Vous êtes sur la page 1sur 7

This content has been downloaded from IOPscience. Please scroll down to see the full text.

Download details:
IP Address: 96.38.113.141
This content was downloaded on 07/08/2014 at 01:44
Please note that terms and conditions apply.
Structural changes of soda-lime silica glass induced by a two-step ion exchange
View the table of contents for this issue, or go to the journal homepage for more
2010 IOP Conf. Ser.: Mater. Sci. Eng. 15 012069
(http://iopscience.iop.org/1757-899X/15/1/012069)
Home Search Collections Journals About Contact us My IOPscience
Structural changes of soda-lime silica glass induced by a two-
step ion exchange
M Suszynska, L Krajczyk and B Macalik
Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
50-950 Wroclaw, ul. Okolna 2, Poland
M.Suszynska@int.pan.wroc.pl
Abstract. Introduction of silver or copper ions in soda-lime silica glass has been investigated
by studying the data obtained from optical absorption measurements and the transmission
electron microscopy performances. It has been stated that the optical and structural
characteristics of the doped specimens are effectively controlled by the dopant concentrations
and parameters of both, the ion-exchange procedures and the annealing treatments applied
afterwards. By sequential ion exchange of as received specimens in molten baths of Cu2Cl2 and
(AgNO3 in NaNO3), the composition and electronic structure of the elemental-nanoclusters
have been altered. Moreover, depending on the order of annealing, different microstructures
were created in the fabricated composites. Like this, the two-step exchange determines a new
engineering way new materials with desired optical properties could be produced.
1. Introduction
Metallic nanoparticles embedded in a dielectric matrix are well known for their attractive properties,
strong optical resonance and fast non-linear optical polarizability associated with the plasmon
frequency of the conduction electrons in the particles [1]. Our previous investigations [2,3] of a
multicomponent soda-lime silica (SLS) glass, exchanged either with silver or copper ions, suggest that
the structure-sensitive properties of the glass composites are strongly affected not only by the peculiar
behaviour of the quantum dots, but also by the microstructure of the host matrix.
A two-step ion exchange of the SLS glass in chemically different salts is expected to alter the
composition and the electronic structure of the dopant-nanoclusters, which would affect both the linear
and non-linear optical properties of the fabricated materials that are not possible with single elemental
colloids [4].
In this work, we report the optical response of metallic nanoclusters formed by sequential ion
exchange of copper and silver in the SLS glass. To obtain a deeper insight into the processes, which
control the related phenomena, transmission electron microscopy (TEM), extended by the high
resolution TEM (HRTEM), and the selected area electron diffraction (SAED) analysis have been
performed. The results are compared with those obtained for the same glass matrix containing the
dopant in the form of elemental silver and copper nanoparticle [2,3].
2. Experiments
The content of the main SLS glass components (SiO
2
/73 mol % and Na
2
O/13 mol %) corresponds to
the miscibility gap in the SiO
2
-Na
2
O system [5]. The applied two-step ion exchange was as follows. As
11th Europhysical Conference on Defects in Insulating Materials (EURODIM 2010) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 15 (2010) 012069 doi:10.1088/1757-899X/15/1/012069
c 2010 IOP Publishing Ltd 1
received specimens were firstly dipped in a bath of molten Cu
2
Cl
2
at 450
0
C for 1h.The second
exchange was in a molten mixture of AgNO
3
(2%) in NaNO
3
at 350
0
C for 2h. Afterwards, the doubly
doped specimens underwent two types of thermal treatment. Namely, either 1h of air annealing at
600
0
C was followed by 5h of annealing in gaseous hydrogen at 500
0
C or 5h of the hydrogen annealing
at 500
0
C was followed by the air annealing at 600
0
C performed versus time up to about 1500h.
According to our knowledge [2,3], these procedures would secure the transformation of both ions into
the colloidal silver and copper nanoparticle.
It should be stressed that the co-doping of glasses, described in the literature, was usually
performed by ion implantation of pure silica [6-8]. Local heating of the doped matrix works as the
reduction agent and leads to the ion/atom-transformation. However, one has to remember that ion
implantation is accompanied by the formation of some radiation damage, and the effects of these
defects are usually omitted in discussion of the obtained results. On the contrary, we have adapted the
ion exchange method for silver as well as copper ions [2,3], and these procedures have been used for
the silver-after-copper exchange applied for the soda lime silica glass.
To characterize the composite materials, optical absorption (OA) and the transmission electron
microscopy (TEM), extended by the high resolution TEM (HRTEM) and the selected area electron
diffraction (SAED) performances, have been used. After each treatment, the optical absorption was
measured in the range from 200 to 1600 nm on a Cary-5E UV-VIS spectrophotometer at room
temperature. The TEM-micrographs were obtained by means of a Philips-CM-20 microscope while
the Philips Scanning Microscope SEM-515 with a roentgenographic analyzer (EDAX-9800) was
exploited to control the composition of the specimens. The sample surfaces were selectively etched in
diluted water solutions of HF and replicated by a single stage technique. These replicas have been
examined under TEM operating at 200 kV with a 0,24 nm point-to-point resolution.
3. Results and discussion
3.1. Optical absorption data
Optical absorption spectra obtained for the commercial SLS glass doubly exchanged with silver-after-
copper, thermally treated afterwards in a different atmosphere and recorded at room temperature, are
shown in figure 1. Figure 2 shows additional data for the exchanged samples annealed in air-after-
hydrogen at 600
0
C for times up to about 1500h.
Figure 1: Optical absorption of the
SLS glass after: 1) ion exchange
with copper and silver (black & red
lines, respectively), 2) annealing of
the exchanged specimens either in
air or hydrogen (green & blue lines,
respectively), and 3) additional
annealing either in hydrogen after
air or in air after hydrogen (cyan &
magenta lines, respectively).
250 500 750 1000
0,0
1,5
3,0
4,5
559
556
401
556
380
411
C48.1 Cu
2
Cl
2
/1h/450
o
C
C48.2 (1)+AgNO
3
(2%)/2h/350
o
C
C48.2a (2)+1h/600
o
C/air
C48.2b (2)+5h/500
o
C/
2
C48.3 (2a)+5h/500
o
C/
2
C48.4 (2b)+1h/600
o
C/air
a
b
!
o
r
b
a
"
#
$

(
a
r
b
.

u
"
i
%
!
)
&a'$l$"g%h ("()
11th Europhysical Conference on Defects in Insulating Materials (EURODIM 2010) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 15 (2010) 012069 doi:10.1088/1757-899X/15/1/012069
2
The linear-OA-measurements made in air from 200 to 1600 nm show significant changes in the
magnitude, width and location of the surface plasmon resonance (SPR) bands when compared with
those of the pure elements, cp. figures 1 and 3 in [2] and [3] for the Ag and Cu ion exchanged SLS
glass, respectively.

Figure 2: Optical absorption
of the doubly exchanged
SLS sample which after the
H
2
- treatment(2b/5h/500
0
C)
was air-annealed at 600
0
C
for time from 1h (C48.4)
up to 1474h. Attention: to
see some of the effects
described in the text, the
OA scale should be strongly
reduced (0.01-0,30).
It has been ascertained that although the exchange with copper ions may be effectively performed
in the air atmosphere, the formation of Cu-nanoclusters was possible only after additional annealing of
the exchanged specimens in the gaseous hydrogen. In contrast to copper, the silver ions can be reduced
during a high temperature treatment of the exchanged specimens in air as well as in the hydrogen
atmosphere. In the first case the Fe
2+
ions, present as impurities in the SLS glass, act as the reduction
agent owing to the (Fe
2+
Fe
3+
+ e
-
) redox reaction. Moreover, already during exchange some of the
silver ions transform into atoms which are the seeds for the nanosized particles formed during the
high-temperature treatment. This effect has also been detected previously [9,10].
During the two-stage exchange of the SLS specimens, copper enters the glass matrix in the form of
mono- and divalent ions. While the monovalent copper and silver ions are not detectable in the studied
spectral range, divalent copper is registered at about 780 nm.
Short annealing of the exchanged specimens in air at 600
0
C (sample 2a) results in appearing of the
SPR band related with nanoparticles of silver at about 411 nm. The H
2
-treatment of this sample
(3=2a+H
2
) induces a slight increase of this band, its shift to 401 nm and distinct broadening. The
hydrogen-treatment induces the formation of additional very small Ag-particles in a superficial layer
of the sample. The band-broadening is a sign of the presence and/or formation of Ag nanoparticles
with different dimensions.
Hydrogen-treatment of the exchanged specimens (2b) at temperatures above 250
0
C may result in
reduction of the silver and copper ions. Because at 500
0
C this process is more effective for copper than
for silver, the SPR-band of silver is small and "covered" by the bands at 380 nm and 556 nm
corresponding to the interband transitions and the surface plasmon resonance band of metallic copper,
respectively [11]. It is suggested that the optical absorption due to the interband transitions dominates
the SPR absorption at the beginning of the reduction process when the nanosized copper particles are
small. The OA data also show that the Cu
2+
ions are not completely reduced during this treatment.
Long air annealing of specimens after the first hydrogenation (2b+air) shows a lot of interesting
changes. First of all, strong increase of the SPR-silver-band occurs. After 23 h of annealing the silver
band decreases and shows a red shift to 425 nm. Moreover, a decrease and shift to 563 nm appear for
the copper-

SPR-band. After 64 h of annealing the OA band related to the SPR of copper disappears. It
250 500 750
0,0
1,5
3,0
4,5
556
354
a
b
!
o
r
b
a
"
#
$

(
a
r
b
.

u
"
i
%
!
)
h/600
0
C/air)
C48.4*
2b+1h/air
2b*$+#h.
+5h/
2

465
443
425
380
411
1
3
6
23
43
64
91
157
204
227
250
418
658
994
1474
2b
&a'$l$"g%h ("()
11th Europhysical Conference on Defects in Insulating Materials (EURODIM 2010) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 15 (2010) 012069 doi:10.1088/1757-899X/15/1/012069
3
is possible that the already formed colloidal copper particles either dissolve inside the matrix or
diffuse toward the sample surface where they become entirely oxidized into the Cu
2
O particles. As will
be shown by the TEM-observations (cp. 3.2), the Cu
2
O components form a shell configuration
around the Cu-core-nanoparticles. The position of the related Cu-SPR peak strongly depends upon the
form and thickness of the Cu
2
O nanoshell.
Further annealing of samples up to 250h and 1474h results in further decrease and red-shift of the
Ag-SPR-band to 443 nm and 465 nm, respectively. At these stages the band becomes broad and the
area under the absorption curves remains nearly constant indicating that the volume fraction of the
formed nanoparticles corresponds to the total amount of silver. The detected red-shift of the band
could be related with some shape changes of the particles, as it was shown previously [12] for silver
doped SLS glass specimens subjected to deformation. At this moment it is not clear how the Ag-
spherical-particles could change their shape to induce the detected OA band.
All the above mentioned changes of the OA spectra are accompanied by a shift of the UV-
fundamental absorption edge. As far as for samples (2b) and (2b+air up to 3h) the shift is toward lower
energies, the reverse behavior of samples was detected for the remain treatments. Moreover, starting
from the annealing for 250h the band related with matrix impurities (different from iron) becomes
detectable at 354 nm.
Preliminary calculations of the extinction spectra, based on the MIE theory [13], support the
suggestion that the produced heterosystem of metal nanoparticles corresponds to solid solutions rather
than some core shell structures.
3.2. TEM data
Figures 3-5 show the most interesting data obtained by using the TEM-related procedures. The main
results are as follows.
Annealing of the exchanged specimens in selected atmospheres results in the formation of new
microstructures within the glass matrix, cp. figure 3. The Na
2
O-rich droplets, present already in as
exchanged samples, grow in size, alter their shape and distribution during the thermal treatment
applied. The small, well separated, droplets characteristic of as exchanged specimens, grow in size
during the air-treatment, and are changing into interconnected structures after hydrogenation. These
effects resemble those observed previously [2,3] either for Ag- or the Cu-exchanged specimens,
respectively.
(a) (b) (c)
Figure 3: TEM-micrographs of
the glass surface showing the
morphology of samples: (a) as
exchanged, (b) after short air-
annealing, (c) after hydroge-
nation.
With respect to the dopant, the TEM-micrographs reveal that nearly spherical colloids are formed
for the exchanged specimens annealed afterwards. Figure 4 exemplifies the particles of copper
surrounded by a layer of Cu
2
O and a particle of silver, the size of which is distinctly smaller than that
related with a copper cluster. The two fast-Fourier-transforms (FFT) correspond to the particles of
Cu
2
O and silver. The SAED-patterns show the presence of both Ag and Cu FCC spotty rings
confirming that separation instead of alloying of the two crystalline species took place. The
interplanar spacing of the nanoparticles are comparable with those of bulk Ag and Cu being in accord
11th Europhysical Conference on Defects in Insulating Materials (EURODIM 2010) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 15 (2010) 012069 doi:10.1088/1757-899X/15/1/012069
4
with the equilibrium Cu-Ag phase diagram. This means that "our Cu-Ag" particles may be a solid
solution in which Cu-atoms replace the Ag-atoms in the FCC-structure.
Figure 4: Copper and silver
nanosized particles in soda lime
silica glass doubly exchanged and
hydrogenated afterwards.
Two other results deserved our attention. Namely, the formation of crystalline Na
2
O particles in the
direct vicinity of the nanosized silver particles and the presence of Cu
2
O particles round the separated
copper nanoparticles. Examples of both have been shown in figure 5.
Figure 5: Two HRTEM micrographs of the
sequentially exchanged SLS glass samples in
which the Cu-nanoparticle is surrounded by
Cu
2
O layers, and the Ag-nanoparticles are
accompanied by the crystalline Na
2
O
nanoparticle.
The electron diffraction patterns confirm that the quantity of crystalline Na
2
O is largest for the
highest exchange time. This amorphous-to-crystalline transformation of the Na
2
O-rich phase is
probably induced by the presence of the copper ions/clusters and can result in the detected
improvement of the mechanical characteristics of the near-surface layer of these specimens [14].
For the Cu-related particles the presence of core/shell structures has been detected. The {111}
lattice fringes of Cu indicate that the cores of nanoclusters are Cu while the shells are Cu
2
O either in
the form of separated particles or as a continuous layer. The geometrical form of the Cu
2
O phase
depends on the time during which the sample is in contact with air. It is possible that the core-
Cu/shell-Cu
2
O structures appear during ion exchange performed in air when the first Cu
o
particles are
working as seeds for the Cu
2
O aggregates. During this process, the Cu
2
O shells are changing their
geometrical form from separated small spherical particles distributed around the large Cu-cores to a
continuous layer surrounding small cores. Sometimes the Cu-nanoparticle become entirely changed
into the Cu
2
O particles. Controlling the formation of Cu
2
O, one obtains additional species in the newly
created multi-structure, which give additional possibilities for manipulating the properties of the
exchanged SLS glass.
4. Summary
In this paper, we demonstrated how sequential ion exchange can modify the wavelength of the SPR
bands of metal colloids in a dielectric matrix.
Combined measurements of the optical and structural characteristics of the (Cu+Ag)-doped SLS
glass showed that:
clear changes of the matrix morphology occur after the high temperature treatment, and the
changes are probably related with the formation of strong chemical bonds between the dopant and
non-bridging oxygen;
11th Europhysical Conference on Defects in Insulating Materials (EURODIM 2010) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 15 (2010) 012069 doi:10.1088/1757-899X/15/1/012069
5
the amorphous-to-crystalline transformation of the Na
2
O-rich phase is probably induced by the
presence of the copper ions/clusters and improves the detected mechanical characteristics of the
near-surface layer of the doped SLS glass [14];
heterostructured nanoparticle, comprising a metal/Cu core and oxide/Cu
2
O shell are formed; they
are interesting for further studies because of their interesting electrical properties;
the copper-plus-silver nanoparticles also as solid solution in the SLS glass specimens seem be
more attractive over monometallic nanoclusters because they induce improved optical
performances of the doped dielectric matrix.
In a general case, the composition of the ion exchanged SLS glass could be an additional degree of
freedom, which provides new possibilities in tailoring the properties of bimetallic nanoparticle besides
the usual size and shape manipulation, and the nucleation of various multicomponent nanoclusters
would be a novel method by which many of the glass properties could be controlled.
References
[1] Hache F, Ricard D, Flytzanis C and Kreibig U 1988 Appl. Phys. 47 347
[2] Berg K J, Grau P, Petzold M and Suszynska M 1993 Proc. of Intern. Confer. on Defects in
Insulating Materials, Schloss Nordkirchen, Germany, World ScientificI, Ed's. Kanert O,
Spaeth M Singapore 914-916
[3] Macalik B, Krajczyk L, Okal J, Morawska-Kowal T, Nierzewski K D and Suszynska M 2002
Rad. Effects and Defects in Solids 157 887-893
[4] Magruder III R H,.Wittig J E and Zuhr R A 1993 J. Non-Crystal Solids 163 162-168
[5] Porai-Koshits E A and Averjanov V J 1965 J. Non-Crystalline Solids 1 29-38
[6] De G, Gusso G M, Tapfer L, Catalano M, Gonella F, Mattei G, Mazolldi P and Battaglin G 1996
J.Appl. Phys. 80/12 6734-6739
[7] Zuhr R A, Magruder III R H and Anderson T S 1998 Surf.Coat.Technol. 103-104 401-405
[8] Ren F, Jiang C Z, Chen H B, Shi Y, Lin C and Wang J B 2004 Physica B 353 92-97
[9] Kreibig U and Fragstein C V 1969 Z. Phys.224 307
[10] Berg K J, Grau P, Nowak-Wozny D, Petzold M and Suszynska M 1995 Mater. Chem.Phys. 40
131-135
[11] Creighton J A and Eadon D G 1991 Chem.Soc.Faraday Trans. 87 3881- 3896
[12] Berg K J, Capelletti R, Krajczyk L and Suszynska M 1996 Proc. of 9th Intern. Symposium on
Electrets(ISE9) Shanghai, China 378-383 eds Xia Zhongfu and Zhang Hongyan
[13] Mie G.1908 An. Phys. 25 377-386
[14] Suszynska M and Szmida M prepared for publication in Appl. Phys. Letters
11th Europhysical Conference on Defects in Insulating Materials (EURODIM 2010) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 15 (2010) 012069 doi:10.1088/1757-899X/15/1/012069
6

Vous aimerez peut-être aussi