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Intense white light emission in Tm3+/Er3+/Yb3+ co-doped Y2O3ZnO nano-composite

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2013 J. Phys. D: Appl. Phys. 46 275101

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IOP PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 46 (2013) 275101 (8pp) doi:10.1088/0022-3727/46/27/275101

Intense white light emission in

Tm3+/Er3+/Yb3+ co-doped Y2O3ZnO
nano-composite
R S Yadav, R K Verma and S B Rai
Laser and Spectroscopy Laboratory, Department of Physics, Banaras Hindu University,
Varanasi 221 005, India
E-mail: sbrai49@yahoo.co.in (S B Rai)

Received 16 January 2013, in final form 10 April 2013

Published 18 June 2013
Online at stacks.iop.org/JPhysD/46/275101

Abstract
The Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 ZnO nano-composite is synthesized using the solution
combustion technique. The structural morphology is monitored using x-ray diffraction,
transmission electron microscopy and scanning electron microscopy. The Yb3+ /Tm3+
co-doped nano-phosphor emits intense blue as well as weak red emissions, while Yb3+ /Er3+
co-doped nano-phosphor emits strong green along with red emissions on excitation with
976 nm laser. Joining these together (i.e. Tm3+ /Er3+ /Yb3+ co-doped phosphor) give very strong
white light, which is further verified by CIE coordinates (0.32, 0.36). The addition of ZnO
with Y2 O3 phosphor gives further enhancement in the intensity of white light. The possible
reason for this enhancement is the removal of optical quenching sites.
(Some figures may appear in colour only in the online journal)

1. Introduction white light emission in Ln : Y2 O3 nano-crystalline phosphor

There are several ways to generate white light. For example,
by emission of a broad band continuum in the visible region,
by mixing of primary colours red, green and blue (RGB) light
and by mixing light of opposite colours, etc. Among these
the most common one is by mixing of RGB. One way to
achieve RGB radiations is through the frequency upconversion
process. Generally, near infrared radiation sources are used
for this purpose [15]. Thus, in a recent report, Li et al have
reported the high colour purity phosphor LaAlGe2 O7 doped
with Tm3+ /Er3+ and obtained vivid blue and green emissions
from these ions [6]. Qin et al have observed the emission of
white light through upconversion in Tm/Er/Yb tri-doped CaF2
phosphor and explained the factors affecting the white light
intensity such as host materials, concentration of rare earth
ions, annealing temperature and excitation power density [7].
Zhou et al obtained the white light emission in Tm/Er/Yb tri-
doped Y2 O3 transparent ceramic and reported the tuning of
emission from multicolour to white light [8]. Lin et al have
studied the white light emission in the La2 O3 : Yb3+ /Er3+ /Tm3+
system and demonstrated the morphological control and
luminescence by adjusting the concentration of rare earth
ions [9]. Recently, Giri et al have reported tunable colour to
(Ln : Tm\Er\Yb). The multicolour tunability depends on
doping concentrations, annealing temperature and laser power
[10]. They have also discussed that the emission intensity
increases on annealing due to removal of quenching sites.
Song et al have also investigated the enhanced white light
emission in Er/Tm/Yb/Li co-doped Y2 O3 nanocrystals and
discussed the effect of modifier on the emission intensity [11].
In spite of these, the investigated materials show a common
problem of lower emission efficiency. In order to enhance the
emission efficiency, the research interests are being emerged
in the new class of materials, namely, composites. Actually,
composites are a category of hybrid materials having two or
more distinct phases and each of these phases have their own
optical characteristics [1214].
The Tm3+ ions exhibit strong blue as well as weak red
emissions, whereas Er3+ ions are well known for green and red
emissions on 976 nm laser excitation. Since the absorption
cross sections of these activators are relatively small, the
overall efficiencies are poor. However, the Yb3+ ion which has
7 times larger absorption cross section for infrared wavelength
976 nm and can easily excite these ions through energy transfer.
Thus, if Yb3+ is also taken together the overall emission
efficiencies of Tm3+ and Er3+ ions can be enhanced by several

0022-3727/13/275101+08$33.00 1 2013 IOP Publishing Ltd Printed in the UK & the USA
J. Phys. D: Appl. Phys. 46 (2013) 275101
times [1523]. Thus, an appropriate combination of these ions
can produce efficient white light.
The host material also plays a crucial role in the
enhancement of the luminescence. Y2 O3 is a host with low
phonon frequency and results in a low non-radiative relaxation
and good quantum yield of dopant. Another advantage with
Y2 O3 host is that it has high chemical stability, thermal
capacity, long durability, etc [24, 25]. The presence of ZnO
with Y2 O3 further reduces the non-radiative relaxation and
enhances the crystallinity of the material [26, 27]. ZnO
is a direct band gap semiconductor and is well known for
fluorescence from the band edge along with different defect
level emissions. These emissions can directly or indirectly
enhance the emissive properties of the localized dopant [28].
In this work, we have synthesized for the first
time Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 : ZnO nano-composite
through the solution combustion method using urea as organic
fuel/reducing agent. The structural characterizations have
been made using different techniques (x-ray diffraction (XRD),
scanning electron microscopy (SEM), transmission electron
microscopy (TEM), energy dispersive analysis of x-rays
(EDAX), etc). The photoluminescence properties of the
synthesized samples have been monitored using the 976 nm
laser radiation. The phosphor emits intense white light. The
presence of ZnO further enhances the intensity of the white
light more than two times.
2. Experimental
2.1. Synthesis of the sample
Following compositions are used for the synthesis of the nano-
phosphor and its nano-composites:
(100 x y z)Y2 O3 + xTm2 O3 + yYb2 O3 + zEr 2 O3 , (1)
where x = 0.5, y = 3.0 and z = 0.3 mol%, 0.5 mol%,
0.7 mol% and 0.9 mol%, respectively.
(100 x y z p)Y2 O3 + xTm2 O3 + yYb2 O3 + zEr 2 O3
+pZnO, (2)
where x = 0.5, y = 3.0 and z = 0.7 and p = 10 mol%,
20 mol%, 30 mol%, respectively.
The stoichiometric ratios of Tm2 O3 , Yb2 O3 and Er2 O3
(99.99% pure) are used for synthesizing the phosphor. These
materials were first dissolved in 5 ml of nitric acid and then
diluted with de-ionized water and mixed with vigorous stirring.
Urea was then added to the solution as organic fuel/reducing
agent. The final solution was stirred at a constant temperature
of 60 C for 4 h and a gel was obtained. The gel was taken in
a platinum crucible and placed in a closed furnace maintained
at 500 C. The auto-ignition took place within few minutes.
Finally, the composition in the form of white powder was
obtained.
For preparation of composites ZnO was added in the
composition mentioned above and the same process was
repeated. The final product thus obtained was grinded in an
agate mortar to convert it into fine powder. To achieve the
crystallinity the powder samples were annealed in batches at
800 C and 1200 C for 5 h separately [29].
2
R S Yadav et al
2.2. Characterization
XRD patterns of as-synthesized and annealed samples were
recorded using Cu, K radiation ( = 0.154 06 nm) from
a RINT/DMAX 2200 H/PC (Rigaku, Japan) machine with
5 min1 scan speed at room temperature. Data from
International Centre for Diffraction (ICDD) were used to
identify the crystallite phase of the as-synthesized and annealed
samples. Surface morphology of the samples was studied
with scanning electron microscopy (SEM) using JEOL-TM
Model JSM 5410 system operated at 15 kV. The transmission
electron microscopy (TEM) was used to record the micrograph
of the samples using a Technai 20G2 , Philips unit. The
EDAX measurement was carried out to verify the presence
of different elements and avoid impurities in the synthesized
sample. The photoluminescence spectra of different samples
were monitored using 976 nm radiation from a diode laser and
iHR320, Horiba Jobin Yvon, spectrometer attached with CCD
and Ocean Optics QE 65000.
3. Results and discussion
3.1. Structural characterizations
3.1.1. X-ray diffraction. The XRD patterns of as-synthesized
and annealed at 1200 C/5 h Tm3+ /Er3+ /Yb3+ co-doped Y2 O3
samples are recorded in the range 20 80 to distinguish the
phase and crystallite size and they are shown in figure 1(a).
As is evident from the figure the as-synthesized sample is
also crystalline. The crystallinity in the samples increases
on annealing at higher temperatures as is also evident from
figure 1(a). The diffraction patterns match well with the ICDD
JCPDS file no 43-1036. The phase of the as-synthesized and
annealed samples is cubic with space group la3 (2 0 6) and the
cell parameters a = b = c = 10.60 with = = .
The average crystallite size (th k l ) for (2 2 2), (4 0 0) and (4 4 0)
lattice planes are calculated using the Debye Scherrer equation
k
th k l = ,
Cos
where is the wavelength of the x-ray radiation, is the
FWHM of the diffraction peak, is the angle of diffraction
and k is a constant equal to 0.90. The average crystallite
size is found to be 25 and 40 nm for the as-synthesized
and annealed nano-phosphor samples, respectively. The inset
in figure 1(a) shows the variation in the full-width at half-
maximum (FWHM) of the peak due to lattice plane (2 2 2)
in the two cases which is also an indication of increase in
crystallinity of the material. The FWHM of the peak is much
larger in the as-synthesized sample than in the annealed one.
The reduction in FWHM confirms the grain growth.
The XRD patterns of Tm3+ /Er3+ /Yb3+ co-doped Y2 O3
ZnO nano-composite sample annealed at 1200 C/5 h recorded
in the same range under the same condition is shown in
figure 1(b). The XRD patterns of ZnO match well with the
JCPDS file no 36-1451 with the tetragonal phase and the cell
parameters are a = 3.249, b, c = 5.206 with = = .
The XRD patterns due to Y2 O3 are shown with (+) sign
while that of ZnO with (*) sign. Figure 1(c) shows the XRD
J. Phys. D: Appl. Phys. 46 (2013) 275101
Figure 1. (a) XRD patterns of as-synthesized and annealed
(at 1200 C/5 h) Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 nano-phosphor
sample. (b) XRD patterns of annealed (at 1200 C/5 h)
Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 ZnO nano-composite sample.
(c) Variation of XRD patterns in the (2 2 2) lattice plane of annealed
(at 1200 C/5 h) Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 and its ZnO
nano-composite sample.
pattern of the lattice plane (2 2 2) in the range 28 30 . This
clearly reveals the variation in FWHM between pure Y2 O3
and its ZnO nano-composite sample. The FWHM of the nano-
composite is smaller than that of pure Y2 O3 and is slightly
shifted towards higher angle side also. The shifting in peak is
due to strain in lattice on addition of ZnO in the pure Y2 O3
3
R S Yadav et al
Figure 2. Scanning electron micrographs of annealed
(at 1200 C/5 h) Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 and
Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 ZnO samples (a), (b).
Transmission electron micrograph (c) and the EDAX pattern (d) of
annealed (at 1200 C/5 h) Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 ZnO
sample.
host [30]. The reduction in FWHM (FWHMY2 O3 = 0.21 and
FWHMY2 O3 +ZnO = 0.17 ) further results an enhancement in
crystallite size from 40 to 48 nm [26, 27].
3.1.2. SEM, TEM and EDAX measurements. The mor-
phology of the annealed Tm3+ /Er3+ /Yb3+ co-doped samples
at 1200 C/5 h is recorded using SEM and TEM. The scan-
ning electron micrographs of the annealed Tm3+ /Er3+ /Yb3+
co-doped Y2 O3 and Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 ZnO
samples at 1200 C/5 h are shown in figures 2(a) and (b). The
morphology of the sample appears fluffy, porous and agglom-
erated in both the cases. The transmission electron micrograph
of the annealed Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 ZnO sample
is given in figure 2(c). This figure clearly shows that the par-
ticles are linked to each other inside the material. The particle
size in the annealed sample is coarser (in 80150 nm range)
which is consistent with the nano-scaled particles and sup-
ports the agglomeration. The EDAX measurement shown in
figure 2(d) is carried out to verify the presence of desired el-
ements (no impurity) in the composite. The EDAX pattern
indicates the presence of Y, Zn, O, Tm, Er and Yb elements
in the annealed ZnO composite sample. The presence of Cu
lines in the EDAX spectrum is originated from the copper grid
mesh used in the measurement.
3.2. Optical characterization
3.2.1. Tm3+ /Yb3+ co-doped Y2 O3 nano-phosphor. The
upconversion emission spectra of the as-synthesized Tm3+ /Yb3+
co-doped Y2 O3 nano-phosphor sample was first monitored
J. Phys. D: Appl. Phys. 46 (2013) 275101
Figure 3. Emission spectra of Tm3+ /Yb3+ co-doped Y2 O3 samples
of as-synthesized and annealed at different temperatures for 5 h
under 976 nm laser excitation.
and optimized exciting with 976 nm radiation. The emis-
sion intensity was optimum for (0.5 mol%) Tm3+ : (3.0 mol%)
Yb3+ ion concentration. The as-synthesized sample was an-
nealed at different temperatures for 5 h and the upconversion
emissions thus obtained are shown in figure 3. Large num-
ber of emission bands are seen extending from the ultravio-
let (UV) to near infrared (NIR) regions at wavelengths 301,
368, 394, 466, 491, 658, 679, 777, 798 and 817 nm and
they are assigned to arise due to 1 I6 3 H6 , 1 D2 3 H6 ,
1
I6 3 H 5 , 1 D 2 3 F 4 , 1 G 4 3 H 6 , 1 G 4 3 F 4 , 3 F 2 3 H 6 ,
1
D2 3 F3 , 1 G4 3 H5 and 3 H4 3 H6 electronic transi-
tions, respectively [1518, 3133]. All these bands are seen
in both the cases i.e. in the annealed samples as well as the as
synthesized one although the intensity of the peaks of annealed
samples is much larger than in the case of the as-synthesized
sample. The most intense emission is observed in the blue
region centred at 491 nm due to the 1 G4 3 H6 transition. A
weak emission in the red region centred at 658 nm appears due
to the 1 G4 3 F4 transition. Another intense emission is ob-
served at 817 nm due to the 3 H4 3 H6 transition in the NIR
region [31]. Tm3+ ions absorb 976 nm radiation very weakly
and give poor emission. However, in the presence of sensi-
tizer Yb3+ , the emission becomes very strong. Actually the
Yb3+ ions are pumped by NIR 976 nm laser from its ground
state (2 F7/2 ) to excited state (2 F5/2 ) and transfer their excita-
tion energy to the Tm3+ ions in the ground state (3 H6 ) due to
which they are promoted to 3 H5 state. The Tm3+ ions are fur-
ther excited to the higher excited states by different excitation
processes such as through excited state absorption (ESA), ex-
cited to excited state energy transfer (EEET), energy transfer
upconversion (ETU), etc. Some of the excited Tm3+ ions relax
from 3 H5 to 3 F4 state also non-radiatively and transfer some
of the Tm3+ in 3 F4 state. These ions are then promoted to 3 F2
state through ESA. Some of these ions in this state relax non-
radiatively and populate 3 H4 state. The transitions from 3 F2
and 3 H4 states to ground state are responsible for the radia-
tive transitions at 679 nm and 817 nm, respectively. Some of
R S Yadav et al
Figure 4. Schematic Energy level diagram of Er3+ /Tm3+ /Yb3+
co-doped Y2 O3 ZnO nano-composite under 976 nm laser excitation.
the ions in 3 H4 state are promoted to 1 G4 state through ESA.
Simultaneously, the Yb3+ ions from its cooperative state also
transfer energy to Tm3+ ions in ground state and promote them
to 1 G4 excited state. The transitions from 1 G4 state to lower
states emit radiations at 491, 658 and 798 nm [32]. Thus, the
658 and 798 nm transitions are ascribed as excited to excited
transitions, namely, 1 G4 3 F4 and 1 G4 3 H5 , respectively.
Some of the ions in 1 G4 state are excited further through ESA
to 1 D2 and 3 P2 states and then relax to 1 I6 state. The ions in 1 I6
state emit radiations at 301 and 394 nm through the 1 I6 3 H6
and 1 I6 3 H5 transitions, respectively. The bands observed
at 368 nm, 466 nm and 777 nm are ascribed to arise due to
1
D2 3 H6 , 1 D2 3 F4 and 1 D2 3 F3 excited to excited
transitions, respectively [18]. Most of these transitions do not
appear in the absence of sensitizer Yb3+ . The Yb3+ ions en-
hance the emission intensity upto orders to make them to be
seen [31, 34]. The insets in figure 3 show the UV and NIR
upconversion emission spectra.
The energy level diagram and possible electronic
transitions in Tm3+ /Yb3+ are shown in figure 4. The possible
absorption, energy transfer and upconversion mechanism can
be easily understood with the help of the energy level diagram.
The power dependence measurements are carried out to
verify the upconversion mechanisms involved in the emission
process. A logarithmic plot of pump power versus emission
intensity for (0.5 mol%) Tm3+ : (3.0 mol%) Yb3+ co-doped
Y2 O3 nano-phosphor sample for 491 nm transition is shown
in figure 5 and the value of n is found to be 2.68 (3).
This suggests that three photons are involved to populate the
1
G4 state of the Tm3+ ion [17]. The CIE colour coordinates
are calculated for this sample. The colour coordinates are
found to be (0.85, 0.19) which comes in the blue region. The
synthesized sample results strong blue light perception to the
naked eye when illuminated with 976 nm radiation.
3.2.2. Er3+ /Yb3+ co-doped Y2 O3 nano-phosphor. The
upconversion emission spectra of the as-synthesized Er3+ /Yb3+
co-doped Y2 O3 nano-phosphor sample were also optimized
for maximum photoluminescence under 976 nm excitation
and the composition found was (0.7 mol%) Er3+ : (3 mol%)
Yb3+ co-doped Y2 O3 . We also monitored the spectra of
4
J. Phys. D: Appl. Phys. 46 (2013) 275101
Figure 5. Pump power versus the emitted intensity dual logarithmic
plot for blue emission of Tm3+ /Yb3+ co-doped Y2 O3 annealed
sample (at 1200 C/5 h) under 976 nm laser excitation.
Figure 6. Emission spectra of as-synthesized and annealed
Er3+ /Yb3+ co-doped Y2 O3 samples at different temperatures for 5 h
on excitation with 976 nm laser.
the optimized samples annealed at different temperatures for
5 h. The spectra thus obtained are shown in figure 6. Two
intense emission bands one in the green and the other in
the red region are observed along with large number of
other bands. The emission peaks are observed at 364 nm,
393 nm, 411 nm, 478 nm, 491 nm, 524 nm, 566 nm, 663 nm
and 855 nm and these peaks are assigned as 2 H9/2 4 I15/2 ,
4
G11/2 4 I15/2 , 2 P3/2 4 I13/2 , 4 F3/2 4 I15/2 , 4 F5/2
4
I15/2 , 2 H11/2 4 I15/2 , 4 S3/2 4 I15/2 , 4 F9/2 4 I15/2 ,
4
I9/2 4 I15/2 transitions, respectively [1923, 32]. The
transition 2 P3/2 4 I13/2 at 411 nm is an excited to excited
state transition and appears with relatively weak intensity.
The emission intensity of the green band is greater than the
red band and they are assigned to arise due to the (4 S3/2 ,
2
H11/2 ) 4 I15/2 and 4 F9/2 4 I15/2 transitions, respectively.
The insets in figure 6 show the emission bands in the violet
and NIR regions. As is evident from figure, on annealing the
sample at higher temperatures [35, 36] the intensities of the
R S Yadav et al
green and red bands are increased. This increase in emission
intensity is a direct consequence of removal of quenching
sites from the as-synthesized sample. The mechanism of
emission in these cases is very similar to the previous case
(i.e. Tm3+ /Yb3+ ). As mentioned earlier the absorption cross
section of Yb3+ ion is high enough for 976 nm laser compared
with Er3+ ion. When Er3+ and Yb3+ both are present together
in the phosphor the excited Yb3+ ions transfer their energy to
Er3+ ions in the ground state as well as in the excited state
making the two photon absorption possible. The excited Yb3+
ions also emit strong broad radiation at 976 nm and cooperative
upconversion emission at 488 nm. The Er3+ ions at the same
time absorb 976 nm radiation and populate the 4 I11/2 state.
Moreover, the excited Yb3+ ions in 2 F5/2 state also transfer
their energy to Er3+ ions and promote them to the excited state
(4 I11/2 ). This process is very efficient and populates 4 I11/2
state very heavily. The de-excitation of some of the ions from
4
I11/2 level populates 4 I13/2 level. The 4 I13/2 as well as 4 I11/2
levels of Er3+ are long lived levels and the ions present in
these levels reabsorb 976 nm radiation and promoted to 4 S3/2 ,
2
H11/2 and 4 F9/2 levels. The 4 S3/2 and 2 H11/2 levels of Er3+ are
populated by energy transfer from cooperatively excited Yb3+
ions. Similarly 4 F9/2 level is populated further by relaxation
of excited ions from 4 S3/2 and 2 H11/2 levels. Some of the ions
present in 4 S3/2 and 2 H11/2 states reabsorb incident 976 nm
radiation and populate higher lying states. Transitions from
these higher lying states to ground state emit UV, blue and blue-
green radiations [22, 23]. Similarly, transitions from 4 S3/2 ,
2
H11/2 states to ground state result intense green emission and
the transition from 4 F9/2 to ground state gives red emission.
The energy levels of Er3+ /Yb3+ and observed transitions are
shown in figure 4. Wang et al have studied the visible
upconversion emission of Er3+ doped ZnO nanocrystals and
observed the effect of annealing on the emission intensity.
The samples heat treated at higher temperatures result intense
emission due to the removal of the optical quenching sites such
as OH and CO from the as-synthesized samples [35, 36]. The
intensity of the green band is larger than the red band and
results a strong orange perception with the naked eye. The
CIE diagram is plotted and the colour coordinates is found to
be (0.34, 0.65) which results the perception of orange colour.
A loglog plot for 566 and 663 nm transitions of Er3+ /Yb3+
co-doped Y2 O3 nano-phosphor sample annealed at 1200 C is
depicted in figure 7. The value of slope (n) is found to be 1.97
and 1.91 (2) for 566 and 663 nm, respectively. This clearly
suggests that two photons are involved in these transitions.
The deviation from the integral value is due to involvement of
non-radiative relaxation inside the host material.
3.2.3. Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 nano-phosphor. The
upconversion emission spectra of the as-synthesized and
annealed at different temperatures for 5 h Tm3+ /Er3+ /Yb3+
co-doped Y2 O3 nano-phosphor samples have been monitored
under 976 nm laser excitation and are shown in figure 8. The
molar concentrations of Tm3+ : Er3+ : Yb3+ are the optimized
value of these ions. The peaks observed in the spectra match
well with peaks present in the individual samples. The insets
in figure 8 show the emissions in UV and NIR regions. The
5
J. Phys. D: Appl. Phys. 46 (2013) 275101
Figure 7. Pump power versus the emitted intensity dual logarithmic
plot for green and red emissions of Er3+ /Yb3+ co-doped Y2 O3
annealed sample (at 1200 C/5 h) under 976 nm laser excitation.
Figure 8. Emission spectra of as-synthesized and annealed
Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 nano-phosphor at different
temperatures for 5 h under 976 nm laser excitation.
emission spectra recorded in the range 280875 nm and it is
shown in three parts for clarity. Further, since the tri-doped
nano-phosphor sample emits primary colours red, green and
blue, their concentrations may be varied so that they can be
used for white light generation. The concentrations of the
Yb3+ as well as Tm3+ ions are fixed at 3 mol% and 0.5 mol%,
respectively, whereas that of the Er3+ ions are made to vary
as 0.3, 0.5, 0.7 and 0.9 mol% so that the light emitted is
white light [711]. It is found that at 0.7 mol% Er3+ ion
concentration, white light emission takes place. The CIE
coordinates corresponding to this combination is found to be
(0.32, 0.36) which is close to the standard value (0.33, 0.33)
for white light [11].
As the concentration of the Er3+ ion is increased, the colour
of the emission of tri-doped nano-phosphor sample changes
from blue to bluish green, whitish green and finally white light.
Thus, it gives a possibility to get colour tunability leading to
white light. If the concentrations of Er3+ ions are increased
further the emission intensity of the white light decreases due
6
R S Yadav et al
Figure 9. Effect of Er3+ concentration on the emission intensity of
white light annealed at 1200 C for 5 h under 976 nm laser excitation.
Figure 10. Effect of ZnO concentration on the emission intensity of
white light annealed at 1200 C for 5 h under 976 nm laser excitation.
to concentration quenching. The effect of concentration on the
emission intensity of white light is depicted in figure 9.
3.2.4. ZnO nano-composite and its effect on the emission of
white light. The emission intensity of white light increases
further on addition of ZnO in the optimized combination. We
analysed the emission efficiency of white light by adding up
the different concentrations, namely, 10, 20 and 30 mol% of
ZnO in it. It is found that the emission intensity of white light
improves with the increase of ZnO in the host. It is optimum
for 20 mol% of ZnO. The effect of ZnO concentrations on the
emission intensity is shown in figure 10.
There may be several reasons for this enhancement. One
of the reasons is that ZnO forms composite with Y2 O3 and
as a result the phonon frequency of the material is reduced.
This decrease in phonon frequency reduces the electron phonon
J. Phys. D: Appl. Phys. 46 (2013) 275101
Figure 11. Emission spectra of as-synthesized and annealed
Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 ZnO nano-composite at different
temperatures for 5 h under 976 nm laser excitation.
coupling and thereby decreases the non-radiative relaxations.
The second and important reason may be the removal of
remaining quenching sites in the presence of ZnO [3941].
Actually in the presence of ZnO, the space vacant in the lattice
is covered by the ZnO which replaces impurities such as OH
and CO present in the host. The third possibility may be an
increase in the crystallinity of the host material in the presence
of ZnO [26, 27]. Wang et al have reported that the emissive
efficiency of rare earth ions is increased in larger crystallite
medium [37]. Jung et al have also reported that the increasing
the crystallite size of the phosphor essentially improves the
fluorescence intensity of the material [38].
The effect of the annealing has also been investigated
in the case of composite host. When the composite sample
is annealed at higher temperature; the emission intensity of
white light increases. The effect of the presence of ZnO on
white light emission as a function of temperature is shown in
figure 11. As has been reported the annealed samples show
an increase in crystallite size. The nanoparticles with larger
diameter can absorb the incident light more efficiently than
those with smaller diameter [4244]. Thus, the enhancement
in the emission intensity of white light is a combined effect of
concentration of rare earth ions, input pump power, annealing
temperature and crystallinity of the material.
The colour coordinates for white light emission is found
to be (0.32, 0.36) which is very close to the standard white
light colour coordinates (0.33, 0.33) [11]. The CIE diagram
of the Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 ZnO nano-composite
sample is shown in figure 12.
4. Conclusions
The tri-doped Tm3+ /Er3+ /Yb3+ : Y2 O3 ZnO nano-composite is
synthesized by the solution combustion method. The nano-
composite emits intense white light on excitation with 976 nm
laser. The XRD and TEM measurements reveal the strong
crystallinity of the nano-composite sample. The Tm3+ /Yb3+
7
R S Yadav et al
Figure 12. CIE diagram of Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 ZnO
nano-composite sample annealed at 1200 C/5 h and its image under
976 nm laser excitation.
co-doped Y2 O3 nano-phosphor sample gives intense blue
emission whereas Er3+ /Yb3+ co-doped Y2 O3 nano-phosphor
sample results strong green and slightly weak red emissions.
The tri-doped Tm3+ /Er3+ /Yb3+ co-doped Y2 O3 nano-phosphor
sample gives intense white light emission with (0.5 mol%)
Tm3+ , (0.7 mol%) Er3+ and (3.0 mol%) Yb3+ concentrations.
Addition of ZnO in the Tm3+ /Er3+ /Yb3+ co-doped Y2 O3
nano-phosphor sample enhances the efficiency of white light
emission further more than two times. The character of the
emitted light is verified by CIE coordinates (0.32, 0.36) which
is very close to the standard CIE coordinates for white light
(0.33, 0.33).
Acknowledgments
The authors are grateful to Professor O N Srivastava,
Department of Physics, for providing facilities for XRD, SEM,
TEM and EDAX. We are also grateful to UGC and DST, New
Delhi, for financial assistance.
References
[1] Auzel F 1973 Proc. IEEE 61 758
[2] Steckl A J, Heikenfeld J and Allen S C 2005 J. Disp. Technol.
1 157
[3] Zhang X, Liu M, Wong O, Lee C S, Kwong H L, Lee S T and
Wu S K 2003 Chem. Phys. Lett. 369 478
[4] Chuen C H and Tao Y T 2002 Appl. Phys. Lett. 81 4499
[5] Milliez J, Rapaport A, Bass M, Cassanho A and Jenssen H P
2006 J. Dis. Technol. 2 307
[6] Li Y C, Chang Y H, Lin Y F and Lin Y J 2006 Appl. Phys.
Lett. 89 081110
[7] Cao C, Qin W, Zhang J, Wang Y, Wang G, Wei G, Zhu P,
Wang L and Jin L 2008 Opt. Commun. 281 1716
[8] Hou X, Zhou S, Jia T, Lin H and Teng H 2011 J. Alloys
Compounds 509 2793
[9] Li G, Shang M, Geng D, Yang D, Peng C, Cheng Z and Lin J
2012 J. Cryst. Eng. Commun. 14 2100
J. Phys. D: Appl. Phys. 46 (2013) 275101
[10] Giri N K, Mishra K and Rai S B 2011 J. Fluoresc. 21 1951
[11] Bai Y, Wang Y, Peng G, Zhang W, Wang Y, Yang K, Zhang X
and Song Y 2009 Opt. Commun. 282 1922
[12] Binnemans K 2009 Chem. Rev. 109 4283
[13] Li Z, Zhang Y, Shuter B and Idris N M 2009 Langmuir
25 12015
[14] Wang F, Han Y, Lim C S, Lu Y, Wang J, Xu J, Chen H,
Zhang C, Hong M and Liu X 2010 Nature 463 1061
[15] Li T, Liu S, Zhang H, Wang E, Song L and Wang P 2011
J. Mater. Sci. 46 2882
[16] Yang H K, Moon B K, Choi B C, Jeong J H, Kim J H and
Kim K H 2012 Solid State Sci. 14 236
[17] Lu Q, Li A, Guo F Y, Sun L and Zhao L C 2008
Nanotechnology 19 145701
[18] Chen G Y, Somesfalean G and Zhang Z G 2007 Opt. Lett.
32 87
[19] Vetrone F, Boyer J C, Capobianco J A, Speghini A and
Bettinelli M 2004 J. Appl. Phys. 96 661
[20] Song H, Sun B, Wang T, Lu S, Yang L, Chen B, Wang X and
Kong X 2004 Solid State Commun. 132 409
[21] Pires A M, Heer S, Gudel H U and Serra O A 2006
J. Fluoresc. 16 461
[22] Singh S K, Kumar K and Rai S B 2009 J. Appl. Phys. B
94 165
[23] Guo H and Qiao Y M 2009 Opt. Mater. 31 583
[24] Tsukuda Y 1988 Japan. Ceram. Soc. Bull. 23 456
[25] Kong J, Tang D Y, Chan C C, Lu J and Ueda K 2007 Opt. Lett.
32 247
[26] Kominami H, Eguchi C, Kottaisamy M, Nakanishi Y and
Hatanaka Y 2004 J. Vac. Sci. Technol. B 22 1386
R S Yadav et al
[27] Jung K Y, Han K H and Ko Y S 2007 J. Lumin. 127 391
[28] Verma R K, Kumar K and Rai S B 2011 J. Lumin. 131 988
[29] Yadav R S, Dwivedi Y and Rai S B 2012 Spectrochim. Acta A
96 148
[30] Cullity B D 1978 Elements of X-ray Diffraction (Reading,
MA: Addison-Wesley)
[31] Mishra K, Giri N K and Rai S B 2011 Appl. Phys. B 103 863
[32] Zheng C B, Xia Y Q, Qin F, Yua Y, Mia J P, Zhang Z G and
Cao W W 2011 Chem. Phys. Lett. 509 29
[33] Dieke G H 1968 Spectra and Energy Levels of Rare Earth Ions
in Crystals (New York: Wiley-Interscience)
[34] Hou X, Zhou S, Lin H, Teng H, Li Y, Li W and Jia T 2010
J. Appl. Phys. 107 083101
[35] Wang X, Kong X, Shan G, Yu Y, Sun Y, Feng L, Chao K, Lu S
and Li Y 2004 J. Phys. Chem. B 108 18408
[36] Wang X, Kong X, Yu Y, Sun Y and Zhang H 2007 J. Phys.
Chem. C 111 15119
[37] Wang F, Deng R, Wang J, Wang Q, Han Y, Zhu H, Chen X and
Liu X 2011 Nature. Mater. 10 968
[38] Jung K Y, Lee C H and Kang Y C 2005 Mater. Lett. 59 2451
[39] Ubaldini A and Carnasciali M M 2008 J. Alloys Compounds
454 374
[40] Repelin Y, Proust C, Husson E and Beny J M 1995 J. Solid
State Chem. 118 163
[41] Panitz J C, Mayor J C, Grob B and Durish W 2000 J. Alloys
Compounds 303/304 340
[42] Ashkin A and Dziedzic J M 1973 Phys. Rev. Lett. 30 139
[43] Boyer J C, Vetrone F, Capobianco J A, Speghini A and
Bettinelli M 2004 Chem. Phys. Lett. 390 403
[44] Liu Y, Xu C and Yang Q 2009 J. Appl. Phys. 105 084701