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Page 1 of 6 AUTHOR SUBMITTED MANUSCRIPT - MRX-110855

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3 Structural and electrical properties of Sb0.5W0.5Se2 ternary alloys
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5 Abhishek Patel1, a*, Sharad Babu Pillai2, K. D. Patel1, b, G. K. Solanki1, P. K. Jha2 and V. M. Pathak1, Pratik
6 Pataniya1, c
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Department of Physics, Sardar Patel University, Vallabh Vidyanagar, Anand-388120, India.
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Department of Physics, Faculty of Science, M.S. University of Baroda, Vadodara-39000, India.
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11 Email: *apatel.abhi52@yahoo.com, bkdptflspu@yahoo.com, cpm.pataniya9991@gmail.com
12 Abstract
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14 In present article, we demonstrated for the first time the synthesis and properties of Sb0.5W0.5Se2 ternary alloy.
15 The crystals of Sb0.5W0.5Se2 ternary alloy were grown by direct vapour transport technique. The XRD results
16 confirm the 2H-hexagonal lattice structure with P63/mmc space group and grown crystals are highly
17 crystallographic c-axis oriented. The screw dislocation mechanism is predominating in the growth process of
18 Sb0.5W0.5Se2 crystals. The results of electrical characterization show n-type semiconducting nature. The Raman
19 spectra exhibits peaks corresponding to out-of plane A1g, in-plane E2g and 2LA modes of vibration which is
20 attributing the 2H-polymorph of grown Sb0.5W0.5Se2 ternary alloy. The results shows substitution of Sb (+5) on
21 W (+4) lattice site due to similar ionic size.
22 Keywords: Growth of single crystal, structural properties, electrical transport, Sb0.5W0.5Se2 ternary alloy.
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24 Introduction:
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The electronic and optoelectronics devices based on two-dimensional transition metal dichalcogenides (2D-
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TMDCs) have raised intensive attention due to their extraordinary performance over devices based on other
27 layered materials like grapheme [1-5]. Apart from high carrier concentration and mobility of 107cm2/Vs, high
28 current on/off ratio and band gap of 1-2 eV make them potential candidates for high performance field effect
29 transistors (FETs) [6]. Recently, band gap engineering is demonstrated for fabrication of electronics devices such
30 as transistors, diodes, solar cells, etc. [10-14]. Owing to great success of vapour transport technique for growth of
31 single crystals of TMDCs, modification of material characteristics has been demonstrated for number of binary
32 and ternary compositions [14-22]. Now a days, photo detectors based on TMDCs have shown great promise for
33 digital optics and sensing application. However, growth temperature of TMDC single crystals are found to be
34 higher and hence, serious problem of chalcogen vacancies arises giving rise to deep-level defect states (DLDS)
35 that dominates the performance of devices. These DLDS acts as carrier-recombination centres and as a results,
36 the photocurrent reduces and response of switching devices becomes slower. This problem can be resolved by
37 alloy engineering or substitutional doping of binary alloys of TMDC family. Guowei Yang and co-workers have
38 demonstrated the enhanced photo detection properties of Mo0.5W0.5S2 ternary compound by alloy engineering [20,
39 21]. The improvement in photo responsivity from 4.88 to 106 mA/W has been demonstrated by compositional
40 modification in VXSn1-XSe2 ternary alloys [17]. Inspired from these reports, here in, Sb0.5W0.5Se2 ternary alloy has
41 been grown in crystalline form with single 2H-WSe2 type structural phase.
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Experimental:
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44 Materials and methods for crystal growth:
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46 The crystals of Sb0.5W0.5Se2 compound were grown in dual zone furnace using direct vapour transport
47 technique. The elemental powder of antimony (Sb), tungsten (W) and selenium (Se) (99.999% purity, Alfa Aesar
48 make) were taken in stoichiometric proportion and filled in the quartz ampoule. Then, the ampoule was evacuated
to 10-6 torr pressure and sealed off. The ampoule was inserted in high temperature dual zone furnace operat. Source
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zone and growth zone temperatures were increased from room temperature at the rate of 33° C/hour to 1000° C
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and 1050° C respectively and kept constant at this level for 100 hrs. The vapour of individual elements interacts
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and form compound in the vapour phase that is transported to the growth zone by the temperature gradient to
52 initiate the growth of crystals. Then, furnace was cooled down to room temperature at the rate of decrement in
53 temperature of 22° C/hr. Grown crystals were found opaque and shiny grey in appearance.
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55 Characterization techniques:
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57 The Sb0.5W0.5Se2 compound was studied by energy dispersive analysis of X-ray for stoichiometric
58 confirmation. The structural phase purity was analysed by powder X-ray diffraction technique using Rigaku
59 Ultima using Cu (Kα) radiation. The surface morphology was studied by Carl-Zeiss (Jena GmbH, West Germany)
60 optical microscope. ESEM EDAX XL-30 scanning electron microscope (SEM) was employed for analysis of
AUTHOR SUBMITTED MANUSCRIPT - MRX-110855 Page 2 of 6

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3 morphology of powder form of Sb0.5W0.5Se2 compound at higher resolution. The grown sample was sonicated in
4 ethanol for 1 hour and mixture having suspended small particles was drop casted on Cu-grid for TEM analysis
5 using Philips make Tecnai-20 transmission electron microscope (TEM) and SAED pattern was taken using 200
6 kV e-beam. Raman analysis was carried out from micro-Raman model STR 500 operated with 785 nm wavelength
7 Nd-YAG laser source mounted with Peltier cooled CCD detector and Nikon microscope with different objective
8 lenses. The electrical resistivity parallel and perpendicular to crystallographic c-axis was measured in temperature
9 range from 308-673K using two probe method. The Hall-effect parameters such as carrier concentration, Hall co-
10 efficient and mobility were measured at ambient temperature using Hall-effect set-up Model-DHE-22 and
11 constant current source Model-DPS175 (Make: Scientific Equipment Services (SES), Roorkee, India).
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27 Fig. 1. EDAX spectra of Sb0.5W0.5Se2 compound.
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29 Table 1 Chemical analysis of Compound using EDAX
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31 Crystals Weight (%) of constituents Atomic (%) of constituents
32 Sb W Se Sb W Se
33 Sb0.5W0.5Se2 18.59 30.58 50.82 16.11 19.54 64.36
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35 Results and discussion:
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Figure 1 presents the EDAX spectra of Sb0.5W0.5Se2 ternary alloy. The measured weight (%) of constituents
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are mentioned in Table 1. The results confirms that the grown sample is stoichiometric and no impurities are
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found. As shown in Figure 2, the powder XRD pattern exhibits strong diffraction peaks and is well indexed to
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hexagonal lattice structure with P63/mmc space group. The most prominent peak at ~13.8° is indexed to (002)
40 indices and other peaks corresponding to (006) and (008) indices are found at 41.9° and 56.8°. The dominance of
41 (00l) peaks on XRD indicates the highly c-oriented stacking of X-M-X layers. The preservation of 2H-polymorph
42 in Sb0.5W0.5Se2 and absence of secondary structure confirms the substitution of Sb (+5) on W (+4) lattice site in
43 WSe2 host network. However, due to small mismatch in ionic size of Sb(+5) and W(+4), XRD peaks are shifted
44 towards higher angle side from 13.6° for pristine WSe2 to 13.8° for present composition owing to decrease in d-
45 spacing of lattice planes [14, 18, 22, 23]. The lattice constants and unit cell volume are determined from XRD
46 results and mentioned Table 2. Additional structural parameters such as crystallite size, dislocation density and
47 micro-strain are determined and mentioned in Table 2. The micro-strain and dislocation density are raised up due
48 to incorporation of Sb and hence causes the reduced crystallite size of grown Sb 0.5W0.5Se2 ternary alloy.
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18 Fig.2. (a) Powder XRD Pettern of Sb0.5W0.5Se2 ternary alloy, (b) magnified image of (002) peak of Sb XW1-XSe2
19 ternary alloys.
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21 Table 2 Structural and electrical parameters of Sb0.5W0.5Se2 crystals.
22 Parameters WSe2 [22] Sb0.1W0.9Se2 [22] Sb0.5W0.5Se2
23 Lattice parameter (a=b) (Å) 3.297 3.292 3.291
24 Lattice parameter (c) (Å) 12.982 12.946 12.935
25 c/a ratio 3.937 3.932 3.930
26 Unit-cell volume (Å)3 122.270 121.499 121.350
27 Crystallite size (nm) 86.913 68.45 37.32
28 Strain (ε × 10-2) (lin-2m-4) 4.175 5.638 5.638
29 Dislocation density (δ × 1016) (lin m-4) 2.935 3.769 3.769
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31 The grown crystals are observed using Carl-Zeiss optical microscope. As shown in Figure 3 (a), the
32 distorted helical spirals are observed on teared crystal layers. They are originated due to dominance of screw
33 dislocation mechanism during growth of crystal. The existence of steps on surface of crystals indicates the
34 layer-by-layer growth of Sb0.5W0.5Se2 ternary alloy, as shown in Figure 3 (b). These are the native features
35 of TMDC crystals which are grown by vapour transport technique [14, 17]. Figure 3 (c) presents the
36 hexagonal flakes with flat terrace that is formed by lateral spreading of grown layers. Figure 3 (d) presents
37 the SEM image of tiny hexagonal flake of Sb0.5W0.5Se2 ternary alloy. The exfoliated suspension of
38 Sb0.5W0.5Se2 sample was analysed by TEM. The Figure 4 (a) shows the hexagonal flakes of lateral dimensions
39 of few hundreds of nm. As shown in Figure 4(b), the bright hexagonal spot pattern indicates the single
40 crystalline nature of tiny flake of Sb0.5W0.5Se2 ternary alloy [14, 18].
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Fig. 3. (a) Optical micrograph of hexagonal spirals (b) optical micrograph of steps due to layered structure,
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(c) SEM image of tiny flakes with smooth surface, (d) SEM image of hexagonal flakes of Sb0.5W0.5Se2 ternary
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48 Fig. 4. (a) TEM image of nan-flake, (b) SAED pattern of Sb0.5W0.5Se2 ternary alloy.
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50 Table 3 Electrical transport properties of Sb0.5W0.5Se2 ternary alloy.
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Electrical transport parameters WSe2 [22] Sb0.1W0.9Se2 [22] Sb0.5W0.5Se2
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Activation energy Parallel to c-axis 0.322 0.181 0.192
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(eV) Perpendicular to c-axis 0.231 0.156 0.156
54 Semiconductor type p-type n-type n-type
55 Hall co-efficient (cm3 Coulomb-1) 686.870 189.667 31.75
56 Carrier concentration × 1016 (cm-3) 0.910 3.295 39.06
57 Room temperature resistivity (ohm cm) 36.320 1.767 0.985
58 Mobility (cm2/V s) 18.911 107.338 1.62
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18 Figure 5 Temperature dependent resistivity measured parallel and perpendicular to crystallographic c-axis of
19 Sb0.5W0.5Se2 ternary alloy.
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Figure 5 presents the temperature dependent variation of electrical resistivity parallel and perpendicular to
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c-axis of Sb0.5W0.5Se2 ternary alloy in temperature range 308-773K. The resistivity falls exponentially on
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increasing the temperature, indicating semiconducting behaviour of grown compound. Absence of discreteness or
23 steps depicts absence of phase or structural transition in studied temperature range. The higher value of resistivity
24 parallel to c-axis than that perpendicular to c-axis is attributing the anisotropic charge conduction mechanism
25 which is due to layered structure of Sb0.5W0.5Se2 ternary alloy. Generally, TMDCs grow in crystallographic ab-
26 plane and W/Sb and Se atoms are bonded with each other via covalent interaction while along the c-axis trilayers
27 are weakly stacked via Van der Wall’s interaction. Owing to relatively larger separation between tri-layer stacks
28 along c-axis, the conduction of carriers becomes poor along the c-axis. The Arrhenius relation [25] is applied to
29 calculate electrical activation energy and Log (Resistivity) is plotted against 1000/T. The plots yield straight line
30 with single slope value. The activation energy is calculated and mentioned in Table 3. The smaller values of
31 activation energy (less than half of the band gap) confirm the extrinsic behaviour of Sb0.5W0.5Se2 ternary alloy.
32 Also, the activation energy for transport along c-axis is larger than that perpendicular to c-axis. The Hall-effect
33 measurements were taken at ambient temperature with applied magnetic field of strength 1kG. The Preliminary
34 observation suggests the n-type semiconducting behaviour of Sb0.5W0.5Se2 ternary alloy. The parameters such as
35 carrier concentration, mobility and Hall Co-efficient are calculated and mentioned in Table 3. The inclusion of Sb
36 (+5) alters the native p-type behaviour of pristine WSe2 into n-type behaviour in Sb0.5W0.5Se2 ternary alloy.
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The Raman spectroscopy is employed for confirmation of phase purity and to understand the vibrational
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modes in Sb0.5W0.5Se2 ternary alloy. Figure 6 presents the Raman spectra of Sb0.5W0.5Se2 ternary alloy alloys,
39 exhibiting peaks at 253 cm-1, 256 cm-1 and 259 cm-1 which are attributing E2g, A1g and 2LA modes of vibration,
40 respectively. The presence of WSe2-type vibrational mode shows the preservation of 2H-polymorph even after
41 the compositional change. However, the mentioned peaks are slightly shifted toward higher wavenumber side as
42 compared to corresponding peaks of pristine WSe2. The results concludes the presence of single crystalline phase
43 and also attribute the proper substitution of Sb (+5) on W (+4) lattice sites [18, 27, 28].
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4 Conclusion:
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The crystals of Sb0.5W0.5Se2 ternary alloy are grown by direct vapour transport technique. The grown
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compound has 2H-WSe2 type hexagonal lattice structure with P63/mmc space group. The surface morphological
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investigation shows the tiny hexagonal flakes and whiskers of micro-sized lateral dimensions. The TEM shows
8 nano-flakes of arbitrary shape. The SAED pattern shows the single crystalline nature of tiny flakes of Sb 0.5W0.5Se2
9 ternary alloy. The results of electrical characterization show the n-type semiconducting nature. The grown crystals
10 are found to having anisotropic charge conduction mechanism. Raman spectroscopy confirms 2H-polymorph of
11 grown ternary alloy and A1g and E2g modes of vibration are detected.
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