Solid State Communications 139 (2006) 70–75

www.elsevier.com/locate/ssc

Structural, thermal and optical studies of mechanical

alloyed Ga40Se60 mixture
S.M. Souza a,*, C.E.M. Campos a, J.C. de Lima a, T.A. Grandi a, P.S. Pizani b
a
Departamento de Fı́sica, Universidade Federal de Santa Catarina, C.P. 476, 88040-900 Florianópolis, SC, Brazil.
b
Departamento de Fı́sica, Universidade Federal de São Carlos, C.P. 676, 13 565-905 São Carlos, SP, Brazil
Received 3 November 2005; received in revised form 13 April 2006; accepted 18 April 2006 by B. Jusserand
Available online 6 May 2006

Abstract
A mixture of elemental Ga and Se with the nominal composition Ga40Se60 was submitted to the Mechanical alloying technique and their structural,
thermal and optical properties were followed by X-ray diffraction, differential thermal analysis, photoacoustic spectroscopy, UV–VIS-NIR absorbance
spectroscopy and Raman spectroscopy techniques. After 10 h of milling the X-ray pattern showed monoclinic Ga2Se3 phase nucleation, which is in the
nanometric form, and also a minority amorphous phase. The DSC results showed exothermic reactions between 430 and 720 K attributed to
amorphous–crystalline phase transition and structural relaxation of Ga2Se3 phase. Based on this a small amount of the as-milled sample was annealed at
723 K. Its XRD pattern showed evidences of grain growth, reduction of the interfacial component, as well as, disappearance of the amorphous phase.
The annealing process induced thermal diffusivity increasing, while the optical band gap energy and Raman profile remained practically unchanged.
q 2006 Elsevier Ltd. All rights reserved.

PACS: 61.82.Rx; 81.20.Ev; 61.43.Bn; 65.80.Cn, 78.40.Kq

Keywords: A. Nanocrystalline materials; B. Powder processing: mechanical alloying; C. X-ray diffraction, simulations; E. Absorption and reflection spectra: visible
and ultraviolet

1. Introduction vacuum deposition [8], melt quench method [7], Bridgman

Mechanical alloying (MA) has been used as an alternative
technique to synthesize amorphous, crystalline phases and solid
solutions as well as nanostructured materials [1–5]. MA has
permitted the production of powders in bulk form and facilitating
the fabrication of massive pieces via consolidation [6].
The Ga–Se system has attracted the attention of many
researchers because of its potential application for IR detector,
MOSFET, solar cell devices [7], optical memory devices [7],
electrothermal devices such as solid solution electrodes [8],
and photovoltaic materials [8,9]. The phase diagram [10]
exhibits the GaSe and Ga2Se3 compounds. According to the
JCPDS Database [11] the Ga2Se3 compound occurs in the
monoclinic, tetragonal, orthorhombic and cubic structures,
while the GaSe one occurs in the rhombohedral and hexagonal
ones. These compounds have been produced by several
techniques such as transport reaction method [12], chemical
* Corresponding author. Tel.: C55 48 33316832; fax: C55 48 33319068.
E-mail address: michielon@fisica.ufsc.br (S.M. Souza).
0038-1098/$ - see front matter q 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ssc.2006.04.017
method [13], heterovalent exchanged mechanism [14], and
molecular beam epitaxy (MBE) [15]. Recently, we produced
an amorphous GaSe alloy by MA process starting from an
equiatomic mixture of elemental Ga and Se specimens milled
for just few hours (%15 h) [16].
We present results on mechanical alloyed Ga40Se60 mixture.
Its structural, thermal and optical properties were investigated
through X-ray diffraction (XRD), differential scanning calori-
metry (DSC), photoacoustic absorption spectroscopy (PAS),
UV–VIS-NIR spectroscopy and Raman spectroscopy techniques.
2. Theoretical considerations
2.1. Open-photoacoustic cell configuration measurements
and determination of the thermal diffusivity
The photoacoustic (PA) effect has been used for measuring
the thermal properties of solid samples [17–23]. The PA effect
looks directly at the heat generated in a sample, due to
nonradiative deexcitation processes, following the absorption
of light. In the conventional experimental arrangement, a
sample is enclosed in an air-tight cell and exposed to a chopped
light beam. As a result of the periodic heating of the sample, the
 S.M. Souza et al. / Solid State Communications 139 (2006) 70–75
pressure in the cell oscillates at the chopping frequency and can
be detected by a sensitive microphone coupled to the cell. The
resulting signal depends not only on the amount of heat
generated in the sample (and, hence, on the optical absorption
coefficient and the light-into-heat conversion efficiency of the
sample) but also on how the heat diffuses through the sample
determined by the thermal diffusivity.
An open-photoacoustic cell (OPC) configuration is well
described in [23–25], and for a thermally thick sample, the
amplitude of the PA signal decreases exponentially pffiffiffi with the
modulation frequency as ð1=f ÞexpðKa f Þ, where
aZ ðpl2s =as Þ1=2 . The thermal diffusivity as can then be obtained
from the signal amplitude data, as a function of the modulation
frequency, by fitting it to the expression
pffiffiffi
S Z ðA=f ÞexpðKa f Þ (1)
Knowing, the coefficient a from the fitting procedure, as is
readily obtained from
as Z pðls =aÞ2 : (2)
2.2. Optical absorbance measurement and determination
of the band gap-energy
The most direct way of extracting the optical band gap is to
simply determine the wavelength at which the extrapolations of
the baseline and the absorption edge cross [26].
More information about the lowest energy interband
transition can be obtained by a McLean analysis of the
absorption edge through the equation [27].
ahy Z ðhyKEg C Ep Þ1=n ; (3)
where a is the absorption coefficient, Eg is the band gap and Ep
is the phonon energy for indirect transitions, h is the Planck’s
constant and n is the frequency of the incident beam. The
analysis consists of fitting the absorption edge to Eq. (3) and
determining experimental values for Eg and n. A value of nZ2
implies a direct allowed transition; nZ2/3 implies a direct
forbidden transition; nZ1/2 implies an indirect allowed
transition; nZ1/3 implies an indirect forbidden transition.
The relationship among the absorbance A, absorption
coefficient a and thickness d of a sample is given by [28]
aZ Ad . For absorbance measurement on powders, the polycrystal-
line or amorphous sample is dispersed into a powder support such
as KBr, and the mixture is pressed in the form of pellet. In this
case, the thickness d and absorption coefficient a of the sample
become unknown. Thus, the Eq. (3) must be modified to
Ahy Z CðhyKEg C Ep Þ1=n : (4)
Here, C represents the thickness of the sample and is a
parameter to be included in the fit procedure.
3. Experimental procedure
Binary mixture of high-purity elemental melted gallium
(Aldrich 99.999%) and powder selenium (Alfa Aesar 99.999%,
71
K200 mesh) with Ga40Sb60 nominal composition was sealed
together with seven steel balls of 11.0 mm in diameter into a
cylindrical steel vial under argon atmosphere. The ball-
to-powder weight ratio (BPR) was 7:1. A Spex Mixer/mill,
model 8000, was then used to perform MA at room
temperature. In our first study on Ga–Se system, on Ga50Se50
mixture [18], a different MA setup was chosen. In the present
study, the sample was milled for 1, 5 and 10 h.
All milled samples were analyzed by XRD in a MiniFlex
Rigaku diffractometer and due to the similarity between their
diffraction patterns only that of the sample milled for 10 h will
be shown in this paper and it will be named as-milled sample. A
XRD pattern of the as-milled sample was also recorded at the
XPD1 beamline at LNLS (Campinas, Brazil). The energy of the
incident beam was 9500 eV (lZ0.13051 nm). No new crystal-
line phases were observed in the pattern collected at LNLS. The
effect of the temperature on the as-milled sample was studied
using DSC technique. DSC curves were recorded from 300 to
773 K, with heating rates of 2.5, 5, 10 and 20 K minK1, in a 2010
DSC cell manufactured by TA Instruments, under flowing
nitrogen. Based on this study a small portion of the as-milled
sample was sealed in quartz tube evacuated to about 10K3 Torr,
annealed for 6 h at 723 K and cooled in air. XRD patterns of the
as-milled and annealed sample were recorded in a Philips Xpert
diffractometer with Cu Ka radiation (lZ0.15406 nm).
PAS measurements were carried out in a home-made
workstation with a 500-W quartz-tungsten-halogen (QTH)
lamp, after being heat filtered by a ZnSe lens, chopped by a
Perkin–Elmer light chopper, model 197. The microphone have
a circular hole of 3-mm. The output voltage from the
microphone is connected to an lock-in amplifier, which is
connected to a PC computer to record the signal amplitude and
phase as a function of the modulation frequency. Absorbance
measurements were carried out in a Perkin–Elmer UV–VIS-
NIR spectrometer, model Lambda 19. In these measurements
the Ga2Se3 and GaSe samples mixed to KBr pressed in the
form of pellet. The KBr was used as support and reference.
Raman measurements were performed with a T64000 Jobin-
Yvon triple monochromator coupled to an optical microscope,
a cooled CCD detector and a conventional photon counting
system. The 5145 Å line of an argon ion laser was used as
exciting light, always in backscattering geometry. The output
power of the laser was kept within 1–3 mW to avoid
overheating the samples. All measurements were made at
room temperature.
4. Results and discussion
4.1. X-ray diffraction and differential scanning calorimetry
measurements
Fig. 1 shows the XRD pattern of the Ga40Se60 sample milled
for 10 h. This typical crystalline pattern was also observed
when the sample was milled for just 1 h and it is quite different
from those corresponding to the pure Ga and Se elements and
that of as-milled Ga50Se50 sample [16]. It was compared with
all the Ga2Se3 ones given in the JCPDS Database [11] and it
72 S.M. Souza et al. / Solid State Communications 139 (2006) 70–75
Intensity (arb. units)
20 30 40 50 60 70 80 90
2θ (degree)
Fig. 1. Experimental (A) and simulated (B) X-ray diffraction patterns for
Ga40Se60 sample milled for 10 h. The gray line (C) shows the difference pattern
from the Rietveld refinement. The pattern marked as (D) is from annealed
Ga40Se60 sample.
was found a good agreement with the monoclinic phase (card
no. 44-1012). This pattern was fitted using the Rietveld
structural refinement procedure [29] through the code DBWS
9807. For that, the crystallographic data (lattice parameter,
space group, atomic positions, etc.) for the monoclinic phase
were taken from the ICSD Database [30] (code 35028), and the
best fitting was reached by considering the lattice parameters
aZ0.6683 nm (0.6661 nm), bZ1.1575 nm (1.1652 nm),
cZ0.6629 nm (0.6649 nm), and bZ109.18 (108.88). Note
that the values of the parameters a and c for the as-milled
sample are smaller than those from the ICSD Database (shown
into the brackets). The simulated pattern is shown in Fig. 1
together with the experimental one, and one can observe an
excellent agreement between them, except by the background
discrepancies in the region between 2qZ25 and 458,
suggesting an amorphous halo. By considering the simulated
XRD pattern we have estimated a relative amount of about 9%
for this amorphous phase.
The experimental XRD pattern of the sample milled for 10 h
shows that all the peaks are broadened compared to those in
bulk samples, indicating a nanometric structure in the as-milled
powder. The nanometric structure is formed by crystallites
having dimensions of few nanometers (from 2 up to 100 nm)
and the mean size of the crystallites can be satisfactorily
estimated from the fitted XRD pattern taking into account the
line broadening caused by both crystallite size and strain
through the relationship [31]
   2
bt cos q 2 1 2 sin q
Z 2 C sp ; (5)
Kl d Kl
where q is the diffraction angle, l is the X-ray wavelength, bt is the
total broadening measured at the peak’s width full-width at half-
maximum (FWHM) in radians, d is the crystal size, sp is the
strain, and K is a constant dependent on the measuring conditions
and on the definition of bt and d. Graphical linearization of
relationship (5), i.e. plotting of b2t cos2 q=l2 versus sin2 q=l2 , yields
the crystal size free from strain effects from the values of the
intercept of the straight line obtained, as well as the strain from the
(a)
–1.4 Tx2
–1.5
Exo
Heat flow (mW)
Tx1
–1.6
D
–1.7
B –1.8
Tg
A –1.9
C 350 400 450 500 550 600 650 700
Temperature (K)
100 110
Fig. 2. (a) DSC spectrum of the as-milled Ga40Se60 sample with a heating rate
of 10 K minK1. Dashed line shows a second-DSC-run performed after heating
the Ga40Se60 sample to 723 K.
slope. The code DBWS 9807 generates the bt and 2q positions for
all the simulated peaks. So, by considering theses values we
obtained dz7.5 nm and spz2.0% for as-milled sample.
Fig. 2(a) exhibits the measured DSC curve of the as-milled
Ga40Se60 sample. One can see a broad endothermic band located
in the 350–500 K range, a broad exothermic band located
between 510 (Tx1) and 640 K (Tx2) and a sharp exothermic peak
located at about 666 K, which is quite different that observed for
Ga50Se50 mixture [16]. The endothermic band centered at about
425 K (Tg) can be associated to glass transition of an amorphous
phase, which is broad because the sample is not homogeneous,
and the exothermic features can be attributed to the crystallization
of such amorphous phase. The glass transition temperature Tg
roughly estimated is greater than that reported in the earlier work
on amorphous GaSe (Tgw350 K) [16]. This can be explained by
the higher connectivity of the Ga2Se3 network as compared to
GaSe one. The enthalpy changes were calculated and the values
found were 3.1 and 1.6 J gK1, respectively. For the Ga50Se50
mixture (completely amorphous) the enthalpy change was much
greater (w51 J gK1) [16]. This is not surprising since, according
to XRD results, the amount of amorphous phase in the as-milled
Ga40Se60 sample is small (!10%). In the same figure there is a
second-DSC-run curve (dashed line), performed with the same
Ga40Se60 sample, which flat profile suggests a near complete
transformation to a crystalline phase.
The activation energy for crystallization E was calculated
using the Kissinger equation [32].
lnðB=T 2 Þ ZKE=RT C constant (6)
where B is the heating rate (2.5, 5.0, 10 and 20 K/min), R is the
gas constant and T is an absolute temperature, such as the peak
temperature. The obtained value was 418 kJ molK1, which is
much greater than those reported by de Lima et al. [33] and Fan
et al. [34] for amorphous-trigonal Se transformation.
The thermal stability of the as-milled sample was also
investigated. For that, based on the DSC results, a small amount
of this sample was annealed at 723 K for 6 h, and its XRD pattern
is shown in both Figs. 1 and 3. A direct comparison between the
as-milled and annealed samples (Fig. 1) shows that there was no
crystalline phase transformation/decomposition, however,
 S.M. Souza et al. / Solid State Communications 139 (2006) 70–75
Intensity (arb. units)
(111)
20 30 40 50 60 70 80 90
2θ (degree)
Fig. 3. Experimental (A) and simulated (B) X-ray diffraction patterns for
annealed Ga40Se60 sample. The gray line (C) shows the difference pattern from
the Rietveld refinement.
significant changes can be observed after annealing: all peaks are
sharper and more intense; the (1 1 0) peak located at 2qZ168
arises, and the amorphous halo disappears.
Based on the XRD results of annealed sample, the
exothermic broad band in the DSC spectrum was attributed
to several features, such as, structural relaxation, elimination of
stress, strain, point and line defects, grain growth processes;
and the sharp exothermic peak was associated to the
amorphous phase crystallization.
The fitted XRD pattern of the annealed sample is shown in
Fig. 3. The best fitting was reached by considering the lattice
parameters aZ0.6657 nm, bZ1.1602 nm, cZ0.6651 nm, and
bZ109.18. From this figure, one can see a good agreement
between the fitted and annealed XRD patterns. It is interesting to
note that the lattice parameters values for annealed sample do not
show the expected behavior, but, excepting the value of c, they
approaches to those taken in the ISCD card. Similar phenomenon
was already reported for CdS thin films annealed at different
atmospheres [35], where the growth of the unit cell after annealing
under vacuum was associated to the rearrangement of ions of Cd
and S inside the CdS lattice and to the diffusion of atoms or ions
into its volume when the lattice tries to transform from the zinc-
blende (ZB) to the W crystalline structure. So, remembering that
our samples have an important sum of total atoms in the interfacial
component, we cannot discard such similar explanation, that
proposed for the CdS thin films, to our results.
The mean crystallites size and strain of annealed sample
were also calculated by using Eq. (5) from the fitted XRD
pattern. The values found were dz10.5 nm and spz1.8%.
The increasing of the mean crystallite size due to annealing can
be associated with the reduction of the interfacial component.
This fact and the reduction of strains corroborate the
improvement of sample crystallinity after annealing.
4.2. Thermal diffusivity measurements
Fig. 4 displays the Neperian logarithm of PA signal
amplitude versus modulation frequency square root for the
as-milled (circles) and annealed (squares) Ga40Se60 samples.
73
8.5
8.0
Ln (PA signal) (arb. units)
7.5
B 7.0
6.5
A 6.0
C 5.5
100 110 3 4 5 6 7 8 9
f1/2 (Hz1/2)
Fig. 4. Ln (PA signal) as a function of the modulation frequency square root for
as-milled (cicles) and annealed (squares) Ga40Se60 samples. The solid lines
represent the fitting using Eq. (4) of the text.
There are three contributions to the PA signal amplitude [36]:
(1) sample to gas thermal diffusion that is well interpreted by
the Rosencwaig and Gersho (RG) theory [37], as described in
the Section 2.1 above, (2) thermoelastic bending that depends
on the nature of the sample, and (3) sample thermal dilation
that has been shown to become important, for instance for
porous materials [36]. In this study, the crystallinity of the
sample has improved after annealing. Thus, it is expected that
changes in the PA signal of annealed sample (Fig. 4) are
associated with the thermoelastic contribution.
From this figure, one can see that there is a discontinuity in the
PA signal amplitude for as-milled sample at about 6.7 Hz1/2,
which is associated with changing of sample thermal behavior.
The RG model is valid for thermally thick regime, the data located
between 3.9 and 6.8 Hz1/2 was fitted according to Eq. (1), and the
obtained value of a, by using Eq. (2), was 0.082 cm2/s. For
annealed sample one can distinguish two modulation frequency
intervals: 3.2–4.5 and 5.5–8.3 Hz1/2. The first interval was
discarded because it is associated with the thermally thin regime.
Then, the a value was calculated for the second interval, and the
obtained value was 0.097 cm2/s. The a value obtained for
annealed sample is slightly greater than that for as-milled sample,
which is associated with improvement of sample crystallinity due
to thermal treatment. Since, no other experimental data of thermal
diffusivity a are available in the literature for the Ga2Se3 alloy, we
cannot compare our results with others.
4.3. Optical UV–VIS-NIR absorbance and Raman
measurements
The Ga2Se3 compound shows a direct allowed transition
(nZ2) [38]. Thus, the band gap energy for both, as-milled and
annealed, samples were fitted by using Eq. (4), and the obtained
absorption edge energies were EgZ1.85 and 1.89 eV,
respectively. These fitting are shown in Fig. 5. The obtained
values agrees with those reported for a Ga2Se3 single crystal
prepared by Bridgman technique [39] (1.793 eV) and for a bulk
amorphous specimen (1.75 eV) [40]. On the other, they are
smaller than those obtained for amorphous Ga2Se3 thin films
74 S.M. Souza et al. / Solid State Communications 139 (2006) 70–75

0.6

0.5 PL

0.4
Absorbance

0.3

0.2 annealed
annealed
0.1
as-milled
0.0
600 800 1000 1200 as-milled
Wavelenght (nm)

annealed as-milled
1.5
1.0
(A x hν)2 (eV)2
(A x hν)2 (eV)2

1.0

0.5
0.5 100 200 300 400 500 600
Raman shift (cm–1)

0.0 0.0 Fig. 6. Raman spectra of as-milled and annealed Ga40Se60 samples. Gray line
1.0 1.5 2.0 2.5 1.0 1.5 2.0 2.5
shows the Raman spectrum of as-milled Ga50Se50 sample. The label PL
Energy (eV) Energy (eV)
indicates the position of plasma line from Ar laser. Thick lines represent the
Fig. 5. Absorption spectra for as-milled and annealed Ga2Se3 samples. The best curves resulting from fitting procedure using Lorentzian profiles.
solid lines represent the fitting using Eq. (8) of the text.
A frequency downshift shift was observed for the main
before (2.65 eV) and after annealing (2.76 eV) [8]. There are Raman peaks of the annealed Ga40Se60 sample as compared
still large differences in the reported values for fundamental with those of the as-milled sample (Fig. 6 and Table 1). This
band gap of Ga2Se3 specimens, as show our results, and one can be associated with a structural relaxation of Ga2Se3 phase
satisfactory explanation for this is the different synthesis due to defects elimination induced by annealing. Moreover, the
methods applied to prepare them. relative intensity increasing and linewidth decreasing of the
Fig. 6 shows the Raman spectra of as-milled and annealed low frequency lines of annealed sample reveals an improve-
Ga40Se60 samples. Both spectra are similar in shape, but that ment in the long range structural ordering, in total agreement
for annealed sample presents the sharpest and more intense with XRD results, while the high frequency lines indicates that
Raman lines. In general, they have a small broad band the short range interactions practically remains unchanged as
composed by two lines between 100 and 130 cmK1, one sharp compared to those lines of the as-milled sample.
line at about 155 cmK1 and other broad band between 200 The most surprising result is that the Raman spectrum of the
and 320 cmK1. In order to better precise the peak position of Ga50Se50 sample [16] (see gray line in Fig. 6) is practically
strongest lines a fitting procedure was performed using identical to that of the Ga40Se60 sample presented in this paper,
Lorentzian profiles and the results are shown in Table 1. although they have completely different long range structural
The experimental spectra of polycrystalline Ga2Se3 sample arrangements. The best peak positions reached by fitting this
associated to lattice dynamics simulations [41] have assigned spectrum are also listed in Table 1. It is important to notice that
Raman lines at 155 and 105 cmK1 to LA and TA modes, the phonon dispersion curve of hexagonal GaSe [43] attributes
respectively, of the X point of the large Brillouin zone of the the 155 cmK1 line to the zone-boundary (ZB) A200 and/or E 0
defect-zincblende structure (which is used as the model there). modes, which are extensively reported in literature as an effect
Moreover, both 155 and 105 cmK1 lines, and also two other caused by the wave-vector selection rules relaxation due to the
lines (at 250 and 290 cmK1) have been attributed to the Raman introduction of defects and/or vacancies in crystalline
active modes of the epitaxial Ga2Se3 layers [14]. Based on the
temperature induced frequency shifts of the strongest Ga2Se3 Table 1
The Raman line positions (in cmK1) resulting from the spectra fitting procedure
peaks reported in Ref. [42], the origin of the phonon structures
using Lorentzian functions
have been assigned. The low frequency lines are related to the
long range ordering of the monoclinic Ga2Se3 phase, while the 1 2 3 4 5 6 7 8 9 10
high frequency ones are due to short range interaction in As-milled Ga40Se60 117 123 155 165 184 241 257 290
defect-zincblende unit cell. Then, the Raman lines observed in Annealed Ga40Se60 106 116 123 145 153 165 184 231 254 288
As-milled Ga50Se50 116 125 153 163 180 229 249 285
the spectra of as-milled and annealed Ga40Se60 samples were
[16]
assigned in the same way.
 S.M. Souza et al. / Solid State Communications 139 (2006) 70–75
structures. Furthermore, other lines, such as that at 130, 235
and 280 cmK1, can also be attributed to A10 and E 00 optical
modes of hexagonal GaSe. Then, several features observed in
the spectrum of the Ga50Se50 sample were assigned in the same
way [16]. This can suggest existence of an equiatomic (GaSe)
amorphous phase in the as-milled Ga40Se60 sample. However,
XRD results on annealed Ga40Se60 sample completely discard
this interpretation, since no GaSe crystalline phase was
observed. Then, one reasonable explanation for this is that
there are similar short range interactions in the local atomic
structure of both amorphous (Ga50Se50) and nanocrystalline
(Ga40Se60) alloys.
5. Conclusions
Mixture of elemental Ga and Se in the atomic proportion
40:60 was submitted to mechanical alloying in an inert ambient
and its structural, thermal and optical properties were
investigated by XRD, DSC, PAS and UV–VIS-NIR absor-
bance measurements. The main conclusions obtained were:
(1) Milling the mixture for 10 h leads to formation of a
majority nanophase of monoclinic Ga2Se3 and a minority
amorphous phase.
(2) Thermal annealing of the milled mixture at 723 K for 6 h
leads to crystallization of the amorphous phase and growth
in grain size of the monoclinic phase from 7.5 to 10.5 nm.
(3) Based on XRD results the exothermic broad band and the
sharp exothermic peak observed in the DSC spectrum of the
as-milled sample were attributed to the structural relaxation;
elimination of stress, strain, and point and line defects as well
as to the grain growth of the monoclinic Ga2Se3 and
crystallization of an unidentified amorphous phase.
(4) The thermal diffusivity value measured for annealed sample
is slightly greater than that measured for as-milled one. This
increase can be attributed to the improvement of the sample
crystallinity and, maybe, due to a contribution of the
thermoelastic component to the PA signal amplitude.
(5) The optical band gap energy measured in this study showed
no important changes after the annealing of the as-milled
sample and a reasonable agreement with the literature values.
(6) Raman active modes of Ga2Se3 phase were identified in the
Raman spectra of as-milled and annealed Ga40Se60 samples.
Similarities in the Raman profiles suggest equivalent local
atomic structures for both Ga50Se50 (amorphous phase) and
Ga40Se60 (nanocrystalline phase) sample.
Acknowledgements
The authors wish to thank FAPESP and CNPq for financial
support. This study was also partially supported by LNLS
(proposal No. D12A-XRD1 # 2416/03). We thank Drs P.B.
Prates and R. Peralta for the XRD and Optical Absorbance
measurements, respectively. We wish to express our gratitude
to Drs N. Cella and C.O. Paiva-Santos for fruitful discussions
about the PA and XRD results, respectively.
75
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