Thin Solid Films 361±362 (2000) 223±228

www.elsevier.com/locate/tsf

In¯uence of the electrochemical deposition parameters on the

microstructure of MoS2 thin ®lms
A. Albu-Yaron a, b, C. LeÂvy-CleÂment a,*, A. Katty a, S. Bastide a, R. Tenne c
a
LCMTR, CNRS UPR 209, 2±8 Rue Henri Dunant, 94230 Thiais, France
b
ARO, Volcani Center, 50250 Bet Dagan, Israel
c
Department of Materials and Interfaces, Weizmann Institute of Science, 76100 Rehovot, Israel

Abstract
Thin ®lms molybdenum dichalcogenide, MoS2, were prepared by cathodic electrochemical deposition from aqueous and non-aqueous
solutions of tetrathiomolybdate ions, at different temperatures. The ®lms were X-ray amorphous as deposited. They consist of an amorphous
matrix in which quantum sized nanocrystallites or clusters were embedded. Upon annealing at high temperatures, the ®lms obtained from
aqueous solutions become crystalline and highly texturized having their van der Waals planes oriented parallel to the substrate, whereas,
those obtained from ethylene glycol solutions kept on the amorphous matrix, with slightly larger sizes MoS2 nanoparticles embedded, than
before annealing. Difference in the mechanism of the electrodeposition in aqueous and ethylene glycol solutions is discussed. q 2000
Elsevier Science S.A. All rights reserved.
Keywords: Electrodeposition; Transition metal dichalcogenide; Thin ®lms; Aqueous solution; Ethylene glycol; Microstructure

1. Introduction of the substrate on the recrystallization process after anneal-

Thin ®lms semiconducting layered molybdenum dichal-
cogenide, MoS2, are very attractive for numerous applica-
tions, which include solar cells [1], catalysis, solid
lubricants and intercalation batteries. Depending on the
type of application, the requirements for the size and orien-
tation of the crystals composing the ®lms are diverse. For
photovoltaic applications, thin ®lms constituted of large
crystals, in the micrometer range, and with their van der
Waals (vdW) planes (i.e. (0002) 2H-MoS2 basal planes)
oriented parallel to the substrate (type II texture) are
required. In contrast, for catalytic applications, thin ®lms
made up of nanometer size particles, with their vdW planes
oriented perpendicular to the substrate (type I texture), are
desirable.
The preparation of MoS2 by electrochemical deposition
has recently received much attention [2±7] as this technique
may provide the ®lm uniformity and coverage required for
large scale photovoltaic technology. This paper presents a
study of the in¯uence of the electrodeposition parameters on
the microstructure of the MoS2 thin ®lms and the in¯uence
* Corresponding author. Tel.: 133-1-49-781-331; fax: 133-1-49-781-
203.
E-mail address: levy-clement@glut-cnrs.fr (C. LeÂvy-CleÂment)
0040-6090/00/$ - see front matter q 2000 Elsevier Science S.A. All rights reserved.
PII: S 0040-609 0(99)00838-X
ing the ®lms at high temperatures.
2. Experimental
Deposition of MoS2 thin ®lms was carried out by a two-
electron reduction of tetrathiomolybdate ions (MoS422)
following the reaction
MoS22 2 1
4 1 2 e 1 4 H ) MoS2 1 2 H2 S 1†
Two electrolytes were used: water and ethylene glycol.
The tetrathiomolybdate was 0.005 M. Potassium chloride
(0.1 M) was the supporting electrolyte in all solvents.
Ammonium chloride (0.57 M) was supplemented as a
proton donor, when the electrodepositon was from ethylene
glycol. Electrodeposition was carried out at room tempera-
ture for both solvents, at 988C in aqueous solutions and at
1658C in ethylene glycol. The substrates were conductive
glass (F-doped SnO2, 10 V/A). Few experiments were done
using molybdenum and Ni±Cr coated conductive quartz
when annealing of the deposited ®lms was performed at
higher temperatures ($9008C). A three electrode set up
was used. Details of the electrodeposition have been
presented elsewhere [3,4].
Electron probe microanalysis (EPMA) was carried out
with a CAMEBAX instrument. A Philips PW 1710 X-ray
224 A. Albu-Yaron et al. / Thin Solid Films 361±362 (2000) 223±228

diffractometer (Cu Ka ) was used. Optical absorption of the

®lms deposited on conductive glass and quartz was calcu-
lated from transmission spectra measured with a Cary 2400
spectrometer. Scanning electron microscopy (SEM) was
done with a JEOL JSM-840 microscope. Conventional
medium resolution transmission electron microscopy
(TEM) and selected area (SAD) electron diffraction were
performed using a Philips 400T electron microscope (120
kV), and high resolution (HREM), with a JEOL 4000EX(II)
microscope (400 kV).

3. Results

Details of sample preparation and annealing are summar-

ized in Table 1. During electrodeposition, brown smooth
layers were formed at the electrodes. When their thickness
exceeded 1.5±2 mm, the layers started to peel off from the
substrate.

3.1. As deposited MoS2 thin ®lms (samples 1±4): in¯uence of

the solvent and temperature

SEM micrographs reveal that the ®lms deposited at room
temperature are fairly continuous without visible cracks.
When obtained at higher temperatures (988C in water and
1658C in ethylene glycol), cracks appear indicating occur-
rence of stress. All the as electrodeposited ®lms are X-ray
amorphous whatever is the deposition temperature. They
exhibit an atomic ratio S/Mo between 1.9 and 2.1
(EPMA) and display a gradual increase of the optical
density towards increasing photon energy, in their absorp-
tion spectra (Fig. 1, curve (a,c). The featureless curves are
typical of amorphous materials [3,6].
The TEM image in Fig. 2a shows that the ®lms deposited
from aqueous solutions on conductive glass at 208C (sample
1) are composed of very thin, small MoS2 clusters of various
lengths, embedded in an amorphous material. Most of the
clusters exhibit three to ten stacks of individual S-Mo-S
Fig. 1. Absorption spectra of a MoS2 thin ®lms: deposited at 208C from
aqueous solution (a) as deposited (1.3 mm thick) and (b) annealed at 5508C
(1 mm thick); deposited from ethylene glycol solution (c) as deposited at
1658C (sample 4) and (d) annealed at 5508C (sample 9).
sheets (2±6 nm thick and 8±25 nm long). The separation
of 0.6 nm between the S-Mo-S sheets corresponds well
with the 0.615 nm spacing of the (0002) vdW basal planes
in 2H-MoS2 structure. The nanocrystallites lie roughly
perpendicular ((0002) planes ') to the substrate surface,
indicating type I texture. The MoS2 particles in the ®lms
deposited at 988C (sample 2) exhibit shorter, slightly bent
(0002) lattice planes, 2±7 sheets thick, embedded in an
amorphous matrix, and quite frequently displaying some
dislocations (Fig. 2b).
Fig. 3a shows that the MoS2 ®lms deposited from ethy-

Table 1
Specimen data a

Samples Deposition conditions Annealing conditions

E (V) Q (C/cm 2) t (s) T (8C) d (nm) Medium Substrate T (8C) t (h) Gas

As-deposited

1 21.2 0.41 318 20 155 A CG

2 21.2 0.80 221 98 A CG
3 21.0 0.65 2029 20 139 EG CG
4 20.4 0.07 100 165 155 EG CG
As-deposited and annealed
5 21.2 3.08 1853 20 600 A CG 550 10 Vac
6 21.2 678 20 A Mo 900 9 Ar
7 20 A Ni±Cr/Q
8 21.0 0.88 2500 20 88 EG CG 550 1 Ar
9 20.4 0.07 100 165 93 EG CG 550 1 Ar
a
A, aqueous; EG, ethylene glycol; CG, conducting glass; Mo, molybdenum foil; Ni±Cr/Q, nickel-chromium alloy on quartz.
 A. Albu-Yaron et al. / Thin Solid Films 361±362 (2000) 223±228 225

Selected area electron diffraction patterns (insets in Figs.

2a,b and 3a,b) are typical of crystalline material of too small
dimensions to give rise to detectable X-ray diffraction
peaks. The well-de®ned rings correspond to those of hexa-
gonal 2H-MoS2 structure. The presence of the (0002) re¯ec-
tion shows that most of the crystallites have their basal
planes oriented perpendicular to the surface (edge orienta-
tion) indicating type I texture.

3.2. Annealed MoS2 thin ®lms (samples 5±9)

Annealing at high temperature (550±9008C), under argon

Fig. 2. TEM images of MoS2 thin ®lms as deposited from aqueous solution:
(a) at 208C (sample 1); (b) at 988C (sample 2). Insets are the corresponding
SA diffraction patterns.

lene glycol at 208C (sample 3) [4] are predominantly consti-

tuted of very small plate-like crystallites, 2±4-nm thick, (3±
6 stacks of individual vdW planes) of approximately same
length, and are mostly oriented with the (0002) planes
perpendicular to the substrate surface (type I texture).
Generally, lattice defects like dislocations were not
observed. HREM of MoS2 layers obtained at 1658C (sample
4) [6] (Fig. 3b) discloses the typical image of an amorphous
material embodying some single or double slightly bent
sheets ,0.6 nm apart (observed under optimum defocus
conditions), indicating the presence of rather small 0.6± Fig. 3. TEM images of MoS2 thin ®lms as deposited from ethylene glycol
1.2-nm thick 2H-MoS2 nanoparticles, approximately 8±12- solution: (a) at 208C (sample 3) and (b) at 1658C (sample 4). Insets are the
nm long. corresponding SA diffraction patterns.
226 A. Albu-Yaron et al. / Thin Solid Films 361±362 (2000) 223±228
atmosphere, for 1 to 10 h, results in a decrease in the ®lm
thickness by 30±50%, which is probably due to the fact that
MoS2 ®lms become more compact upon crystallization and/
or to some material loss by evaporation.
Those produced in aqueous medium (samples 5±7), crys-
tallize when annealed (grains of 20±100 nm or larger are
observed in TEM), irrespective of the substrate material. An
example of large, well crystallized MoS2 particles, consti-
tuting layers prepared on conducting glass substrate at 208C
and annealed at 5508C (sample 5) is shown in Fig. 4. Those
deposited on molybdenum substrate and annealed at 9008C
(sample 6) exhibit the largest crystal size (,100 nm). X-ray
diffraction (XRD) spectra reveal that the ®lms are highly
texturized (type II texture) with the vdW (0002) basal planes
oriented parallel to the substrate (Fig 5, spectrum (a)) [3].
This preferential orientation is retained for all electrodepos-
ited layers independent of their thickness.
Annealed ®lms produced in aqueous solution exhibit a
metallic lustre. The optical density in the absorption spectra
(Fig. 1, curve (b)), increases sharply between 1.6 and 2.0 eV
and remains almost constant above 2.2 eV, revealing a
direct transition, and the characteristic MoS2 band-gap of
,1.8 eV. The two peaks at 1.8 and 2.1 eV can be assigned to
the A and B excitons [8,9]. Both the as-deposited and
annealed ®lms contain appreciable amounts of oxygen [3].
Although the MoS2 crystals are formed with the desired
orientation, the ®lms are not photoactive presumably due
to the relatively small crystal size, and the consequent larger
number of dangling bonds on the non-vdW surfaces acting
as recombination centers for photogenerated carriers.
The size of the MoS2 crystals was considerably increased
when MoS2 layers were electrodeposited from aqueous
Fig. 4. TEM image of MoS2 thin ®lms deposited on conducting glass from
aqueous solution at 208C and annealed (sample 5). Inset is the correspond-
ing SA diffraction pattern.
solution, on quartz substrate coated with a thin Ni±Cr
layer, with subsequent annealing at high temperature, in a
sulfur containing atmosphere (sample 7). During annealing
(at 9508C), the sulfur reacts with the Ni, forming a relatively
low melting point (6358C) Ni-S eutectic 33 at.% of S, on
which the MoS2 crystals grow like on a liquid phase, leading
to micron size crystals (Fig. 6). The (0002) XRD Bragg peak
becomes extremely intense and narrow revealing the high
degree of crystallinity of the ®lm of type II texture (Fig. 5,
inset). The MoS2 ®lms are photoactive with a direct band
gap of about 1.7 eV (photoconductivity measurements) [5].
The TEM images of the layers produced from ethylene
glycol at 20 and 1658C and annealed at 5508C for 1 h in Ar
atmosphere (Fig. 7a (sample 8) and 7b (sample 9), respec-
tively), reveal a network of small, bent, tangled interlocking
structures consisting of 2±5 stacks of (0002) 2H-MoS2
planes, occasionally enclosing voids. Sometimes, particles
are joined with a common crystal plane or exhibit disloca-
tion-like or stacking fault-structures. In addition, although
in small numbers, heavily bent stacks comprising 3±4 MoS2
vdW planes, which de®ne rectangular or triangular nanopar-
Fig. 5. X-ray diffraction spectra of annealed MoS2 ®lms. Films deposited at
208C from aqueous solution, (a) conductive glass substrate and annealed
during 1 h at 5508C in Ar (1 mm thick), (inset) Ni±Cr/quartz substrate and
annealed 6 h at 9508C in S vapor (0.9 mm thick). Films deposited on
conductive glass from ethylene glycol solution, (b) deposited at 208C and
annealed at 5508C (sample 8), (c) deposited at 1658C and annealed at 5508C
(sample 9).
 A. Albu-Yaron et al. / Thin Solid Films 361±362 (2000) 223±228 227

in ethylene glycol, as a result of an additional chemical

reduction reaction of ethylene glycol itself acting as a redu-
cing agent [6,10]. The in¯uence of the chemical reduction
reaction is particularly important in the case of the deposi-
tion at 1658C. However, the two processes are not indepen-
dent, since otherwise complete reduction of the precursor
before electrodeposition of the ®lm would take place.
Therefore, a mixed reduction of the tetrathiomolybdate
(by ethylene glycol)-electroreduction mechanism must be
envisaged.
Annealing the as deposited layers at high temperatures
(Table 1), had a different impact on the control of their

Fig. 6. SEM picture of an electrochemical deposited MoS2 ®lm on Ni±Cr/

quartz substrate annealed for 1 h at 9508C in sulfur atmosphere (sample 7).

ticles are observed in the annealed sample prepared at 1658C

(arrowed in Fig. 7b) [6]. The respective XRD spectrum of
the layers deposited in ethylene glycol and annealed, exhi-
bits only a very broad (0002) peak, of extremely low inten-
sity (Fig. 5, spectra (b,c)), indicating very poor crystallinity
for the obtained MoS2 small particles.

4. Discussion and conclusion

A common feature of the experiments in this work is that

all the deposited ®lms when grown, were found X-ray amor-
phous, while HREM revealed them nanostructured, with
very small MoS2 nanoclusters or nanocrystallites embedded
like in an amorphous matrix. The formation of these crystal-
line embryos, densely scattered in the disordered structure,
was found to be strongly in¯uenced by the parameters of
electrodeposition process (temperature, medium and
composition, or substrate (cathode) material). At 208C,
when deposition was from aqueous solutions, ¯at, plate-
like nanocrystallites, 2±6 nm-thick and 8±25-nm long
sizes, lying roughly normal to the substrates surface, were
observed embedded in the amorphous material. While, from
ethylene glycol, quantum sized, 2±4-nm thick, smaller clus-
ters, although with much less amorphous matrix, were
obtained (Figs. 2a and 3a). Generally, at 208C deposition,
lattice defects as twins or dislocations were not observed.
An increase in the temperature of deposition in the both
used solvents (98 and 1658C in aqueous and ethylene glycol
solutions, respectively), produced smaller sizes MoS2 nano-
particles composing the as grown thin ®lms, whereas creat-
ing some defects, which probably result in bending of the
vdW planes (Figs. 2b and 3b). Note in Fig. 3b that, deposi-
tion at 1658C, from ethylene glycol, resulted in single or
double (0002) plane-sized 2H-MoS2 nanoplatelets (,2±3
nm) embedded in an amorphous matrix. We explain the
Fig. 7. TEM images of MoS2 ®lms deposited on conductive glass from
differences in size and morphology between nanoparticles ethylene glycol solution and annealed at 5508C, (a) deposited at 208C and
obtained in aqueous and in ethylene glycol solutions, as annealed (sample 8), and (b) deposited at 1658C and annealed (sample 9).
being due to a more rapid nucleation process taking place Insets are the corresponding SA diffraction patterns.
228 A. Albu-Yaron et al. / Thin Solid Films 361±362 (2000) 223±228
morphology. While, annealing of samples deposited from
aqueous solutions, on conducting glass or on molybdenum
substrates, induced highly textured ®lms, made up of large
,25±100 nm crystals, with their basal (vdW) planes
oriented parallel to the substrate (Fig. 4), annealing the
samples as deposited at 20 and 1658C, in ethylene glycol
solutions, maintained their nanostructured character (Figs.
1,5,7) as well as, the amorphous matrix. The occurrence of
some polyhedral nanostructures with triangular, (arrowed in
Fig. 7b), or rectangular projection in the annealed ®lms
prepared at 1658C (sample 9), was also, although barely,
observed. They resemble to the closed polyhedral nanos-
tructures (i.e. fullerenes previously reported [11]. We note
that these features were not present when deposition was
from aqueous solutions. These results, indeed, may suggest
that more than one reaction mechanism [6] might possibly
be involved which account for the various resulting
morphologies.
Photoactive MoS2 thin ®lms of type II texture, formed of
micron sized crystals, have been obtained when the deposi-
tion is made on Ni±Cr/quartz substrate from aqueous solu-
tion and after annealing at very high temperatures under
sulfur atmosphere. A vdW rheotaxy mechanism has been
proposed to explain the growth of the crystals during
annealing [5].
The variety of microstructures observed for the electro-
chemically grown MoS2 thin ®lms shows that the cathodic
reduction of tetrathiomolybdate is an interesting alternative
growing technique to control their structures and morphol-
ogies in a wide range (from macro to nanostructures) and
create related materials with a wide range of applications
(solar cells, catalysis, etc.).
Acknowledgements
The authors would like to thank M. Rommeluere for the
EPMA analysis of the ®lms and E.A. Ponomarev for tech-
nical assistance. Part of this work was funded within the
frame of the AFIRST program (project no. 980 MENRT 3).
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