Materials Letters 201 (2017) 216–220

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Continuous and large-area transition metal disulfides films deposited by

pulsed laser/chemical vapor-combined process as a counter electrode for
dye-sensitized solar cells
Yuqiao Wang a,⇑, Yichao Bai a, Junting Xi b, Meiting Liu a, Mengtian Li a, Kunquan Hong c,⇑, Yueming Sun a
a
School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China
b
School of Science, China Pharmaceutical University, Nanjing 211198, China
c
School of Physics, Southeast University, Nanjing 211189, China

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

Article history: The continuous and large-area films of transition metal disulfides (MS2, M = Mo, W, Fe, Co, Ni) were pre-
Received 31 March 2017 pared on the conducting glass using pulsed laser deposition followed by chemical vapour deposition. The
Received in revised form 2 May 2017 metal oxide precursor was deposited onto the substrate by pulsed laser deposition, and then the oxides
Accepted 4 May 2017
were rapidly sulfurized by chemical vapour deposition. As a result, the functional films exhibit excellent
Available online 4 May 2017
electrocatalytic activity as a counter electrode for dye-sensitized solar cells due to their uniformity, crack-
free and adhesive.
Keywords:
Ó 2017 Elsevier B.V. All rights reserved.
Chemical vapour deposition
Pulsed laser deposition
Transition metal disulfide
Electrocatalytic activity
Solar energy materials
Thin films

1. Introduction Generally, the preparation methods of TMDs were mostly based

Transition metal disulfides (TMDs) have attracted extensive
research interest due to the opportunity for acting as a high effi-
cient catalyst in the emerging clean and renewable energy tech-
nologies, such as hydrogen evolution reaction [1–3], lithium ion
batteries [4,5] and solar cells [6,7]. In particular, the catalyst activ-
ity of TMDs for the photoelectrochemical devices depends on not
only the chemical compositions and structures but also the reliable
assembly and integration technology. For instance, the transfer-
free growth of MoS2 or WS2 has been achieved by spin-coating a
liquid chalcogen precursor onto the transition metal oxide layer,
followed by a laser irradiation annealing process [8], indicating
that the air-stable and low-power photodetectors was easily inte-
grated by the spin coating/laser irradiation annealing combination.
Some reports suggested that MoS2 [9], NiS2 [7] and CoSe2 [10]
coated fluorine doped tin oxide (FTO) can be employed as a counter
electrode (CE) in dye-sensitized solar cell (DSSC), which is a cheap
and promising alternative to Pt during the electrocatalytic reduc-
tion from triiodide (I3 ) to iodide (I ) ions.
⇑ Corresponding authors.
E-mail addresses: yqwang@seu.edu.cn (Y. Wang), hongkq@seu.edu.cn (K. Hong).
on the solution approaches, including the hydrothermal/cast-
coating [11] and precursor impregnation/pyrolysis [12] processes.
Furthermore, the sputtering/sulfurization-combined synthesis of
WS2 can be considered as a large-scale fabrication of CEs [13]. In
this work, we report a scalable method to produce a series of high
quality TMDs (MS2, M = Mo, W, Fe, Co, Ni) decorated-FTO CEs for
DSSC, developing an effective strategy to combine the pulsed laser
deposition (PLD) of transition metal oxides with the rapid sulfur-
ization by chemical vapour deposition (CVD). The continuous and
large-area throughput synthesis can be expected to improve the
uniformity and crack-free of TMDs films, control the thickness,
and enhance the adhesive strength between films and substrates.
2. Experimental details
2.1. Preparation and assembly
The vacuum chamber with the base level of 2  10 4 Pa was
adjusted to 5 Pa by adding oxygen. The PLD operation was per-
formed by pulsing laser ablation from transition metal oxide on
FTO substrates, using a pulsed Nd:YAG laser (harmonic component
k = 532 nm, repetition rate m = 10 Hz, energy of 450 mJ and pulse
numbers of 2000). Then the sulfurization process was employed

http://dx.doi.org/10.1016/j.matlet.2017.05.027
0167-577X/Ó 2017 Elsevier B.V. All rights reserved.
 Y. Wang et al. / Materials Letters 201 (2017) 216–220 217

Fig. 1. HRTEM images of (a) MoS2, (b) WS2, (c) FeS2, (d) CoS2 and NiS2. (f) Raman spectra of various TMDs. Inset: selective area electron diffraction.

by CVD process under N2 flow at 550 °C for 20 min to convert tran-
sition metal oxide to MS2 (M = Mo, W, Fe, Co, Ni). The device
assembly was described in our previous work [14]. Pt-coated FTO
counter electrode was prepared by the conventional pyrolysis [15].
2.2. Characterization and photovoltaic performance
The crystal structure was investigated by X-ray diffraction
(XRD, Bruker D8 advance) and high-resolution transmission elec-
tron microscopy (HRTEM, Tecnai G2T20). The morphology was
observed by scanning electron microscopy (SEM, FEI-F50). Raman
spectroscopy was also performed at 514 nm wavelength (Horiba
JY HR800) to perceive the crystal quality of TMDs. All electrochem-
ical characterizations were conducted on an electrochemical
workstation (CHI760D). The cyclic voltammogram (CV) was
measured in a three electrode system: TMDs/FTO CE as a working
electrode, Pt wire as a counter electrode and saturated calomel
electrode (SCE) as a reference electrode. The electrolyte was
composed of LiClO4 (0.1 M), LiI (10 mM) and I2 (1 mM) in an
acetonitrile solution. The symmetric TMDs/FTO cell with an
active area of 0.25 cm2 was used to perform electrochemical
impedance spectroscopy (EIS) and Tafel polarization curves,
using the electrolyte of 1-methyl 3-propyl imidazolium iodide
(1 M), I2 (0.15 M), guanidinium thiocyanate (0.1 M) and 4-tert-
butylpyridine (0.5 M) in 3-methoxypropionitrile.Tafel was
performed at a scan rate of 10 mV s 1. EIS was carried out in the
frequency range from 0.01 Hz to 105Hz with an amplitude of
10 mV. The current density-voltage (JV) curves were tested by
Newport Oriel 91192 and recorded by Keithley 2400 at
100 mW cm 2 (AM1.5).
218 Y. Wang et al. / Materials Letters 201 (2017) 216–220

Fig. 2. SEM images of (a) MoS2, (b) WS2, (c) FeS2, (d) CoS2 and (e) NiS2 on FTO substrates. (f) XRD patterns. Inset: EDX elemental spectra.

3. Results and discussion
HRTEM images show the representative structures of MS2
(M = Mo, W, Fe, Co, Ni) in Fig. 1(a–e). The crinkly and ripped
MoS2 and WS2 demonstrated a few-layered characterization with
a typical interlayer distance of 0.62 and 0.65 nm, respectively.
The fringe spaces of FeS2 were referred to 0.29 and 0.58 nm, corre-
sponding to the inter-planar spacing of (2 0 0) and (0 1 1) planes of
cubic FeS2, respectively. The clear inter-planar spaces were 0.32
and 0.39 nm, corresponding to the (1 1 0) and (1 1 1) planes of cubic
CoS2, respectively. The inter-planar spaces of 0.28 and 0.40 nm
agreed with the (0 2 0) and (1 0 1) lattice spacing of cubic pyrite
NiS2, respectively. Fig. 1f shows the Raman spectra of TMDs: (1)
Two characteristic peaks of MoS2 (377 and 403 cm 1) and WS2
(348 and 414 cm 1) were indicators of the in-plane (E2g, metal
and sulfur atoms) and out-of-plane (A1g, sulfur atoms) vibration
modes [16]. (2) As for FeS2, the two strong peaks at 333 and
369 cm 1 and a weak peak at 420 cm 1 corresponded to the S2
vibration (Eg), S–S in-phase stretch (Ag), and coupled vibration
and stretch (Tg) modes, matching well with pyrite FeS2 [17]. (3)
The peaks at 275 and 378 cm 1 were consistent with the character-
istic E2g and A1g modes of CoS2, respectively [5]. (4) The weak peak
at 265 cm 1 was assigned to Eg mode followed by a strong peak at
468 cm 1 (Ag), corresponding to pyrite NiS2 [18]. As a result, the
HRTEM and Raman analysis demonstrate that TMDs obtained by
PLD/CVD-combined process have a good crystallinity and purity.
The surface morphology of TMDs coated FTO was examined
with SEM in Fig. 2(a–e). The uniform and crack-free films were
tightly bound with FTO substrates. Under the ordinary sticky tape,
the union between films and substrates were still very strong. The
 Y. Wang et al. / Materials Letters 201 (2017) 216–220 219

Fig. 3. (a) CV plots of TMDs/FTO CEs. (b) Tafel polarization. (c) EIS plots. (d) JV curves of DSSC.

Table 1
Electrochemical properties fitted by CV, EIS and Tafel curves, and the photovoltaic performance of solar cells.

CE Rs (X
cm2) Rct (X
cm2) Ip,c (mA cm 2

) Epp (mV) J0(mA
cm 2
) Voc(V) Jsc (mA
cm 2
) FF g(％)
Pt 4.35 6.35 -0.83 326 3.88 0.70 10.77 0.71 5.22
MoS2 5.47 8.88 -0.79 421 1.72 0.68 10.52 0.67 4.86
WS2 7.02 17.62 -0.71 521 0.28 0.69 9.66 0.63 4.30
FeS2 6.26 17.27 -0.66 318 0.37 0.70 10.67 0.60 4.46
CoS2 7.22 12.59 -0.65 301 0.81 0.71 10.63 0.60 4.58
NiS2 5.49 8.95 -0.70 383 1.61 0.73 10.34 0.62 4.75

excellent morphology of TMDs/FTO CE can improve the electrocat-
alytic performance. Fig. 2f shows all XRD reflections of TMDs/FTO
CEs and bare FTO for reference. The FTO substrate-related peaks
were clearly noticed in SnO2 XRD patterns (JCPDS 41-1445). Com-
pared with the intense peaks of SnO2, the characteristic peaks of
TMDs were so weak that they can be hardly observed, because
TMDS film was much thinner than SnO2 coating on FTO. The crys-
tallinity and purity of TMDs were analyzed by HRTEM and Raman
in Fig. 1. The results corroborated well with the standard patterns
of MoS2 (JCPDS 37-1492), WS2 (JCPDS 87-2417), FeS2 (JCPDS 42-
130), CoS2 (JCPDS 41-1471) and NiS2 (JCPDS 65-3325), agreeing
with energy dispersive X-ray (EDX) elemental spectra (inset of
Fig. 2).
The electrocatalysis and reversibility of TMDs/FTO CEs were
investigated by CV plots in Fig. 3a. The reduction of I3 to I was
considered as a rate determining step among the two pairs of redox
peaks. The higher cathodic peak current density at the relative
negative position revealed the faster reduction velocity (vred):
vred(Pt) > vred(MoS2) > vred(WS2) > vred(NiS2) > vred(FeS2) > vred(CoS2).
The smaller peak-to-peak potential separation (Epp) for the relative
negative pair reflected the better reversibility of the redox
reaction: Epp(CoS2) < Epp(FeS2) < Epp(Pt) < Epp(NiS2) < Epp(MoS2) <
Epp(WS2). Furthermore, Tafel and EIS plots were used to quantify
interfacial charge transfer parameters for TMDs/FTO CEs. In Tafel
polarization zone of Fig. 3b, the exchange current density (J0) can
be estimated by the intersection of the extrapolated linear anodic
and cathodic branches to provide the electron exchange rate at
the electrolyte/electrode interface. EIS curves can offer more
impedance information about the interfacial electron transfer in
Fig. 3c. The equivalent circuit based on fitting EIS analysis mainly
consists of the following RC elements: a charge-transfer resistance
(Rct), a series resistance (Rs), a Warburg impedance (Zw) and a con-
stant phase element (CPE). Especially, Rct and Rs are closely related
to the catalytic activity of reduction of I3 to I and the contact
220 Y. Wang et al. / Materials Letters 201 (2017) 216–220
resistance between electrocatalysts and substrates, respectively.
As shown in Fig. 3d, the photocurrent density-voltage (JV) curves
illustrate the device performance assembled by TMDs/FTO CEs,
including an open-circuit voltage (Voc), a short-circuit photocur-
rent density (Jsc), a fill factor (FF), and a photon-to-electron
conversion efficiency (g). All electrochemical properties and pho-
tovoltaic performance are listed in Table 1. The results demon-
strate that the Jsc values were in agreement with the tendency of
J0 and Rct values: J0(Pt) > J0(MoS2) > J0(NiS2) > J0(CoS2) > J0(FeS2) >
J0(WS2), and Rct(WS2) > Rct(FeS2) > Rct(CoS2) > Rct(NiS2) > Rct(MoS2)
>Rct(Pt), suggesting that the lower Rct helps achieve the higher
electrocatalytic activity at the electrolyte/electrode interface. The
deposition of TMDs on FTO substrates by PLD/CVD-combined
method can significantly enhance the conductivity of CEs accord-
ing to the Rs values, which is comparable with Pt/FTO CEs. The
result indicated that the electroactive films of TMDs can be tightly
attached to FTO substrates.
4. Conclusions
In short, five typical TMDs films were successfully deposited on
FTO substrates by PLD/CVD-combined process. The continuous,
large-area and non-noble metal films could substitute for Pt as a
CE in the high performance DSSC.
Acknowledgements
This work was financially supported by the National Basic
Research Program of China (2013CB932902), Natural Science Foun-
dation of Jiangsu Province of China (BK20141338, BK20150694),
Fundamental Research Funds for the Central Universities
(3207047410), and Priority Academic Program Development of
Jiangsu Higher Education Institutions (1107047002).
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