International Journal on Recent and Innovation Trends in Computing and Communication

Volume: 2 Issue: 11

ISSN: 2321-8169
3578 3582

_______________________________________________________________________________________________

MoS2 and MoSe2 Single Crystal Growth of Transition Metal Dichalcogenides

Bupendra Mor

Dr. Madhvi Dave

Vidhi Raval

Lecturer in Physics,
Government Polytechnic,
Chhotaudepur,
Gujarat, India
e-mail: bhupendra_mor@yahoo.com

Research Guide,
CRD,RAI University,
Ahmedabad,Gujarat, India
e-mail:
drkalpendupathakmhm2010@gmail.com

Research Scholar,
CRD,RAI University,
Ahmedabad,Gujarat, India
e-mail: vidhiraval@yahoo.com

Abstract Molybdenum/tungsten Dichalcogenides constitute a well-defined family of com-pounds which crystallize in a layertype structure. These compounds have properties tailored for use as storage electrodes in rechargeable photo electrochemical solar
energy storage cells. Single crystals of MoS2 and MoSe2 were grown by chemical vapour transport method using iodine as a
transporting agent and characterized by optical microscopy, Energy dispersive analysis (EDAX), X-ray powder diffraction (XRD)
and Hall mobility at room temperature. The variation of electrical resistance under pressure was monitored in a Bridgman anvil
setup up to 6.5 GPa to identify occurrence of any structural transition. MoS 2 and MoSe2 do not undergo any structural transitions
under pressure. The high quality of the crystals grown by using this method is confirmed by X-ray diraction studies, Raman
spectroscopy and electrical resistivity measurements, and proved to be higher than that of commercially available MoS 2 crystals.
Keywords- Crystal Growth; Single crystals; Chemical Vapour Transport Method; Dichalcogenides;

__________________________________________________*****_________________________________________________
I. INTRODUCTION
The transition metal dichalcogenides (TMDC) have layered
structure and attracted many researchers due to their
interesting properties like superconductivity, charge density
waves, intercalation compound formation etc. Most of the
TMDC compounds studied can be considered structurally as
strongly bonded two-dimensional XMX (M = metal, X =
chalcogen) layers loosely coupled to one another by relatively
weak Van der Waals type forces 1. In MoS2 and MoSe2, the
metal atom has trigonal prismatic coordination within the
sandwich layer and a number of stacking poly-types are
possible depending upon the way in which the sandwich
layers are stacked one upon the other 7. Molybdenum
dichalcogenides as p or n-type semiconductors have been
extensively studied 2,3,4,5,6. In earlier measurements of
MoS2 and MoSe2, it was observed that electrical
resistivity decreases with pressure, while Hall mobility is
relatively pressure independent. Measurements in a
Drickamer anvil set up to 38 GPa on MoS2, showed a 500
fold decrease in R up to 15 GPa and a saturation thereafter.
The pressure tetrahedral anvil apparatus up to 5 GPa.
The growth of large and high quality single crystals of metal
grown by the chemical vapor transport method (CVT),
because of their high melting points and the lack of, or at least
the scarce, knowledge of the phase diagrams, ruling out the
possibility of using any growth method involving the liquid
state. In the CVT method, a volatile substance, in most cases
iodine, is added to the mixture of the raw materials in order to
transform the nonvolatile metal into some molecular species
that permit its diusion in the atmosphere. As soon as the

partial pressure is high enough, the crystallization can occur

in the cold part of the reaction ampule.24
As a matter of fact, iodine appears to be an excellent vapor
transport vector only for some MX2 compounds. MoS2 exists
in nature, it has been largely studied and crystals are
commercially available.
By controlling the temperature of the source, the starting ratio
between the metal and its chloride, large crystals (1mm2 to
1cm2) of molybdenum and tantalum dichalcogenides have
been successfully grown within a growth time shorter than
one week. We report the details of our chloride-driven CVT
growth method as well as a wide characterization of the single
crystals, by means of X-ray diraction, electron microscopy
and X-ray spectroscopy, Raman spectroscopy and transport
measurements. In this paper we report room temperature
resistance mea segments as a function of pressure on MoS2
and MoSe2 single crystals. In each case the resistance
decreases under pressure due to an increase in the carrier
concentration.
II. EXPERIMENTAL
Single crystals of MoS2 and MoSe2 have been grown by
chemical vapour transport technique using iodine as a
transporting agent. Pure elements (99.95%) of molybdenum,
sulphur and selenium (make: Aldrich, USA) in stoichiometric
proportions and narrow capillary with I2 (2 mg/cc) of
ampoule volume were sealed in an evacuated quartz ampoule
for the crystal growth. The growth parameters are given in
table 1.The crystals under magnification revealed hexagonal
spirals on the growing face as shown in figure 1. The
chemical composition of the crystals grown was confirmed by
3578

IJRITCC |November 2014, Available @ http://www.ijritcc.org

_______________________________________________________________________________________

International Journal on Recent and Innovation Trends in Computing and Communication

Volume: 2 Issue: 11

ISSN: 2321-8169
3578 3582

_______________________________________________________________________________________________
carrying out energy dispersive analysis by X-ray(EDAX)
as shown in table 2. The lattice parameters obtained by
X-ray diffraction are listed in table 3.The electrical resistance
of the crystals along the basal plane was determined by
van der Pauw method. Hall measurements were carried out
to determine Hall coefficient, mobility and carrier
concentration. The results of measurements are listed in table
4.
The room temperature measurements of resistances for these
crystals, as a function of pressure were taken up to 6.5 GPa.
Pressure was generated with a Bridgman type tungsten
carbide opposed anvil apparatus with in situ bismuth pressure
calibration. The crystals were contained in a pyrophillite
gasket with talc as pressure transmitting medium
(Bridgman 1941). A two-probe technique was used to
evaluate the resistances of MoS2 and MoSe2 crystals. The
resistance variation with pressure was determined. Raman
spectroscopy was performed with a homemade micro Raman
spectrometer equipped with an argon laser ( = 514.5 nm),
described in ref 27, with a spectral resolution of 1 cm1.
Resistivity versus temperature was measured using the
standard four-probe method over the temperature range
4.2300 K
III. RESULTS AND DISCUSSION
The chemical vapor transport technique has been used to
grow single crystals of MoS2 and MoSe2 because it yields
large single crystals with relative ease. The presence of
hexagonal spirals on the growing face of the grown crystals
suggests that growth involves a screw dislocation mechanism.
The EDAX studies confirmed that MoS2 and MoSe2 single
crystals are stoichiometrically perfect. The XRD analysis
confirms that MoS2 and MoSe2 possess hexagonal crystal
structure. From the sign of the Hall coefficient it is clear that
both crystals are p-type in nature. The variation of resistance
with pressure for MoS2 and MoSe2 are shown in figure 2. In
both the cases it is seen that the resistance for each crystal
decreases gradually with pressure up to 6.5 GPa. No phase
transition is found in both these crystals up to 6.5 GPa.
However, the samples became more conducting in nature at
higher pressures. This decrease of resistance is probably
attributed to the charge carriers of valence band contributing
to the conduction band carriers.
In MoS2 and MoSe2 the valence band is an energy band
derived from sulphur to selenium, 3p and 4p orbitals,
respectively. These bands are separated by nearly 1.75 eV and
1.4 eV energy as shown in figure 3. The separation of band
decreases and the charge carriers of the sulphur 3p orbitals
from valence band increases as the pressure in-creases on
these crystals, which explains the decrease of resistance with
increase in pressure as seen in MoS2 and MoSe2. In addition
the electronegativity of sulphur is more than selenium and so
the band overlap in MoS2 is expected to be smaller or non-

existent. The decrease of resistance of the chalcogenide

compounds with pressure is in line with the behavior of most
of the metals and semimetals.
High resolution scanning electron microscopy provides
further indications about the growth mechanism. All MX2
crystals grown in this study are found to crystallize in the
2H crystal.
Whereas this is not surprising for MoS2 and MoSe2, for which
this is the most favored structure, the other compounds could
crystallize in di erent structures (2H and 1T), but the
temperature at which crystal growth occurred (T cold) is
always below the lower stability limit of the 1T crystal
structure (which is above 800 C).29 The growth method we
used was therefore selective toward the crystal structure, and
the existence of poly type defects in large fraction in the
crystals is excluded. Figure 4 shows a typical Raman
spectrum obtained on MoS2 at room temperature. The figure
compares one crystal grown.
IV. CONCLUSIONS
(I) The single crystals of MoS2 and MoSe2 were grown using
chemical vapour transport technique.
(II) The presence of hexagonal spirals on the growing face of
the grown crystals suggests that growth involves a screw
dislocation mechanism.
(III) The EDAX studies confirmed that MoS2 and MoSe2
single crystals are stoichiometrically perfect.
(IV) The XRD analysis confirms that MoS2 and MoSe2
possess hexagonal crystal structure.
(V) From the sign of the Hall coefficient it is clear that both
crystals are p-type in nature.
(VI) The electrical resistance decreases with pressure and is in
line with the behavior of most of the metals and semimetals..
(VII) The growth of these materials was found to occur layerby-layer, and no 3D defects like screw dislocations and spirals
were found by local inspection of SEM images of the crystal
surfaces.
(VIII) Conventional X-ray direction indicates that no
detectable fractions of poly-type defects are formed. As a
consequence, these crystals are suitable for mechanical
exfoliation for the production of electronic Nano devices
based on stable suspended atomic monolayers.
(IX) The crystal growth occurring at temperatures lower than
the stability limit of the 1T poly-type structure, this method
is selective of the crystal structure of the final product and no
polytypic defects and intergrowth can form.
(X) The physical characterization of these crystals, carried out
by electrical resistance measurements and Raman
spectroscopy, has put in evidence an anomalous and
unexpected behavior of MoTe2. This material is found to have
a transition from a semi-conducting behavior at low
temperature to a bad metallic state at high temperature.
3579

IJRITCC |November 2014, Available @ http://www.ijritcc.org

_______________________________________________________________________________________

International Journal on Recent and Innovation Trends in Computing and Communication

Volume: 2 Issue: 11

ISSN: 2321-8169
3578 3582

_______________________________________________________________________________________________

Figure 1. Microstructure of (a) MoS2 and (b) MoSe2 single Crystals

Figure 2. The variation of resistance with pressure for MoS2 and MoSe2 single crystals.

Figure 3. Energy schemes and approximate relative energetic positions of MoS2 and MoSe2 single crystals

3580
IJRITCC |November 2014, Available @ http://www.ijritcc.org

_______________________________________________________________________________________

International Journal on Recent and Innovation Trends in Computing and Communication

Volume: 2 Issue: 11

ISSN: 2321-8169
3578 3582

_______________________________________________________________________________________________

Figure 4. Raman spectrum of MoS2. Commercial samples (black) and crystals grown with the new chloride route (red) are acquired under the same
conditions and compared. Nonindexed peaks ascribable to impurities are present in the commercial sample (black curve). The small (5 cm1)
shift between the dierent patterns is an artifact of the measurement, due to the dierent alignment of samples with dierent thicknesses.
TABLE 1. GROWTH PARAMETERS OF MOS2 AND MOSE2 SINGLE CRYSTALS GROWN USING IODINE VAPOUR TRANSPORT TECHNIQUE.

Ampoule
dimension

Initial material
Crystal

Temperature

Physical characteristics of crystals

Plate
area

Weight
(g)

Transporting
Agent

Length
(mm)

Inner
Diameter
(mm)

Hot
zone
(K)

Cold
zone
(K)

Growth
time
(h)

(mm )

MoS2

10

I2

250

22

1130

1073

336

0.020

MoSe2

10

I2

250

22

1183

1123

284

0.015

Thickness
(mm)

Color
Grey
Black
Grey
Black

TABLE 2. WEIGHT % OF ELEMENTS TAKEN FOR GROWTH AND OBTAINED FROM EDAX ANALYSIS.

Crystal

Element
Mo
S
Mo
Se

MoS2
MoSe2

Weight % of elements taken from EDAX

59.94
62.19
40.06
37.81
37.80
38.00
62.20
62.00

TABLE 3. LATTICE PARAMETERS OF MOS2 AND MOSE2 SINGLE CRYSTALS OBTAINED USING X-RAY DIFFRACTION(XRD) ANALYSIS.

Crystal
MoS2 (Traill 1963)
MoSe2 (Cech et al 1973)

Standard value
a = b ()
c ()
3.160
3.287

18.330
12.925

Calculated value (in present work)

a = b ()
c ()
3.110 0.0405
3.157 0.0098

18.89 0.6840
12.926 0.1958

TABLE 4. RESULTS OBTAINED FROM RESISTIVITY, HALL EFFECT AND OPTICAL ABSORPTION MEASUREMENTS FOR THE SINGLE CRYSTALS OF MOS2 AND MOSE2

Crystals

Resistivity (ohm cm)

Hall coefficient (cm3/coul.)
Hall mobility (cm2/Vohms)
Carrier concentration (cm3)

MoS2

829.54
1910000
92335.7
3.4 1012

MoSe2

0.9096
1655.05
1819.53
3.8 1015
3581

IJRITCC |November 2014, Available @ http://www.ijritcc.org

_______________________________________________________________________________________

International Journal on Recent and Innovation Trends in Computing and Communication

Volume: 2 Issue: 11

ISSN: 2321-8169
3578 3582

_______________________________________________________________________________________________

References
[1]
[2]

[3]
[4]

[5]
[6]
[7]

[8]
[9]

[10]

[11]
[12]
[13]

[14]
[15]

[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]

Dartigeas K et al 1997 J. Electron Spectrosc. & Rel. Phenom.83

45
Frey G L, Elani S and Hamyonfer M 1998 Phys. Rev. B, Condensed Matter (USA) 57 11 Grant A J 1970 Ph.D. Thesis,
University of Cambridge, UK Grant A J, Griffiths T M, Pitt G D
and Yoffe A D 1975 J. Phys.C: Solid State Phys. 8 17
Huisman R, Jonge R de, Haas C and Jellinek F J 1971 Solid State
Chem. 3 56
Title R S and Shafer M W 1972 Phys. Rev. Lett. 28 808 Title R S
and Shafer M W 1973 Phys. Rev. B8 615 Traill 1963 Can
Mineral 7 524
Wilson J A and Yoffe A D 1969 Adv. Phys. 18 193
Yoffe A D 1974 Proc. 12th int. conf. on physics and semiconductors (ed.) M Pilkuhn (Stuttgart: Teubner-Verlag) pp. 129
Zvyagin B B and Soboleva S V 1967 Sov. Phys. Cryst. 12 46
Radisavljevic, B.; Radenovic, A.; Brivio, J.; Giacometti, V.; Kis,
A. Nat. Nanotechnol. 2011, 6, 147150.
Paorici, C.; Attolini, G. Prog. Cryst. Growth Charact. Mater. 2004,
4849, 241.
Morosan, E.; Zandbergen, H. W.; Dennis, B. S.; Bos, J. W. G.;
Onose, Y.; Klimczuk, T.; Ramirez, A. P.; Ong, N. P.; Cava, R. J.
Nat. Phys. 2006, 2, 544550.
Shishidou, T.; Freeman, A.; Asahi, R. Phys. Rev. B 2001, 64,
180401. Lee, C.; Li, Q.; Kalb, W.; Liu, X.-Z.; Berger, H.; Carpick,
R. W.; Hone, J. Science 2010, 328, 7680.
Chiritescu, C.; Cahill, D. G.; Nguyen, N.; Johnson, D.; Bodapati,
A.; Keblinski, P.; Zschack, P. Science 2007, 315, 351353.
Braga, D.; Gutierrez Lezama, I.; Berger, H.; Morpurgo, A. F.
Nano Lett. 2012, 12, 52185223.
Splendiani, A.; Sun, L.; Zhang, Y.; Kim, T.; Li, J.; Kim, J.; Chim,
C.-Y.; Galli, G.; Wang, F. Nano Lett. 2010, 10, 12711275. Reed,
C. A.; Cheung, S. K. Proc. Natl. Acad. Sci U.S.A. 1977, 74,
17801784.
Puthussery, J.; Seefeld, S.; Berry, N.; Gibbs, M.; Law, M. J. Am.
Chem. Soc. 2011, 133, 716719.
Novoselov, K. S.; Jiang, D.; Schedin, F.; Booth, T. J.; Khotkevich,
V. V.; Morozov, S. V.; Geim, A. K. Proc. Natl. Acad. Sci. U.S.A.
2005, 102, 1045110453.
Radisavljevic, B.; Whitwick, M. B.; Kis, A. ACS Nano 2011, 5,
99349938.
Larentis, S.; Fallahazad, B.; Tutuc, E. Appl. Phys. Lett. 2012, 101,
223104.
Mak, K. F.; Lee, C.; Hone, J.; Shan, J.; Heinz, T. F. Phys. Rev.
Lett. 2010, 105, 136805.
Yun, W. S.; Han, S. W.; Hong, S. C.; Kim, I. G.; Lee, J. D. Phys.
Rev. B 2012, 85, 033305.
Tongay, S.; Zhou, J.; Ataca, C.; Lo, K.; Matthews, T. S.; Li, J. B.;
Grossman, J. C.; Wu, J. Q. Nano Lett. 2012, 12, 55765580.
Towle, L. C.; Oberbeck, V.; Brown, B. E.; Stajdohar, R. E.Science
1966, 154, 895896
Tiong, K. K.; Shou, T. S. J. Phys.: Condens. Matter 2000, 12,
50435052.
Hu, S. Y.; Liang, C. H.; Tiong, K. K.; Lee, Y. C.; Huang, Y. S. J.

[24]

[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]

[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]

[46]
[47]
[48]
[49]

Cryst. Growth 2005, 285, 408414.

Bougouma, M.; Batan, A.; Guel, B.; Segato, T.; Legma, J. B.;
Reniers, F.; Delplanke-Ogletree, M.-P.; Buess-Hermann, C.;
Doneux, T. J. Cryst. Growth 2013, 363, 122127.
Sands, D. E.; Zalkin, A. Acta Crystallogr. 1959, 12, 723726.
Akrap, A.; Tran, M.; Ubaldini, A.; Teyssier, J.; Giannini, E.; van
der Marel, D. Phys. Rev. B 2012, 86, 235207.
Honig, R. E. Kramer, D. A. RCA Review, 1969, 30, 285305.
Villars, P. Pauling File Binaries Edition 2002, MPDS and
Crystal Impact.
Sekine, T.; Izumi, M.; Nakashizu, T.; Uchinokura, K.; Matsuura,
E. J. Phys. Soc. Jpn. 1980, 49, 10691077.
Zhang, X.; Han, W. P.; Wu, J. B.; Milana, S.; Lu, Y.; Li, Q. Q.;
Ferrari, A. C.; Tan, P. H. Phys. Rev. B 2013, 87, 115413.
Holy, J. A.; Woo, K. C.; Klein, M. V.; Brown, F. C. Phys. Rev. B
1977, 16, 36283637.
Naito, M.; Tanaka, S. J. Phys. Soc. Jpn. 1982, 51, 219227.
Sorgel, T.; Nuss, J.; Wedig, U.; Kremer, R. K.; Jansen, M. Mater.
Res. Bull. 2006, 41, 9871000.
Mandal, K. C.; Savadogo, O. Jpn. J. Appl. Phys. 1991, 30, 34843487.
Wagner, K. E.; Morosan, E.; Hor, Y. S.; Tao, J.; Zhu, Y.; Sanders,
T.; McQueen, T. M.; Zandbergen, H. W.; Williams, A. J.; West,
D. V.; Cava, R. J. Phys. Rev. B 2008, 78, 104520.
Revolinsky, E.; Beerntsen, D. J. Appl. Phys. 1964, 35,
20862089.
Vellinga, M. B.; de Jonge, R.; Haas, C. J. Solid State Chem. 1970,
2, 299302.
Hughes, H. P.; Friend, R. H. J. Phys. C: Solid State Phys. 1978,
11, L103L105.
Ding, Y.; Wang, Y.; Ni, J.; Shi, L.; Shi, S.; Tang, W. Phys. B
2011, 406, 22542260.
Dunnill, C. W.; Edwards, H. K.; Brown, P. D.; Gregory, D.
H.Angew. Chem., Int. Ed. 2006, 45, 70607063.
Dunnill, C. W.; MacLaren, I.; Gregory, D. H. Nanoscale 2010, 2,
9097.
Kidd, T. E.; OShea, A.; Griffith, Z.; Leslie, S.; Shand, P. M.;
Boyle, K. R.; Strauss, L. H. J. Nanopart. Res. 2012, 14, 903.
Wagner, R. S.; Ellis, W. C. Appl. Phys. Lett. 1964, 4, 8990.
Choi, H.-J. In Semiconductor Nanostructures for Optoelectronic
Devices; Yi, G.-C., Ed.; Springer-Verlag: 2012, pp 137.
Shi, W. S.; Peng, H. Y.; Zheng, Y. F.; Wang, N.; Shang, N. G.;
Pan, Z. W.; Lee, C. S.; Lee, S. T. Adv. Mater. 2000, 12,
13431345.
Seo, W.-S.; Koumoto, K. J. Am. Ceram. Soc. 1996, 79,
17771782.
Zhang, Y.; Wang, N.; Gao, S.; He, R.; Miao, S.; Liu, J.; Zhu, J.;
Zhang, X. Chem. Mater. 2002, 14, 35643568.
He, R.; Law, M.; Fan, R.; Kim, F.; Yang, P. Nano Lett. 2002, 2,
11091112.
(49) A Ubaldini, J Jacimovic, N Ubrig, and E Giannini, Crystal
Growth & Design,2013

3582
IJRITCC |November 2014, Available @ http://www.ijritcc.org

_______________________________________________________________________________________