderer, X.Vilanova, J.Bremers, E.Sueiras, X.Correig,
J.Electrochen, Second edition, 147.776 (2000).
6. M.D. Antonik, J.E.Scheinder,E.L.Wittman,K.Snow, J.F.Vetelino, R.J.Cad, Thin Solid Film
256, 247- 252 (1995).
7. K.J. Lethy, D.Beena, R.Vinod Kumar, V.P.Mahadevan Pillai, V.Ganesan, V.Sathe,
D.M.Phase, Appli. Phys. A91 638 639 (2008).
8. S.C. Moulzolf, L.J. LeGore, R.J. Lad, Thin solid films, 400 (2001) 56-63.
9. Huiyao Wang, Pei Xu, Tianmin Wang, Thin solid films, 388 (2001) 68-72.
10. Christian Salinga, Hansjrg Weis, Matthias Wuttig, Thin solid films, 414 (2002) 27511. Toshikazu Nishide, Fujio Mizukami, Thin solid films 295 (1995) 212-217.
12. A. Elshafie et al.: Dielectric Properties of Tungsten Oxide Thin Film, phys. stat. sol. (a) 174,
301 (1999).
13. P.S. Patil, P.R.Patil, E.A. Ennaoui, Thin solid films, 370 (2000) 38-44.
14. M.J. Hutchins et al.: Preparation and Properties of Tungsten Oxide Films, phys. stat. sol.
15. P.V. Ashrit, Thin solid films, 385 (2001) 81-88.
16. G. Macrelli, E. Poli, H. Demiryont, R.Gtzelmann, Journal of non-crystalline solids, 218
(1997) 296-301.
17. G. Leftheriotis, S. Papaefthimiou, P. Yianoulis, A. Siokou, Thin solid films, 384 (2001) 298306.
18. H.Y. Wong, C.W.Ong, R.W.M. Kwok, K.W. Wong, S.P. Wong, W.Y. Cheung, Thin solid
films, 376 (2000) 131-139.
19. I. Porqueras, E. Bertran, Thin solid films, 377-378 (2000) 8-13.
20. J.H. Huh, H.R. Hwang, J.H. Paik, D.D. Lee, J.O.Lim, Thin solid films, 385 (2001) 255-259.
Advances
_____________________________________________________________________________________
CU TRC V TNH CHT CA MNG VANADIUM OXIDE (V2O5) TO BNG

PHNG PHP PHN X MAGNETRON D.C
Nguyn c Ho a, L Vn Hiu a, Hong Lng Cng a, Trn Quang Hin b
a)
i hc Khoa hc T nhin Tp.HCM

b)
i hc Tin Giang
Tm tt: Mng Vanadium pentoxide, V2O5 c ch to bng phng php phn x

magnetron dc. Tt c cc mng u c to thnh t bia kim loi Vanadium vi tinh khit
99,5%. Mng c ph trn thy tinh quang hc. Cc tnh cht ca mng c kho st bng
cc php o ph truyn qua quang hc, ph nhiu x tia X (XRD) v ph Raman. Kt qu XRD
cho thy mng V2O5 c phn nhit 2000C c cu trc tinh th v 4000C thy
xut hin cu trc a tinh th vi cc nh c trng ca tinh th V2O5 nh (001), (110), (210),
(400) . Ph Raman ca cc mu c lng ng cng cho thy s kt tinh ca mng tng theo
nhit .
T kha: Mng mng; Phn x magnetron d.c ; Vanadium pentoxide; V2O5.
1. M u
V2O5 c cu trc trc thoi, c xy dng t nhng gc chung v nhng cnh chung ca
hnh khi tm mt VO6, trong c cc lin kt V-O l khng u nhau thay i t 0,159-0,279.
Tinh th V2O5 c kt tinh t nhng n v khi trc thoi vi hng s mng a=11.519A0,
b=3.564A0, c=4.373A0. cu trc tinh th V2O5 l cu trc lp ( khong 4A0 mi lp) d dng
bc tch ra theo mt (001)[2].
Vanadium pentoxide l mt trong nhng oxide kim loi bn dn thu ht nhiu s quan tm
nghin cu v kh nng ng dng rng ri, c bit khi c ch to dng mng mng. Vi cc
tnh cht a ha tr, cu trc lp, vng cm quang hc rng, bn nhit v ha hc tt, c tnh
in sc, V2O5 tr thnh vt liu tim nng trong vic ch to cc thit b vi in t, in
ha, quang in, in sc
Mng tinh th Vanadium pentoxide (V2O5) c cu trc lp v c s dng nh vt liu c
a ha tr. c bit, kh nng tch tr ln nhng ion kim loi kim c kch thc b nh Li, Na
bn trong mng V2O5 cng li cun cc nh khoa hc nghin cu ch to pin np li dung lng
cao cng nh trong nhng thit b in sc, ch to ca s thng minh. Ngoi ra, mng mng
V2O5 cn c s dng rng ri trong b nh my tnh, sensor nhy kh pht hin v xc nh
nng ca mt s cht kh c hi trong mi trng,....
c tnh in sc c th c s dng trong cc bng thng tin quang in t hay nhng ca
s c truyn qua thay i c. S nhum v ty mu ca mng in sc V2O5 din ra khi cc
ion A+ c tim vo v ly ra khi mng tinh th V2O5 theo phng trnh phn ng sau:
V2 O5 + xA + + xe AxV2 O5
(1)
Trong , A l cc ion Na hoc Li.

Gi tr ca x c 0.1 trong mng c ty trng (fully bleached film) v c 0.5-0.7 trong mng
c nhum hon ton (fully colored film) [3].
Mng V2O5 c th c ch to bng nhiu phng php: bc bay chn khng [2], phn x
RF phn ng, phn x RF t bt V2O5, phn x magnetron d.c [3], v phng php sol-gel
[4].Trc y nhm nghin cu ch to thnh cng mng V2O5 bng phng php bc bay
nhit trong chn khng, nhng v phng php ny cn rt nhiu hn ch vi nhng nhc im
khng th khc phc c nh bm dnh mng khng tt khi nung nhit cao. V th
trong khun kh ca ti ny nhm nghin cu ch to mng V2O5 bng phng php phn
Nhng
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x magnetron d.c t bia kim loi vanadium v kho st mt s tnh cht ca mng. Vi phng
php ny ta c th to ra sn phm trong phm vi ph ln, c kh nng trin khai sn xut cng
nghip. iu ny cc phng php khc rt kh thc hin c.
2. Thc nghim
Mng in sc Vanadium pentoxide c ch to bng phng php phn x magnetron d.c
t bia kim loi Vanadium (vi tinh khit 99.5%). Mng V2O5 c ph trn thu tinh
quang hc kho st cu trc mng. H chn khng to mng c to ti Khoa Vt L,
Trng H Khoa Hc T Nhin TpHCM vi mt s iu kin ban u nh: p sut phn x
3mmtorr, thi gian phn x 15 pht. Vi vic c nh cc thng s trn chng ti thay i
mt s thng s khc nh t l kh O2/(O2+Ar) (10%, 15%, 20%, 25%, 30%), dng phn x
(0.1A, 0.2A, 0.3A, 0.4A), khong cch bia- (5cm, 6cm, 7cm) v nhit (2000C, 3000C,
4000C). Bng vic o ph truyn qua ti Phng th nghim Vt liu K Thut Cao, Trng
HKHTN, ph XRD ti Vin du kh Vit Nam (TpHCM), ph Raman ti Phng th nghim
Cng Ngh Nano, HQG TpHCM, chng ti c c mt s kt qu kh quan ph hp vi
mt s cng trnh ca nc ngoi.
3. Kt qu v bn lun
3.1. Kho st nh hng ca cng dng phn x vi cc t l khc nhau
3.1.1. Mu sc ca mng sau khi phn x
Sau khi phn x ta thy tt c cc mng c ph cng dng 0.1A, vi cc t l kh
khc nhau u cho mu vng c trng ca V2O5. Khi tng cng dng phn x t 0.1A n
0.4A, mng chuyn t mu vng nht sang m dn. iu ny c gii thch l do dy mng
tng. Tuy nhin, tip tc tng dng phn x cc t l Oxy thp (15% v 20%), mng chuyn
sang mu vng xanh, ri xanh l cy nht. c bit, iu kin thiu nhiu Oxy (10%), mng c
mu xanh m ngay khi tng cng dng 0.2A. Mu xanh ca mng l du hiu ca s
chuyn pha t V2O5 sang cc pha Vanadium thiu Oxy. Cng nhn thy, cng dng xy ra
chuyn mu t vng sang xanh tng khi iu kin Oxy tng (0.1A n 0.4A khi t l t 10% n
25%). R rng rng, vi t l kh 25% Oxy/ (Oxy+Ar), cng dng phn x c th tng n
0.4A m mng vn gi mu vng V2O5.
3.1.2. Tc lng ng
V tc lng ng : n v nanomet/pht
Bng 1: Tc lng ng (nm/pht) ca ca mng Vanadium oxide trn nhit 2000C,
khong cch bia- 5cm, p sut phn x 3mTorr.( xm l nhng mu c mu vng xanh, xanh l).
0.1A
0.2A
0.3A
0.4A
15%
14,93
15,8
20
58,2
20%
14,53
16,33
16,66
19,53
25%
10
14,86
24,86
33,6
30%
5,33
30
31
T l kh
Dng
Advances
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Cng dng phn x cng tng th

tc lng trn cng tng. Trong iu
kin cng dng phn x v t l kh
Oxy cho kt qu mng c mu vng, ta
nhn thy, vi cng dng 0.1A, th
hm lng Oxy 15% l to hp thc
cho mng. Vi hm lng Oxy cao hn,
phn Oxy d trong bung s c tc dng
lm gim kh nng lng ng ca mng
trn . Do , tc lng ng t ti a
15% Oxy. Khi tng dng ln 0.2A, r
rng mng cn nhiu Oxy hn hp thc
nn t l kh 20% l la chn ti u. Khi
Hnh 1 : Ph truyn qua ca mng theo khong

cch bia khc nhau
dng phn x l 0.3A, th t l kh phi t

30% mi c th cung cp Oxy cho
mng hp thc. Vi cng dng 0.4A,
mng khng cn gi mu vng (tr mu
25%) nn khng th kt lun c g.
Vy, ng vi mi t l kh, ta c 1
cng dng ngng cho php mng to
ra c mu vng v tc lng ng ln
nht.
3.1.3. Kho st ph truyn qua
a. Theo khong cch bia-
Theo hnh 1 ta thy khong cch bia cng ln, truyn qua cc i ca
mng cng tng dn. Tuy nhin, dng ph
truyn qua khng khc bit nhiu lm.
Vy, khong cch bia- khng nh
hng nhiu n mng V2O5 ngoi tr
dy v ng u ca mng.
Hnh 2: Ph truyn qua ca mng Vanadium oxide

p sut phn x 3mTorr, khong cch bia- 5cm,
cng dng 0.2A, t l kh 25% vi cc nhit
khc nhau
b. Theo nhit
Da vo hnh 2, d dng nhn thy tnh
cht mng c s thay i. C th,
truyn qua ca mng gim nhiu khi tng
nhit . ng thi, dng b hp thu
cng thay i v c s dch b v pha
sng ngn. iu ny lin quan n s thay
i v cu trc tinh th s c trnh by
phn tip theo.
3.1.4. Kho st ph nhiu x tia X
a.Thay i theo dng
Hnh 3: Ph nhiu x tia X vi cc dng khc nhau

cng t l kh 25%, nhit 200oC, khong cch
bia- 5cm, p sut phn x 3mTorr.
Nhng
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Da vo ph nhiu x tia X hnh

3, ta thy dng phn x cng c nh
hng rt nhiu n cu trc ca mng.
C th nh dng 0.1A, ph xut hin
mt mng (-101) l cu trc ca tinh
th V3O5, tuy nhin dng ny c
s xut hin ca mt (001), mt mng
c trng ca cu trc V2O5. cc
dng 0.2A, 0.3A c s chuyn i
dn v dng 0.4A th xut hin
thm mt s mt mng khc thuc cu
trc tinh th ca V2O5. Hay ni cch
khc, mng c ph cng dng
0.1A c cu trc tinh th vanadium
oxide, nhng pha V3O5 chim a s
hn pha V2O5. Khi dng tng ln 0.2A,
pha V3O5 gim mnh, ch cn 1 nh
nh khong 2theta = 180, pha V2O5
tng mnh, nh hng mnh theo mt
mng (001). Khi dng phn x l 0.3A,
pha V3O5 hon ton bin mt, mng ch
cn pha V2O5 gc 2theta = 200 (mng
n tinh th!), tuy cng nh c
phn gim so vi dng 0.2A. Vi dng
0.4A, cu trc a tinh th xut hin
cng vi s xut hin tr li pha V3O5.
Nh vy, vi t l kh 25% Oxy, mng
c phn cng dng 0.2A v
0.3A cho cu trc tinh th V2O5 tt.
Hnh 4: Ph nhiu x tia X vi cc t l kh khc nhau

cng dng phn x 0.2A, nhit 2000C, khong cch
bia- 5 cm, p sut phn x 3 mTorr.
b. Theo t l kh O2/(O2+Ar) khc

nhau
Da vo ph nhiu x tia X hnh
4 ca mng ph dng 0.2A vi cc t
l kh khc nhau, ta thy mng ch pht
trin pha V2O5. Trong , ngoi t l
20% c xut hin thm nh (210), tt
c cc mng u xut hin mt mng
c trng (001) ca tinh th V2O5. c
Hnh 5: Ph nhiu x X ca mng Vanadium
bit c th thy t l 25%, peak tinh
cc nhit khc nhau.
th c cng cao nht mc d tc
lng ng mng khng phi l ln nht (bng 1).
Bng cc thng s phn x nh trn chng ti tin hnh kho st v xc nh c mt s
kt qu, da vo chng ti chn t l kh 25%, dng 0.2A, mng V2O5 ln tinh th tt v
pht trin theo hng (001) nh kt qu ca mt s bi bo nc ngoi.
c. Theo nhit
Tin hnh phn tch ph nhiu x tia X ca cc mu ph nhit khc nhau (hnh 5),
chng ti nhn thy, 2000C mng c cu trc tinh th, pht trin mnh theo hng [001] (
trnh by phn trn). Khi nhit trong qu trnh ph l 4000C, ngoi mt mng (001),
mng pht trin thm cc mt mng khc c bc tinh th cao hn (210) v (202). ng thi xut
hin thm peak (0-11) ca pha tinh th V4O7. y l pha vanadium thiu ht Oxy. iu ny
Advances
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chng t, nu tip tc to mng trong iu

kin nhit cao, c th lng ng c
mng vanadium oxide thiu Oxy (v d,
VO2). Vn ny c khng nh bi
nhiu tc gi nc ngoi.
3.1.5. Ph Raman
Da vo ph Raman (hnh 6) ca cc
mu mng lng ng nhit khc
nhau, ta thy cc mng u th hin s kt
tinh tt. Khi nhit tng, cng
nh raman tng cao. Tt c cc nh u
c xc nh l ca tinh th V2O5 (ch sai
khc vi cm-1 so vi ph chun).
R rng rng, vic lng ng mng
nhit cao (n 4000C) lm tng s kt
tinh th ca tinh th V2O5 ln nhiu ln.
Tuy nhin, s xut hin pha V4O7 trong
ph XRD khng c th hin trong ph
Raman.
Hnh 6: Ph Raman ca mng Vanadium oxide

p sut phn x 3 mTorr, khong cch bia- 5 cm,
cng dng 0.2A, t l kh 25%.
4. Kt lun
Cng trnh ch to thnh cng mng mng V2O5 trn thy tinh t bia kim loi
Vanadium bng phng php phn x magnetron DC. ng thi cng xc nh c mt s
thng s to mng nh sau: t l kh O2/ (O2 +Ar) 25%, cng dng phn x 0.2A, nhit
2000C, p sut phn x 3 mmtorr. Vi iu kin lng ng ny, mng c to thnh c cu
trc tinh th tt, pht trin mnh theo mt mng (001). nhit cao hn (4000C ) mng bt
u xut hin cu trc a tinh th vi s pht trin ca cc mt mng khc nh: (001), (110),
(210),.. l nhng hng pht trin ca tinh th V2O5.
Ti liu tham kho
1. L.Holland, F.Inst.P., Vacuum Deposition of Thin Films, Chapman and Hall Ltd, 1970.
2. D.Mangalaral and Sa.K.Nadayandass, Structural properties of V2O5 thin films prepared by
vacuum evaporation, Material Science in Semiconductor Processing, Volume 6, Issues 5-6,
October-December 2003, Pages 543-546.
3. S. Ramamurthi, M. Rubin, Sputtered electrochromic V205 films, Thin Solid Films, 182(1989)
79-85.
4. Nilgun Ozer, Sevsen Sabuncu, John Cronin, Electrochromic properties of sol-gel deposited
Ti-doped vanadium oxide film, Thin Solid Films 388 (1999) 201-206.
Nhng
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MT S TNH CHT QUANG CA HT VNG C KCH THC NANOMET

Ngc An Bang a, Nguyn Trng Thnh b, Phng Th Thm a,
Dng nh Thng c, Ng B Thng a
a)
b)
Khoa Vt l, Trng HKH T nhin, HQG H ni, 334 Nguyn Tri, H ni, Vit nam
Vin Khoa hc Vt liu, Vin Khoa hc v Cng ngh Vit nam, 18 Hong Quc Vit, H ni
c)
Trng H S phm H ni 2, Xun Ha, Vnh Phc
E-mail: ngacanbang@googlemail.com
Tm tt: Cc ht vng (Au) c kch thc trung bnh di 100 nm c ch to thnh cng s
dng phng php quang ho v phng php ha kh. Cc thanh Au vi h s AR = 2,5 c
ch to bng phng php ha kh. Hnh dng v kch thc ca cc ht Au c kho st
nh gi thng qua nh TEM. Cu trc v thnh phn ca mu ch to c xc nh thng qua
ph XRD. i vi cc mu ht Au c hnh dng ta cu, ph hp th xut hin mt nh cng
hng plasmon b mt (SPR) duy nht trong vng kh kin. Ph hp th ca mu thanh Au gm
hai nh SPR phn bit khong 517 v 659 nm tng ng vi hai mode dao ng ngang v dao
ng dc.
1. M u
Cc ht v thanh vng (Au) c kch thc di 100 nm c nhiu ng dng c bit trong
nhiu lnh vc khc nhau [1]. Nhm kim sot v khng ch hnh dng, kch thc v ng
nht v kch thc ca ht kim loi hng lot cc phng php ch to khc nhau [1] v d nh
phng php ho kh [2], quang ho [3, 4]... v ang c nghin cu v s dng rng ri.
Trong phn ng quang ho, cc ion vng b kh thnh cc nguyn t vng s dng cc cht kh
khc nhau nh Triton X 100 [3, 4], Irgacure-2959 di tc dng ca tia , tia X [4], UV [3] v
ngay c nh sng mt tri [4]. Phng php ha kh l phng php thng dng ch to cc
ht Au c kch thc di 100 nm. Thng thng cc ht Au c ch to t vng halogenide s
dng cc cht kh khc nhau nh NaBH4 [1], Na3C6H5O7 [2]. Cc thanh Au vi t l aspect ratio
(AR, c nh ngha l t l gia ng knh v chiu di ca thanh) khc nhau ch yu c
ch to bng phng php ha kh qua hai giai on [5, 6].
Trong bo co ny, mt s kt qu nghin cu ch to ht Au c kch thc di 100 nm s
dng hai phng php ha kh v quang ha c trnh by chi tit. Mt s kt qu ban u
nghin cu ch to cc thanh Au bng phng php ha kh s c tho lun. Bo co cng
cp n mt s kt qu kho st hin tng cng hng plasmon b mt (Surface Plasmon
Resonance, SPR) ca cc ht v thanh Au.
2. Thc nghim
Cc ht vng (Au) c ch to s dng hai phng php khc nhau l phng php ha
kh [2] v phng php quang ho [3, 4]. i vi phng php ha kh, cc tin cht ban u
HAuCl4.3H2O (Sigma-Aldrich, 99,9 %) v Na3C6H5O7.2H2O (Scharlau, 99 %) c ha tan
trong nc kh ion ha vi t l mole xc nh. Hn hp HAuCl4 v Na3C6H5O7 vi t l nng
khc nhau c un si v khuy lin tc trn my khuy t. Mu sc ca dung dch thay i
t mu vng c trng ca Au3+ sang trong sut v tm en, cui cng l mu sm hay hng
tm ty thuc vo t l v nng gia cc tin cht ban u.
Phng php quang ha s dng cc tin cht ban u HAuCl4.3H2O v C14H22O(C2H4O)n
(Scharlau, 98 %). C14H22O(C2H4O)n cn c tn thng mi l Triton X 100 (TX 100). Cc tin
cht ban u c ho tan hon ton trong nc ct hai ln. Hn hp dung dch HAuCl4 v TX
100 vi t l mole xc nh c trn khuy u trn my khuy t nhit phng. Phn ng
quang ho kh cc ion Au3+ thnh Au0 c thc hin s dng ba (03) ngun bc x photon
Advances
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khc nhau. Cc ht Au kim loi hnh thnh v pht trin khi hn hp Au3+/TX 100 c khuy
trn u v chiu bng bc x tia X c trng K vi bc sng 1,54 ca Cu (40 kV, 40 mA,
Siemens D5005) trong 40 pht. Mt s mu ht vng cng c ch to s dng tc nhn kh
l bc x UV t n thu ngn cao p HPK 125W (Phillips) v nh sng mt tri. Cc mu thu
c sau phn ng trong sut v c mu hng nht n hng tm tu thuc vo t l mole gia
cc tin cht ban u.
Cc thanh Au c ch to bng phng php ha kh thng qua hai giai on [5, 6].
Dung dch mm cha cc ht Au c kch thc nh, di 4 nm, c ch to bng cch kh cc
ion Au3+ trong mi trng CTAB (hexadecylcetyltrimethylammonium bromide, Aldrich, 95 %)
s dng cht kh mnh l NaBH4 (Kanto, 92 %). Cc thanh Au hnh thnh v pht trin trong 24
h sau khi mt lng nh dung dch mm c a vo dung dch hn hp gm HAuCl4 (SigmaAldrich, 99,9 %), CTAB (Aldrich, 95 %), AgNO3 (Merck, 99,9 %)v C6H8O6 (Kanto, 99,5 %).
Cu trc tinh th ca cc mu keo vng c phn tch thng qua ph nhiu x tia X. Php o
c thc hin trn h nhiu x k Siemens D5005. Hnh dng v kch thc ca cc ht Au
c kho st thng qua nh chp s dng knh hin vi in t truyn qua TEM JEM-1010. Hin
tng cng hng plasmon b mt ca cc ht vng c kch thc nanomet c kho st
thng qua ph hp th ca mu nhit phng s dng h o UV-Vis-2450PC.
3. Kt qu v tho lun
Cc mu dung dch keo vng do chng ti ch to ra u hon ton trong sut, khng c hin
tng kt ta hay sa lng. i vi cc mu ch to bng phng php ha kh, sau phn ng,
cc ion m citrate bm ln trn b mt ca cc ht Au to thnh lp bo v ngn cn qu trnh kt
t ca cc ht Au. Khi c bo qun nhit di 100C trong bng ti, cc mu ha kh c
th gi c n nh trong 4 tun. Cc mu ch to bng phng php quang ha hon ton
trong sut, khng c hin tng kt ta hay sa lng ngay c sau khi bo qun trn ba thng trong
iu kin phng th nghim. TX 100 ng vai tr va l cht kh trong phn ng quang ho to
ra cc nguyn t vng trung ho v va l cht n nh v hot ho b mt bo v cc ht vng.
Cu trc tinh th ca cc mu c kho st thng qua ph nhiu x tia X. Ph nhiu x
tia X ca mu ch to bng phng php ha kh v quang ha c trnh by ln lt trn cc
hnh 1 v 2. Trong c hai trng hp, trn nn ph XRD ca dung mi v thy tinh, c th
quan st v xc nh c hai nh nhiu x tng ng vi cc vch nhiu x c trng ca cc
mt {111} v {200} trong mng fcc ca vng kim loi (PDF: 04-0784). nh nhiu x khong
38,250 (mu ha kh, hnh 1) v 38,330 (mu quang ha, hnh 2) ca mt {111} c d = 2,354
(mu ha kh) v d = 2,348 (mu quang ha) l sc nt v v tr ca cc nh l khp vi ph
chun nn c th gi thit cc ht Au trong c hai loi mu u c cu trc tinh th. Hng s
mng a c xc nh s dng nh {111} ca hai mu ha kh v quang ha ln lt l 4,08 v
4,07 . Bn rng FWHM ca nh nhiu x tng ng vi vch nhiu x c trng ca mt
{111} kh ln chng t kch thc ca cc ht Au l nh.
350
(111)
250
d111 = 2,3475 , a = 4,066
d200 = 2,0411 , a = 4,082
200
150
(200)
100
400
Intensity (a. u.)
Intensity (a. u.)
300
(111)
300
200
(200)
100
50
0
25
500
d111 = 2,3538 , a = 4,077
30
35
40
2
45
50
Hnh 1. Ph XRD ca mu ht Au ch to bng

phng php ha kh.
55
0
25
30
35
40
45
50
55
Hnh 2. Ph XRD ca mu ht Au ch to bng

phng php quang ha.
Nhng
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Hnh dng v kch thc ca cc ht vng c kho st thng qua nh TEM s dng
phn mm chuyn dng. nh TEM ca mt trong s mu ha kh c trnh by trn hnh 3.a.
Do c bao bc v bo v bi lp ion m citrate nn cc ht vng phn tn tt v khng c hin
tng kt m. Hnh 3.b l phn b kch thc trung bnh ca 126 ht Au xc nh t nh TEM
trn hnh 3.a. Kch thc ca cc ht Au phn b tng i tp trung vi trn 64 % s ht c
kch thc nm trong khong t 14 n 17 nm. Kch thc trung bnh ca cc ht c c
lng l 15,4 2,3 nm bng cch fit phn b kch thc ht s dng phn b Gauss. C th quan
st thy t nh TEM (hnh 3.a.), phn ln cc ht Au c hnh dng ta hnh cu. Hnh dng ca
cc ht Au c nh gi thng qua trn (circularity) C = 4 A P2 vi A v P ln lt l din
tch v chu vi ca ht xc nh t php phn tch nh lng nh TEM ca mu. Phn b trn
C c
Relative frequency (%)
Relative frequency
Gaussian fit
Hnh 3.b
25
Average size = 15.4 2.3 nm
20
15
10
5
0
12
16
20
24
28
Particle size (nm)

Hnh 3.c
30
Average circularity = 0.87 0.04
25
20
15
10
5
0
0.5
0.6
0.7
0.8
0.9
1.0
Circularity
Hnh 3. nh TEM (3.a), phn b kch thc (3.b) v trn (3.c) ca mu ht Au ch to bng phng
php ha kh.
Relative Frequency
Gaussian fit
40
Hnh 4.b

30
20
10
0
2
7 8 9 10 11 12 13 14 15
Particle size (nm)
Hnh 4.c
30
25
20
15
10
5
0
0.3
0.4
0.5
0.6
0.7
Circularity
0.8
0.9
1.0
Hnh 4. nh TEM (4.a), phn b kch thc (4.b) v trn (4.c) ca mu ht Au ch to bng phng
php quang ha s dng bc x tia X c trng K, bc sng 1,54 , ca Cu.
Advances
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Relative frequency
Gaussian fit
Hnh 5.b
20
15
10
12
16
20
Particle size (nm)
24
28
20
Relative Frequency (%)
Hnh 5.c
15
10
0
0.5
0.6
0.7
0.8
Circularity
0.9
1.0
Hnh 5. nh TEM (5.a), phn b kch thc (5.b.) v trn (5.c.) ca mu ht Au ch to bng phng
php quang ha s dng bc x UV ca n thy nhn cao p HPK 125W.
th hin trn hnh 3.c. Trn 80 % s ht c trn C ln hn 0,86 nhng khng c ht no trn
tuyt i (C = 1). trn trung bnh thng k l 0,87 0.04 .
nh TEM v cc kt qu phn tch nh TEM ca cc mu ch to bng phng php quang
ha s dng bc x UV v tia X c ln lt trnh by trn cc hnh 4 v 5. Do c bao bc v
bo v bi cht hot ho b mt khng tch in TX 100 nn cc ht vng phn tn kh tt v
khng c hin tng kt m. Kch thc trung bnh ca 205 ht Au trong nh TEM hnh 4.a.
ca mu ch to s dng bc x tia X c c lng l d = 9, 2 1, 6 nm bng cch fit phn b
kch thc ht s dng phn b Gauss (hnh 4.b). Kch thc ca cc ht Au trong mu phn b
tng i tp trung vi 84 % s ht c kch thc nm trong khong t 8 n 10 nm. Phn b
trn C ca 205 ht Au xc nh t nh TEM (hnh 4.a) c th hin trn hnh 4.c. Trn 75 % s
ht c trn C ln hn 0,85 nhng khng c ht no trn tuyt i. trn trung bnh thng
k l 0,84 0,09 . i vi mu ch to s dng bc x UV (hnh 5), kch thc v trn trung
bnh ca 129 ht Au (hnh 5.a) c xc nh ln lt l 8,0 3,3 nm (hnh 5.b) v
0,85 0,08 (hnh 5.c). Mc ng nht c v hnh dng v kch thc ca mu ch to s dng
bc x t n HPK 125W thp hn so vi mu ch to s dng bc x tia X c trng K ca Cu.
Mc n sc ca ngun photon kch thch ng vai tr quan trng v c nh hng trc tip
n ng nht v hnh dng v kch thc ca cc ht Au. Trong khi , cng sut ca ngun
kch thch nh hng n kch thc trung bnh ca cc ht [4].
Tnh cht quang ca cc ht vng c kch thc nanomet c kho st thng qua ph hp
th. Do hin tng cng hng plasmon b mt (SPR) [7], ph hp th ca cc ht Au kim loi
c kch thc nanomet c nh nm trong vng kh kin. V tr v s lng nh hp th SPR
ph thuc vo hnh dng, kch thc, hng s in mi ca bn thn ht kim loi v ph thuc c
vo hng s in mi ca mi trng xung quanh. Ph hp th ca mt s mu ht vng ch to
bng phng php ha kh c trnh by trn hnh 6. Vic ph hp th ca cc mu ht vng
ch xut hin mt nh hp th SPR duy nht khong 522 nm cho thy cc ht Au trong cc
mu c hnh dng cu hoc ta cu c kch thc nanomet vi duy nht mt mode dao ng
lng cc. Khi tng nng HAuCl4 tham gia phn ng, hp th cc i tng mnh (hnh 6).
Ph hp th, c chun ho, ca cc mu ht Au c ch to vi cc t l nng khc
nhau gia hai tin cht ban u (HAuCl4 v Na3C6H5O7) c th hin trn hnh 7. Bng cch
Nhng
_____________________________________________________________________________________
MR = 0.26
1.0
1.5
1.0
0.5
0.10
0.15
0.20
0.25
0.30
Molar ratio MR
MR = 0.21
MR = 0.14
0.5
0.8
0.6
0.39
0.17
0.26
520
540
560
Wavelength (nm)
0.4
550
540
0.2
MR = 0.10
MR=
0.29
Absorbance (a.u.)
1.5
1.0
2.0
SPR
522 nm
Absorbance (a.u.)
Absorbance (a.u.)
2.0
Maximum Absorbance (a.u.)
thay i t l nng gia hai tin cht ban u kch thc ca cc ht Au v do v tr ca

nh SPR ca mu c th thay i c trong vng kh kin (Hnh 7).
530
520
0.15 0.20 0.25 0.30 0.35 0.40
0.0
350 400 450 500 550 600 650 700 750 800
0.0
Wavelength (nm)
Hnh 6. Ph hp th ca cc mu ht Au ch
to bng phng php ha kh.
520
0.4
518
0.2
516
0.3
0.0
-3
CHAuCl = 15.8x10 mM
4
5 10 15 20 25 30 35
-3
Concentration of HAuCl4 (10 mM)
0.2
0.1
525 532
Under X-ray irradiation

Under UV irradiation
Under ordinary day light
543
1.0
Absorbance (a. u.)
Absorbance (a. u.)
0.4
1.2
Absorbance (a. u.)
-3
CHAuCl = 31.6x10 mM
SPR(nm)
0.5
Wavelength (nm)
Hnh 7. S ph thuc ca v tr ca nh SPR vo

t l mole gia cc tin cht ban u.
0.6
522
Molar ratio MR
350 400 450 500 550 600 650 700 750 800
0.8
0.6
0.4
0.2
-3
CHAuCl = 3.16x10 mM
4
0.0
350 400 450 500 550 600 650 700 750 800
0.0
400
Wavelength (nm)
Hnh 8. Ph hp th ca cc mu ht Au ch to
bng phng php quang ha s dng bc x UV
ca n HPK 125W.
500
600
700
800
Wavelength (nm)
Hnh 9. Ph hp th ( chun ho) ca cc mu

ht Au ch to s dng cc tc nhn kh khc
nhau.
0.8
659
Absorbance (a. u.)
0.6
517
0.4
0.2
0.0
400
500
600
700
800
900
Wavelength (nm)
Hnh 10. nh TEM ca mu thanh Au.
Hnh 11. Ph hp th ca mu thanh Au.
Trn hnh 8 l ph hp th ca cc mu keo vng c ch to bng phng php quang ho

vi nng HAuCl4 khc nhau trong khi gi nguyn nng ca cht kh TX 100 s dng bc
x UV ca n HPK 125W. Tng t nh i vi mu ha kh, ph hp th ca cc mu trn
ch c mt nh SPR duy nht ng vi cng hng plasmon lng cc. Khi nng HAuCl4
tng, hp th cc i tng mnh v c hin tng dch chuyn ca nh hp th SPR (Hnh
8). Bng cch thay i iu kin ch to, hon ton c th thay i v khng ch c kch
thc v, do , tnh cht quang ca cc ht Au.
Ph hp th ca ba mu ht Au c ch to bng phng php quang ho vi cng t l
nng gia HAuCl4 v TX 100 nhng s dng cc tc nhn kh khc nhau (bc x tia X c
trng K ca Cu, bc x ca n thu ngn cao p HPK 125W, v nh sng mt tri) c th
Advances
_____________________________________________________________________________________
hin trn hnh 9. tin so snh, cc ph hp th ny c chun ho s dng hp th cc

i tng ng. V tr ca nh hp th cng hng plasmon b mt SPR thay i mnh khi s
dng tc nhn kh khc nhau. C th, v tr ca nh SPR ca cc mu ch to s dng n HPK
125W, my nhiu x k D5005 v nh sng mt tri ln lt l 525nm, 532 nm v 543 nm. Ph
hp th ca mu ch to s dng nh sng mt tri c bn rng FWHM ln nht, bt i xng
v m rng v pha sng di. iu ny chng t mu ch to s dng ngun kch thch l nh
sng mt tri gm cc ht Au c kch thc trung bnh ln hn nhng km ng nht hn so vi
cc mu ch to s dng ngun n HPK 125W v bc x tia X c trng K ca Cu. nh SPR
ca mu ch to s dng vch K ca Cu c bn rng nh nht trong ba mu. Mc n sc
ca tc nhn kh nh hng mnh n ng nht v hnh dng v kch thc ca cc ht Au
v, do , bn rng ca nh SPR. Trong khi , cng sut ca ngun sng kch thch nh
hng mnh n kch thc trung bnh ca cc ht.
nh TEM v ph hp th ca mu thanh Au c th hin ln lt trn hnh 10 v 11. Mu
ch yu gm cc thanh Au vi mt sn phm ph rt nh. Tuy nhin, mc ng nht v
kch thc ca cc thanh trong mu cha cao. H s AR (Aspect ratio, c nh ngha l t l
gia ng knh v chiu di ca thanh) trung bnh c xc nh t nh TEM l 2,5. Ph hp
th ca mu gm hai nh SPR phn bit khong 517 v 659 nm c trng ca thanh Au vi
AR khong 2,5. nh SPR 517 nm tng ng vi mode dao ng lng cc ngang. nh SPR
659 nm tng ng vi mode dao ng dc v ph thuc mnh vo h s AR ca thanh.
4. Kt lun
Cc ht Au c hnh dng ta cu vi kch thc nanomet c ch to thnh cng s dng

phng php ha kh v phng php quang ha. Kt qu phn tch ph XRD ca cc mu
khng nh s tn ti ca cc ht vng kim loi c kch thc nanomet vi cu trc lp phng
tm mt fcc. Kt qu phn tch nh TEM ca cc mu cho thy phn ln cc ht Au c hnh dng
ta cu. Bng cch thay i t l gia cc tin cht ban u, HAuCl4 v Na3C6H5O7, phng
php ha kh c th s dng ch to cc mu ht Au c kch thc trung bnh trn 12 nm vi
ng nht kh cao v hnh dng v kch thc. Cng sut v mc n sc ca ngun
photon kch thch nh hng mnh n kch thc v ng nht v kch thc ca cc ht Au
ch to bng phng php quang ha. Vic ph hp th ca cc mu ht vng ch xut hin mt
nh hp th SPR duy nht trong khong t 516 n 550 nm cho thy cc ht Au trong cc mu
c hnh dng cu hoc ta cu c kch thc nanomet vi duy nht mt mode dao ng lng
cc. Cc thanh Au vi h s AR trung bnh khong 2,5 c ch to thnh cng s dng
phng php ha kh vi t l sn phm ph thp. Ph hp th ca mu thanh Au gm hai nh
SPR phn bit 517 v 659 nm ln lt tng ng vi mode dao ng lng cc ngang v dc.
Li cm n: Cng trnh ny c h tr v ti chnh t ti QT-08-14 ca HQG H ni. Cc
tc gi chn thnh cm n PGS. TS. L Vn V (CMS) gip thc hin cc php o ph
XRD, Trung tm Khoa hc Vt liu (CMS), Khoa Vt l, Trng HKHTN, HQG H ni
to iu kin cho cc tc gi thc hin nghin cu ny.
Ti liu tham kho
1.
2.
3.
4.
5.
6.
7.
Marie-Christine Daniel and Didier Astruc, Chemical Review 104 (2004) 293-346.
Turkevitch, J.; Stevenson, P. C.; Hillier, J., Discuss. Faraday Soc. 11 (1951) 55-75.
Mandal, M.; Ghosh, S. K.; Kundu, S.; Esumi, K.; Pal, T., Langmuir 18 (2002) 7792-7797.
Ngc An Bang, L Vn V, Tuyn tp bo co ti Hi ngh VLCR ln th V (2007) 773-776.
Nikoobakht, B.; El-Sayed, M. A. Chem. Mater. 15 (2003), 1957-1962.
Jana, N. R.; Gearheart, L.; Murphy, C. J. AdV. Mater. 13 (2001), 1389-1393.
Mie,G. Ann. Phys. 25(1908) 377-445.
Nhng
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INVESTIGATION OF SOME OPTICAL PROPERTIES OF

POLYMER-CAPPED Mn DOPED ZnS NANOCRYSTALLINE THIN FILMS
SYNTHESISED BY CHEMICAL METHOD
.
Tran Minh Thi a, Nguyen Minh Vuong b, Le Thi Thu Huyen c,
Pham Van Hai a, Dang Xuan Thu d
a)

b)
Laboratory center, Quynhon University, Vietnam
c)
Faculty of Physics, Military Technical Academy , Vietnam
d)
Faculty of chemistry, Hanoi University of Education, Vietnam
E-mail: tranminhthvl@gmail.com
.
1. M u
Vt liu ZnS l bn dn c b rng vng cm ln v thng. rng vng cm t c 3,6
eV i vi mu khi ZnS, v t ti 3,98 eV i vi vt liu nano ZnS 300 K [6], hoc 4,4 eV
[4] trong cu trc Wurzite. Hn na, nhit nng chy ca vt liu AIIBVI l rt cao. V vy
nano ZnS l mt trong cc vt liu c nhiu ha hn ng dng trong cc thit b quang in, diot
pht quang, cc thit b in hunh quang v cc ng dng khc.
Cc tnh cht quang ca vt liu nano ZnS rt nhy vi cc iu kin ch to nh [1] [2]: cc
ha cht ban u, pH, nng pha tp, ch x l nhit B rng vng cm ca vt liu
ZnS c th c iu khin bng vic pha thm tp cht, bc ph polymer v thay i iu kin
ch to khc. Polymer c vai tr nh mt mi trng bo v i vi cc ht nano ZnS. Cc tnh
cht quang ca cc ht nano ZnS c tng ln ng k khi chng c phn tn vo trong nn
polymer vi hm lng ti u [5]. Vn ny c gii thch bi hiu ng giam cm lng t,
hiu ng thay i kch thc ht v hiu ng b mt ca cc ht nano bc ph polymer 46
Cc ht nano ZnS pht ra hunh quang c bc sng trong di 420 480 nm. nhn c
bc x trong di nh sng nhn thy, ngi ta c th pha tp thm cc kim loi chuyn tip nh:
Mn2+, Cu2+, Ni.Trong cc kt qu nghin cu trc y, chng ti ch to thnh cng bt
nano ZnS pha tp Mn [7] c ph hunh quang mnh nht i vi mu pha tp 9% Mn .
pht trin cc nghin cu ng dng ca chng, trong bi bo ny chng ti trnh by cc
kt qu nghin cu v cc tnh cht quang ca mng mng ZnS pha tp 9% Mn bc ph polymer
vi cc hm lng PVA khc nhau. Cc nghin cu v nh hng ca hm lng PVA ti ph
hunh quang, kch thc ht v b rng khe nng lng ca cc mng mng ny cng c trnh
by.
2. Thc nghim
Cc vt liu nano ZnS pha tp Mn c ch to bng phng php ha t [7]. Cc dung
dch ha cht c tinh khit cao nh: dung dch I l Zn(CH3COO)2.2H2O 0,1M, dung dch II l
Mn(CH3COO)2.4H2O 0,1M v dung dch III l Na2S.9H2O 0,1M. Cht xc tc CH3OH:H2O
c s dng i vi cc dung dch I v II theo t l 1:1. Nc tinh khit H2O l dung mi cho
dung dch III.
Ch to mng mng nano tinh th ZnS pha tp Mn bc ph polymer vi hm lng PVA khc
nhau.
u tin, dung dch I v dung dch II c trn vi nhau theo t l thch hp nhm to ra vt
liu ZnS pha tp 9% Mn. pH c vai tr quan trng trong s tao thnh cc kt ta ZnS:Mn2+.
Bng tnh ton l thuyt, chng ti chn pH = 5 nhn c kt ta ZnS:Mn2+ nhng khng c
cc kt ta Zn(OH)2 trong dung dch. Sau ln lt cho cc lng 1g, 2g, 4g, 5g PVA ha tan
vo 100 ml dung dch I v II. Hn hp dung dch c PVA c nung nng 80oC, sau gim
Advances
_____________________________________________________________________________________
xung nhit phng. Dung dch III c nh tng git vo hn hp dung dch trong ng
nghim. Cc phn ng ha hc xy ra nh sau:
Mn(CH3COO)2+Na2S = MnS+2CH3COONa
Cc kt ta thu c sau phn ng c phn tn vo cht xc tc CH3OH:H2O vi t l 1:1.
Cc mng mng ZnS pha tp 9% Mn bc ph PVA trn thy tinh c thc hin bng
phng php quay ph vi tc ly tm 3000 vng/pht.
nghin cu cc tnh cht quang, cu trc ca vt liu, tnh ton rng khe nng lng,
kch thc ht, cc mu ny c o ph hunh quang bng ph k HP340-LP370 dng
ngun laser c bc sng 325nm nhit phng, o ph hp th bng ph k t ngoi JASCO
-V670 v o kch thc ht bng knh hin vi in t truyn qua TEM.
3. Cc kt qu v tho lun
3.1. Cc kt qu ph hunh quang
Trong hnh 1, chng ti k hiu cc mng mng nano tinh th ZnS pha tp 9% Mn bc ph
cc hm lng PVA khc nhau: MPVA0, MPVA1, MPVA2, MPVA4, MPVA5 (ln lt tng
ng vi cc lng 0g, 1g, 2g, 4g, 5g PVA ha tan vo hn hp dung dch). Hnh 1 cho thy rng
thy tinh khng nh hng ti ph hunh quang ca cc mng mng nano tinh th ZnS pha
tp 9% Mn bc ph PVA. iu ch rng, cc tham s quay ph c gi khng i khi to
cc mng mng, v vy, b dy ca cc mng mng khc nhau khng ng k. So snh ph
hunh quang ca cc mng mng MPVA1, MPVA2, MPVA4, MPVA5 vi ph hunh quang
ca mng mng MPVA0 (ng cong b), c th d dng thy cng hunh quang ca mng
mng MPVA5 (ng cong f) tng mnh hn trong gii bc sng 540 700 nm, tuy nhin
cng hunh quang ca cc mng mng MPVA1, MPVA2, MPVA4 dng nh tng mnh
trong ton b gii nh sng nhn thy.
thy r nh hng ca hm lng PVA ti ph hunh quang ca cc mng mng nano
tinh th ZnS pha tp 9% Mn, ph hunh quang ca cc mng mng MPVA0, MPVA1, MPVA2,
MPVA4, MPVA5 c phn tch bng phng php Gaussian
Hnh 2 cho thy th tch nh ph hunh quang ca mu tiu biu MPVA5. Ph hunh
quang ca mu ny bao gm 4 gii vi cc vch tng ng D1 (407 nm), D2 (470 nm), D3 (539
nm) v D4 (652 nm). Cc vch D2 v D3 tng ng vi hunh quang xanh v da cam ca vt liu
nano ZnS:Mn 7. Trong trng hp ny, vch D2 c quy cho s chuyn di t mc 4A1+4E1
6A1(S) do cc pht x ni ti ca cc khuyt tt, vacancy khi pha tp Mn vo bn dn ch
ZnS. Vch D3 c quy cho s chuyn di 4T1-6A1 hay A2-A1 ca ion Mn2+ trong trng tinh
th nano tinh th ZnS. Vch D1 c quy cho s ti hp ca cc electron b by bi cc defect
mc donor di vng dn.
D1
5500
D2
D3
505 nm
5000
4500
483 nm
Intensity (a.u)
4000
472 nm
3500
593 nm
D4
(a)
(b)
(c)
(d)
(e)
(f)
(f)
(e)
3000
(d)
2500
2000
glass
MPVA0
MPVA1
MPVA2
MPVA4
MPVA5
(b)
(c)
1500
D3 593 nm
5000
4500
4000
3500
D2 470 nm
3000
D4 652 nm
2500
D1407 nm
2000
1500
1000
500
5500
Intensity (a.u)
6000
(a)
1000
500
-500
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
Wavelength (nm)
Fig. 1. The spectra PL of MPVA0, MPVA1,

MPVA2, MPVA4, MPVA5 samples
0
300
400
500
600
700
800
900
1000
Wavelength (nm)
Fig. 2. The separated peak of PL spectrum

by Gaussian method for MPVA5 thin film
Nhng
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Vch D4 tng ng vi hunh quang c quy bi pht x do hiu ng b mt hoc cc

khuyt tt trong ZnS:Mn. Hnh 1 cng cho thy cc vch D3 (chnh l cc nh D3 ca cc ph)
khng dch chuyn khi hm lng PVA tng. Khi so snh cc nh ph hunh quang ca cc
mu trong vng 450 550 nm, c th thy rng cc nh ph 472 nm, 483 nm v 505 nm ca cc
mu MPVA1, MPVA2, MPVA4 thay i r rt vi hm lng PVA v cng hunh quang
tng mnh nht i vi mu MPVA1.
Cc s liu thng k v cng hunh quang ca cc vch D1, D2, D3, D4 v t s cng
gia cc vch D1, D2, D3 v vch D4 nh trong bng 1.
Bng 1: Cng ca cc vch D1, D2, D3, D4 v t s cng gia cc vch
D1, D2, D3 i vi vch D4 ca cc mu PVA1, PVA2, PVA4, PVA5
MPVA1
MPVA2
MPVA4
MPVA5
ID1
ID2
ID3
ID4
(.v.t.y)
(.v.t.y)
(.v.t.y)
(.v.t.y)
1030
1561
990
983
3350
3940
3220
2551
4493
2653
2237
3763
1298
1379
879
1244
ID1/ID4
0,31
0,39
0,31
0,38
ID2/ID4
1,3
0,67
0,69
1,47
ID3/ID4
0,39
0,35
0,27
0,49
T cc kt qu phn tch trn, c th nhn thy rng:

Mng mng MPVA1 c cc vch hunh quang 470 nm v 593 nm mnh nht (vo
khong 2 2,5 ln so vi mu MPVA0)
- Mng mng MPVA5 c vch 593 nm vi cng hunh quang tng 2,5 ln so vi mu
mng
MPVA0.
3.2. Cc kt qu ph hp th.
Cng nh sng truyn qua mi trng hp th c biu th bng nh lut Beer-Lambert:
(1)
I ( ) = .I 0 ( ).e ( ) d
Trong I 0 ( ) , I ( ) l cng nh sng ti mt trc v mt sau ca mi trng, ( ) l
h s hp th ca mi trng ny v lin quan ti photon c nng lng h ; d l b dy ca
mi trng.
Cng thc (1) c th vit di dng logarit:
I ( )
I ( )
( ).d = ln 0
= ln 10. lg 0
= 2,3. A
(2)
I ( )
I ( )
110
1.5
c
d
90
80
70
2
a: ZnS-9%Mn-MPVA1
b: ZnS-9%Mn-MPVA2
c: ZnS-9%Mn-MPVA4
d: ZnS-9%Mn-MPVA5
e: ZnS-9%Mn-MPVA0
2.0
(Ah ) (eV)
Absorption (a.u)
2.5
100
1.0
60
50
ZnS-9%Mn-MPVA0
ZnS-9%Mn-MPVA1
ZnS-9%Mn-MPVA2
ZnS-9%Mn-MPVA4
ZnS-9%Mn-MPVA5
Eg=3.79 eV
Eg=3.89 eV
Eg=3.86 eV
Eg=3.77 eV
Eg=3.73 eV
40
30
0.5
20
10
0.0
300
400
500
600
700
800
Wavelength (nm)
Fig. 3: The absorption spectra of MPVA0,

MPVA1, MPVA2, MPVA4, MPVA5 thin film
0
1.50 1.75 2.00 2.25 2.50 2.75 3.00 3.25 3.50 3.75 4.00 4.25 4.50
h (eV)
Fig. 4. The dependence of the ( Ah ) 2 and h for

the PVA0, PVA1, PVA2, PVA4
and PVA5 thin films.
Advances
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I 0 ( )
l hp th. Hnh 3 cho thy s ph thuc ca hp th A (hoc h s
I ( )
) vo bc sng nh sng. Mi lin h gia h s hp th v nng lng photon c trnh
by bi phng trnh sau 246:
n
K (h Eg ) 2
(3)
=
h
Trong K l hng s, E g l b rng khe nng lng; n = 1 i vi vt liu bn dn vng
cm thng.
T phng trnh (2) v (3), c th nhn c:
Kd 2
( Ah ) 2 =
(h Eg )
(4)
2,3
Hnh 4 biu th s ph thuc ca ( Ah ) 2 vo h i vi cc mu PVA0, PVA1, PVA2,
PVA4 and PVA5. T hnh 4, cc gi tr ca khe nng lng Eg c xc nh bng cch ngoi
suy phn thng ca cc ng cong ( Ah ) 2 - h ti giao im vi trc nng lng h . Cc
gi tr khe nng lng l 3,79 eV, 3,89 eV, 3,86 eV, 3,77 eV and 3,73 eV tng ng i vi cc
mu mng mng PVA0, PVA1, PVA2, PVA4 v PVA5. Cc kt qu ny c a ra trong
bng 2.
D thy rng, gi tr Eg gim i khi tng hm lng PVA. Tuy nhin cc gi tr khe nng
lng ca cc mu c PVA vn ln hn khe nng lng ca mu khi ZnS (3,6 eV).
T lch khe nng lng g ca mu mng mng so vi khe nng lng ca mu khi,
bn knh tinh th c th c xc nh theo mi lin h sau 46:
h2
1,8e 2
E g = E g (mng ) E g (khi ) =
(5)
r
8r 2
Vi A = lg
me*mh*
trong me* = 0,34mo , m h* = 0,24mo , mo l khi
Vi Eg (khi) = 3,6 (eV), = *
*
me + mh
lng ca electron t do, l hng s in mi. Cc kt qu tnh ton bn knh tinh th r i vi
cc mng mng ny c a ra trong bng 2.
Bng 2: Khe nng lng v bn knh tinh th ca cc mng mng MPVA0, MPVA1, MPVA2,
MPVA4, MPVA5
Mng mng
MPVA0
MPVA1
MPVA2
MPVA4
MPVA5
Eg(eV)
3,79
3,89
3,86
3,77
3,73
r(nm)
4,8
3,6
3,9
5,5
7,4
Cc kt qu cho thy rng cc gi tr Eg gim v bn knh

tinh th tng khi tng hm lng PVA. Mng mng MPVA1
l tt nht vi Eg = 3,89 eV v r = 3,6 nm.
S gim kch thc ht khi tng hm lng PVA c th
gii thch nh sau: khi tng hm lng PVA, nht ca
hn hp dung dch tng, nhng tc quay ph l nh nhau
i vi cc mu, do kch thc cc ht tng ln do s kt
m ca cc ht . Chng ti cho rng c th nhn c gi
tr Eg ln v kch thc ht nh khi hn hp dung dch c
rung siu m vi tn s v thi gian thch hp.
Trong nh TEM (hnh 5), kch thc trung bnh ca ht
Hnh 5. nh TEM ca mu PVA1
Nhng
_____________________________________________________________________________________
vo khong 3 nm i vi mu MPVA1. Vt liu nano c cc tnh cht c bit so vi vt liu

khi. Khi kch thc ht ca mu ZnS t ti bn knh exiton Bohr (rB) ca ZnS (vo khong 2,5
nm) v c tnh theo cng thc 4:
h 2
h 2 1
1
rB = 2 = 2 * + *
(6)
e e me mh
(Vi = 8,76 l hng s in mi ca vt liu).
Cc kt qu trn cho php gii thch cc tnh cht quang ca chng bng hiu ng giam cm
lng t ca cc ht nano ZnS:Mn2+ trong nn polymer PVA.
4. Kt lun
Cc mng mng ZnS pha tp 9% Mn bc ph polymer PVA vi hm lng khc nhau c
ch to thnh cng trn thy tinh bng hng ph quay ph. Cc kt qu nghin cu tnh cht
quang, vi cu trc, ph hunh quang cho thy rng PVA c vai tr ca lp bo v nhng khng
nh hng ti bc sng pht quang ca cc ht nano. Vi hm lng PVA thch hp, cng
hunh quang v b rng khe nng lng ca mng mng nano tinh th tng ln ng k. Cc kt
qu nghin cu cho thy tim nng ng dng ca vt liu ny..
Li cm n: Bi bo c hon thnh c s h tr ca ti cp B v khoa hc v cng ngh

m s 17TC-08-12
Ti liu tham kho
1. Balram Tripathi, Y.K. Vijay, Sanjay Wate, F. Singh, D.K. Avasthy, Synthesis and
luminescence properties of mangansese-doped ZnS nanocrystals, Solid-State Electronics
51(2007) 81-84.
2. ChuanweiCheng , Guoyue Xu , Haiqian Zhang, Jieming Cao, Peipei Jiao, Xiaoxia Wang,
Low-temperature synthesis and optical properties of wurtzite ZnS nanowires, Materials
Letters 60 (2006) 35613564.
3. Poulomi Roy, Jyoti R. Ota, Suneel Kumar Srivastava, Crystalline ZnS thin films by chemical
bath deposition method and its characterization, Thin solid Films 515 (2006) 1912-1917.
4. P.K. Ghosh, S. Jana, S. Nandy, K.K. Chattopadhyay, Size-dependent optical and dielectric
properties of nanocrystalline ZnS thin films synthesizes via rf-magnetron sputtering
technique, Matterials Research Bulletin 42 (2007) 505-514.
5. Kevin J.Huang, Poorna Rajendran, Chekesha M. Liddell, Chemical bath deposition synthesis
of sub-micron ZnS coated polystyrene, Journal of colloid and Interface Science 308 (2007)
112-120.
6. R.Maity, U.N. Maiti, M.K. Mitra, K.K. Chattopadhyay, Synthesis and optical
characterization of polymer-capped nanocrystalline ZnS thin films by chemical process,
Physica E33(2006)104109.
7. Nguyen Minh Thuy, Do Thi Sam, Tran Minh Thi, Nguyen The Khoi. Synthesis of MnDoped ZnS and the dopant-induced photoluminescence properties. Journal of Nonlinear
Optical Physics & Materials. Vol. 17, No. 2 (2008) 1-8
Advances
_____________________________________________________________________________________
HUNH QUANG CA MU BT NANO SnO2:Sb

CH TO BNG PHNG PHP THY NHIT
Nguyen Ngoc Long, Nguyen Tu Niem, Le Thi Thanh Binh,
Nguyen Thanh Binh, Nguyen Viet Duc
Faculty of Physics, Hanoi University of Science
334 Nguyen Trai road, Thanh Xuan distr., Ha Noi, Viet Nam
E-mail: binhltt@vnu.edu.vn
Tm tt: Bt nan SnO2 pha tp Sb c ch to bng phng php thy nhit. Cu trc tinh th
v hnh thi hc cc ht c kho st bng ph nhiu x tia X v nh hin vi in t truyn qua.
Kt qu cho thy SnO2:Sb c cu trc rutile vi ng knh trong khong 5 nm. Hunh quang ca
cc mu SnO2:Sb c kho st ti nhit phng v so snh vi hunh quang ca cc mu SnO2
khng pha tp ch to cng cc iu kin. Cc ph kch thch hunh quang cho thng tin v b
hp th ca cc mu.
1. Gii thiu
Oxyt kim loi SnO2 l bn dn loi n c rng vng cm ln 3,64 eV l mt trong cc vt
liu quan trng ch to cc linh kin in t, quang in t v cc loi senso nhy kh. Cc
c tnh ca SnO2 c th thay i khi pha tp. Mt trong cc tp cht thng c s dng cho
SnO2 l Sb. Nhiu nhm nghin cu trn th gii quan tm n quy trnh ch to SnO2 di
dng bt nan v tnh cht quang ca chng [1, 2]. Trong bo co ny chng ti trnh by v nh
hng ca tp cht Sb ln tnh cht hunh quang ca SnO2 ch to bng phng php thy nhit.
2. Thc nghim
ch to SnO2 cu trc nan bng phng php thy nhit chng ti s dng vt liu
ngun l SnCl4.5H2O v cht pha tp l dung dch SbCl3 0.018M. u tin cho 43,7 gam
SnCl4.5H2O ha tan hon ton trong 70 ml dung dch C2H5OH trn my khuy t quay vi tc
3 trong thi gian 1 h. Sn phm ca qu trnh ny l 75 ml dung dch c cha mt kt ta mu
trng sa. Chia i sn phm, mt phn gi nguyn cn phn kia pha 10 ml dung dch tp cht
SbCl3 0.018 M c hn hp c cha nng ion Sb l 3%. Ton b hn hp ny c
khuy trn lin tc trn my khuy t nhit 500C v tc 3, trong khi khuy cht xc tc
NH3 c cho vo hn hp cho n khi t pH = 9. Sn phm thu c l mt hn hp mu
vng nht. Ra cc sn phm nhiu ln bng nc ct hai ln, sau chia mi sn phm thnh 3
phn bng nhau. Tip theo cc mu c a vo ni hp thy nhit. Qu trnh thy nhit c
thc hin 3 ln, mi ln gm 2 mu (mt mu SnO2 tinh khit v mt mu SnO2:Sb3%), thi
gian mu l 24 h, nhit c chn khc nhau: 1800C, 2000C v 2200C. Kt qu cho thy
cc mu SnO2 tinh khit u c mu trng sa, cn cc mu c pha tp cht c mu xanh xm
nht, mu c nhit cao hn th c mu nht hn. Cc mu c lc ra nhiu ln bng
nc ct hai ln v c sy kh nhit 1000C trong 6 h v cho sn phm cui cng l bt
kh, mn.
Cu trc tinh th v hnh thi hc cc ht c kho st bng ph nhiu x tia X trn thit
b Brucker D5005 v nh hin vi in t truyn qua trn thit b JEOL JEM 1010. Ph hunh
quang v kch thch hunh quang c o trn thit b FL3-22 Jobin Yvon Spex.
3. Kt qu v tho lun
Trn hnh 1 l ph nhiu x tia X ca cc mu SnO2 v SnO2:Sb ch to ti cc nhit khc
nhau. Kt qu kho st ph nhiu x tia X cho thy cc mu gm cc ht a tinh th, c cu trc
Nhng
_____________________________________________________________________________________
mng t gic. Kch thc trung bnh ca ht tinh th trong cc mu c xc nh theo cng
thc Scherrer v tng hp trong bng 1. Cc kch thc ht tnh t ph nhiu x tia X kh ph
hp vi kch thc hnh hc ca ht xc nh t nh TEM cc mu c tng hp trong bng 1.
Trn hnh 2 l mt nh TEM ca mu SnO2 ch to 1800C v mt mu SnO2:Sb ch to
2000C. nh TEM ca cc mu khc cng c phn b ht v kch thc tng t. C th thy
rng kch thc ht tng khng ng k khi nhit tng i vi c hai loi mu khng pha tp
v c pha tp. Kch thc ht ca mu c pha tp nh hn ca mu khng pha tp khi chng
c ch to cng mt nhit .
Hnh 1. Ph nhiu x tia X cc mu SnO2 v SnO2:Sb
Hnh 2. nh TEM ca cc mu SnO2 v SnO2:Sb

Bng 1. Kch thc trung bnh ca ht xc nh t ph X-Ray (1) v t nh TEM (2)
Mu
SnO2
SnO2
SnO2
SnO2:Sb
SnO2:Sb
SnO2:Sb
Nhit T(0C)
180
200
220
180
200
220
Kch thc ht (1)

4,5 nm
4,7 nm
5,0 nm
4,7 nm
4,8 nm
5,1 nm
Kch thc ht (2)

4,2 nm
4,3 nm
4,3 nm
5,1 nm
5,1 nm
5,3 nm
Ph hunh quang v kch thch hunh quang ca cc mu c o ti nhit phng. Trong

bo co ny chng ti i su phn tch c im hunh quang ca cc mu SnO2 khng pha tp
v pha tp Sb vi cc ch nhit thy nhit khc nhau. Trn hnh 3a v 3b l cc ph
hunh quang ca tt c 6 mu vi bc sng kch thch ti 267 nm v 314 nm.
Advances
_____________________________________________________________________________________
1.50x10
1.25x10
1: SnO2:Sb 180 C
1: SnO2:Sb 180 C
2: SnO2:Sb 200 C
4x10
3: SnO2:Sb 220 C
Cng (.v.t.)
Cng (.v.t.)
4: SnO2 180 C
o
7.50x10
5: SnO2 200 C
6: SnO2 220 C
5.00x10
2.50x10
0.00
300
3: SnO2:Sb 220 C
1.00x10
2: SnO2:Sb 200 C
4: SnO2 180 C
5: SnO2 200 C
o
3x10
6: SnO2 220 C
2x10
3
5
1x10
2
350
400
450
500
Bc sng (nm)
Hnh 3a. Ph hunh quang ca cc mu SnO2 v
SnO2:Sb ch to cc nhit khc nhau, bc sng
kch thch 267 nm
0
350
400
450
500
550
Bc sng (nm)
Hnh 3b. Ph hunh quang ca cc mu SnO2 v
SnO2:Sb ch to cc nhit khc nhau, bc sng
kch thch 314 nm
So snh cc ph hunh quang c kch thch bng bc sng 267 nm c th nhn thy cc
mu pha tp u pht hunh quang 336,7 nm (3,68 eV). Trong khi cc mu khng pha tp
ch quan st c di hunh quang 400 nm 475 nm vi cc nh pht yu ti 397,8 nm (3,11
eV), 421,3 nm (2,94 eV), 440,9 nm (2,81 eV), 450,7 nm (2,75 eV), 471,7 nm (2,63 eV), ln
trong nn ca di.
quan st r hn di hunh quang xanh l cy, bc sng kch thch c chn bng
314 nm. Hnh 3b cho thy khi c kch thch bng bc sng 314 nm, ph hunh quang cc
mu khng pha tp c mt nh rng ti 508,5 nm (2,44 eV). nh hunh quang ny cng
c mt s cng trnh [3] nghin cu v cu trc nan SnO2 quan st c v a ra gi thit
v s tham gia ca cc sai hng trong qu trnh hnh thnh cu trc nan nh l cc tm hunh
quang. Ring ph hunh quang ca mu ch to ti 2000C c thm hai vai ph ti 416 nm (2,99
eV) v 442 nm (2,80 eV). Cng trn hnh 3b di hunh quang 400 nm 500 nm ca cc mu pha
tp cho thy cc nh nh thay i t mu ny sang mu khc. Mu ch to 2000C pht hunh
quang ti cc nh 382 nm (3,24 eV), 416 nm (2,99 eV), 4,42 nm (2,80 eV). Ph hunh quang
ca cc mu khc ch c hai nh. i vi mu ch to 2200C, cc nh l 390 nm (3,18 eV)
v 435 nm (2,85 eV), cn i vi mu ch to ti 1800C, cc nh tng ng l 398,6 nm
(3,11 eV) v 442 nm (2,8 eV). C ch hunh quang ca cc nh trong di tm thng c quy
cho ti hp cp Donor - Acceptor [4, 5] hoc ti hp gia in t vng dn vi tm sai hng
mng nh Vo++ [1, 6, 7, 8].
Nng lng cc nh ph kch thch hunh quang tng ng vi nng lng hp th photon
cho qu trnh ti hp bc x. V vy, i vi tt c cc mu, ph kch thch hunh quang ti mt
s bc sng pht x c kho st. Trn hnh 4a l ph kch thch hunh quang ca mu
khng pha tp ch to ti 2200C. Cc ph ny c kho st ti cc bc sng nh hunh quang
tng ng l 505 nm, 469 nm, 449 nm, 440 nm, 421 nm. C th nhn thy rng tt c cc ph
u c mt di rng min sng ngn (k hiu l di A) vi nh trong khong 311,2 nm 321
nm v mt s nh nh trong min sng di (k hiu l di B) trong khong 369 nm 432 nm.
Nh vy c th nh gi rng trong mu khng pha tp ch to ti 2200C xy ra mt s qu
trnh hp th ng vi nng lng cc nh ph kch thch hunh quang, c th l 310,7 nm (3,99
eV), 321 nm (3,86 eV), 369,9 nm (3,35 eV), 383,6 nm (3,23 eV), 391 nm (3,17 eV), 402 nm
(3,08 eV), 431 nm (2,87 eV). Kt qu kho st ph kch thch hunh quang i vi cc mu ch
to ti 1800C v 2000C cng cho cc gi tr nng lng tng t, tuy nhin cng hunh
quang min A nh hn min B rt nhiu.
Ph kch thch hunh quang ca cc mu pha tp cng c kho st ti cng cc bc sng
pht x nh i vi cc mu khng pha tp tin so snh. Trn hnh 4b l cc ph ca mu ch
to ti 2200C. Trong cc ph kch thch hunh quang ny cng quan st c hai di pht x. Di
Nhng
_____________________________________________________________________________________
7x10
6x10
5x10
4x10
1: 337 nm
2: 380 nm
3: 397 nm
4: 421 nm
5: 440 nm
6: 449 nm
7: 469 nm
8: 505 nm
1
2
Cng (.v.t.)
Cng (.v.t.)
1.2x10
1: 505 nm
2: 469 nm
3: 449 nm
4: 440 nm
5: 421 nm
3
3x10
2x10
1x10
1.0x10
8.0x10
3
5
6.0x10
4.0x10
2.0x10
5
300
350
400
450
500
Bc sng (nm)
Hnh 4a. Ph kch thch hunh quang ti cc nh
pht hunh quang ca cc mu SnO2 ch to ti
T=2200C
0.0
250
250
300
6
350
400
Bc sng (nm)
Hnh 4b. Ph kch thch hunh quang ti cc nh
pht hunh quang ca cc mu SnO2:Sb ch to ti
T=2200C
7x10
1: SnO2:Sb 180 C
6x10
3: SnO2:Sb 220 C
Cng (.v.t.)
Cng (.v.t.)
1.2x10
2: SnO2:Sb 200 C
5x10
4x10
2
6
3x10
2x10
1
3
1x10
0
220
1: SnO2 220 C
1.0x10
2: SnO2 200 C
o
3: SnO2 180 C
8.0x10
6.0x10
4.0x10
2.0x10
0.0
240
260
280
300
320
340
360
380
400
280
Bc sng (nm)
Hnh 5a. Ph kch thch hunh quang ca cc mu
SnO2:Sb ti bc sng bc x 421 nm
300
320
340
360
380
400
420
440
460
Bc sng (nm)
Hnh 5b. Ph kch thch hunh quang ca cc mu
SnO2 ti bc sng bc x 505 nm
min sng ngn (di A) c nh ti 261 nm (4,75 eV) v 269 nm (4,61 eV), di rng min
sng di (di B) c nh vo c 358 nm (3,46 eV). Nh vy ph kch thch hunh quang ca cc
mu pha tp v khng pha tp ( cng cc ch to mu v ch kho st ph) c s khc
bit v gi tr nng lng hp th gy bc x hunh quang
so snh nng lng hp th ca cc mu, cc ph kch thch hunh quang ti cng mt
nh bc x c biu din trn cng mt th. Trn hnh 5a, ti bc sng pht x 421 nm,
ph kch thch hunh quang ca cc mu pha tp th hin mt nh hp th ln cn 367 nm
(3,38 eV) v mt b hp th 269 nm (4,61 eV) i vi mu ch to ti 2000C v 2200C, b hp
th dch v 290 nm (4,27 eV) i vi mu ch to ti 1800C. Ph kch thch hunh quang ti mt
vi bc sng khc cng cho kt qu tng t.
B hp th ca cc mu khng pha tp c xc nh qua ph kch thch hunh quang ti
nh bc x 505 nm. Trn hnh 5b c th nhn thy tt c cc mu khng pha tp u cho mt
nh ph ti ln cn bc sng 320 nm (3,87 eV), cc nh 383 nm (3,23 eV), 430 nm (2,88 eV),
434 nm (2,85 eV) c th quan st c trong cc ph vi cng thay i t mu ny qua mu
khc. Nh vy, so vi nng lng vng cm ca cc mu SnO2 n tinh th (3,64 eV) th b hp
th ca cc mu khng pha tp m rng v pha nng lng cao c 0,24 eV. Cn b hp th ca
cc mu pha tp m rng v pha nng lng cao mt lng ln hn nhiu, l 0,97 eV i vi
mu ch to ti 2000C v ti 2200C v 0,63 eV i vi mu ch to ti 1800C. Nguyn nhn ca
Advances
_____________________________________________________________________________________
s dch nh nng lng ny c th quy cho hiu ng gim kch thc ca cc ht SnO2 ti thang
nan. i vi cc mu khng pha tp tng nng lng vng cm c 0,24 eV ng vi kch
thc 5,2 nm ph hp vi kch thc ca cc ht SnO2 c xc nh t ph X-Ray v nh TEM
trong bng 1. Tuy nhin nu tnh theo cng thc tng rng vng cm ca cc ht nan hnh
cu th rng vng cm ca SnO2 tng c 0,97 eV th kch thc ht nan SnO2 phi
gim xung ti 3 nm, tng ng vi mc tng 0,63 eV l kch thc 3,5 nm. Trong khi cc
kt qu t ph X-Ray v nh TEM trong bng 1 u cho thy cc mu pha tp c kch thc ln
hn 4 nm (bn knh ht c 2 nm). Chnh v vy vic dch b hp th trong cc mu SnO2: Sb cn
phi nghin cu thm lm sng t nguyn nhn. Vic dch b hp th ny ngoi nh hng
ca s gim kch thc ht cn c s ng gp ca tp cht Sb.
4. Kt lun
Cc mu bt SnO2 v SnO2:Sb kch thc nan c ch to bng phng php thy
nhit.Trong khong nhit t 1800C 2200C kch thc ht vo c 5 nm v t thay i theo
nhit . B hp th ca cc ht SnO2 dch chuyn vo c 0,24 eV do nh hng ca hiu ng
lng t khi kch thc cc ht gim xung di bn knh Bohr. S c mt ca cc tp cht Sb
gp phn lm tng s dch b hp th trong cc mu c pha tp.
Li cm n: Cng trnh ny c hon thnh vi s h tr ca ti nghin cu c bn cp
nh nc 4 05 506. Cc tc gi xin cm n PGS.TS L Vn V gip cc php o nhiu x
tia X.
Ti liu tham kho
1.
2.
3.
4.
5.
6.
7.
8.
D. Chen, L. Gao, J. Colloid Interface Sci. 279 (2004) 137 - 142.

Z. Li, X. Li, X. Zhang, Y. Qian, J. Crystal growth 291 (2006) 258 - 261
J. Q. Hu, Y. Bando, D. Golberg, Chem. Phys. Lett. 372 (2003) 758 - 762.
T. W. Kim, D. U. Lee, D. C. Choo, J. H. Kim, H. J. Kim, J. H. Jeong, M. Jung, J. H. Bahang,
H. L. Park, Y.S.Yoon, J. Y. Kim, J. Phys. Chem. Solids 63 (2002) 881- 885.
N. T. Bnh, L. T. T. Bnh, L. D. Khnh, N. N. Long, VNU. J Sci. Math. Phys. 20 (2004) 14 16.
F. Gu, S. F. Wang, M. K. Lu, G. J. Zhou, D. Xu, D.R.Yuan, J.Phys. Chem. B 108 (2004),
8119 - 8123.
J. Jeong, S. P. Choi, C.I. Chang, D.C.Shin, J. S. Park, B.T. Lee, Y. J. Park, H. J. Song, Solid
State Com. 127 (2003), 595 - 597.
C. Terrier, J. P. Chatelon, J. A. Roger, Thin Solid Films 295 (1997), 95 - 100.
Nhng
_____________________________________________________________________________________
MT S NGHIN CU QUANG PH V VT LIU N TINH TH

LiCaAlF6 PHA TP Eu.
V Phi Tuyn a, Nguyn Trng Thanh a, V Xun Quang a, Phan Tin Dng a
Kiyoshi Shimamura b, Garcia Villora b
a)

b)
National Institute of Materials Science, Japan
1. Gii thiu
Vt liu nn LiCaAlF6 ang c ch nhiu khai thc cc tnh nng nhm ng dng ca
cng ngh hin i, nh cc linh kin quang hc s dng trong di UV v VUV (112nm), [1],
hay lm vt liu laser iu tn vi bc sng t ngoi hoc tinh th nhp nhy (scintilator )
ghi nhn nhng tn hiu X-ray hay bc x hay . N cng c th c ng dng lm linh kin
vi k thut quang khc vi nhng kch thc nh ti c 157nm. Mt trong nhng ng dng
tim nng c th c khai thc khc nhm tng hiu sut pht quang khi vt liu ny c lm
nn bt pht quang dng cho linh kin hin th trn c s phng in xenon (172nm).
Nhng nghin cu v vt liu ny hin nay cha nhiu, ch yu tp trung cc mu pha cc tp
kim loi chuyn tip v cc loi t him khc nh Ce [2], Tm [3]. Mt s t mu pha tp Eu
cng c nghin cu, nhng ch yu nghin cu v hiu ng truyn nng lng trong vng
VUV.[5] y chng ti ch nghin cu hin tng hunh quang v tp trung trong vng UV v
Vis
2. Th nghim v kt qu
Cc mu th nghim trong bi bo ny l tinh th LiCaAlF6: Eu2+ c ch to theo phng
php nui tinh th ca Czochralski ti phng tinh th hc ca Vin nghin cu khoa hc vt liu
Nht bn (NIMS).[4] Tuy nhin nhng nghin cu c tnh ca loi vt liu ny ti nay vn ch
bc u Trong bo co ny chng ti mun nh gi v hiu sut hunh quang ca loi vt
liu ny. Mt trong nhng thng s lin quan nh gi hiu sut quang hc ca loi vt liu
ny l vic xc nh h s Huang Rhys thng qua cc php oca ph hp th, hunh quang v
Raman. Cc mu th nghim c ct v mi mng vi hai mt song song d thc hin cc
php o quang hc. Tinh th LiCaAlF6 ti nhit phng c cu trc i xng theo nhm khng
gian P31c vi hai nhm c bn l AlF6 v LiF6 c cu trc bt din v c lin kt cnh bi hai
ion F- gp chung. Ion Ca chim v tr ti tm ca lc gic theo mt phng chiu vung gc vi
trc C v c lin kt bi cc Ion F- ti gc bt din ca AlF6 theo i xng trc bc 3 (Hnh 1).
Tinh th ca vt liu nn ny c kch thc mng a=b=5,008A0; c=9,643A. [4],[6].
Hnh 1: Cu trc mng tinh th ca LiCaAlF6
Advances
_____________________________________________________________________________________
Qu trnh pha tp Eu2+ vo vt liu nn LiCaAlF6 ny c thc hin trong mi trng kh.
iu kin ny gip vic thc hin vic pha tp Eu2+ thnh cng vi t l cao. Vi kch thc ca
ion Al3+: 67,5pm v Ca2+: 114pm th c th d thy cc ion Eu2+ vI bn knh 98pm gn vi
114pm hn, do vy nhiu kh nng Ion Eu2+ s thay th vo v tr ca Ca2+. Hn na iu ny
cng d c thc hin, khi ho tr ca chng l tng ng m bo iu kin cn bng
in tch trong iu kin lin kt.
Ph hp th ca tinh th LiCaAlF6:Eu2+ (Hnh 2a) c thc hin trn h o UV2450PC
ti khoa vt l, trng i hc Khoa hc T nhin. Trong ph hp th ny, ta ghi nhn c
5 di hp th ti 254nm, 298nm, 308nm, 328nm v 351 nm. iu c th hiu c , nu so
snh vi gin nng lng ca Eu2+ t trong trng tinh th (Hnh 2b), vi s kch thch bng
nh sng t ngoi thch hp ( khong di 300 nm), ta s thu c cc chuyn di f-d, vi in
t kch thch 5d1 . Di tc dng ca trng tinh th , mc 5d vn c suy bin bc 5 s b tch
thnh 5 mc, t d1-d5. iu ny cho php c th tn ti 5 mc hp th tng ng t mc c bn
4f ln cc mc suy bin ca in t ti mc 5d ni trn. Chng ti may mn ghi c ph hp
th ca 5 mc ny nh th hin ti hnh 2a.
Cc ph hunh quang ca LiCaAlF6:Eu2+ c kch thch bi bc sng 488nm, c
ghi nhn r nt bao gm hunh quang ti 550 nm v 750 nm bi h hunh quang
FLUOROLOG3 ti khoa Vt l, trng i hc Khoa hc T nhin (Hnh 3b). Tuy nhin bn
cht ca cc tm hunh quang ny vn cha c bit r. Cng trong nhng ph hunh quang
thu c, ta cn thy c mt vch hunh quang hp ti 590 nm, bc x ny c bit n nh
ca Eu3+
Hnh 2a: Gin tch mc ca ca Eu2+ t

trong trng tinh th
Hnh 3a: s chng chp Ph hunh quang 2 v

hp th 1 ca Eu2+ trong nn LiCaAlF6
Hnh 2b: Ph hp th ca Eu2+ trong nn

LiCaAlF6
Hnh 3b: Ph hunh quang ca LiCaAlF6:Eu2+
iu ny cho thy rng, khi vn cn tn ti mt lng Eu3+ khng mong mun vi mt t l

no , cng ngh ch to vn cha t n hon ho. Cng nh cc ti liu c cng b,
chng ti rt ch n di hunh quang rt quan trng c trng cho chuyn di d1 v g0 tng
ng vi 375nm (Hnh 3a.2). Tuy nhin, vic ghi ph hunh quang do gp kh nhiu kh khn.
Nhng
_____________________________________________________________________________________
cuong do
9000
Do bc x ny c phn trng vi di hp th
1: Eu:LiCaAlF6
2: Pr:LiCaAlF6
8000
khong 370nm, nn nng lng bc x c xc sut
560 3: Pr:LiSrAlF6
7000
ti hp th rt cao. ghi nhn c tn hiu ny,
6000
cc th nghim cn phi thc hin trn cc mu
5000
mng v c nng tp thch hp. Kt qu tm
4000
thy trn cng ph hp vi mt s kt qu
2
432
3000
cng b bi nhm Shiran [7].
1
3
2+
2000
Ph dao ng ca LiCaAlF6:Eu c thc
1000
hin qua php o Raman bi my Labram ca vin
0
Khoa hc Vt liu, ghi nhn nng lng dao
100
200
300
400
500
600
700
800
ng mnh ti 560cm-1 thuc dao ng mng.
S sng(cm )
iu ny cng c ngha nng lng mt mt trong
Hnh 4: Ph dao ng Raman
chuyn di quang hc s c s ng gp quan trng ca mode dao ng mng ni trn. Nh
ni trn, mt i lng c trng cho tng tc phonon-electron c th dng nh gi hiu
sut hunh quang l h s Hoang Rhys (S).
Nh ta bit, thng s S c th xc nh theo cng thc [8]:
EAbs-EEms= Es= (2S-1)*
S: H s Hoang Rhys
EAbs: nng lng hp th gn nht vi di hunh quang Ems. l nng lng phonon c
xc nh t ph Raman.
T kt qu thc nghim m t th 3a v 4, ta tnh c S=2. iu cho php ta c th
c lng s phonon tham gia vo mi chuyn di quang hc qua c ch tng tc phononelectron vo c 2. So snh chung, ta thy s tng tc electron-phonon vt liu ny l tng
i yu, s mt mt nhit l nh. y l u im ca vt liu ny khi s dng n vi t cch l
mt vt liu hunh quang.
-1
3. Kt lun
Cc th nghim quang hc cho thy vi S=2, chng t hiu sut bc x quang hc ca loi
vt liu ny c th cao. iu ny s m ra nhng hng nghin cu tip tc vt liu ny nhm
to ra cc vt liu hunh quang c trin vng. y ch l nhng nghin cu nghin cu bc u,
chng ti s tin hnh cc nghin cu tip sau, nh nhit quang nhm a ra nhng kh nng
ng dng loi vt liu trin vng ny.[9]
References
1. M. Kirm,M.True,S.Vielhauer,G.Zimmerer, N.V.Shiran, K.Shimamura, IN.Ichinose. Nuclear
Instrumentand Methods in Physics Research, A 537 (2005) 291-294
2. M.Yamaga, N.Kodama J.of Alloys and Compounds 408-412, (2006), 706-710.
3. M.True, Y.Chen, M.Kirm, S.Vielhauer,G.Zimmerer J.of Luminescence 124, (2007) 279-285
4. Zeng Z, Chen J, Mizuseki H, Sato H, Shimamura K, Ichinoseki K, Fukuda T, Kawazoe Y,
(2004) Numerical Study on LiCaAlF6 Czochralski Crystal Growth, Phys. Chem. Minerals
45,1515-1521.
5. M.Kirm, Y.Chen, N.Neicheva, K.Shimamura, N.Shiran, M.True Phys,Status.solidi
( c )2,(2005), 418-421
6. S.Kuze, D.Boulay, N.Ishizawa, N.Kodama, M.Yamaga, B.Henderson J.of Solid State
Chemistry 177, (2004), 3505-3513
7. N.V.Shiran, A.V.Getin N.Neichera, V.A.Kornienko,
K.Shimamura,
N.Ishinose
J.of.Luminescence, 1020103, (2003) 815-818
8. A.B.Lever (1968) Inorganic Electronic Spectroscopy, Elsevier Publishing Company.
9. S.Neicheva, N.Shiran, A.Getkin, A.Shelyakin, K.Shimamura,,N.Ichinose
10. Phys.Stat.Solidi, ( c) 2, 531-534, (2005).
Advances
_____________________________________________________________________________________
XY DNG PHN MM TNH TUI KHO C BNG PHNG PHP

NHIT HUNH QUANG
Phan Tin Dng a, L Hng Khim b, Hunh K Hnh c
a)
Vin Khoa hc vt liu Vin Khoa hc v Cng ngh Vit nam

b)
Vin Vt l Vin Khoa hc v Cng ngh Vit nam
c)
Vin nghin cu v ng dng cng ngh Nha Trang Vin Khoa hc
v Cng ngh Vit nam
Tm tt: Tnh tui kho c bng phng php nhit hunh quang ang c ng dng rng
ri trn th gii v ln u tin Vit Nam c nghin cu ng dng ti phng Quang ph
ng dng v Ngc hc thuc Vin Khoa hc Vt liu Vin Khoa hc v Cng ngh Vit
Nam. Quy trnh xc nh tui kho c cng ang c nghin cu hon thin ng dng
thun tin trong iu kin thc t Vit Nam. V vy nhu cu xy dng phn mm thc hin
quy trnh tnh tui kho c mt cch t ng l cn thit. Chng ti xy dng phn mm tnh
tui kho c TLDating da chnh trn liu hp th tng cng xc nh bng o nhit hunh
quang v liu hng nm xc nh bng phng php m alpha, phn tch hm lng kali. Phn
mm c nhng chc nng chnh sau y:
- Phn tch s b cc ng cong nhit pht quang
- c cc ng cong nhit pht quang o c bng h ph k
- V cc ng cong nhit pht quang
- Xc nh vng Plateau
- Xc nh liu tng cng, liu hng nm v tnh tui ca mu kho c
Phn mm c vit trn ngn ng Visual Basics vi giao din thun tin cho vic s dng.
tin cy ca phn mm c kim tra bng cch phn tch cc s liu o chun trn h o ca
trng i hc Bicocca-Minano (Italia).
1. M u
Cho n nay, trong s nhng phng php khoa hc t nhin dng xc nh nin i c
vt gm v t nung, ng ch l phng php o tui nhit hunh quang [1,2]. Trn th gii,
cc nc c trnh khoa hc cng ngh tin tin, phng php ny rt c ch trng. Cc
nh kho c hc rt quan tm ng dng v hon thin phng php ny v coi y l mt trong
nhng phng php c kh nng xc nh nin i c vt hu hiu vi tin cy cao.
Cc mu kho c gm, t nung cha trong n cc khong vt t nhin nh thch anh,
feldspar, zircon..Cc mu ny lun lun b chiu x bi cc tia ion ho pht ra t cc nguyn t
phng x trong lng t v tia v tr. Khi b chiu x cc nguyn t trong khong vt b ion ho
to thnh in t v l trng. Cc in t b bt bi cc khuyt tt cn cc l trng nh x ta
cc tp in m trong tinh th. Cc in t ngy cng lp y cc by do c sinh ra lin tc
bi cc ngun phng x t nhin. Khi c cung cp mt nng lng- nhit nng, cc in t
c gii phng khi by ti hp vi l trng v pht hunh quang. Mu kho c cng b chiu
x lu th cng hunh quang pht ra cng ln. i vi t st nung, gm, c mt thi
im c bit nh du l lc a vo l nung, thng nhit t 1000oC-1600oC. Khi
ton b in t tch lu trc c gii phng, ngi ta gi y l thi im ng h thi
gian c xo v zero. Bt u t thi im ny, cc by in t ca khong vt trong gm
tch lu in t do b chiu x. Phng php nhit hunh quang c dng gii phng nng
lng ny di dng quang hc: o c nng lng ny, s suy ra c thi gian tn ti ca n
t khi nung. Cng cn lu , phng php tnh tui nhit hunh quang c sai s khong 5-7%.
Nu so snh hai phng php nhit hunh quang v C-14, chng ta thy: phng php C-14
em li nhiu thnh cng, to ra mt cuc cch mng trong kho c, thay cho phng php tnh
tui theo su khai qut, nhng cng ngh phc tp v chi ph kh cao. Phng php ny c
gii hn trong khong 5-6 chc ngn nm tr li, thng p dng cho mu c ngun gc hu c.
Nhng
_____________________________________________________________________________________
Trong phng php nhit hunh quang cho php tnh tui tut i ca mu. V nguyn tc,
phng php nhit hunh quang khng b gii hn bi tui ca vt nung, c bit thch hp cho
mu t nung, gm snh. Chi ph xc nh tui gm bng phng php ny kh r, c th chp
nhn c. Khi ly mu, ngi ta ch khoan mt l nh nhng v tr khng lm nh hng n
gi tr ca c vt, khi lng mu khng ng k.
Phng php nhit hunh quang c p dng cc nc t nhiu nm nay, cn Vit
Nam th mi bt u. Trong khun kh hp tc gia hai chnh ph Vit Nam v Italia v khoa
hc v cng ngh, phng th nghim Quang hc ng dng v Ngc hc thuc Vin Khoa hc
Vt liu (Vin Khoa hc v Cng ngh Vit nam) ang trin khai ti xy dng phng th
nghim tnh tui kho c bng phng php nhit hunh quang di s gip ca trng i
hc Milano (Italia). H ph k dng o bc x nhit hunh quang c chng ti lp ghp
v ang c hon thin c th ng dng vo bi ton xc nh tui kho c. Song song vi
vic ch to thit b v lp rp h ph k, chng ti cng xy dng phn mm TLDating t
ng ha cc giai on khc nhau ca quy trnh tnh tui. Cn nhn mnh rng hin nay mt s
cng ty ni ting v thit b nhit hunh quang xy dng phn mm cho mc ch thng
mi. Tuy nhin, iu kin dng c cc phn mm ny l thit b phi c nhp ca chnh
hng. Gi thnh ca cc phn mm ny kh t. Bn cnh , nhc im chnh ca cc phn
mm thng mi l ngi dng khng lm ch c thut ton v do vy kh c th ci tin cho
mc ch ring. Hn na, vi cc h o t ch to th cc phn mm ny hon ton khng tng
thch. Bi bo ny gii thiu v phn mm tnh tui TLDating m chng ti xy dng.
2. Cu trc ca phn mm TLDating
Phn mm TLDating c vit bng ngn ng Visual Basics v sau c dch thnh file
TLDating.exe c th chy trc tip trong mi trng ca h iu hnh Windows. Thut ton
dng tnh tui da vo quy trnh thit lp ca Phng th nghim Quang hc ng dng v
Ngc hc [3,4]. Phn mm c nhng chc nng chnh sau y:
- Phn tch s b cc ng cong nhit pht quang
- c cc ng cong nhit pht quang o c bng h ph k
- V cc ng cong nhit pht quang
- Xc nh vng Plateau (vng c nh nhit hunh quang n nh)
- Xc nh liu tng cng, liu hng nm v tnh tui ca mu kho c
Giao din ny bao gm nhng chc nng sau
y :
Glowcurve Plot: dng biu din cc
ng cong nhit hunh quang o c bng
ph k. File s liu cha th mc :
C:\TLdating\data. C th cng mt lc biu
din nhiu ng cong khc nhau v vi cc
mu khc nhau do ngi dng la chn trn giao
din my tnh. Hnh 2 biu din mn hnh ng
vi chc nng ny. Trc tung l s m cn trc
honh biu din nhit tnh theo n v
Kelvin. C th d dng c s m ng vi tng
nhit trn ng cong bng ng tc kch
chut.
Hnh 1 : Giao din chnh ca phn mm xc

nh tui TLDating
Advances
_____________________________________________________________________________________
Hnh 2 : Giao din ca chc nng biu din ng

cong nhit hunh quang
Hnh 4 : Xc nh h s
K v sai s
Hnh 3 : Chc nng trung bnh ha cc ng cong

nhit hunh
Hnh 5 : Xy dng ng cong Plateau v xc nh

liu P-Dose bng phng php ngoi suy
Average: S m ti mi gi tr nhit tun theo thng k Poisson. gim sai s do thng

ging, thng ng cong nhit hunh quang ti mt gi tr ca liu chiu uc o lp li mt s
ln trong cng mt iu kin. ng cong nhit hunh quang ti liu chiu ny sau s nhn
c bng php ly trung bnh thng thng. Chc nng Average cho php ngi dng la
chn cc ng cong cn phi ly trung bnh v tnh ng cong trung bnh phc v cho vic
tnh ton tip theo. Hnh 3 minh ha chc nng ly trung bnh 3 ng cong nhit hunh quang.
ng cong nhit hunh quang trung bnh c biu din trn cng mt th v c ghi li
vo th mc ring trong a.
K-Coefficient: Dng xc nh h s K . H s ny c xc nh t thc nghim bng
cch tin hnh hai th nghim b sung dng hai loi ngun chiu khc nhau : ngun th nht pht
bc x v ngun th hai pht bc x , t ta nhn c cc gi tr Q v Q . H s K
c xc nh bng cng thc : K = Q / Q . Chc nng ny cho php xc nh h s K v sai
s tng ng t cc ng cong nhit pht quang o c khi chiu bng cc ngun pht v
. Hnh 4 minh ha chc nng ny.
P-Dose: dng xc nh liu tch ly bng phng php chiu liu b sung. Mu cn xc
nh tui c chia thnh 20 a mu ng u v c chiu vi cc liu khc nhau. Cng
nhit pht quang trong vng plateau s t l tuyn tnh vi liu chiu. Khp s ph thuc ny vi
ng thng, ta d dng xc nh c liu tch ly. Hnh 5 minh ha cch xc nh liu tch ly
theo phng php liu chiu b sung.
Date Calculation: dng tnh tui ca i tng ang o v sai s ca n. Cc kt qu tnh
t cc chng trnh con c t ng truyn cho chng trnh ny. Mt s i lng cn li s
c nhp vo t bn phm (hm lng kali, s m alpha, m..). Sai s ca i lng tui
c tnh bng phng php Monte-Carlo. Hnh v 6 biu din giao din ca DateCalculation.
Nhng
_____________________________________________________________________________________
Hnh 6 : Giao din ca chc nng tnh tui v nh gi sai s ca TLDating
3. Kim tra kt qu lm vic ca phn mm TLDating

kim tra tin cy ca phn mm TLDating, chng ti s dng chng trnh phn
mm ny phn tch cc s liu tnh tui ca mt s mu kho c bng t nung ca thnh a
M Sn. H o ph ti Vit nam ang c hon thin nn cc s liu dng phn tch c
o ti phng th nghim tnh tui kho c bng phng php nhit hunh quang ca i hc
Bicocca, Milano ca Italia. Kt qu tnh tui ca cc mu kho c trn phn mm TLDating
hon ton ph hp vi kt qu c tnh tui ti i hc Bicocca, Milan, Italy.
4. Kt lun
Trong bi bo ny chng ti gii thiu v phn mm TLDating dng t ng ha quy
trnh tnh tui kho c bng phng php nhit hunh quang. Phn mm ny ch l phin bn
ban u. Khi h o ph c hon thin, chng ti s s dng n xc nh tui kho c v
hon thin dn trong qu trnh s dng.
Ti liu tham kho

1. S.W.S.McKeever, Thermoluminescence of Solids, Cambridge University Press (1985).
2. M.J.Aitken, Thermoluminescence Dating, Academic Press, London (1985)
3. V.X.Quang, Xy dng quy trnh tnh tui bng nhit hunh quang cho kho c v a cht v
h tr thit b hon thin phng th nghim tnh tui theo m hnh ca i hc Milano Bo co tng kt ca ti. Nm 2007.
4. H. K.Hnh, Tnh tui vt liu gm, t st nung bng phng php nhit hunh quang-Lun
vn thc s, i hc lt 2006.
Advances
_____________________________________________________________________________________
M PHNG QU TRNH VA CHM ELECTRON-ARGON V VA CHM ION

ARGON- ARGON TRUNG HO TRONG VNG ST TH CATT - H PHN X
MAGNETRON DC BNG THUT TON MONTE CARLO.
L Sn Hi a, L V Tun Hng b, Hunh Thnh t c
Dng i Phng b, Giang Vn Phc d.
a)
Trng i Hc S Phm K Thut Tp. HCM; b) Trng H Khoa Hc T Nhin

Tp.HCM; (c)Trng H Quc Gia Tp. HCM; d) Trng H An Giang.
Tm tt: Trong bi bo ny, chng ti dng thut ton Monte Carlo m phng hai qu trnh
chnh trong vng target nh sau:
1. M phng s chuyn ng ca cc ht electron trong vng st th catt gn target, tnh ton
n 3 loi va chm chnh: va chm n hi, kch thch v va chm ion ha gia electron v ht
trung ho Ar. Qu trnh m phng cng tnh ton n qu o chuyn ng theo dng xycloit ca
ht electron khi c mt ca in t trng. T trng lm gia tng ng k ng i ca electron
lm gia tng cc qu trnh va chm, v qu trnh ion ha ht trung ha.
2. M phng qu trnh chuyn ng ca cc ht ion Ar v s va chm ca chng vi cc ht Ar
trung ho trong qu trnh chng c gia tc v target. Chng ti cng tnh ton c nng lng
v gc ti ca cc ht ion Ar khi bay v target.
Cc kt qu thu c, chng ti so snh v nh gi vi cc kt qu ca cc tc gi khc trn th
gii.
1. Gii thiu
K thut phn x to mng trong h mangetron DC c ng dng rng ri trong nghin cu
ch to mng mng. Trong bi bo ny chng ti s dng m hnh Monte Carlo (MCC) kho
st v m phng mt s qu trnh xy ra trong h, c bit l in t v ion Ar v m hnh
Langevin v Hass m phng va chm gia ion v ht trung ha [3].
Di tc dng ca in t trng, electron s chuyn ng t catt v va chm vi mi
trng kh Ar xung quanh theo mt xc sut xc nh. Chng trnh m phng s tnh ton nng
lng in t trong h ti tng v tr theo bc nhy thi gian, t xc nh loi va chm l n
hi, kch thch hay ion ha. Chng trnh cng thng k s ion c to thnh theo s in t
ban u v phn b ca chng trong min khng gian.
T kt qu ion dng to thnh do va chm ca in t trn, ion c tng tc trong in
trng v hng v b mt bia. Trong qu trnh chuyn ng ca ion chng va chm vi kh lm
vic (Ar) theo mt xc sut xc nh. Chng trnh tnh s phn b nng lng v gc ti ca
ion trn b mt bia.
Cc kt qu thu c c so snh vi kt qu tnh ton bng cc phng php khc ca cc
tc gi trn th gii.
2. L thuyt
2.1. Phng php va chm Monter Carlo MCC
Phng php MCC l m hnh tnh xc sut va chm ca mt ht i vi cc ht xung quanh,
ng thi cng vi vic chn mt s ngu nhin xc nh li va chm kh d gia chng. Gi
s ht loi a (in t, ion,) c N loi va chm vi ht ch. Ht ch c th l ht loi a hay cc
loi ht khc nh: nguyn t, phn t trung ha
Xt ht th i ca ht loi a. ng nng ca ht th i c xc nh bi
1
1
i = m a v i2 = m a (v ix2 + v iy2 + v iz2 )
(1)
2
2
Tit din va chm tng cng: T ( i ) = 1 ( i ) + ... + j ( i ) + ... + N ( i )
(2)
Nhng
_____________________________________________________________________________________
Xc sut ht th i va chm trong khong bc nhy thi gian t l:

Pi = 1- exp{-ni(r) T(i) gi t} ,
vi Pi < 1
(3)
Trong : ni(r), gi, T(i) l mt a phng ht ch ti v tr r ca ht th i, vn tc tng
i ca hai ht trc khi va chm, v tit din va chm tng cng.
2.2. M hnh chuyn ng v va chm ca electron vi nguyn t Ar trong h magnetron DC

M phng c bt u vi electron pht ra r catt (z=0), di tc dng ca in t trng
n chuyn ng theo phng trnh (gia hai ln va chm):
e
e
a x (t ) = V z B; a y (t ) = 0; a z (t ) = (E ( z ) V x B )
(4)
m
m
Trong ax(t), ay(t), az(t), Vx, Vz l gia tc v vn tc ca electron theo cc phng; e, m l
in tch v khi lung electron, B l t trng, E(z) l in t trng theo phng z.
r
r
Tnh ta ri v vn tc v i ca ht th i theo bc nhy thi gian t , t tnh nng lung
mv2i
(5)
2
Sau xt va chm ht th i vi mi trng xung quanh, y ch tnh va chm ca in t
vi nguyn t trung ha.
ht th i ti tng thi im: E i =
a. Va chm n hi gia electron vi nguyn t Ar: e + Ar etanxa + Ar

Sau khi va chm electron s b tn x theo gc lch v gc quay so vi chiu ca vn tc
ban u. Do nguyn t Ar c khi lng rt ln so vi electron nn s thay i hng bay v
nng lng rt nh, c th b qua trong m hnh va chm ny. Nng lng ca in t tn x:
E tanxa = Ei cos2
(6)
(7)
Gc tn x v gc quay ca in t sau va chm cos = 1 Ri ; =2R2
Ri, , l s ngu nhin t [0:1], gc lch tn x so vi phng ti (0 ) v gc quay
tn x 0 2. Vn tc ca electron sau va chm n hi:
2 E tan xa
2 E tan xa
2 E tan xa
v' x =
sin cos ; v' y =
sin sin ; v' z =
cos (8)
m
m
m
b. Va chm kch thch gia electron vi nguyn t Ar: e + Ar etanxa + Ar*
Nng lng cn thit kch thch nguyn t kh Ar t mc nng lng c bn ln mc nng
lng kch thch u tin l: Ekt = 11.55 eV. Nng lng cn li ca in t sau va chm kch
thch l: Etanxa = Ekt.Gc lch v gc quay ca in t tn x sau va
2 + E tan xa 2(1 E tan xa )1 / 2
chm: cos =
; = 2R4
(9)
E tan xa
Vn tc electron sau va chm kch thch tnh theo (8)
c. Va chm ion ha gia electron vi nguyn t Ar:
Nu electron nng lng ln, khi ti va chm ion ha vi nguyn t kh trung ha Ar, to
thnh mt ion Ar+ v mt electron mi: e + Ar etanxa + Ar+ + emoi.
Nng lng ion ha ca nguyn t kh Ar: E ion = 15.75eV . Nng lng ca electron sau va
chm ion ha:
Eion
E
Etanxa = B tanR3 arctan truoc
2B
(10)
Vi B l hng s nng lng ca Ar, B=10eV [6]. Nng lung ca electron mi c sinh ra:
Emoi = Etruoc Eion Etanxa. Gc cc ca electron mi sinh ra tun theo hm phn b cosine:
cos = 1 2 R4 ; = 2R5
(11)
Vn tc ca in t mi c sinh ra sau va chm ion ha c tnh nh sau:
Advances
_____________________________________________________________________________________
v' ' x =
2 Emoi
2 Emoi
2 Emoi
sin cos ; v' ' y =
sin sin ; v' ' z =
cos
m
m
m
(12)
2.3. M hnh chuyn ng v va chm gia ion v ht trung ha

Loi va chm xy ra gia ion vi ht trung ha c xc nh bng cch tnh xc sut va
chm Pc ca ion:
Pc = n0 .g . T .t
(13)
Trong , n0, T, g = |V - v|, V, v, t l nng ht ca kh Ar, nng ht ca kh Ar, vn
tc tng i gia ion v ht trung ha, vn tc trc va chm ca ion v ht trung ha tng
ng, bc nhy thi gian.
Sau va chm n hi, vn tc ca ion v ht trung ha c xc nh theo cng thc:
r
r
r r
r r
r
r
M
M
v'= v +
g (1 cos ' ) + h sin ' ; V ' = V
g (1 cos ' ) + h sin ' (14)
m+M
m+M
r
Trong , m, M l khi lng ca ion v ht trung ha tng ng. vi h l cc thnh phn
Descartes [3].
Xc sut xy ra va chm chuyn in tch Pce l hm theo thng s va chm b v nng lng
nhit ng = g2/2 (: khi lng rt gn). S dng m hnh li rn kt hp vi th phn cc
n gin vic tnh xc sut va chm chuyn in tch Pce. Gi (-a/r4) l mt th phn cc, r l
d e2
khong cch ht nhn bn trong v a =
= const (d l gi tr phn cc). t thng s
2(4 0 ) 2
4
va chm khng th nguyn: = b .
4a
Nu = 1, tng tc xy ra ngay ti bn knh li rn. Khi , gii hn qu o tng tc l:
1
a 4
rlm =
=
(15)
2
Nu >1 tng tc xy ra bn ngoi li rn, <1 tng tc xy ra bn trong li rn, gc tn x:
= 20.
2 .
Gc 0 cho <1 l 0 ( ) =
F ,
(16)
1
2
vi = 0 / 1; 0 = [2 (4 1)1/2]1/2 ; 1 = [2 + (4 1)1/2]1/2, F ( , ) l hm tch phn elip [3].
trnh s phn ly ca tit din tng cng, ta dng gi tr ngng khi gi tr || nh c
3
th b qua. Khi y, gc lch l: = 4 , v tit din va chm tng cng:
16
blm
4a 4
T = b vi b = . Thay T vo (13) ta c xc sut va chm:

2
8a 2
Pc = 2 n0 t = const

Xc sut va chm chuyn in tch c xc nh li l:
ce ( )
Pce = 1 / 2
Pce =
> ce ( )
Pce = 0
* M hnh li rn rt gn:
Trong trng hp < 1
r
r r
r
r
r
r
r
1
1
v'=
(mv + MV MgR ) ; V ' =
(mv + MV + MgR)
m+M
m+M
(20)
(21)
(22)
Nhng
_____________________________________________________________________________________
r
Trong , g = |g|, R l vn tc tng i ban u ca ion - ht trung ha v vector n v
vi hng ngu nhin.
Qu trnh m phng ca ht c thc hin lin tc cho n khi electron chuyn v ant v
ion p vo catt. Kt qu ghi nhn bao gm:
* Nng lng electron ti tng v tr trong vng catt, s lng ion to thnh v v tr ca n
theo nng lung in t trng.
* Phn b nng lung v gc ti ca ion ti taget.
3. Kt qu v bn lun
Electron t catt c gia tc v nhn nng lung bi in trng v s tc ng ca t
trng ngang lm tng qung ng i trc khi chng thot n ant. Qung ng chuyn
ng ca in t di hn lm tng kh nng ion ha ca in t vi Ar, tng hiu sut phn x.
S phn b s in t theo nng lng ti cc v tr trong min catt nh c tnh hnh 1.
1500
Soelectron
Soelectron
600
400
200
0
100
300
400
Soelectron
2000
100
200
300
400
500
Soelectron
Soelectron
5000
100
200
300
100
4
10000
400
200
300
400
500
Na
ng lng (d=0.3D)
2000
15000
100
4000
Na
ng l ng (d=0.45D)
6000
4000
500
500
Na
ng l ng (d=0.15D)
6000
Soelectron
200
1000
200
300
400
500
Na
ng lng (d=0.6D)
2
1
0
500
x 10
100
Na
ng l ng (d=0.75D)
200
300
400
500
Na
ng lng (d=0.9D)
Hnh 1: S phn b nng lng ca in t ti cc v tr trong vng st th catt

S in t ban u l 10.000, U=400V v t trng B=0.03T
Ta nhn thy nng lung electron thay i theo tng v tr khc nhau ca vng st th catt,
cng tin n bin ca vng st th th nng lung cng gim.V lc ny xy s va chm kch
thch v ion ha ca electron vi cc ht kh. Kt qu cho thy cng ph hp tt vi mt s tc
gi khc [2].
4
x 10
x 10
2.5
2.5
1.5
Soelectron
2.5
Soelectron
Soelectron
1.5
1.5
0.5
0.5
0.5
50
100
150
200
250
300
Na
ng lng (d=0.9D)
350
400
450
50
100
150
200
250
300
Na
ng lng (d=0.9D)
350
400
450
x 10
50
100
150
200
250
300
350
400
450
Na
ng lng (d=0.9D)
Hnh 2: S phn b nng lng ca in t ti cc v tr 0.9 D trong vng st th catt. S electron

ban u l 10.000, U=400V v t trng B=0T, B=0.03T, B=0.6T, t tri sang.
Advances
_____________________________________________________________________________________
r
Bng 1: nh hng ca t trng B ln vng st th catt, s electron ban u
l 10.000, hiu in th 450V.
S va chm
S va chm
kch thch
ion ha
19098
11857
0.04
20507
12918
0.06
31911
21287
B[T]
r
T hnh 2, ta nhn thy t trng B t nh hng n dng phn b nng lung ca in t,
tuy nhin khi t trng gia tng th s va chm ion ha gia tng rt nhiu do electron b by
trong t trng, bng 1.
Ion Ar c to thnh bi s va chm ca in t trong h c gia tc v catt, di tc
dng ca in trng, lm phn x cc ht vt liu to mng, (hnh 3 v 4) l kt qu phn b s
ion theo nng lung v gc ti ti b mt bia.
OTHPHA
N BOI ON THEO NA
NG LNG
OTHPHA
N BOI ON THEO NA
NG LN G
350
OTHPHA
N BOI ON THEO NA
NG LN G
500
500
450
450
400
400
200
150
100
Sohat tai bema

t bia
250
Sohat tai bema

t bia
Sohat tai bema

t bia
300
350
300
250
200
150
350
300
250
200
150
100
100
50
50
50
100
150
200
250
300
350
400
450
500
50
100
200
300
400
500
600
100
200
Na
ng lng cu
a ion tai bema
t bia
Nang lng cu
a ion tai bema
t bia
300
400
500
600
700
Na
ng lng cu
a ion tai bema
t bia
Hnh 3: S phn b nng lng ca ion ti b mt bia, t trng B=0.04T, U=450V, U=550V,
U=600V, t tri sang
OTHPHA
N BOION THEO GO
C T
I
OTHPHA
N BOION THEO GO
C T
I
100
90
90
80
80
80
70
70
70
60
50
40
Pha
n tra
m sohat (%)
100
90
Pha
n tra
m sohat (%)
Pha
n tra
m sohat (%)
OTHPHA
N BOION THEO GO
C T
I
100
60
50
40
60
50
40
30
30
30
20
20
20
10
10
20
40
60
80
100
Goc t
i
120
140
160
180
10
20
40
60
80
100
120
Goc t
i
140
160
180
20
40
60
80
100
120
140
160
180
Goc t
i
Hnh 4: S phn b ion ti b mt bia theo gc ti, t trng B=0.04T, U=450, U=550,
U=600, t tri sang
T hnh 3 v 4 ta thy in th ch to nng lng cho ion v khng nh hng nhiu ln dng
phn b ca n. Hu nh tt c ion p vo catt vi gc ti l 900, iu ny cng ph hp vi
nghin cu ca cc tc gi khc
4. Kt lun
- Chng ti vit c mt chng trnh m phng tnh ton s va chm ca electron vi Ar v
va chm ca ion Ar vi ht trung ha trong vng st th catt.
- Chng trnh m phng cho ta thy nng lng electron ph thuc vo tng v tr trong vng
st th catt v n t ln nht gn bin.
- S nh hng ca t trng ngang trong h c tc dng nh mt by electron lm tng xc sut
va chm ca in t vi kh lm vic dn ti tng va chm ion ha ca Ar.
Nhng
_____________________________________________________________________________________
- Th p vo h phn x lm gia tng nng lng ca ion Ar v electron, tuy nhin khng lm
nh hng ti nng lng cng nh gc ti ca ion bn ph vo bia (phn ln gc ti l 900).
- Kt qu tnh ton cng kh ph hp vi mt s kt qu ca cc gi khc, c th lm c s cho
vic nghin cu qu trnh phn x to mng trong h magnetron.
Ti liu tham kho

1. C.K. Birdsall, Particle in Cell charged particle simulations, plus Monte Carlo collisions
with neutral atoms, PIC MCC, IEEE Transactions on Plasma Science, vol. 19, No. 2, pp.
65 85,1991.
2. Jun Li, Monte Carlo simulation of electron motion in the cathode region of a magnetron
glow discharge in argon, J. Phys. D: Appl. Phys. 28, pp. 681 688, printed in the UK,1995.
3. Kenichi Nanbu, An ion neutral species collision model for particle simulation of glow
discharge, J. Phys. D: Appl. Phys. 28, pp. 324 330, printed in the UK,1995.
4. Kenichi Nanbu, Probability Theory of Electron-Molecule Ion- Molecule, Molecule- Molecule,
and Coulomb Collisions for Particle Mondeling of Materials Processing Plasma and
Gases,Tohoku University, Sendai, Japan,2000.
5. Jun Li, Simulation of ionization in a magnetron-like glow discharge, Hauzhong University of
Science and Technology. China.
6. V. Vahedi, A Monte Carlo simulation of the particle-in-cell method: applications to argon
and oxygen discharges, University of California. Berdeley. CA 94720. USA,1995.
7. Michael A. Lieberman, Principles of plasma discharges and materials processing, John
Willey & Sons, inc, New York.
8. R. Rejoub, Determination of the absolute partial and total cross sections for electron-impact
ionization of the rare gases, Department of Physics and Atronomy,2002.
9. Patrick Mwangi Karimi, Atomic Mechanisms of Stress Formation of Group IVB-VIB
Transition Metal Nitrides Deposited by DC Magnetron Sputtering, PhD thesis, I.
Physikalisches Institut 1A der RWTH Aachen, Germany, 2007.
10. Nguyn Hu Ch, Vt l Plasma (Kh ion ha), T sch i hc Khoa Hc T Nhin TP. H
Ch Minh, 1998.
Advances
_____________________________________________________________________________________
S HNH THNH ION Sm2+ CA VT LIU THU TINH SOL-GEL

Al2O3.SiO2: Sm3+ BI QU TRNH CHIU TIA X
N.T.Thnh a, V.X.Quang a, N.Q.Lim a, V.P.Tuyn a, M.Nogami b, N.A.Bang c
a)
Vin Khoa hc Vt liu, Vin Khoa hc v Cng ngh Vit Nam,

18 Hong Quc Vit, H Ni.
b)
Department of Materials Science and Technology ,Nagoya Institute of Technology,
Showa Nagoya 466-8555, Japan
c)
Khoa Vt l, Trng i hc Khoa hc T nhin, i hc Quc Gia H Ni,
334 ng Nguyn Tri, H Ni
E-mail: thanhnt@ims.vast.ac.vn
Tm tt. Trong bi bo ny, chng ti trnh by mt s kho st c trng quang hc: hp th,
hunh quang ca vt liu thu tinh Al2O3.SiO2 pha tp in t him Sm3+ c ch to bng
phng php sol-gel. Ch phm gel c nung trong mi trng khng kh v mi trng kh CO
(vi bt Graphite) ti nhit 800 oC vi thi gian 2 gi. Vi mu nung trong khng kh sau
c chiu tia Rnghen Co-K, ch 20 KV - 5 mA trong 5, 10 v 20 gi. Ph hp th ca
cc mu quan st c ch c trng cho cc chuyn di t trng thi c bn 6H5/2 n cc trng
thi kch thch 4D7/2, 4D3/2 , 6P7/2, 6P3/2 ca ion Sm3+. Ph hunh quang ca mu sau khi chiu Xray, tn hiu hunh quang th hin s c mt ca c hai loi ion Sm3+ v Sm2+ trong khi vi mu
trc khi chiu X-ray ch xut hin cc gii hunh quang c trng ca in Sm3+. S hnh thnh
tm quang hc v thay i ha tr ca ion Samarium bi qu trnh chiu x v nung trong mi
trng kh kh bc u c tho lun.
Keywords: Sm3+, Sm2+, Aluminosilicate glasses, PSHB.

1. Gii thiu
Nhiu vt liu pha tp t him c tnh cht ph hole burning bn vng (PSHB). Tuy nhin
nhng quan st PSHB cn hn ch, thng thc hin ti nhit thp. Vt liu thu tinh pha tp
Sm3+, Eu3+ l trng hp c bit, ta c th quan st ph PSHB ca chng ti nhit phng [1,
2, 3,]. iu ny cho thy trin vng ng dng vt liu ny trong vic to ra cc b nh quang hc
c mt ln, dung lng cao. Cc nghin cu gn y v thu tinh Aluminosilicate,
Sodiumborate pha tp Samarium cho thy ph PSHB thng quan st c khi ion Sm tn ti
ha tr 2+ [1, 5]. c nh vy, vt liu cha Sm3+ thng c nung nhit cao trong
mi trng kh kh nh H2 hoc nung mi trng khng kh sau c chiu x bi cc tia
c nng lng ion ho nh tia Roenghen, Gamma v.vBi bo ny, trnh by mt s kt qu
kho st cc tnh cht quang (Hp th, Hunh quang) ca vt liu thu tinh sol-gel
10Al2O3.90SiO2: Sm3+ 5 % wt trc v sau qu trnh chiu bc x tia Roenghen v tm hiu qu
trnh hnh thnh ion Sm2+.
2. Thc nghim
Vt liu thu tinh 10Al2O3.90SiO2: Sm3+ 5 % wt c ch to bng phng php sol-gel. Cc
tin cht chnh c s dng l Si(OC2H5)4, Al(OC4H9)3, tp Sm3+ c a vo t mui
SmCl3.6H2O. Trc tin, Si(OC2H5)4 b thy phn trong dung dch c H2O v C2H5OH v c
khuy 1 gi. Sau Al(OC4H9)3 c thm vo vi t l Al/Si = 1:9 Vt liu dng gel c hnh
thnh qua qu trnh ca hai phn ng thu phn v trng ngng. Mt lng nh axt HCl c
thm vo v ng vai tr ca cht xc tc nhm y nhanh tc phn ng. Mu gel
10Al2O3.90SiO2: Sm3+ 5 % wt c x l theo hai cch:
+ Nung cng bt Graphite(to mi trng kh kh CO) ti 8000C trong 2 gi.
Nhng
_____________________________________________________________________________________
+ Nung trong mi trng khng kh ti 8000C trong 2 gi, sau mu c chiu x bi tia
X t bia Co ca n RORIX RFT, Germany, ch pht 20 KV-5mA trong khong thi gian
khc nhau 5, 10 v 20 gi.
Ph hp th (OA) ca mu trn c kho st trong gii ph t 200 800 nm bng my o
UV.Vis 2450PC Shimatzu. Ph hunh quang v kch thch hunh quang(PL, PLE) c ghi
nhn trn h o Fluorolog3 JOBINYVON SPEX ti Trung Tm KHVL, Trng H KHTN
HNi. Php o TL c thc hin trn h o TL-Reader, Harshaw.3500, USA ti PTN Quang
ph ng dng v Ngc hc, Vin KHVL, VAST.
3. Kt qu v tho lun
3.1 Ph hp th v hunh quang
Kt qu o ph hp th c trnh
by trong hnh 1 (ng cong a,b).
Vi mu nung trong khng kh trc
v sau khi chiu tia X, ph hp th u
xut hin cc nh c cng yu ti
cc bc sng 342, 358, 373, 401 nm
tng ng vi cc chuyn di c
trng ca ion Sm3+ t trng thi c bn
6
H5/2 n cc trng thi kch thch
4
D7/2, 4D3/2 , 6P7/2, 6P3/2. Mu sau khi
c chiu x, ngoi cc nh hp th
c trng ca ion Sm3+, nhn thy
hp th tng trong gii ph t 300 nm
n 600 nm.
Hnh 1: Ph hp th ca thu tinh 10Al2O3.90SiO2: Sm3+

5% wt nung 800oC trong khng kh (a) trc khi chiu tia
X, (b) Sau khi chiu tia X, (c) Ph kch thch mu khng
chiu tia X
Hnh 2 trnh by kt qu o ph
hunh quang ca cc mu thu tinh vi cc iu kin x l khc nhau. Ph hunh quang ca cc
mu ny u xut hin cc nh hunh quang bc sng c 562, 599 v 645 nm, nhng nh
hunh quang ny tng ng vi chuyn di t trng thi kch thch 4G5/2 v cc trng thi c bn
6
H5/2, 6H7/2, 6H9/2 ca ion Sm3+. Vi cc mu c x l nhit cng vi bt Graphite hoc c
chiu x bi tia X, ngoi cc nh hunh quang c trng ca ion Sm3+, chng ti quan st thy
c s xut hin mt s nh hunh quang ti cc bc sng c 684, 702 v 725 nm (Hnh 2:
ng b,c, d v e). Cc nh hunh quang ny l hunh quang c trng ca ion Sm2+ tng ng
vi cc chuyn di in t t mc 5D0 n cc mc 7F0, 7F1 v 7F2. Nh vy l c s hnh thnh
ion Sm2+ trong nhng mu thu tinh ny l rt r rt. Trong khi nhng mu c nung trong mi
trng khng kh, cc ion Samarium ch yu tn ti dng ho tr 3 (Sm3+) iu ny c minh
chng bng kt qu o ph PL nh trnh by ng a trong hnh 2.
3.2 S hnh thnh ion Sm2+
* Trng hp trong mi trng kh kh:
Nh chng ta bit, Graphite (Carbon-C ) trong mi trng khng kh nhit cao s phn
ng vi O2 qua hai giai on:
C + O2 + = 2CO
2CO + O2 = 2 CO2
(I)
(II)
giai on (I), kh CO c to ra v c tnh kh mnh, cc ion Sm3+ trong mu thu tinh

c nung ti nhit cao 800 oC d b tng tc bi mi trng kh ny. Theo mt s nghin
cu ca M. Nogami v cng s [3,4,5] , mu thu tinh Aluminosilicate pha Sm3+ c nung
Advances
_____________________________________________________________________________________
trong mi trng kh 80 % N2-20% H2 th ion Sm2+ c to thnh t ion Sm3+ l do s xy ho

cc Oxygen xung quanh ion Sm3+ bi kh H2. Cc Oxygen ny ch yu thuc nhm Octahedra,
AlO6 v Tetrahedra AlO4 m mt phn ca chng l khng cu ni v gy nh hng ti ion
Sm3+. ng thi cc Oxygen xung quanh ion Sm3+ thng lin kt vi Si4+ hoc Al3+ trong vt
liu thu tinh Al2O3.SiO2. Nh chng ta bit, kh CO cng c tnh kh tuy nhin so vi kh H2
th mc kh yu hn, iu ny ch nh hng ti hiu sut ca phn ng. Tuy vy loi phn
ng kh ca hai kh ny l nh nhau. Chnh v vy chng ti cho rng phn ng kh gia ion
Sm3+ trong vt liu ny vi kh CO din ra nh sau:
2Sm3+ + O2- + CO = 2Sm2+ + CO2.
Cng theo nhm tc gi M. Nogami v cng s th.
** Trng hp chiu x bi tia X:
G5/2
H5/2,7/2,9/2
10000000 e
8000000
Sm
F0
D0
20000000
2100000
18000000
F2
F1
1400000 d
c
700000
b
a
670
680
690
700
710
720
730
740
B- c sng (nm)
2+
6000000
Sm
D0
F0,1,2
4000000
c
2000000
b
a
550
Tng c- ng PL (a.u)
C- ng PL (cps)
12000000
Sm
C- ng PL (cps)
3+
16000000
1600000
14000000
1400000
10000000
8000000
650
700
750
D0
F0
20 h
1000000
800000
600000
F2
10 h
F1
400000
200000
6000000
5h
0
650
4000000
600
2+
Sm
5
1200000
12000000
C- ng PL (cps)
2+
2800000
14000000
700
750
B- c sng (nm)
10
15
20
25
30
35
Thi l- ng (gi)
B- c sng (nm)
Hnh 2 : Ph hunh quang ca thu tinh

10Al2O3.90SiO2: Sm3+ 5% wt nung 800oC, (a) trong
khng kh,(b) nung cng bt Graphite), Sau khi chiu
tia X trong 5 gi (c), 10 gi (d), 20 gi (e).
Hnh 3 : th biu din s ph thuc ca

cng hunh quang ca ion Sm2+ theo thi
lng chiu tia X Co-K, 20 KV- 5 mA
Mu thu tinh Aluminosilicate c ch to c cc thnh phn chnh l Al2O3-SiO2 trong

cu trc ca Al2O3 ch yu tn ti bi cc nhm polyhedra Al-O. Cc ion Sm thng tn ti
ha tr 3 khi xung quanh chng tn ti cc nhm Al-O ny. iu ny th hin r rng bng kt
qu o ph hunh quang (ng a trong hnh 2) ca mu thu tinh nung 800 oC trong mi
trng khng kh. Khi nung mu nhit cao, cc nhm polyhedra in hnh thng dng
phi v bn Al-O4 v phi v su Al-O6. Nhm Al-O4 c in tch m v d mt in t c
xem nh l mt in t b by, nhm ny d dng kt hp vi ion Sm3+ in tch dng bi
tng tc Culng [5]. Khi b chiu bi bc x c nng lng ion ho nh tia X, nng lng ny
s gii phng in t b by v truyn cho ion Sm3+ v to thnh ion Sm2+, qu trnh ny c th
minh ha nh sau:
X-ray
Si O Al O + Sm3+
Si O Al O + Sm2+
T kt qu o ph hunh quang ca cc mu thu ting c chiu tia X vi thi lng khc

nhau nh ch ra trong hnh 2 (ng c, d, e), chng ti nh gi s b s thay i cng
hunh quang c trng ca ion Sm2+ theo thi lng, Kt qu tnh ton c trnh by nh th
hnh 3 (V da trn s liu ly tch phn ton b din tch di cc nh hunh quang ca ion
Sm2+, tr Baseline). Khi ch to vt liu ny, lng Sm3+ c pha vo vi nng c
tnh ton ti u cho s pht quang. V th cng pht quang ca ion Sm2+ cng t l vi lng
ion ny c to ra. T th hnh 3, thy rng lng ion Sm2+ c to ra tng t l vi thi
lng mu c chiu tia X. bit c s ph thuc ny mt cch tng minh hn chng ti
Nhng
_____________________________________________________________________________________
cn tin hnh th nghim ny vi s thay i khng ch vi thi lng chiu x m cn vi cng

sut cng nh nng lng c trng K ca tia X.
4. Kt lun
Ion Samarium trong vt liu thu tinh Aluminosilicate thng tn ti ho tr 3+ khi c x
l nhit trong mi trng khng kh.
thay i ho tr ca ion Samarium t Sm3+ thnh Sm2+, ngoi cch nung mu trong mi
trng kh kh, chng ti dng bc x tia X c nng lng ln (Co-K) lm thay i ho tr
ca ion ny. Cc kt qu thc nghim kt hp vi tham kho mt s cng b khoa hc[2, 3, 5]
minh chng c s hnh thnh ca ion Sm2+ t ion Sm3+ trong vt liu thu tinh
Aluminosilicate bi qu trnh chiu x. Vai tr ca cc Oxygen (O2-) thuc cc nhm AlO4 v
AlO6 xung quanh ion t him l rt quan trng i vi qu trnh thay i ho tr ca ion
Samarium.
Cc kt qu thu c cho thy thu tinh Aluminosilicate cha ion Sm3+, Sm2+ l vt liu
thch hp cho cc kho st hiu ng Persistent spectra hole burning(PSHB), ng gp phn no
vo nhng hiu bit v c ch ca qu trnh ny.
Li cm n: Nhm tc gi xin trn trng cm n: S h tr kinh ph t ti nghin cu c
bn (N0- 4 080 06)/ 2008 ca B KH&CN, Vin KHVL,VAST lm ch nhim. Trung tm KHVL
trng i hc KHTN H Ni gip thc hin cc php o thc nghim v GS. M. Nogami
thuc Vin Cng ngh Nagoya Institute of Technology, Japan v s hp tc v trao i khoa
hc.
References
1. A. Osvet, S. Emelianova, R. Weissmann, Valeriy I. Arbuzov and A. Winnacker, Spetral hole
burning in Sm2+-doped alkaliborate glasses and Tb3+-doped silicate and borate glasses,
Journal of Luminescence vol 86 (2000), 123-332.
2. Wei Chen, Mainzeng Su, Stimulated luminescence and photo-gated hole burning in
BaFCl0.8Br0.2:Sm2+, Sm3+ phosphors, Journal of Physics and Chemistry of Solids 60, 371-378
(1999).
3. M. Nogami and Y. Abe, Fluorescence spectroscopy of silicate glasses codoped with Sm2+
and Al3+ ions, Journal of Apply Physics, 81, 6351-6356 (1997).
4. M. Nogami and Y. Abe, Sol-gel Processing of Sm2+- Doped Glass and Its Spectral Hole
Burning at Room Temperature, Journal of Sol-Gel Science and Technology 8, 867-870
(1997).
5. M. Nogami, N. Hayakawa, N. Sugioka, and Y. Abe, Formation of Sm2+ ions in sol-gelderived glasses of the system Na2O-Al2O3-SiO2, Journal of American Ceramic Society., 79,
1257-1261 (1996)
6. N. T. Thnh1 , V. X. Quang1,3, N. Q. Lim1, V.P. Tuyn1,.N. Q. Thnh 2, M. Nogami 3, L. H.
H4, N. A Bang4 Mt s nghin cu ban u v hiu ng ph bn vng hole burning(PSHB)
ca vt liu thu tinh xit pha tp ion t him, Proceeding Hi ngh vt l cht rn ton
quc ln th 5.
Advances
_____________________________________________________________________________________
INFLUENCE OF ANNEALED TEMPERATURE ON THE PHOTOLUMINESCENCE

SPECTRA AND THE BAND GAP OF ZnS:Mn2+ NANO POWDER AND THIN FILMS
Nguyen Minh Vuong a, Tran Minh Thi b, Le Thi Thu Huyenc
a
Laboratory Center, Quynhon University, Vietnam

c
Faculty of Techical Physics and Chemistry, Military Techical Academy, Vietnam
E-mail: nmvuongk23@gmail.com
b
Abstract: The report presented on the productions of the ZnS:Mn2+_12%_pH=3,6 powder

sample annealed at temperatures of 800C, 1500C, 2500C, 3500C; the ZnS:Mn2+_9%_pH=5
powder sample annealed at temperatures of 800C, 2000C, 3000C, 4000C and the ZnS:Mn_9% thin
film sample with pH=5 annealed at temperatures of 800C, 2000C, 3000C, 4000C.
From the X-ray spectra, we can canculate the average partical size about 2,5 nm to 5 nm. These
results agree to the results of TEM. The photoluminescence spectra of samples was measured
using the laser source with the wavelength of 325 nm. The results shown that the annealed
temperature was effected to the photoluminescence spectra of samples. The analytical results
shown that the ZnS:Mn2+ samples with 800C annealed temperature have best photoluminescence
spectra. The band gap of the ZnS:Mn2+_9% thin film decreased with enhancement of annealed
temperature. Some of the explanation on this is propertier also given out.
Keyword: ZnS:Mn2+ nano-powder, thinfilms annealed at hight temperature , PL and band gap.
1. M u
ZnS l bn dn truyn thng v c nghin cu ng dng rng ri. Trong cc vt liu nano,
ZnS l mt trong nhng vt liu c nhiu nh nghin cu quan tm. N l hp cht c vng
cm thng, rng vng cm ln nht trong cc hp cht AIIBVI, c nhit nng chy cao
(2103 K)Error! Reference source not found.. Ngi ta c th iu khin rng vng cm ca
ZnS bng cch pha thm tp cht, thay i nng pha tp v thay i iu kin ch to mu. V
vy m ZnS c ng dng trong nhiu lnh vc khoa hc v i sng.
Theo [2] cho thy hm lng Mn nh hng ti ph PL v thu c cc mu bt nano ZnS
pha tp 9% Mn c ph hunh quang kh mnh. Trong bi bo ny chng ti trnh by cc
nghin cu ch to cc h mu bt ZnS:Mn2+_12%_pH=3,6; ZnS:Mn2+_9%_pH=5, mu mng
ZnS:Mn2+_9%_pH=5 v nh hng ca nhit nung ln ph PL v khe nng lng ca cc
cc h mu bt nano v mng mng ZnS pha tp Mn2+ ni trn.
2. Thc nghim
2.1. Ch to h mu ZnS:Mn2+_12%_pH=3,6 nung cc nhit 800C, 1500C, 2500C, 3500C;
v h mu ZnS:Mn2+_9%_pH=5, nung 800C, 2000C, 3000C, 4000C.
Cc dung dch ha cht tinh khit cao c s dng trong qu trnh ch to: dung dch I l
Zn(CH3COO)2.2H2O 0,1M, dung dch II l Mn(CH3COO)2.4H2O 0,1M, dung dch III l
Na2S.9H2O 0,1M. Dung mi dng cho dung dch I v II l CH3OH:H2O (t l 1:1), cn dung mi
dng cho dung dch III l H2O. u tin pha dung dch I v II vi t l thch hp nhm to ra cc
vt liu ZnS:Mn_12% ; ZnS:Mn_9%. Cc tnh ton cho thy rng c th chn pH=3,6 v pH
=5 to kt ta ZnS:Mn2+ nhng khng to thnh kt ta Zn(OH)2. pH ng vai tr quan
trng trong s to thnh kt ta ZnS:Mn2+. Nh t t tng git dung dch III vo hn hp dung
dch I v II. Thi gian phn ng ht dung dch khong 30 pht. Cc phn ng xy ra nh sau:
Mn(CH3COO)2+Na2S = MnS+2CH3COONa
Nhng
_____________________________________________________________________________________
Cc kt ta c tch ra bng my quay li tm v ra bng CH3OH:H2O (vi t l 1:1). Sau

mu c lm kh p sut thp (200 mbar) nhit 500C trong 48 gi. Sau cc quy trnh
trn ,bt ZnS:Mn2+_12%_pH=3,6 c nung cc nhit 800C, 1500C, 2500C, 3500C;v bt
ZnS:Mn2+_9%_pH=5 c nung cc nhit 800C, 2000C, 3000C, 4000C.
2.2. Ch to mu mng ZnS:Mn2+_9%_pH=5
Theo [2], bt nano ZnS:Mn2+vi hm lng 9% Mn cho ph PL mnh nht. Do vy chng
ti nghin cu ch to mu mng ZnS:Mn2+_9%_pH=5. Cc kt ta ZnS:Mn2+ phn tn vo
trong dung mi CH3OH:H2O (t l 1:1). Mng c ch to bng phng php quay ph.
Cc mu mng ZnS:Mn_9% vi pH=5 c x l nhit 800C, 2000C, 3000C, 4000C trong
mi trng kh Nit bng l c iu khin nhit nhit theo quy trnh nh sau: tng nhit
ln n gi tr mong mun vi tc 6 (/pht) gi nhit ny trong vng 1h, sau
ngui n nhit phng.
3. Kt qu v tho lun
3.1. Cc mu bt
3.1.a. H mu bt ZnS:Mn2+_12%_pH=3,6
* Kt qu o nhiu x tia X (XRD)
Cuong do (Cps)
Gin XRD ca tinh th nano ZnS:Mn_12% vi pH=3,6 nung cc nhit khc nhau
c m t trn hnh 1a.
350 C
250 C
o
150 C
o
80 C
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
2 ()
Hnh 1.b. nh TEM ca mu

bt ZnS:Mn_12%, pH=3,6
Hnh 1.a. Ph tia X ca mu

ZnS:Mn_12%_pH=3,6 vi nhit nung khc
Hnh 1a: Ph tia X ca mu ZnS:Mn_12%_pH=3,6
vi nhit nung khc nhau
T gin X-ray cho thy: tinh th ZnS:Mn_12% vi pH=3,6 l n pha, c 3 mt phn x

chnh l (111) (220) v (311) ng vi cc gc nhiu x ln lt l 2=28,800; 48,360 v 56,930.
Mu c cu trc lp phng gi km vi hng s mng a=b=c=5,4A0 tng ng vi nhm khng
gian Td2 F43m (216).
Tnh kch thc trung bnh ca ht tinh th da vo cng thc Scherrer:
0,9.
(1)
D=
. cos
Trong : D l ng knh ht tinh th, (rad) l bn rng ca nh nhiu x, () l

gc nhiu x ng vi v tr nh. Kt qu tnh kch thc ht da vo (1) c cho trong bng 1:
Bng 1: Kch thc ht tinh th tnh t cng thc (1) i vi mu ZnS:Mn_12%_pH=3,6
Nhit nung
(oC)
D1 (nm)
80
150
250
350
2,6
2,7
2,8
3,4
Advances
_____________________________________________________________________________________
R rng ta thy rng khi nhit x l mu tng ln

th kch thc ht cng tng theo. iu ny c gii
thch l do khi nhit x l mu tng ln th cc ht c
xu hng kt m li v hnh thnh nn ht c kch
thc ln hn. Kt qu o kch thc ht t nh TEM
(hnh 1b)cng ph hp vi cc tnh ton kch thc ht
trong bng 1
9000
D2
*Kt qu kho st hunh quang
(1)
(2)
(3)
(4)
(1)
8000
7000
80 C
o
150 C
o
250 C
o
350 C
6000
5000
(2)
D1
4000
3000
(3)
D3
2000
(4)
1000
0
Hnh 2 l ph PL ca mu bt nano ZnS:Mn_12%

pH=3,6 x l cc nhit khc nhau. Khi o ph PL
chng ti c gng gi cho khi lng mu l xp x nh
nhau. Da vo th ph PL ta thy nhit nung
G
Mn2+
A1
E
A2
E
T1
500
600
A1+E
T2
400
600
700
5000
A1+4E
Cng hunh quang (.v.t.y)
300
A1
A1
Mng lp phng
Mng lc gic
900
1000
Ph hunh quang ca mu
-ng fit nh
-ng fit nh 1
-ng fit nh 2
-ng fit nh 3
D2
4000
3000
D3
D1
2000
651
479
1000
300
Hnh 3. S cc mc nng lng ca ion Mn2+

khi c lp v khi trong trng tinh th ca mng
lp phng v mng lc gic.
800
B-c sng (nm)

quang ca mu
Hnh 2. Ph hunh
Hnh 2: Ph hunh quang ca mu ZnS:Mn_12%_pH=3,6
ZnS:Mn_12%_pH=3,6
nhit
vi cc nhit nung vi
khc nhau
nung khc nhau.
400
500
600
700
800
900
1000
Bc sng (nm)
Hnh 4. ng fit nh ca mu mu
ZnS:Mn_12%, pH=3,6 x l nhit 1500C
thp 800C, mu ZnS:Mn_12% pht quang mnh trong vng kh kin v quan st thy c ba nh
hunh quang ti cc nh D1, D2, D3 ng vi bc x mu xanh lam, bc x mu da cam v bc
x mu .
Ngun gc ca bc x xanh lam do sai hng ca bn dn ch ZnS, ngun gc ca bc x
mu da cam l do s chuyn ca in t t mc 4T1 6A1(trong trng tinh th ca mng lp
phng) hoc A2A1 (trong trng tinh th ca mng lc gic) ca ion Mn2+ 16.
Hnh 3 l s cc mc nng lng ca ion Mn2+ khi c lp v khi trong trung tinh th
ca mng lp phng v trong trng tinh th ca mng lc gic 6.
Hnh 4 l kt qu tch nh hunh quang ca mu ZnS:Mn_12% vi pH=3,6 (x l 1500C)
bng phng php Gaussian. Tng t i vi mu nung cc nhit 800C, 2500C v 3500C ta
thu c bng s liu v cng nh hunh quang nh bng 2.
Bng 2: Bng so snh cng hunh quang ca h mu ZnS:Mn_12%, pH=3,6 x
l cc nhit khc nhau
t 0C
D1(xanh)
I
(nm)
D2(Cam)
I
(nm)
D3()
I
(nm)
Ix
Ic
80
469
3359
601
6729
656
2106
0,50
150
479
1432
600
3004
651
1567
0,48
250
500
135
597
1439
638
1165
0,09
598
686
662
590
350
Nhng
_____________________________________________________________________________________
Ta thy khi nhit x l mu tng ln, cng cc nh hunh quang gim dn; ng thi
bc x xanh lam dch chuyn v pha sng di v hu nh b dp tt ng vi nhit nung mu
l 3500C. iu ny chng ti d on l do khi nhit tng, dn ti kch thc ht tng, do
rng vng cm gim v bc x hunh quang ch yu do s ti hp ca cc in t b by
cc mc donor nh x nm ngay di vng dn vi cc mc nng lng thp hn. Cc mc by
donor ny hnh thnh do cc trng thi khuyt tt, sai hng ca mng tinh th.
3.1.b. H mu bt ZnS:Mn2+_9%_pH=5
* Kt qu o nhiu x tia X
Cc kt qu trn cng tng t i vi mu ZnS:Mn2+_9%_pH=5. Gin nhiu x tia X v
kt qu tnh ton kch thc ht ca lot mu ny c m t trong hnh 5 v trong bng 3.
Bng 3. Kch thc ht tinh th tnh t cng thc (1) i vi mu ZnS:Mn_9%_pH=5 .
Nhit nung (oC)

D2 (nm)
80
2,6
200
2,7
300
3,9
400
4,9
120
100
80
60
40
20
0
120
400 C
300 C
80
40
0
800
200 C
600
400
200
0
120
80 C
80
40
0
20
30
40
50
60
70
Cng (Cps)
T gin X-ray hnh 5 ta thy: tinh th ZnS:Mn_9% vi pH=5 c cu trc lp phng gi

km vi hng s mng a=b=c5,4 A0; tng ng vi nhm khng gian Td2 F43m (216).
2 ()
Hnh 5: Gin nhiu x tia X ca mu ZnS:Mn_9% vi pH=5
25000
22500
20000
17500
15000
12500
10000
7500
5000
2500
0
1000
D1
D3
D2
(a)
(b)
80 C
o
200 C
(c)
(d)
300 C
o
400 C
(a)
(b)
800
(c)
600
400
(d)
200
0
350
400 450
500 550
600 650
700
750
800
850
900
950
B- c sng (nm)
Hnh 5. Gin nhiu x tia X ca mu

ZnS:Mn_9%, pH=5 x l cc nhit khc
nhau
Bc sng (nm)
Hnh 6. Ph hunh quang ca mu ZnS:Mn_9%,
pH=5 x l cc nhit khc nhau
Tuy nhin khi nhit nung mu t 3000C tr ln, trn gin nhiu x ta thy cn xut
hin pha c trng ca ZnO vi cu trc lc gic (Hexagonal). iu ny nhm tc gi chng ti
d on c th l do vi pH cao hn, sn phm to thnh sau phn ng c xut hin km
hydroxit Zn(OH)2. Chnh Zn(OH)2 khi nung nhit cao to thnh ZnO.
to
Zn(OH)2 = ZnO+H2O
*Kt qu kho st hunh quang
Hnh 6 l ph hunh quang ca mu bt tinh th nano ZnS:Mn_9% vi pH=5 x l nhit
cc nhit 800C, 2000C, 3000C, 4000C khi kch thch mu bng bc sng 325 nm nhit
phng vi thi gian ly tn hiu mu l 10ms. Da vo hnh 6 ta thy i vi mu nung mu
800C, ta cng thy mu ZnS:Mn pht quang mnh trong vng kh kin v quan st thy c ba
nh hunh quang D1 (xanh lam), D2 (da cam-vng) v D3 (bc x ).
Khi nhit x l mu tng ln th cng nh hunh quang ca cc nh cng gim dn,
bc x D1 dch v pha bc sng di v hu nh b dp tt khi nhit nung mu l 4000C. Tuy
Advances
_____________________________________________________________________________________
nhin ta thy nh hunh quang D2 dch v bc sng ngn khi nhit nung mu tng.
Vic tch nh hunh quang ca h mu ny bng phng php Gaussian ta thu c s liu
v cng nh hunh quang tng i nh trong bng 4 .
Bng 4. Bng so snh cng hunh quang ca h mu ZnS:Mn_9%, pH=5 x l
cc nhit khc nhau.
Nhit
(0C)
(nm)
(nm)
(nm)
Ix
Ic
80
470
20890
589
6651
660
10302
3,14
200
491
14620
585
5198
676
7241
2,81
300
492
171
572
436
646
363
0,39
400
486
18
582
193
658
92
0,09
D1(xanh)
D2(Cam)
D3()
578
700
1: Ph hunh quang ca mu)

2: -ng fit nh )
3: -ng fit nh 1)
4: -ng fit nh 2)
5: -ng fit nh 3)
1
600
500
T hnh 6 v bng 4 c th thy rng: Khi nhit x l mu tng ln th cng nh

hunh quang ca cc nh cng gim dn, bc x ng vi bc sng xanh lam dch v pha bc
sng di v hu nh b dp tt khi nhit nung mu l 4000C, bc x ng vi bc sng da
cam dch v pha sng ngn. iu ny c th d on nguyn nhn l do khi nhit x l mu
tng ln, bn cnh vic b rng vng cm hp li, ng thi trong nn bn dn ch xut hin
nhiu pha ZnO. Kt qu ny ph hp vi kt qu phn tch Ronghen cho cc mu nung nhit
cao trn 3000C.
400
691
4
300
200
487
3
100
5
0
300
400
500
600
700
800
900
1000
Bc sng (nm)
3200
D1
3000
D2
D3
2800
2600
2400
2200
2000
(1)
(2)
(3)
(4)
(5)
80 C
o
200 C
o
300 C
o
400 C
thy tinh
1800
1600
1400
1200
1000
800
600
400
(1)
(2)
(3)
(4)
(5)
200
0
-200
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
Bc sng (nm)
Hnh 7. ng fit nh ca mu ZnS:Mn_9% vi

pH=5 x l 3000C
Hnh 8. Ph hunh quang ca mu mng

ZnS:Mn_9% vi pH=5 x l cc nhit khc
nhau vi bc sng kch thch 325 nm v thi gian
ly tn hiu l 10 ms
Cc ph PL ca cc mu 3000C v 4000C c lm khp bng phng php Gaussian

nh trong hnh 7 th hin s chng cht ca cc vch 487 nm, 578 nm v 691 nm.
3.2. Cc mu mng ZnS:Mn_9% vi
pH=5
Bng 5. rng vng cm ca mu mng

ZnS:Mn_9%, pH=5 nung cc nhit khc nhau
Hnh 8 l ph PL ca mu mng tinh

Nhit nung
th nano ZnS:Mn_9% vi pH=5 ch to
80
150
250
350
(oC)
bng phng php quay ph. Kt qu
Eg(eV)
cho thy i vi mu x l nhit
3,79 3,30 2,89 2,82
800C, hunh quang ca mu kh mnh
trong vng nh sng nhn thy v xut hin ba nh D1, D2, D3. Ging vi kt qu mu bt trn,
nh D1 dch chuyn v bc sng di cn nh D2 dch chuyn v bc sng ngn hn.
Nhng
_____________________________________________________________________________________
Hnh 8 cn cho thy c s dch nh ca cc nh v pha bc sng nh sng . Cng

tng i ca nh D3 () cng gim khi nhit x l mu tng ln. Chng ti d on
nguyn nhn xut hin nh D3 l do s tng tc gia cc ion tp cht vi mng tinh th vi
nhau cng nh gia cc ion tp cht, cng vi s sai hng mng, nt khuyt (do mng khng
hon ho) nn s hnh thnh nn nhiu mc nng lng nm gn nhau trong vng cm. Khi nhit
x l mu tng ln, cu trc mng tinh th c dn n nh v cc mc nng lng nm
trong di cm mt dn, v th cng nh hunh quang tng ng ( D1, D3) gim dn v s b
dp tt khi nhit x l mu tng i cao.
* Kt qu kho st ph hp th
S thay i ca ( Ah ) 2 vo nng lng (h ) i vi cc mng mng ZnS:Mn_12% (pH=5)
x l cc nhit khc nhau c biu din trn hnh 9.
Cc gi tr ca b rng di cm thng c xc nh bng cch ngoi suy ng thng ct
trc nng lng ( h )78. Cc gi tr ca b rng vng cm (Eg) tnh t th ngoi suy tuyn
tnh ny c cho trong bng 5:
iu ny cho thy rng vng cm gim khi nhit x l mu tng ln. i vi mu
mng x l nhit 800C, rng vng cm l 3,79 (eV) gi tr ny ln hn gi tr rng vng
cm ca mu khi.
4. Kt lun
Bng phng php ha t, chng ti ch to thnh cng h mu bt ZnS:Mn_12%
(pH=3,6); ZnS:Mn_9% (pH=5) v ch to mu mng ZnS:Mn_9% (pH=5) bng phng php
quay ph. H mu bt ZnS:Mn_12% (pH=3,6) v ZnS:Mn_9% (pH=5) c cu trc lp phng
gi km khi mu c x l nhit n 3500C v 4000C. Tuy nhin, i vi h mu bt
ZnS:Mn_9%, pH=5, khi nhit mu 3000C tr ln c xut hin cu trc ca km oxit (ZnO).
Kt qu cho thy vi pH thp (pH=3,6) cht lng mu ch to c tt hn, khi nhit x l
mu tng ln th kch thc ht tinh th ca mu tng, kch thc ht trung bnh t 2,5 n 5 nm,
ng thi b rng vng cm gim trong khong t 3,8 n 2,8 (eV). Ph hunh quang o nhit
phng cho thy cc mu ZnS:Mn c cng hunh quang mnh trong vng nh sng nhn
thy. Cng ca cc nh hunh quang ny gim mnh khi nhit x l mu tng ln, c
bit l bc x xanh lam hon ton b dp tt khi nhit mu l 350-4000C. Nh vy ty vo
mc ch s dng ca vt liu ZnS:Mn m ta c th chn nhit x l mu cho ph hp.
Li cm n: Bi bo ny c hon thnh vi s gip v ti chnh ca ti cp B Khoa

hc v Cng ngh s 17TC-08-12
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MaterialsLetters 60 (2006) 35613564.
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Advances

in Optics, Photonics, Spectroscopy and Applications

NANOCRYSTALLINE TIO2 FILMS: PREPARATION AND CHARACTERIZATION

College of Technology, Vietnam National University, Hanoi

Market share of the

RoadSoundproof walls, tunnel Self-cleaning,

Tiles, wallpaper, window

Air cleaners, air

Fibers, clothes, leathers,

Facilities for agricultural

3. Results and Discussion

The crystalline structure of a TiO2

(105), (211) (204)

Fig.1. XRD patterns of a TiO2 film deposited on

Fig. 3. Photo-catalys treatment of MB solution vs. doping AgNO3 concentration.

Fig. 4. Transmittance spectra of MB before (the

Fig. 5. The comparison of photo-catalys

Fujishima, K. Honda, Nature 238, 38 (1972)

EFFECTS OF THERMAL TREATED ENVIRONMENT ON SOME PROPERTIES OF

Doping content (%)

Fig.1. X-rays diffraction of ZnO:Co films at

Fig. 5 shows the optical absorbtion spectra of

Doping content (%)

Fig.3. Doping content dependence of

Fig.4. SEM of ZnO0.95Co0.05 thin film

Fig.5. Absorption spectra of Zn1-xCoxO with x=0(a); 0.01(b); 0.05(c).

The effect of cobalt doping on optical property

Luminescence spectra of pure (a) and at 5% (b)

Fig.7. Photoluminescence spectra of ZnO(a) and

Fig.8. Photoluminescence spectra of ZnO0.95Co0.05

Magnetic field intensity (Oe)

Fig.9. The M-H curve magnetic field dependence

Fig.10. The M-H curve magnetic field dependence

OPTICAL PROPERTIES OF Zn1-x-yCoxCuyO

Fig.2. XRD patterns for Zn0.95-y Co0,05CuyO

Fig.1. XRD patterns for Zn1-xCoxO

Table 1: The lattice constants of Zn1-xCoxO and Zn1-x-yCoxCuyO

Fig.3. Raman spectra for Zn1-x-yCoxCuyO

Fig. 4. Raman spectra for Zn1-x-yCoxCuyO (x=0.05;

Fig. 5. PL spectra of Zn1-xCoxO ( x=0.025) excited by

Fig. 6. PLE spectra of Zn1-xCoxO

Fig.7. PL spectra for Zn1-xCoxO powders excited by

Fig.8. PLE spectrum of Zn1-xCoxO for the emission

Peak Position (nm)

Dopant Concentration (%)

Fig. 9. Peak position and dopant concentration

Fig.10. PL spectra for Zn1-x-yCoxCuyO powders

an emission doublet, one of that in shorter wavelength is subject to self-absorption by Co2+

FABRICATING AND STUDYING STRUCTURE,

Faculty of Physics, Hanoi National University of Education

Photoluminescence (PL) spectra of 0.01 M, 0.02 M, 0.04 M, 0.06 M samples at room

Raman Shift (cm-1)

Figure 5: Raman spectra of 0.02 M and 0.06 M samples

EFFECT OF ZnS SHELL THICKNESS AND TEMPERATURE ON

Institute of Materials Science, Vietnamese Academy of Science & Technology,

Abstract: We report an investigation of photoluminescence (PL) decay behavior with temperature

It means the area under the normalized decay curve I(0) = 1.

Fig.1. Luminescence decay curves of CdSe QDs

Fig.2. Comparison of two decay curves of

Fig.3. PL decays (logarithm scale) from 6.1 nm

Fig.4. XRD patterns of CdSe powder nanocrystals

Fig.5. Luminescence decay curves at the three