Phys. Status Solidi B 253, No. 6, 1033–1037 (2016) / DOI 10.1002/pssb.

201552551

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Part of Topical Section on
Amorphous and nanostructured chalcogenides www.pss-b.com
basic solid state physics

Amorphous thin films in the

gallium–chalcogen system
} rinczi1, A. Velea1, I. D. Simandan1, A. C. Galca1, E. Matei1, G. Socol2, F. Gherendi2,
M. Popescu*,1, F. Sava**,1, A. Lo
3 3
D. Savastru , and S. Miclos
1
National Institute of Materials Physics, Atomistilor 405A, P.O. Box M.G. 7, Magurele, 077125 Ilfov, Romania
2
National Institute for Laser, Plasma and Radiation Physics, Atomistilor 409, P.O. Box M.G. 36, Magurele, 077125 Ilfov, Romania
3
Institute for Research and Development in Optoelectronics – INOE2000, Atomistilor 409, Magurele, 077125 Ilfov, Romania

Received 26 August 2015, revised 19 April 2016, accepted 22 April 2016

Published online 11 May 2016

Keywords amorphous materials, chalcogenides, optical properties, thin films, X-ray diffraction

* Corresponding author: e-mail mihaip58@yahoo.com, Phone: þ4021 2418195, Fax: þ4021 3690177
** e-mail fsava@infim.ro, Phone: þ4021 2418195, Fax: þ4021 3690177

Thin amorphous films based on gallium–chalcogen (Ga–Ch),
namely Ga2S3, Ga2Se3, Ga2Te3, and GaTe have been prepared
by pulsed laser deposition (PLD). The films were characterized
by X-ray diffraction, extended X-ray absorption fine structure
(EXAFS), energy-dispersive X-ray spectroscopy (EDX),
optical transmission spectroscopy, ellipsometry, and electrical
measurements. Structural measurements showed that Ga is
threefold coordinated, except the Te-based alloys were, it
seems, only twofold coordinated, while the chalcogen is
usually twofold coordinated. In all the compositions, layered
and chain-like structures are assumed. The bandgaps range
between 1.09 eV for Ga2Te3 and 2.21 eV for Ga2Se3.

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1 Introduction Compositions based on gallium–
chalcogen (Ga–Ch) are promising materials for optoelectronics
[1] and information technology [2]. They are wide-bandgap
semiconductors and good hosts for rare-earth doping [3, 4],
promising for photovoltaics and electrothermal devices
such as solid electrolytes [5]. The Ga–Ch materials exhibit
good optical and thermal properties that make them suitable
for laser materials in the near- and midinfrared range [6],
waveguides [7], or optical fiber drawing [8]. Plasmonic effects
are present in the Ga–Ch thin films [9] and they can also be
used for switching [10] and phase-change memory devices
[11]. Since the compositions in the Ga–Ch systems have
better mechanical properties and higher thermal stability as
compared to the similar compositions in the As–Ch system
[12–14], there is a tendency to develop new optoelectronic
devices with Ga-based chalcogenide compounds instead
of As-based ones. This will also reduce the possible toxic
effects due to the presence of As. Even though the
compositions are good for applications, the Ga–Ch amorphous
systems are not yet well understood and characterized.
For the preparation of Ga–Ch thin films, mostly vacuum
evaporation [15], metal-organic chemical vapor deposition
(MOCVD) [16–18], aerosol-assisted chemical vapor depo-
sition (AACVD) [18], and low-pressure chemical vapor
deposition (CVD) [19] have been used. All these methods
are suitable for obtaining polycrystalline films. Pulsed laser
deposition (PLD) is a successful method for preparing
amorphous chalcogenide films [20, 21].
We present here our results regarding PLD preparation
of Ga–Ch amorphous thin film series and their structural
(XRD and EXAFS), optical (transmission and ellipso-
metry), and electrical (resistivity) characterization. In
addition to the thin films, thick films have also been
prepared in order to get a better signal from the XRD, REDD
analysis. As far as we know, this is the first comparative
study on amorphous films in the Ga–Ch system.
2 Materials and methods
2.1 Ceramic disks The Ga2Se3, GaTe, and Ga2Te3
targets (purity 99.99%) were bought from PVD Products,
USA. The Ga2S3 disk was prepared [22] by spark plasma
sintering (SPS) using Ga2S3 powders (purity 99.99%) from
Alpha-AESAR.
2.2 Thin-film deposition The amorphous Ga–Ch
(Ch ¼ S, Se, Te) films were deposited onto glass substrate
by PLD using a KrF laser source (l ¼ 248 nm, tFWHM ¼
25 ns), model COMPexPro 205, Lambda Physics-Coherent.

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1034 M. Popescu et al.: Amorphous thin films in the gallium–chalcogen system

The targets were irradiated with a laser fluence of 1.5 J cm2 1200
and the repetition rate was 5 Hz. The depositions were 1000
carried out at room temperature while the pressure of the
residual gas inside the deposition chamber was 4  104 Pa. Ga2Te3

The substrate was rotated during deposition to obtain
homogeneous films and the target-substrate distance was
5 cm, to obtain samples with thicknesses between 16 and
47 mm, suitable for X-ray diffraction measurements. The
number of laser pulses was 1.8–4.4  105. For ellipsometric
measurements, samples with 0.3–0.64 mm thicknesses were
needed.
2.3 Analysis methods For X-ray diffraction, the
scattering vector (Q ¼ 4p sinu/l) was in the range of 0.213–
16.655 Å 1. The measurements have been carried out on a
Bruker A8 Advanced diffractometer, with CuKa and MoKa
target tubes and a scintillation counter. The measuring time
per angular position was 70 s. The diffraction curves were
processed using a dedicated computing program written in
FORTRAN, and the radial electron density distribution
(REDD) curves were obtained. These REDD curves were
obtained by Fourier transform of the structure factor, S(Q),
of each sample. The structure factor (expressed in electron
units) is obtained from the diffraction curve, I(Q), according
to the protocol given by Warren [23]: I(Q) is corrected
for polarization, obtaining the I(Q) curve, then S(Q) is
calculated with formula S(Q) ¼ (I–hf 2 i)/hf i2 , where hf i is the
mean atomic scattering factor over atomic concentrations.
Extended X-ray absorption fine structure (EXAFS)
measurements were performed at the microXAS beam-
line from the Swiss Light Source using a double Si(111)
crystal monochromator. The incoming X-ray intensity
(Io) is measured by an ionic chamber and the EXAFS
spectra were collected in fluorescence mode using a
single-element Si drift diode detector (from Ketek,
160 eV resolution). Investigations were performed at
the K edges of Ga (10.367 keV) and Se (12.658 keV).
In both cases, the beam size was 300  300 mm2. Data
were analyzed using the Athena and Artemis software
packages.
To optically characterize the thin films, a Woollam
vertical-variable angle spectroscopic ellipsometer (V-VASE)
has been used. Measurements were performed from the
UV to near-IR (275–1770 nm), at three different angles of
incidence (AOI): 45, 60, and 758.
Intensity (q/s)
800
600 GaTe
400 Ga2Se3
200 Ga2S3
0
10 20 30 40 50 60
2θ (°)
Figure 1 X-ray diffraction patterns for Ga–Ch amorphous thin
films.
the first sharp diffraction peak (FSDP) in the case of Ga2S3
and Ga2Se3 amorphous thin films, while the FSDP is
missing for GaTe and Ga2Te3 amorphous thin films.
The radial electron density distributions (REDD) of the
samples are shown in Fig. 2. The REDDs of the Ga2S3 and
Ga2Se3 amorphous thin film samples show a well-defined
first coordination sphere. At the same time, these Ga2S3
and Ga2Se3 amorphous thin films show FSDP peaks on their
X-ray diffractograms. This means that their structures might
consist either of a 3D-connected network with GaCh4/2
units, or a 2D connected network with GaCh3/2 units. These
kinds of structures show large interstitial voids and the
X-ray scattering on their walls generates the FSDP [24, 25].
The REDDs of the GaTe and Ga2Te3 show a
superposition of the first two atomic coordination spheres.
This property, along with the lack of FSDP in Ga–Te
compositions, leads us to imagine that their structure does
not have a well-defined 3D structure, but rather a 2D-like
structure accommodating all the valences of the given
atoms.
Table 1 shows the characteristics of the first coordina-
tion spheres obtained from the REDD curves for each
composition.
In order to understand the local order in the four
amorphous samples, we have calculated the area of the first
peak of REDD using different network models. Thus, for
1 st
20 rmax, 1 peak
Ga2S3
REDD (10 e /Å )

0
The resistivity of the amorphous thin films was measured
3 2 3

50
using the four-point inline resistivity measurement tech- r1max, 1st peak
Ga2Se3
nique, with a Cascade Microtech C4S four-probe head 0 1 st
coupled with two Keithley 2601A SourceMeter Systems. 50 rmax, 1 peak
GaTe
The elemental analysis of the samples was performed 0
using a scanning electron microscope EVO 50 XVP (Carl 1 st
50 rmax, 1 peak
Zeiss NTS) with an energy-dispersive X-ray (EDAX) Ga2Te3
attachment (Bruker). 0
2 4 6 8 10
r (Å)
3 Results and discussion The X-ray diffraction
curves of the four Ga–Ch samples are shown in Fig. 1. All Figure 2 The radial electron density distribution (REDD) curves
the films are amorphous. One can observe the presence of for Ga–Ch amorphous thin films.

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Phys. Status Solidi B 253, No. 6 (2016) 1035

Table 1 Characterization of the first coordination spheres in the

amorphous thin films of gallium–chalcogen samples.
4
Ga2Te3
composition position, r1max (Å ) peak area (e2/Å 2)
GaTe

k2χ(k) (Å-1)
Ga2S3 2.325 1406 2
Ga2Se3 2.405 2581 Ga2Se3
Ga2Te3 2.621 3924
GaTe 2.628 2889 Ga2Se3
0
Ga2S3

4 6 8 10
Ga2S3 considering that Ga is tetra- and tricoordinated in Wavenumber (Å-1)
equal percentages and S is dicoordinated, we have obtained
an area of 1397 e2/Å 2. This value is very close to the Figure 3 k2-weighted back-Fourier transformed EXAFS oscil-
experimental one (1406 e2/Å 2). lations at the Ga edge (black, red, blue, and green dots) and at Se
For Ga2Se3 considering that Ga is tricoordinated and edge (magenta dots). The fits are represented by purple lines.
Se is dicoordinated (like in layered structure of As2Se3),
we have obtained an area of 2530 e2/Å 2 compared to
2581 e2/Å 2, obtained from the experimental curve, which Table 2 Distance and coordination number computed from the
is a very good agreement. EXAFS fits. NSe ¼ 1.96  0.40.
In the case of the amorphous Ga2Te3 sample supposing composition r (Å ) NGa
Ga and Te are dicoordinated, forming a structure of chains,
linked by S bridges on Ga atoms from the neighboring Ga2S3 2.271  0.015 2.67  0.36
chains, the area of the first peak of REDD will be Ga2Se3 2.405 3.21  0.58
3951 e2/Å 2, close to the experimental value (3924 e2/Å 2). Ga2Te3 2.605  0.023 2.24  0.52
For the GaTe amorphous sample, if we consider that it GaTe 2.616  0.012 2.57  0.66
has a structure like ZnS (or diamond-like carbon that also
does not show FSDP in its diffractogram), Ga and Te are
tetracoordinated, then the area is 6448 e2/Å 2, which is far a-Ga2Te3: Eg ¼ 1.09 eV. A bandgap of 2.65 eV was found
from the experimental value (2889 e2/Å 2). If we consider for Ga2S3 by Afifi et al. [27] for evaporated amorphous
that Ga is tetracoordinated and Te is tricoordinated, forming films. For cubic g-Ga2S3 thin films, a value of 3.47 eV for
a layered structure, an area of 5122 e2/Å 2 is obtained. If we the optical bandgap was reported [19]. The bandgap for
consider that Ga and Te are dicoordinated, forming a cubic Ga2Se3 thin films (ZnS structure with defects) is
structure of chains, then the area of the first peak of REDD is 2.1 eV [17], while in Ref. [18] a value of 2.74 eV was
3224 e2/Å 2, far from the experimental value. This means obtained. The optical energy gap of the single cubic
that it is possible for the chains to be very short, so at the crystals Ga2Se3 was found to be 2.07 eV [28], while for
ends of the chains the atoms are monocoordinated. amorphous (bulk) Ga2Se3 the obtained value was 1.75 eV
EXAFS data were processed using as starting values the [29]. The stoichiometric monoclinic GaTe thin films is a
bonding distances already found from XRD (r1max) at the moderate bandgap semiconductor with optical bandgaps of
first coordination spheres, except Ga2Se3 where the bonding 1.7 eV [17] while the hexagonal GaTe thin film has optical
distance was fixed at this value. We computed the numbers bandgaps in the range of 1.75–1.9 eV [17]. The optical
of the nearest neighbors from the first coordination shell
by employing only single scattering paths. An amplitude- 500 1000 1500
reduction factor was fixed at 1 for all the compositions. The
results are shown in Fig. 3 and are summarized in Table 2. 3.0
ref. index,

Ga is threefold coordinated in Ga2S3 and the Ga–S

2.5
distance is of 2.271 Å . In Ga2Se3, Ga and Se are threefold
n

Ga2S3 GaTe
and twofold coordinated, as also suggested by the XRD 2.0 Ga2Se3 Ga2Te3
results. In Ga2Te3 and GaTe alloys, Ga is twofold
coordinated as in XRD, while some small differences are 1.0 Ga2S3
ext. coeff.,

observed in Ga–Te distances. Ga2Se3

The results of the spectroscopic ellipsometry measure- 0.5 GaTe
k

ments are shown in Fig. 4. We use for fitting of ellipsometric Ga2Te3

measurements the Tauc–Lorentz dispersion formula [26]. 0.0

500 1000 1500
The thickness of the Ga–Ch thin films extracted from fitting
λ (μm)
are Ga2S3: 645 nm, Ga2Se3: 541 nm, GaTe: 302 nm, Ga2Te3:
345 nm. The inferred optical bandgaps are a-Ga2S3: Figure 4 Refractive index (n) and extinction coefficient (k) for
Eg ¼ 2.17 eV, a-Ga2Se3: Eg ¼ 2.21 eV, a-GaTe: Eg ¼ 1.30 eV, amorphous thin films of Ga2S3, Ga2Se3, GaTe, and Ga2Te3.

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1036 M. Popescu et al.: Amorphous thin films in the gallium–chalcogen system

bandgap for single cubic crystals Ga2Te3 was reported as
1.22 eV [30] at 273 K.
Figure 4 shows the dispersion curves for the refractive
index (n) and the extinction coefficient (k). The dispersion
curves obtained for amorphous Ga2Se3 thin films are very
similar to those obtained for glassy (bulk) Ga2Se3 [29].
Comparison between the experimental and calculated
transmittance curves (Fig. 5) from ellipsometric measure-
ments for Ga–Ch amorphous thin films shows a good
agreement.
Electrical measurements of Ga–Ch amorphous thin
films was made using the four-point inline resistivity
measurement technique. In this technique, four collinear
Kelvin probes are disposed at equal distances s. The current
(I) injected by one of the SourceMeter systems through
the probes situated at the extremities generates a voltage
distribution over the film surface. The voltage (V) drop
between the middle probes is measured by the second
SourceMeter system, and the resistivity of the film is given
by [31]
p   V
1  e4s   t;
d
r¼
lnð2Þ I for a-Ga2S3, Eg ¼ 2.21 eV for a-Ga2Se3, Eg ¼ 1.30 eV for
where d is the transversal film size and t the film thickness.
All the samples are insulators, as suggested from the
resistivity values in Table 3.
From the energy-dispersive X-ray (EDX) spectra, we
have obtained that the concentration of the chalcogen in the
thin films is lower than that corresponding to their
stoichiometry. Thus, in fact the Ga2S3 sample has the
exp model
1.0
0.5
Ga2S3 / SiO2
0.0
Transmittance
formula Ga2S1.79, Ga2Se3 is Ga2Se1.93, GaTe is GaTe0.86,
and Ga2Te3 is Ga2Te2.56.
4 Conclusions Thin amorphous films of Ga–Ch were
successfully prepared by PLD. From XRD and EXAFS
measurements, we have deduced the local order of these
amorphous films. In a-Ga2S3, gallium is threefold coordi-
nated, sulfur is twofold coordinated, and the average Ga–S
distance is 2.298 Å . In a-Ga2Se3, gallium is threefold
coordinated, sulfur is twofold coordinated, and the average
Ga–Se distance is 2.405 Å . In a-Ga2Te3, gallium is twofold
coordinated, sulfur is twofold coordinated, and the average
Ga–Te distance is 2.613 Å . In a-GaTe, which seems to have
a structure of short chains, gallium is undercoordinated,
sulfur can be considered to be onefold or twofold
coordinated (i.e., also undercoordinated), and the average
Ga–Te distance is 2.622 Å . The optical constants n(l) and
k(l) have been inferred from ellipsometry. For the near-IR
range (750–1700 nm), the refraction indexes are as follows:
Ga2S3: 2.51–2.42, Ga2Se3: 2.48–2.38, GaTe: 3.10–2.75,
Ga2Te3: 2.69–2.47. Optical bandgap (Eg) values have also
been determined for all thin film samples: Eg ¼ 2.17 eV
a-GaTe, Eg ¼ 1.09 eV for a-Ga2Te3. All the samples are
electrical insulators.
Acknowledgements The authors kindly acknowledge the
financial support of the Ministry of National Education (Romania)
in the frame of the contract 45N/1.03.2009, and of the project
NANOVISMAT PN2-162/2012. They also thank their colleagues
Dr. Aurel Mihai Vlaicu, Dr. Iuliana Pasuk, Dr. George Stan, and
Dr. Liviu Nedelcu from the National Institute of Materials Physics,
for changing the X-ray tube and making the allignment of the
Bruker D8 diffractometer.
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