Journal of Non-Crystalline Solids 351 (2005) 1819–1824

www.elsevier.com/locate/jnoncrysol

Study of structural and optical properties of

InSb-doped SiO2 thin films
B. Capoen a,*, V.Q. Lam b, S. Turrell b, J.P. Vilcot c,
F. Beclin d, Y. Jestin a, M. Bouazaoui a
a
Laboratoire de Physique des Lasers, Atomes et Molécules (CNRS UMR 8526), Bât P5, Centre d’Etudes et de Recherches Lasers et
Applications (CERLA), Université des Sciences et Technologies de Lille, F-59655 Villeneuve d’Ascq, France
b
Laboratoire de Spectrochimie Infrarouge et Raman (CNRS UMR 8516), Bât C5, Centre d’Etudes et de Recherches Lasers et Applications
(CERLA), Université des Sciences et Technologies de Lille, F-59655 Villeneuve d’Ascq, France
c
Institut dÕElectronique, de Microélectronique et de Nanotechnologie (CNRS UMR 8520) Cité Scientifique,
Avenue Poincaré, BP69, 59652 Villeneuve d’Ascq cedex, France
d
Laboratoire de Structure et Propriétés de l’Etat Solide (CNRS UMR 8008), Bât C6 Université des Sciences
et Technologies de Lille, 59655 Villeneuve d’Ascq, France

Available online 23 May 2005

Abstract

The non-linear absorption and the structure of rf-cosputtered SiO2:InSb films were investigated after different heat-treatments at
temperatures ranging from 200 to 900
C. The heat-treatment was 1 min or 4 h in an atmosphere of nitrogen or under vacuum,
respectively. After annealing at a temperature higher than 200
C, the presence of nanocrystallites in the layers was detected by
transmission electron microscopy (TEM) and Raman spectroscopy. The growth of either Sb or InSb nanocrystals essentially
depends on both the annealing temperature and the heat-treatment time. Particularly, it was shown that a rapid thermal annealing
(RTA) is necessary to obtain crystals of InSb with size estimated to be about 15 nm. The largest positive non-linear coefficient b, as
measured by the Z-scan method at 1064 nm in a nanosecond regime, was found to be equal to 1.8 · 10
3 cm/W when the films con-
tain InSb particles of larger size (up to 100 nm). However, when increasing the incident irradiance on the sample, the non-linear
effect does not increase and seems to saturate, which can explain the discrepancies observed with previous works on similar mate-
rials. This disagreement may also be due to different response times of the non-linearities related to thermal effects in the continuous
wave (CW) open-aperture Z-scan configuration.
 2005 Elsevier B.V. All rights reserved.

PACS: 61.46.+w; 81.15.Cd; 63.22.+m; 61.16.Bg; 42.65.
k

1. Introduction feasibility of using PbS quantum dot glasses instead of

The use of semiconducting particles with nanometer
sizes to dope glasses as non-linear absorbers may lead
to important applications in the field of pulsed laser
mode-locking [1] or all optical devices, such as switchers
[2]. In recent years, several works have demonstrated the
*
Corresponding author. Tel.: +33 3 20 33 70 19; fax: +33 3 20 33 70
20.
E-mail address: bruno.capoen@univ-lille1.fr (B. Capoen).
the expensive [3] epitaxially grown semiconductor satu-
rable absorbers to generate mode locking at 1.3 lm [1]
or Q-switching in a 1.5 lm laser [4]. In the case of PbS
nanoparticles, it seems that the separation of the excit-
ing wavelength and the exciton band maximum is
important to the selection of either an induced or a sat-
urated absorption effect [5]. The reason for this depen-
dency is the competition between different magnitudes
and time scales of both effects [5]. Hence, the convenient
wavelength for obtaining a non-linear effect appears to

0022-3093/$ - see front matter  2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2005.04.023
1820 B. Capoen et al. / Journal of Non-Crystalline Solids 351 (2005) 1819–1824

be constraining. However, in the case of rf-sputtered
SiO2:InAs films, a self-starting saturable absorber mode
locking has been experimentally demonstrated, despite a
broad particle size distribution and consequently an ab-
sence of exciton peak [6]. For these films, a rapid ther-
mal annealing (RTA) is generally performed under
nitrogen atmosphere to reduce the deep trap states at
the surface of the nanocrystallites, thus improving the
saturation dynamics [3,6].
InSb is, like InAs, a semiconductor with one of the
smallest bandgaps (0.17 eV), presenting a very large
exciton Bohr radius (78 nm) and consequently a strong
confinement effect when the particle size is a few tens
of nanometers [7]. Quantum confinement leads to the
possibility of changing the bandgap and thus to increase
non-linear optical effects in a larger range of wave-
lengths. Despite this interesting property, few studies
on the synthesis of InSb-doped transparent materials
have been reported in the literature to our knowledge.
Zhu et al. [8] investigated the structural and the linear
optical properties of InSb nanocrystallites rf-co-sput-
tered with silica. After deposition, their samples were
submitted to a thermal annealing (LTA) for 4 h under
vacuum. Recently, the non-linear absorption coefficient
[9] was measured using a continuous laser, giving larger
non-linear absorption coefficients b.
In this paper, we present the preparation of rf-sput-
tered InSb-doped silica films, of thickness in the 40–
100 nm range, and their linear and non-linear optical
properties, using pulsed laser technique. We report here
the preliminary results on the third-order non-linear
optical absorption of films prepared with 12.5% InSb
in SiO2 and heat-treated in different conditions (RTA
and LTA). The structure of these doped glasses was also
investigated using micro-Raman spectroscopy and
transmission electron microscopy, to detect InSb parti-
cles and to determine if the non-linear properties were
correlated with the particles and their sizes.
quent heat-treatments were performed between 200
C
and 900
C. One set of samples was annealed using a
RTA furnace for 1 min under nitrogen flow. After such
a treatment and except for the 900
C temperature, the
samples had a ÔdustyÕ layer on their surface, which could
be removed by cleaning. This ÔdustyÕ layer is attributed
to a diffusion of In and Sb to the surface of the samples
during heat-treatment. Such a dopant diffusion and a
loss of matter has been already observed for rf-sputtered
SiO2:InAs films when heat-treated [3] and testifies to
the porosity of the rf-sputtered SiO2 layers. Indeed, sil-
ica layers deposited by the RF-sputtering methods
are always porous before any heat-treatment [11].
Furthermore, the surfaces of these RTA-treated films
were inhomogeneous at the micrometer scale, as ob-
served with an optical microscope. A second set of
samples has been heat-treated under vacuum in a con-
ventional tubular furnace for 1 or 4 h. The surfaces of
these samples are more homogeneous and have no
observable metal diffusion. The variable preparation
conditions of the studied samples are compiled in
Table 1.
The optical absorbance of the films was measured
using a double beam spectrophotometer (Perkin Elmer
Lambda 19) at room temperature. The Raman spectra
were obtained in confocal configuration using a triple-
grating spectrometer (Jobin-Yvon T64000) and the
514.5 nm line of an Ar+ laser as the excitation source.
The micro-structural characterization was performed
by transmission electron microscopy (TEM) on a Philips
CM 30 with an electron beam accelerated at 300 kV.
Thin foils used for TEM observations were prepared
from SiO2:InSb-coated silica slices by mechanically
polishing to 30 lm thickness, followed by argon ion
milling. The thickness of the doped-glass coating could
also be determined using TEM by a cross-sectional
observation.
The non-linear absorption coefficient at 1064 nm
was measured using the conventional Z-scan single-

2. Experiments
Table 1
Deposition times and heat-treatment parameters of the different
Silica films doped with InSb were prepared by the samples used in this study
magnetron rf sputtering technique [10]. The targets con-
Sample Deposition Annealing Annealing
sisted of SiO2 glass disks with crystalline pure InSb wa- name time temperature (
C) conditions
fers (Wafer Technology Ltd) attached to cover a desired
UT 6H20 Untreated
percentage of the total surface area. The argon gas was LTA400 6H20 400 4H under vacuum
maintained at a pressure of a few mTorr and the Ar+ LTA900 6H20 900 4H under vacuum
flow was 50 sccm with a rf power of 50 W. Silica films LTA900-1H 6H20 900 1H under vacuum
doped with 12.5% InSb were generally deposited on sil- RTA200 3H 200 60 s under N2
RTA300 3H 300 60 s under N2
ica glass substrates. Such a nominal doping concentra-
RTA400 3H 400 60 s under N2
tion corresponds to the surface ratio of the targets and RTA500 3H 500 60 s under N2
we assume that this ratio is, nominally, the atomic ratio RTA600 3H 600 60 s under N2
in the resulting layers. For film thickness measurements RTA900 3H 900 60 s under N2
by scanning electron microscopy (SEM), some of the The other parameters are common to all the samples (InSb ratio
SiO2:InSb layers were deposited on Si substrates. Subse- 12.5%, rf power 50 W).
 B. Capoen et al. / Journal of Non-Crystalline Solids 351 (2005) 1819–1824
beam technique [12]. In this method, the 8 ns pulse of a
Q-switched Nd:YAG laser (10 Hz) was first spatially fil-
tered to get a Gaussian beam profile. This beam was
then focused with a lens of 10 cm focal length. The sam-
ple was moved along the z-axis through the focal plane
where the beam waist radius was set to 25 or 15 lm,
depending on the desired peak irradiance. The laser
pulse energy, I0, was allowed to vary from 0.2 to 60 lJ
using neutral density filters. The maximum of the trans-
mitted signal was collected via a photodiode, amplified
and then recorded by an oscilloscope as a function of
z. In most cases and especially after each high power
experiment (Ec > 25 MW/cm2), linear effects due to
inhomogeneities, permanent photo-ablation or photo-
darkening were recorded through a Z-scan at very low
irradiance (Ec < 7 MW/cm2). The high-energy Z-scan
curves were then divided by the low-energy data to ex-
tract the non-linear part of the absorption. For all the
samples, the refractive non-linear coefficient, c, could
not be measured because of the non-linear absorption.
Indeed, to obtain the typical peak-valley feature in a
closed-aperture Z-scan experiment [13], c must be much
greater than bk/4p, where b is the non-linear absorption
parameter and k the radiation wavelength. This would
give a value of c > 1.5 · 10
12 m2/W, which is scarcely
encountered, even in quantum dot glasses [14].
3. Results and discussion
3.1. Optical absorption
Each sample (untreated or heat-treated) had a dark
brown color by transmission and the absorption spectra
showed an onset wavelength depending on the initial
concentration. Fig. 1 shows the transmission curves of
the as-deposited and some RTA annealed samples.
The magnitude of the absorption does not change
monotonically with increasing heat-treatment tempera-
ture. This absence may be due to inhomogeneities in
the sample and to the previously mentioned dopant dif-
fusion, which may be different according to the densifi-
Fig. 1. Optical transmission spectra of the RTA SiO2:InSb (12.5%)
thin films at different annealing temperatures. Dotted lines represent
the absorption edges.
1821
Fig. 2. Optical transmission spectra of the LTA SiO2:InSb (12.5%)
thin films at different annealing temperatures and different durations.
cation rate [15]. The observed bump on the low energy
tail of the transmission spectra was ascribed to an inter-
ference effect due to the InSb-doped layer. In the case
where InSb nanoparticles actually exist, the absorption
edge does not shift, within errors of measurement, with
increasing annealing temperature. The blue shift in com-
parison to the InSb bandgap indicates that such parti-
cles would have a 12–16 nm mean diameter [8], with a
size distribution greater than 10% since the exciton peak
is not observed [16]. We note here that the RTA treat-
ment is also responsible for the diffusion of In or Sb ele-
ments out of the porous silica films. Because of this
diffusion, a part of the absorbing matter is lost when
the surface of the sample is cleaned, leading to a reduc-
tion in magnitude of absorption. Hence, it is not possi-
ble to deduce the changes of the particle size from the
absorption spectra. In Fig. 2, the transmission for the
LTA-treated samples is reported. In comparison with
the RTA samples, there is no measurable change in
the absorption edge energy at about 1 eV, but the stee-
per slope of the transmission spectra can be explained
by a larger final dopant concentration. This apparent in-
crease may be caused by a less efficient dopant diffusion
inside the matrix, related to the gradual temperature in-
crease in the case of LTA. The temperature and the
duration of the heat-treatment do not measurably affect
the absorption spectra, contrary to the observation of
Zhu et al. [8].
3.2. Electron microscopy
For a radio-frequency power of 50 W, the thickness
of the sputtered layer depends on the deposition time
and the subsequent heat-treatment conditions [11], be-
cause of the densification phenomenon. It has been
measured using SEM photographs to 51 ± 5 nm for
1-h deposition of untreated material (sample labeled
UT) and to about 41 ± 4 nm after a 900
C RTA heat-
treatment (sample RTA900). Fig. 3 shows the TEM
micro-graphs of the as-deposited film (UT), as well as
the samples RTA200 and RTA900. The growth of crys-
talline particles is observed by the dark-field images
and by the electron diffraction patterns shown in
1822 B. Capoen et al. / Journal of Non-Crystalline Solids 351 (2005) 1819–1824
Fig. 3. TEM dark-field micro-graphs and electron diffraction patterns
of: (a) the untreated layer UT, (b) the sample RTA200 and (c) the
sample RTA900.
Fig. 3(a)–(c). For the as-deposited film UT (Fig. 3(a)),
the diffraction pattern exhibits only glassy scattering
rings. In the RTA200 sample, some crystallites are pres-
ent in small quantity and with size ranging from 1 to
20 nm, as shown in Fig. 3(b). The electron pattern ob-
tained from this sample is a spotty ring pattern of differ-
ent cubic phases (not only InSb) [JCPDS database [17]].
The Fig. 3(c), related to the sample RTA900, shows
nanoparticles with a size distribution up to 100 nm in
their largest dimension and with a good crystallinity,
as demonstrated by the periodicity of the diffraction pat-
tern. For this sample, a TEM chemical micro-analysis
reveals that the thin film contains between 1 and
10 at.% In and Sb after heat-treatment, depending on
the analyzed region. The electron diffraction represents
a (1 0 1) plane of the cubic InSb structure. The lattice
parameter of the cubic unit cell was found equal to
6.628 Å, close to the bulk InSb value of 6.461 Å [17].
Fig. 4. Micro-Raman spectra of: (a) RTA and (b) LTA layers for
different heat-treatment temperatures.
3.3. Raman spectroscopy
Raman spectra recorded at a microscopic scale at the
surface of the heat-treated samples are presented in Fig.
4. Concerning the untreated layer UT and the lowest
temperature RTA-treated films, the spectra acquisition
gave results, which were of little use because of damage
to the porous silica. Indeed, photo-ablation holes due to
light absorption could be seen under microscope after
exposure of the films to continuous irradiance (>1 kW/
cm2) at 514.5 nm. As can be seen from Fig. 4(a), for
RTA temperature lower than 900
C, a weak band is de-
tected around 152 cm
1. This vibration band is larger in
a sample after the 400
C LTA (Fig. 4(b)). We attribute
this band to Sb clusters [18] or to amorphous antimony
dispersed in the matrix. In the RTA process, the ampli-
tude of the band at 430 cm
1, associated with the silica
matrix network Si–O–Si bending vibrations [19], de-
creases in proportion as the annealing temperature in-
creases. This phenomenon is to be related to the
increasing resonance of the laser light with the electronic
transitions of the growing InSb nanoparticles (resonant
Raman phenomenon) [20], as the loss of matrix signal
occurs, to the advantage of the crystalline band around
180 cm
1. The latter vibration can in fact be decomposed
into bands at 179 cm
1 and 190 cm
1, which correspond,
respectively, to the 1TO and 1LO phonons of InSb [21].
Thus, the presence of Raman-active InSb nanocrystals is
confirmed only for the sample RTA900. For the samples
LTA900 and LTA900-1H (Fig. 4(b)), two peaks reveal
the predominance of crystalline structures. These peaks
at 115 and 152 cm
1 are, respectively, assigned to the
first-order Eg and A1g modes of c-Sb [18]. This result
indicates that the remaining In atoms are not in a
Raman-active form in the films. Furthermore, based on
 B. Capoen et al. / Journal of Non-Crystalline Solids 351 (2005) 1819–1824
the width of these bands (8 cm
1 for the A1g mode) and
on the absence of frequency shift from the energy of these
vibrations in the crystalline Sb, we argue that the Sb crys-
tallites are larger than 5 nm [18]. For the four-hour heat-
treatment (LTA900), the amplitude of the Raman bands
increased from that observed after a 1-h annealing
(LTA900-1H). This enhancement may be due to the in-
crease in the particles concentration with the treatment
duration at 900
C or to a better crystallization at higher
temperature.
3.4. Non-linear optical absorption measurements
Most of the RTA-treated samples having low damage
threshold, the layers were photo-destroyed when the
laser power was increased and no non-linear effect could
be detected. The sample RTA900 is the only one for
which an unambiguous non-linear absorption effect
could be measured. Even for this sample, the open-aper-
ture rough Z-scan curves, recorded at increasing laser
energies, show that the films are photo-ablated for inci-
dent irradiance greater than 35 MW/cm2. However, we
extracted the non-linear part of the normalized trans-
mission by dividing after each measurement the rough
curves by the curves recorded at low energy. As seen
from Fig. 5, the resulting Z-scan curve is well fitted by
the first-order term of Sheik-Bahae function [12]:
b  Leff  T lin  Ec
T ¼1
  ; ð1Þ
c 2
23=2 1 þ ½z
z
z0
 culty due to the poor signal-to-noise ratio. The magni-
where b is the non-linear absorption coefficient, Leff =
[1
exp(
aL)]/a represents the effective layer thickness,
a is the linear absorption coefficient, L the film thick-
ness, zc the beam waist position, z0 = pw0/k the Rayleigh
Fig. 5. Induced optical absorption Z-scan curves obtained in the
samples RTA900 (a) and LTA900 (b). The smooth solid lines are fit to
the Eq. (1).
1823
range, w0 is the beam waist radius, k the laser wave-
length and Ec the incident irradiance on the sample. In
Fig. 5(a), the fit of the experimental data to the Eq.
(1) is given at two different laser energies for the sample
RTA900. The absorption coefficient b = 1.8 · 10
3 cm/
W, obtained from this fit at smaller laser power, is sev-
eral orders of magnitude larger than the one measured
in bulk semiconductors in the near-infrared region
[12,22], and even larger than the non-linearities mea-
sured in most semiconducting nanoparticles [23]. Unfor-
tunately, this larger b is to be counterbalanced by a
saturation of the non-linearity. Indeed, the third-order
coefficient b is severely reduced when the irradiance is
increased over 10 MW/cm2. In Fig. 6, we have reported
the minimum transmittance Tm (at z
zc = 0) against
the laser pulse energy for both the RTA900 and the
LTA900 layers. In the case of the RTA-treated sample,
higher order non-linear effects are shown to tend toward
a saturation of the absorption. However, this interesting
high order absorption saturation, reached at incident
irradiance greater than 200 MW/cm2, cannot be
exploited for pulsed laser applications. From the initial
slope of this curve, we can also deduce the real third-
order non-linear absorption coefficient b = (1.8 ± 0.6) ·
10
3 cm/W. As expected, this result is the same as the
one directly found using Eq. (1) at low irradiance.
The experimental Z-scan curve of the sample
LTA900 is shown in Fig. 5(b) for an irradiance of
93 MW/cm2. We obtained the b coefficient with diffi-
tude of this parameter is much less than the previous
one. In fact, the damage threshold was found to be lar-
ger in the case of the LTA-treated samples (about
140 MW/cm2), but as no InSb nanoparticles could be
detected, the non-linearity is much smaller. The scat-
tered plot of the transmittance minimum against the en-
ergy in Fig. 6 confirms the difficulty of finding a net
1.00
Minimal Transmission
0.95
0.90
0.85
0.80
0 5 10 15 20
Pulse Energy (µJ)
Fig. 6. Minimum of the normalized transmission (at the waist
position) against the laser pulse energy for the samples RTA900 (j)
and LTA900 (s).
1824 B. Capoen et al. / Journal of Non-Crystalline Solids 351 (2005) 1819–1824
slope. It can be deduced from the initial slope of this
graph that b < 1.4 · 10
4 cm/W.
It is interesting to compare our results with the previ-
ous work of Zhu et al. [9]. These authors used a contin-
uous 633 nm laser to perform their Z-scan experiments
on samples prepared in a way similar to our prepara-
tion. For the excitation energy to band gap energy ratio
Eexc/Eg close to 1, they found an absorption saturation
effect. Although our preparation conditions may differ,
we did not reproduce this result. This failure may be
due to the generation of non-equilibrium electrons by
the pulsed excitation [13]. The contribution of such a
hot electron cloud to the non-linear absorption is posi-
tive and may become predominant. Moreover, our abso-
lute magnitude of b is 100 times less than the CW
parameter. This discrepancy could be explained by the
saturation we observed in Fig. 6, since the initial slope
might be less than the sensitivity of our apparatus. A
second suggestion is that the various dynamics probed
in pulsed conditions differs from those probed in CW
conditions. This assumption has been previously noted
by Liao et al. [24] to explain their observations in the
case of Au nanoparticles. Because of the different time
scales involved in the non-linear susceptibility, v(3),
when using a nanosecond laser pulse, the slow compo-
nent would not have enough time to respond. As a re-
sult, the shorter the laser pulse, the smaller is the
measured non-linearity. The slow component could be
caused by thermal electronic band fluctuations, thus
producing the observed larger v(3) in CW measurements.
Pump-probe experiments using very short pulses would
be necessary to clarify this point.
4. Conclusion
Combining Raman spectroscopy and transmission
electron microscopy, we have shown that a RTA heat-
treatment at 900
C causes the growth of InSb nanocrys-
tals inside a SiO2 matrix. For lower temperature, a phase
mixing seems to be observed. On the other hand, only
antimony nanocrystals are produced when heat-treating
the layers for a long time (4 h), but the material is better
densified and more homogeneous. The Z-scan proce-
dure was used to investigate the non-linear absorption
in these doped silica films. The low temperature RTA-
treated samples, as well as the LTA-treated ones, con-
tained essentially Sb particles and the non-linearity
was too small to be detected unambiguously. An in-
duced absorption with a coefficient b = 1.8 · 10
3 cm/
W was measured in the 900
C RTA-treated layer. This
result, obtained with a pulsed laser at 1.06 lm, corre-
sponds to a fast non-linear absorption, which should
be exploited in all-optical components.
Acknowledgments
The Centre dÕEtudes et de Recherches Lasers et
Applications (CERLA-FR CNRS 2416) is supported
by the Ministère Chargé de la Recherche, the Région
Nord/Pas de Calais and the Fonds Européens de Dével-
oppement Economique des Régions.
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