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ELSEVIER Thin Solid Films 280 (1996) 86-89

Electrochemical deposition of MoS2 thin films by reduction of

tetrathiomolybdate
E.A. Ponomarev ~ ", M. Neumann-Spallart ~, G. Hodes b, C. L~vy-el6ment "'*
a Laboratoire de Physique des Solides de Bellevue, CNRS, UPR 1332, 1 Place Aristide Briand, 92195 Meudon, France
b Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot 76100, Israel
Received 6 June 1995; accepted 20 October 1995

Abstract

Molybdenum sulphide was cathodically electrodeposited from aqueous solutions of sodium tetrathiomolybdate. The as-deposited films
were X-ray amorphous with a composition, measured by microprobe analysis, close to MoS2. Annealing these films in Ar resulted in highly-
textured films of MoS2 with the van der Waals planes parallel to the substrate. A small expansion in the c spacing of the annealed films was
explained by the presence of oxygen in the crystals. A direct bandgap of 1.78 eV was found for the annealed films.

Keywords: Electrochemistry;Semiconductors;Molybdenumdisulphide; Depositionprocess

1. Introduction
Molybdenum dichalcogenides appear to be very promising
semiconductor materials for various applications such as
solar cells [1,2], rechargeable batteries [3] and solid lubri-
cants [4 ]. These applications arise from the optical, electro-
chemical and mechanical properties of these compounds.
They exhibit a layer-type structure in which monolayers of
Mo are sandwiched between monolayers of sulphur or sele-
nium, which are held together by relatively weak van der
Waals forces. These materials have bandgaps well-matched
to the solar spectrum. The gaps are derived from non-bonding
molecular orbitals which leads to high corrosion resistance.
Despite all these promising characteristics, the wide use of
molybdenum dichalcogenides in op~.oelectronic devices is
held back by the difficulty in preparing thin films of these
compounds with the desired properties. With the exception
of (electro)catalytic applications, most projected uses of
these compounds require films with the basal plane parallel
to the substrate, while most deposition methods result in films
with the basal plane perpendicular, to a greater or lesser
extent, to the substrate. Electrochemical deposition (ED) has
been widely used to deposit semiconductors. However only
a few papers have appeared describing ED of transition metal
chalcogenide compounds. Deposition from high-temperature
" Correspondingauthor.
On leave from: Institute of Energy Problems of Chendcal Physics
(Branch), 142432Chernogolovka,Moscow region. Russia.
0040-6090/961515.00 © 1996 Elsevier Science S.A. All tights reserved
55Di 0040.6090 ( 95 ) 08204- 2
molten salts has been shown to give large, well-defined crys-
tals of these compounds (see Ref. [ 5 ] and references cited
therein), but is clearly not a convenient method. Electrolysis
of aqueous solutions of molybdates (tungstates) and SeO2
resulted in poorly-defined mixtures of Mo(W) and Se com-
pounds [ 6,7]. The most promising method is cathodic reduc-
tion of an aqueous solution of ammonium tetrathiomolybdate
((NH,02MoS4) [8] (anodic oxidation of the same solution
results in amorphous MoS3 [9,10] ).
In this communication we report preliminary results on the
chemical composition, structural and optical properties of
films obtained by cathodic electrodeposition from thiomo-
lybdate solutions and on the change in these properties after
annealing the films. In particular, we show that highly-tex-
tured films of MoSs with the basal planes parallel to the
substrate can be obtained by this technique.
2. Experimental
The deposition was performed on Mo foil and conducting
glass (F-doped SnO2, 10 [I/D). The substrates were cleaned
in trichloroethylene, acetone and then rinsed with water. Just
before electrodeposition, the glass slides were dipped for a
few seconds into sulphochromic acid and rinsed with water.
This treatment increases the adhesion of the electrodeposited
layers to the substrate and allows deposition of thicker layers
before they start to peel off. Electrodeposition was carried
 E.A. Ponomarev et al. /Thbz Solid Films 280 (1996) 86--89
out under potentiostatic conditions using a standard three-
electrode set-up. We used a standard calomel electrode
(SCE), against which all potentials are reported, and a plat-
inum wire as a counter electrode. The solvent was Milli-Q
water. Analytical grade chemicals were used as received. The
solutions were stirred during deposition. Electron probe
microanalysis (EPMA) was performed using a CAMEBAX
instrument. The crystallographic parameters of the deposited
films were studied with a Philips PW 1710 X-ray diffracto-
meter using Cu Ka radiation. Optical absorption of the films
deposited on conductive glass was calculated from transmis-
sion spectra measured with a Cary 2400 spectrometer with
correction for reflection losses. Thickness of the deposited
layers was measured with a Tencor P-I long scan profiler
(Tencor Instruments). For scanning electron microscopy
(SEM), a Jeol JSM-840 microscope was used.
3. Results and discussion
Attempts to electrodeposit MoS2 in a way somewhat sim-
ilar to that used for MoSe2 [6] from solutions of molybdate
and thiosulphate under various conditions of pH and temper-
atur:~ were unsuccessful. However, electrolytic reduction of
molybda'te itself can be easily carded out in aqueous solu-
tions. In alkaline solutions, the resulting film has been shown
to be amorphous with a composition of MoO2_,(OH)2,
[ 11 ]. We found that reduction of MoO42- at a potential of
- 1.3 V resulted in formation of a brown film which was X-
ray amorphous. Annealing this film at ~50 0(2 in Ar for 1 h
gave crystalline MOO2. If we designate the as-deposited film
as MOO:,, the above reduction can be given as:
MoO 2- + 2e- + 2H20 ~ MoO2 + 4OH-
By analogy, we expect the electrolytic reduction of the
tetrathiomolybdate ion (MoS 2- ) to proceed as follows:
MoS~- + 2e- + 2H20 ~ MoS2 + 2SH- + 2OH-
as these ions have a similar structure to that of MoO~- with
the oxygen atoms replaced by sulphur.
Tetrathiomolybdate ions can be formed by dissociation of
ammonium tetrathiomolybdate which is commercially avail-
able or can also be readily prepared by reaction between
molybdate and hydrogen sulphide (or sulphide ions at a suf-
ficiently low pH) as follows:
MoO24- + 4H2S ** MoS~- + 4H20
In our experiments, we used mainly solutions of freshly-
prepared tetrathiomolybdate formed in a chemical reaction in
a solution of 5 mM Na2MoO4 and excess Na2S in Milli-Q
water. Hydrochloric acid was added to the stirred solution
until a pH of 8.0 was reaC~ed. The solution turned to dark
red as thiomolybdate was formed.
The chemical composition, X-ray diffraction (XRD) pat-
tern and optical spectra of the films deposited from ammo-
nium tetrathiomolybdate and from solutions where the
87
1 . 5 .... , t ,
I
s
I .~ •
t
r~
1.0 ,'
I::i
0
.,.-i •
,,"
@
.~
'o
0.5 ¥'~°
lid
@
pw
0.0 ''
0 1
'
2 3
'
4
charge, C/era 2
Fig. I. The dependence of the thickness of the layeron the charge passed
through the cellduring the deposition.
tetrathiomolybdate was formed by a reaction between mol-
ybdate and sulphide ions were identical.
Electrodeposition starts at - 0 . 9 V, reaches a maximum
efficiency of about 30% in the region of - 1.2 V to - 1.4 V
and gradually decreases at more negative potentials due to
hydrogen evolution. Deposition time was varied from 30 s to
20 rain which resulted in layers of different thickness. During
electrodeposition, smooth brown layers were formed at the
electrodes. When their thickness exceeded 1.5--2 p,m, the
layers started to peel off from the substrate. After drying, a
network of cracks appeared in films thicker thar~ 0.5 p.m.
The dependence of the film thickness on the charge passed
during deposition at a constant potential of - 1.4 V giving a
current density of ca. 2 mA cm-2 at room temperature is
shown in Fig. 1. The thickness increases linearly with charge
and a current efficiency of ca. 30% can be calculated assum-
(l)
ing a two-electron transfer as in Eq. (2) and formation of
MoS2 with bulk density. For thick films, the current efficiency
drops to ca. 15% (not shown in Fig. I ).
In contrast to the results of Byker and Austin [8], who
(2) apparently found their films to give an XRD pattern charac-
teristic of MoS2, our films were X-ray amorphous as depos-
ited (also when deposited at 95 °C). Very little detail was
given in the short abstract of Byker and Austin, but the dif-
ference could possibly be due to the different substrate (Pb)
used by them. EPMA analysis of our films gave a S:Mo
atomic ratio of between 1.9 and 2.1.
Annealing the films at 550 °C in Ar for 1 h resulted in a
major change in all the measured properties. The brown col-
(3) our of the as-deposited films changed to a reflecting metallic
surface typical of MoS2. For films thicker than ca. 0.1 p.m,
cracks formed after annealing (Fig. 2(a)) which were not
present in the as-deposited films. Higher magnification SEM
showed the annealed film to be comprised of closely packed
grains of a few hundred nanometres in size (Fig. 2(b) ). The
as-deposited films were featureless with no visible grain
structure. The S:Mo ratio decreased by 15-20% and the film
thickness decreased by 30--50% after annealing. While some
of the thickness decrease could probably be attributed to
88 E.A. Ponomarev et al. / Thin Solid Films 280 (1996) 86--89

counts/-,

5000

4000

3000

2000

1000 i

0 . . . . A. . . . J~
0 20 30 40 50 60 70
d e g r e e . 28
Fig. 4. XRD pattern of a MoS2 fihn deposited on molybdenum foil. The film
was annealed for 9 h at 880 °C in Ar.

evidence of any edge peaks, usually observed in films of these

materials, is seen. The films are highly textured with the basal
(van der Waals) planes parallel to the substrate. This property
is of particular importance where such films are to be used
for either photovoltaic cells or for their tribological charac-
teristics. This high degree of texture is preserved for all films,
independent of their thickness. The crystal size can be esti-
mated from the peak widths to be about 25 . m (this assumes
crystal size broadening; another possibility is the presence of
Fig. 2. SEM picture of the electrochemically deposited MoS2 film on con-
ductive glass annealed for ! h at 550 *C in Ar: (a) low magnification; (b)
MoO,,S2 with a range of different values of x, see below).
high magnification. The c lattice constant, measured from the XRD data, is in
the range 12.36--12.70/~. This value is slightly higher than
the literature value of 12.298/~, [ 12]. The increase in the c
o0unt./0
, _ SnO e value of sputtered films of MoS2 has been attributed to elec-
04 tronic effects caused by the presence of oxygen, either sub-
2500 0
0
stituted for sulphur [ 13] or in addition to sulphur [ 14]. For
oxygen-substituted films, MoS2_=O~,. (Fig. 4 in Ref. [ 13] )
2000
translated into a range of x from 0.001-0.01 for our films.
For the MoOxS2 films described in Ref. [14], this would
1500 result in a range of compositions for our films from MoOo.:S2
to MOOo.6S 2.
1000 Neither of the above possibilities would, by themselves,
explain the decrease in S:Mo ratio we find after annealing.
500 Preliminary X-ray photoelectron spectroscopy (XPS) anal-
~ _ °_ * co*2 " ~° | ~'* * i yses show a considerable amount of oxygen in the films which
does not decrease after sputter etching of the films. More
20 30 40 50 60 70 importantly, XPS reveals the presence of appreciable
degree, 20 amounts of Mo (in both as-deposited and annealed films) in
Fig. 3. XRD pattern ofa MoS2 film deposited on conduclve glass. The film a higher oxidation state equivalent to MoO3 (or MoS3; the
was annealed for I h at 550 *C in At. latter, however, is unstable at the temperatures used in anneal-
ing). This suggests that our films, in particular the annealed
increasing density and compactness of the films, the change ones, contain some MoO3_x (see also below), which would
in composition suggests some material loss by evaporation. explain the values of S:Mo less than two. The presence of
The most important change after annealing was the for- oxygen in the films can be understood by consideration of
mation of a well-developed XRD pattern (Fig. 3 and Fig. 4). equilibrium (3). Some MoO42- can be expected to exist
The most intense peak corresponds to the (002) plane and together with MoS 2-, resulting in the formation of a Mo-O
all the other peaks to the (~04), (006) and (008) planes. No species (or a mixed Mo-O-S compound). Adsorption of
 F,.A. Ponomarev et al. / Thin Solid Films 280 (1996) 86--89
OD," ~;a
" o 30 . a
\,
3 20 P-"
/ 1°
2
"...........,.....11.6
0 -----1-- :,_~
1.8
1
400
I
600 800
I i
I000 k, n m
Fig. 5. Absorption spectra of a MoS 2 thin film: curve 1, as deposited, thick-
ness 1.3 p,m; curve 2, after annealing for 1 h at 550 °C in Ar, thickness 1
p,m.
water from the electrolyte on ~he growing film is another
possibility for the presence of oxygen.
The optical absorption spectra of the as-deposited and
annealed films are shown in Fig. 5. As-deposited films show
a gradual increase of the optical density (OD) with increasing
photon energy, hr. After annealing the optical density of the
film increases sharply between 1.6 and 2.0 eV and remains
almost constant afterwards. A plot of (OD.hv) 2 vs. (hv)
gave a value of 1.78 eV for the direct bandgap (Fig. 5), in
agreement with literature data [ 15].
While thin annealed films appear brown by transmitted
light, they are visually transparent, i.e. there is little scattering,
which would degrade the transmission, even in the sub-band-
gap region where no absorption should occur. Since the
absorption spectra show appreciable absorption in the sub-
gap region, there must be absorption in this region by some
impurity. As noted above, films deposited from sulphur-free
molybdate solutions and annealed under the same conditions
as the M o S 2 films form M o O 2 (possibly with some MOO3)
which were found to absorb strongly in this low energy
region. This absorption provides further support for the pres-
ence of MoO3_x (where x < l ) in the films. This absorption
precludes measurement of the indirect gap of the M o S 2 ( a t
ca. 1.3 eV [ 15] ) which would be distorted, if not altogether
swamped, by the MoO3_x absorption.
4. Conclusions
Films containing Mo and S in an approximately 1:2 atomic
ratio have been cathodically electrodeposited from thiomo-
89
lybdate solutions. The as-deposited films are X-ray amor-
/ phous. Annealing in argon results in highly textured,
polycrystalline MoS2 with the basal planes parallel to the
substrate. The annealed film ~ h,ve an optical spectrum char-
acteristic of MoS2, with a d~r~ct bandgap of 1.78 eV. The
spectrum of as-deposited films is very different with no clear
eV
absorption onset. Both the as-deposited and annealed films
contain appreciable amounts of oxygen. These films may be
useful for both solar cell and lubrication applications, where
the high degree of basal plane texture is very important.
Acknowledgements
The authors are grateful to M. Rommeluere for the electron
microprobe analysis and to C. Vard for electron microscope
images of the films.
This work was supported by a CEE contract JOU2-CT93-
0352. We acknowledge the Minist~re des Affaires Etrang~res
(France) and the Israeli Ministry of Science and Arts fo,
support through an Arc en Ciel (Keshet) project.
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