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Materials Chemistry and Physics 117 (2009) 350–354

Contents lists available at ScienceDirect

Materials Chemistry and Physics

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

Growth and transport property measurements of rhenium doped tungsten

diselenide single crystal
M.P. Deshpande ∗ , J.B. Patel, Nilesh N. Pandya, M.N. Parmar, G.K. Solanki
Department of Physics, Sardar Patel University, Vallabh Vidyanagar, 388 120, Gujarat, India

a r t i c l e i n f o a b s t r a c t

Article history: Single crystals of rhenium doped tungsten diselenide i.e. Rex W1−x Se2 (x = 0, 0.0005, 0.001, 0.05, 0.1) are
Received 24 May 2008 grown by vapour phase technique. The stoichiometry of grown single crystals is confirmed by energy
Received in revised form 11 May 2009 dispersive analysis of X-rays. X-ray powder diffractograms obtained of these compounds were used for
Accepted 28 May 2009
lattice parameter determination based on hexagonal system similar to that of host WSe2 .The crystallite
size for each sample for different reflection is calculated using Scherrer’s formula. Surface morphology as
PACS:
observed under optical microscope reflects that screw dislocation mechanism is responsible for growth
68.55.a
of crystals. Electrical properties viz. Hall effect at room temperature, resistivity measurements at low
68.55jk
81.10jt
temperature, and high pressure resistivity measurements indicates the semiconducting behaviour of
Rex W1−x Se2 (x = 0, 0.0005, 0.001, 0.05, 0.1) single crystals. Thermoelectric power measurements shows
Keywords: p-type nature of host WSe2 whereas n-type nature of rhenium doped WSe2 which matches with the
Semiconductors results of Hall effect.
Crystal growth © 2009 Elsevier B.V. All rights reserved.
Electrical properties
Microstructure

1. Introduction The transport properties of the host material WSe2 can be

Rex W1−x Se2 (x = 0, 0.0005, 0.001, 0.05, 0.1) single crystals are
semiconducting materials and belong to the family of transition
metal dichalcogenides [1,2]. These compounds have interest-
ing practical applications as catalyst for hydrodesulfurization in
petroleum industry [3,4], high temperature solid lubricant [5,6],
battery cathode in rechargeable lithium batteries [7–9], anode and
cathode materials in photoelectrochemical solar energy conversion
[10], and also as SQUID detector [1]. It has been observed that WSe2
(tungsten diselenide) provides an atomically flat substrate surface
for the deposition of thin organic films such as Langmuir–Blodgett
films and related systems [11]. Scanning tunneling microscopy
studies have shown that this material also possesses unique prop-
erties for nanometer scale structuring [12] and potential candidate
for application in high mobility field effect transistors [13]. Recently
WSe2 can work as a new insulation material with the lowest ther-
mal conductivity ever measured for a fully dense solid [14].
Structurally, these compounds are formed by stacking “sand-
wiches” consisting of a layer of transition metal atoms between two
layers of selenium atoms. There is strong covalent bonding within
the sandwich layers but weak van der Waals bonding between
them.
∗ Corresponding author. Tel.: +919427597979 (mobile)/2692226846x310.
E-mail address: vishwadeshpande@yahoo.co.in (M.P. Deshpande).
altered by doping or intercalation of foreign atoms/ions/molecules
in WSe2 lattice because of weak van der Waals forces existing
between layers. We report in this paper a systematic study on
growth and transport property measurements of Rex W1−x Se2 (x = 0,
0.0005, 0.001, 0.05, 0.1) single crystals.
2. Experiment
2.1. Growth by vapour phase technique
In the present work, single crystals of Rex W1−x Se2 (x = 0, 0.0005,
0.001, 0.05, 0.1) are grown by vapour phase technique. The elements
used for the growth are having the purity of 99.99% (tungsten,
selenium and rhenium metals). The total charge used in each exper-
iment is about 10 g. For compound preparation in polycrystalline
form, the quartz ampoule in which these elements were placed was
evacuated and sealed at a pressure of 10−5 Torr and then shaken
well for proper mixing of the powder. This ampoule is then placed
in the two-zone horizontal furnace having a linear temperature gra-
dient with the powder distributed along the length of the ampoule.
Furnace temperature is increased in steps of 50 ◦ C from room tem-
perature to a final temperature of 800 ◦ C. After heating period of 3
days, the furnace power is switched off and ampoule is allowed to
cool down to room temperature.
Taking the polycrystalline compound prepared as above of
Rex W1−x Se2 the growth of single crystals is proceeded in quartz

0254-0584/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2009.05.058
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M.P. Deshpande et al. / Materials Chemistry and Physics 117 (2009) 350–354 351

Table 1
Values of Hall coefficient (RH ), carrier concentration, resistivity () and mobility () for Rex W1−x Se2 (x = 0, 0.0005, 0.001, 0.05, 0.1) single crystals.

Sample Hall coefficient RH (cm3 C−1 ) Carrier concentration (cm−3 ) Resistivity  ( cm) Mobility  (cm2 V−1 S−1 ) Type

WSe2 1398.28 4.462 × 10 15

5.55 251.8 p
Re0.0005 W0.9995 Se2 −65.27 9.562 × 1016 2.95 22.2 n
Re0.001 W0.9990 Se2 −138.61 4.503 × 1016 4.22 32.9 n
Re0.05 W0.95 Se2 −43.68 3.875 × 1017 0.63 14.9 n
Re0.1 W0.9 Se2 −5.73 1.098 × 1018 0.37 15.6 n

ampoules evacuated to 10−5 torr respectively. The ampoule is kept
into a two-zone horizontal temperature gradient furnace in which
higher temperature zone of the furnace is maintained at 1080 ◦ C
while the lower temperature zone is kept at 1060 ◦ C. The tempera-
ture of the furnace is increased slowly at the rate of 50 ◦ C h−1 till it
attains the required temperature and is kept in the furnace for 10
days. The furnace is then allowed to cool down slowly to room tem-
perature resulting in growth of large number of crystals at the cooler
end of the ampoule. All these crystals are black, opaque and plate-
like. The same growth conditions are repeated for all composition
of Rex W1−x Se2 single crystals.
2.2. Structural characterization
technique. Fig. 2 shows a plot of resistivity versus reciprocal of
temperature for all these samples. In all cases, it is observed that
resistivity decreases with increase in temperature and from the lin-
ear region in the plots the corresponding activation energies are
determined and displayed in Table 2.
2.6. Thermoelectric power measurement
Thermoelectric power measurements on Rex W1−x Se2 single
crystals are carried out in the temperature range of 300–420 K. The
Seebeck coefficient is found to be positive for WSe2 whereas neg-
ative in rhenium doped samples of WSe2 and supports our Hall
measurement results and also matches with [18].

Before studying the transport properties of Rex W1−x Se2 single

crystals the stoichiometry of the grown crystals is confirmed by
energy dispersive analysis of X-rays. The values of lattice param-
eters calculated from X-ray diffractograms lie between a = 3.28 Å
and c = 12.95 Å for each of these compounds. Rhenium doped and
undoped tungsten diselenide samples are showing particle sizes
varying between 150 Å and 880 Å for different reflections as calcu-
lated using Scherrer’s formula [15].

2.3. Microstructural study

The topographical study of as-grown Rex W1−x Se2 single crystals

is carried by optical microscope (Axiotech Model) purchased from
Carl Zeiss, Japan. All samples exhibit the presence of spiral on their
as-grown faces which are hexagonal in shape originating from a
single screw dislocation. The parameters of these spirals were mea-
sured and the critical size of nucleus, and degree of polygonisation
are determined. Fig. 1(a and b) shows a pattern of a hexagonal spiral
for undoped and Re doped WSe2 single crystals, respectively. Calcu-
lations regarding the degree of polygonisation [16] are made from a
ratio of the radius of curvature R of a growth front to its distance D
from the centre of the spiral. The degree of polygonisation obtained
is 0.5.
The size of critical nucleus is determined by [17] and is equal to
be 3.058 ␮m.

2.4. Hall effect measurement

Hall effect measurement (at 300 K) on these samples is carried

out by using sophisticated instrument purchased form “Lakeshore”,
USA. Prior to this measurement, I–V characteristics for each contact
(here R12–12 is the resistance between contacts 1 and 2 and R34–34 is
the resistance between contacts 3 and 4) have been verified which
clearly indicates the ohmic behaviour of contacts. Then the Hall
measurements at different magnetic field with constant current are
carried out on all Rex W1−x Se2 single crystals and the parameters
obtained are shown in Table 1.

2.5. Resistivity measurements

Resistivity measurements are carried out on Rex W1−x Se2 sin- Fig. 1. (a) A pattern of a hexagonal spiral for WSe2 single crystal. (b) A pattern of a
gle crystals in the temperature range of 80–300 K by four probe hexagonal spiral for Re doped WSe2 single crystal.
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352 M.P. Deshpande et al. / Materials Chemistry and Physics 117 (2009) 350–354

Fig. 2. Plot of conductivity versus reciprocal of temperature for Rex W1−x Se2 (x = 0,
0.0005, 0.001, 0.05, 0.1) single crystals.

To study the temperature dependence of thermoelectric power

of a p-type/n-type semiconductor, the expression by Perluzzo et al.
[19] is used.
k
  E 
F
S=± A+ (1) Fig. 3. Variation of Seebeck coefficient with inverse of temperature for WSe2 single
e kT crystals.

where ‘k’ is the Boltzmann constant, e is the electronic charge, A is a

constant determined by the dominant scattering process and EF is
the separation of the fermi level from the top of the valence band. with four lead arrangements to measure electrical resistance of the
‘S’ is the Seebeck coefficient. samples under high pressure is used.
For a small temperature range, if ‘S’ is plotted against the recipro- The resistance is measured on many independent runs on all the
cal of temperature (T−1 ), a straight line is expected. To know about samples of Rex W1−x Se2 single crystals as a function of pressure. The
the nature of scattering we determined the constant A from the plot of log R vs. log P is shown in Fig. 5 for these samples.
intercept of this straight line.
Figs. 3 and 4 show the variation of Seebeck coefficient with
inverse of temperature for WSe2 and Rex W1−x Se2 single crystals
respectively. The values of ‘A’ and scattering parameter ‘s’ obtained
from the intercept of the plots are listed in Table 3.

2.7. High pressure measurements

A tungsten carbide opposed anvil set-up [20] with pyrophyllite

gasket and talc or silver chloride pressure transmitting medium is
used for high pressure studies upto 8 GPa. Bridgman anvil set-up

Table 2
Values of activation energy (eV) determined for Rex W1 −x Se2 (x = 0,
0.0005, 0.001, 0.05, 0.1) single crystals.

Sample Activation energy (eV)

WSe2 0.027
Re0.0005 W0.9995 Se2 0.031
Re0.001 W0.9990 Se2 0.032
Re0.05 W0.95 Se2 0.036
Re0.1 W0.9 Se2 0.047

Table 3
Values of constant (A) and scattering parameter (s) of Rex W1 −x Se2 (x = 0, 0.0005,
0.001, 0.05, 0.1) single crystals.

Sample A s = (5/2) − A

WSe2 0.21 2.48

Re0.0005 W0.9995 Se2 3.13 0.63
Re0.001 W0.9990 Se2 2.32 0.18
Re0.05 W0.95 Se2 9.28 6.78
Fig. 4. Variation of Seebeck coefficient with inverse of temperature for Rex W1−x Se2
Re0.1 W0.9 Se2 8.35 5.85
(x = 0.0005, 0.001, 0.05, 0.1) single crystals.
 Author's personal copy
M.P. Deshpande et al. / Materials Chemistry and Physics 117 (2009) 350–354
Fig. 5. Plot of log R vs. log P for Rex W1−x Se2 (x = 0, 0.0005, 0.001, 0.05, 0.1) single
crystals.
3. Discussion
Energy dispersive analysis of X-rays confirms the stoichiome-
try of rhenium doped tungsten diselenide crystals. X-ray powder
diffractograms of compounds were analyzed to determine lattice
parameters ‘a’ and ‘c’. Due to low concentration of rhenium signif-
icant amount of changes in lattice parameters are not observed in
the present work.
Fig. 1 shows a hexagonal spiral seen on the as-grown face of these
samples, which originates from a single screw dislocation having
nearly regular spacing between successive arms. Since the mor-
phology of the spirals follows the symmetry of the face, basal plane
of a hexagonal crystal should show hexagonal spiral as is being
observed in our case of Rex W1−x Se2 single crystals. From this, it
may be inferred that these crystals grown by us exhibit 2H poly-
type. Further, etching can be conducted on the as-grown crystals to
reveal the formation of etch pits indicating that these crystals are
nucleated at the sites of screw dislocation.
Hall effect measurements shown in Table 1 indicate that tung-
sten diselenide is p-type in nature while addition of rhenium in
it converts the material to n-type. But as reported in [9] undoped
WSe2 and rhenium doped WSe2 both are n-type in nature which
differs from our result. The reason for this might be that [9] have
used Br2 as transporting agent for the growth of these samples
353
whereas we have not added any transporting agent for the growth.
Similar kind of observations with different dopants in tungsten
diselenide has been reported [21–24]. As reported in [15] that
besides changing the material from p-type to n-type the values
of carrier concentration increases whereas the mobility decreases
with substitutional doping or intercalation. Thus our results have a
close resemblance with the above-observed results. The decrease
in mobility may be attributed due to the presence of more defects
in rhenium doped tungsten diselenide and increase in carrier con-
centration may be due to the donation of more electrons to the host
material.
As shown in Fig. 2 it appears that conductivity for all samples
increases with increase in temperature showing the typical semi-
conducting behaviour and from the region of straight lines the
slopes are being determined which gives the activation energy.
The values of activation energies as determined for all the sam-
ples are listed in Table 2 respectively. For n-type Rex W1−x Se2 the
donor levels lies between 0.031 and 0.047 eV below the conduc-
tion band which means that the electron from a donor atom can
be transferred to the conduction band by simply ionizing the donor
atom at the expense of only 31–47 meV which is very small and
also indicates that the conductivity of n-type semiconductor is
several orders higher than the intrinsic materials whereas for p-
type WSe2 the acceptor levels lies 0.027 eV above the valence band
edge and is again very small as compared to the size of Eg (band
gap).
The variation of Seebeck coefficient as a function of temperature
as shown in Figs. 3 and 4 shows the semiconducting behaviour of
these material and henceforth also supports the results of Hall effect
and resistivity measurements. From the respective plots shown in
Figs. 3 and 4 the values of constant A and scattering parameter ‘s’
are obtained and listed in Table 3.
As seen from Table 3, the constant A determined has values
below 4 for three samples, i.e. WSe2 , Re0.0005 WSe2 and Re0.001 WSe2
indicating that charge impurity scattering is dominant whereas
for Re0.05 WSe2 and Re0.1 WSe2 the values of A obtained are nearly
equivalent to 9 which are higher values then the other three sam-
ples.
High pressure measurements on Rex W1−x Se2 single crystals
reveals that the resistance decreases monotonously with increase
in pressure for all the samples. When a graph of log R vs. log P is
plotted as shown in Fig. 5, it shows a straight line with slope vary-
ing from 0.5 to 1.67 as shown in Fig. 5 and their values are shown
in Table 4.
From Table 4, it appears that with increasing concentration of
rhenium in WSe2 the slope also increases. In the case of high con-
centration of impurity, impurity band is likely to be formed in the
place of stabilized impurity level only. The density of electronic
states follows the density of states of phonons when there is strong
electron phonon coupling. The phonon density of states is given
by
D(ω) = Aω2 (2)
Table 4
Values of slopes obtained from the graph of log R vs.
log P for Rex W1−x Se2 (x = 0, 0.0005, 0.001, 0.05, 0.1)
single crystals.
Sample Slope
WSe2 0.494
Re0.0005 W0.9995 Se2 0.643
Re0.001 W0.9990 Se2 1.142
Re0.05 W0.95 Se2 1.657
Re0.1 W0.9 Se2 1.670
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354 M.P. Deshpande et al. / Materials Chemistry and Physics 117 (2009) 350–354

within the Debye approximation, where A is constant and ω is Acknowledgements

phonon frequency.
The electrical conductivity is proportional to the carrier concen- Authors are thankful to UGC for granting UGC project to us as
tration, which is in turn proportional to the density of states. The well as DRS/SAP programme to the department, which helped sub-
total number of filled states is given by stantially to carry out this work.

A ω3
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