Materials Science & Engineering B 261 (2020) 114623

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Materials Science & Engineering B

journal homepage: www.elsevier.com/locate/mseb

CVT and PVT growth and characterization of GaS crystals T

a,⁎ a,b a c c
Giovanni Attolini , Marco Negri , Tullo Besagni , Bela Pecz , Ildiko Cora
a
IMEM-CNR Institute, Parco Area delle Scienze 37A, 43124 Parma, Italy
b
Axcelis Technologies, via de Capitani 2, Agrate Brianza, Italy
c
Centre for Energy Research (EK), Institute of Technical Physics and Materials Science, Konkoly Thege 29-33, 1121 Budapest, Hungary

ARTICLE INFO ABSTRACT

Keywords: Gallium sulphide (GaS) has been prepared by chemical vapour transport (CVT) and physical vapour transport
GaS (PVT). The obtained crystals show two different morphologies: large layers and little microstructures respec­
2D materials tively, both indicated hexagonal crystal structure.
Cathodoluminescence Energy-dispersive X-ray spectroscopy (EDX) measurements confirm the correct stoichiometry; the hexagonal
Transmission electron microscopy
structure has been confirmed with x-ray analysis and transmission electron observations (TEM).
Optical study by cathodoluminescence shows direct bandgap with energy gap at 2.5 eV for both samples.

1. Introduction
Two-dimensional (2D) materials have gathered a great interest in
recent years because of their unique chemical and physical properties,
such as sizable bandgaps and indirect to direct transitions when
monolayers are isolated. They appear as lamellar structures from which
single monolayers can be extracted with exfoliation or can be directly
synthesized with different techniques, graphene has been one the main
studied 2d material [1–4].
Among the monolayers that have been isolated laterare2D transition
metal chalcogenides of families IV-VI (MoS2, MoSe2, WS2….…..), III-VI
(GaS, GaSe, GaTe).These species have in some cases semiconducting
behaviours (III-VI’s, MoS2, MoSe2, WS2, WSe2, MoTe2, WTe2), semi­
metallic (TiS2, TiSe2) or they can present peculiar physical behaviour
such as superconducting, metallic or charge density waves (NbSe2,
NbS2, NbTe2, TaS2, TaSe2, TaTe2) [5,6].
2D transition metal chalcogenide monolayers are interesting for
their excellent optical and electronic properties, direct gap in the visible
region, flexibility and high electronic mobility that can be applied to
non-linear optics [7,8].
As for those previously mentioned, compounds belonging to III-VI
family of semiconductors having a lamellar morphology can be ex­
foliated to obtain monolayers [9,10].There are different compounds
with III = Ga, In and VI = S, Se, like GaS and GaSe, although there are
other compositions as well [11].
The bulk form of these compounds is characterized by wide
bandgap making them useful for the realization of optoelectronic de­
vices, sensors and application in electrochemistry [12].
Two stable forms of GaSx have been found: GaS and Ga2S3, both are
showing wide bandgap characteristics [13,14].
GaS is interesting to realize photoelectric devices, gas sensors and
for application in non-linear optic, thin layers exhibit an increase in
photoluminescence of orders of magnitude compared to the bulk form
and excellent mechanical properties make GaS ideal for flexible elec­
tronics [15–17].
Different morphologies of GaS can be obtained: nanobelts, nano­
tubes, nanosheets, nanowires [18–21], thin films [22,23], while the
bulk, composed of large overlapping sheets, is useful to be exfoliated
obtaining nanosheets [15].
GaS can be obtained from vapour phase by using metalorganic
compounds as precursors [23,24] but the most used method for the
preparation of the bulk GaS is vapour phase chemical transport (CVT)
with iodine which allows to obtain large-sized crystals [25].
The purpose of this work was to prepare the GaS with two different
growth methods and to study its structural and optical properties with
CL.
GaS crystals were prepared using two different methods: CVT
(Chemical Vapour Transport) in closed tube like in Lieth et al.[26] and
PVT (Physical Vapour Transport) [27] in open tube on silicon substrate.
The obtained crystals have been studied by Scanning Electron
Microscopy (SEM), Energy- Dispersive X-ray spectroscopy (EDX), X-ray
powder diffraction (XRD), Transmission Electron Microscopy (TEM)
and Cathodoluminescence (CL).

⁎
Corresponding author.
E-mail address: giovanni.attolini@imem.cnr.it (G. Attolini).

https://doi.org/10.1016/j.mseb.2020.114623
Received 25 February 2020; Received in revised form 22 May 2020; Accepted 6 July 2020
Available online 31 July 2020
0921-5107/ © 2020 Elsevier B.V. All rights reserved.
G. Attolini, et al. Materials Science & Engineering B 261 (2020) 114623

Fig. 1. Morphology of GaS crystals grown by CVT (Sample 1) a) optical image, b) SEM image of the surface.

transported in the deposition zone resulting in the nucleation of the

Fig. 2. SEM image of GaS crystals grown on silicon substrate (Sample 2).
2. Materials and methods
GaS crystals have been prepared using two different methods: CVT
(sample 1) in closed tube and PVT (sample 2) in an open tube.
Polycrystalline GaS powder was used as starting material for both
methods.
a) In CVT 1.5 g of powder were placed in a quartz tube (2 cm inner
diameter and 18 cm long) with iodine concentration of 4 mg/cm3 as
transporting agent, evacuated and sealed.
The closed tube was placed in a temperature gradient of interest
with the source material at the higher temperature. The growth con­
ditions were: source temperature at 850 °C and deposition temperature
750 °C for ten days.
b) For PVT 2–3 g of powder were added in a quartz boat and put in a
quartz tube with silicon substrate downstream at a distance of 15 cm
then in a tubular furnace, purged with argon; temperature was in­
creased to 900 °C, and kept for 1 h.
This method exploits the sublimation of GaS powder because in the
range of temperature used in this preparation its vapour can be
Table 1
Mass data of sample 1 ( ± 2%).
Sample 1 S Ga
Mass percent (%) 33.26
Molarity 0.96
S/Ga atomic ratio 1.09
crystals at 850 °C.
The morphology was observed by Scanning Electron Microscopy
(SEM) using a Zeiss Merlin SEM equipped with Oxford EDX (Energy
Dispersive X-ray analysis) for measuring the composition,
X-ray powder diffraction was measured by means of a Siemens D500
diffractometer which makes use of CuKα radiation in scanning mode
from 10 to 90° 2Θ with a step size of 0.05° and counting time of 10 s.
The microstructure of the grown crystals was studied with Transmission
Electron Microscopy (TEM) using a FEI THEMIS 200 image corrected
TEM/STEM microscope.
An Attolight Rosa SEM-CL microscope was used for the CL mea­
surements. All the CL maps were obtained at room temperature under
UHV conditions. The e-beam current on the sample was about 1nA with
an accelerating voltage of 2 kV. The CL signal is sent to a spectrometer
with 32 cm of focal length by means of a reflective objective of NA 0.71
placed in the electronic optics of the microscope. The signal is detected
by a Peltier-cooled charge-coupled device (CCD) after dispersion on a
600 l/mm diffraction grating.
3. Results and discussion
The crystals obtained by CVT (sample 1) appear with yellow colour
in different sizes and as overlapping layers as shows in Fig. 1a while in
Fig. 1b a SEM micrograph of the top layer shows the typical growth
terraces. The crystals grown on silicon substrate with PVT (sample 2)
are showed in Fig. 2. It is possible to see the different crystal habits: in
the lower part, a large thin lamella, at the top, belts with different
widths. The size of these structures deposited downstream on silicon
ranges from micrometric dimensions to several hundred nm.
Bulk GaS can grow with different morphologies depending on the
synthesis conditions [26]. On the nanometric scale, as layered crystal,
GaS tends to grow along directions perpendicular to the c-axis, forming
ribbons [18] or layers [15]. A second family of GaS nanohorns or na­
nowires with c-axis parallel to the axis of the nanostructure have been
synthesized thanks to the presence of a catalyst with a Vapor − Li­
quid − Solid Growth mechanism [20,28].
The ribbon morphologies highlighted in Fig. 2 are part of the first
family described above and they were already observed in GaS obtained
with vapor–solid mechanism but different precursors [18].
The composition of the samples was measured by EDX analysis
confirming the correct stoichiometry as shown in Tables 1 and 2.
Table 1 reports the mass % calculated from EDX data for sample 1
grown by CVT, while Table 2 shows the values for sample 2 where
66.17
silicon from the substrate and oxygen from Si native oxide are also
0.88
measured by EDX on these crystals.
The structural properties, studied by X-ray diffraction, are reported

2
G. Attolini, et al. Materials Science & Engineering B 261 (2020) 114623

Table 2 in Fig. 3 for sample 1 and 2. Both cases confirm the hexagonal phase for
Mass data of sample 2 ( ± 2%). gallium sulphide.
Sample 2 O Si S Ga All the reflections of these patterns can be indexed to hexagonal
gallium sulfide; in the graphs we also note the Kβ as minor reflections of
Mass percent (%) 1.77 50.3 14.2 33.7 the GaS.
Molarity 0.11 1.79 0.44 0.48
In the graph of samples 2 the peaks marked with * are related to our
S/Ga atomic ratio 0.95
silicon substrate directly measured; unfortunately, some GaS peaks are
not visible because the measured signal is very low due to the very
small sizes of GaS crystals.
On the basis of experimental data of sample 1 and 2 we have ob­
tained the Table 3 where d-spacing is also included.
After refining using PDF2 (CARD GaS 84–0499(8) we have the
structure of GaS P63/mmc, a = 3.592 Å, c = 15.466 Å.
TEM technique has been used to confirm the structural properties of
sample 1, for this reason cross sectional specimen was prepared by FIB
(Focused Ion Beam), 2 keV Ga ions FEI SCIOS2 unit.
In Fig. 4 the HRTEM image and its Fast Fourier transformed pattern
prove that this material is the hexagonal GaS (a = 3.592 Å,
c = 15.465 Å; P63/mmm [29]). Investigating the top surface of the
crystal a very thin layer was detected and easily identified as hexagonal
Ga2S3(a = 3.68 Å, c = 6.02 Å; P63mc [30]) (Fig. 4).
The presence of Ga2S3 was not highlighted with x-rays because the
very thin layer, the sensitivity of the measure did not allow it.
The presence of Ga2S3 is possible when CVT growth method is used
as reported by Lieth [26].
CL measurement was carried out at room temperature using a 2 keV
electron beam on CVT and PVT samples and the spectra are shown in
Fig. 5. The intensity of the two spectra cannot be directly compared
because the interaction volume of the beam with a bulk sample (CVT
Fig. 3. X-ray diffraction patterns of sample 1 and sample 2. grown) is much higher than with nanostructures (PVT), so a higher
signal amplification was used in the latter measurement.
The main peak of both spectra can be ascribed to the near band edge
Table 3 emission of GaS and its position is in both cases around 490–500 nm,
Experimental X-ray data. which corresponds to 2.52 eV, the indirect bandgap as reported in lit­
erature [15,31]. In particular, the peak of sample 1 (bulk GaS) is
2Theta d(Å) Irel H K L
centred at 496 nm, while the peak of sample 2 (GaS on Si) is centred at
Sample 1 11.51820 7.6565 54 0 0 2 491 nm. The small red shift of the peak in sample 1 can be caused by the
Sample 2 11.40 7.7639 3 0 0 2 presence of defects. Other peaks are related to defects luminescence in
Sample 1 23.05132 3.8769 100 0 0 4
the lower energy region [31,32]. A secondary peak generated by the
Sample 2 22.92 3.8802 3 0 0 4
Sample 1 34.82173 2.5834 50 0 0 6
Ga2S3 luminescence can be identified at 525 nm in the sample 1 spec­
Sample 2 34.67 2.5876 1 0 0 6 trum. The higher intensity of the defects related peaks in the nanos­
Sample 1 46.97973 1.9380 24 0 0 8 tructured sample suggests a higher defect density. Details of the spec­
Sample 1 59.72083 1.5505 5 0 0 10 trum deconvolution and the peaks positions are reported in the
Sample 1 73.33780 1.2919 48 0 0 12
supporting information.
Sample 1 88.28753 1.1075 43 0 0 14
A Montecarlo simulation was carried out to evaluate the impinge­
ment of a 2 keV electron beam on a bulk GaS sample. A 5 nm Ga2S3

Fig. 4. HRTEM image of Sample 1 in [1–10] projection from the top of the crystal with the corresponding FFTs.

3
G. Attolini, et al.
Fig. 5. CL spectra of GaS samples. Sample 1 is GaS bulk grown by CVT, Sample
2 is GaS nanostructured grown by PVT on Si substrate.
layer was added on top to mimic the structure of the sample as resulting
from TEM measurements. Figs S4–S6 in the Supporting information
document report the results of the simulation of the electron beam in­
teraction with the sample, in particular, the variation of the CL emission
with the depth. The interaction has a discontinuity at 5 nm depth,
corresponding to the limit between the Ga2S3 layer and the GaS sub­
strate.
Indications from the simulation show that the 11.3% of the total CL
signal is generated by the Ga2S3 and 88.7% by the underlying GaS.
4. Conclusions
Two different synthesis processes were employed to obtain GaS bulk
crystals and microstructures. EDX and XRD confirmed respectively the
composition and crystalline structure of the material and
HRTEM and corresponding FFTs confirmed the GaS hexagonal
structure of the samples and identified layers of Ga2S3 on the top/sur­
face of the crystals.
CL measurements allowed to estimate the near band edge emission
of GaS at ambient temperature at 491–496 nm (2.52–2.50 eV) and
confirmed the presence of defects.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ­
ence the work reported in this paper.
Acknowledgements
The work was supported by the bilateral project 2019-2.1.11-TÉT-
2019-00066. B. Pecz thanks the support of VEKOP-2.3.3-15-2016-
00002 of the European Structural and Investment Funds.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.mseb.2020.114623.
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