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Photoelectrochemical-type sunlight photodetector based on MoS2/graphene heterostructure

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2015 2D Mater. 2 035011

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 2D Mater. 2 (2015) 035011 doi:10.1088/2053-1583/2/3/035011

PAPER

Photoelectrochemical-type sunlight photodetector based on MoS2/

RECEIVED
6 March 2015
graphene heterostructure
REVISED
12 June 2015
ACCEPTED FOR PUBLICATION
Zongyu Huang1,2, Weijia Han1,2, Hongli Tang2, Long Ren2, D Sathish Chander1, Xiang Qi1,2 and Han Zhang1
2 July 2015 1
Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, Shenzhen University,
PUBLISHED Shenzhen 518060, People’s Republic of China
2
30 July 2015 Hunan Provincial Key Laboratory of Micro-Nano Energy Materials and Devices, Xiangtan University, Hunan 411105, People’s Republic
of China
E-mail: hzhang@szu.edu.cn

Keywords: graphene, molybdenum disulfide, photoresponse

Abstract
We have fabricated a novel sunlight photo-detector based on a MoS2/graphene heterostructure. The
MoS2/graphene heterostructure was prepared by a facile hydrothermal method along with a
subsequent annealing process followed by a substrate-induced high selective nucleation and growth
mechanism. The microstructures and morphologies of the two-dimensional MoS2/graphene
heterostructure can be experimentally confirmed by x-ray diffraction (XRD), Raman spectroscopy,
scanning electron microscopy (SEM), transmission electron microscopy (TEM) and a UV–vis
absorption spectrometer. Photoresponse investigations performed by a photoelectrochemical (PEC)
measurement system indicate that the synthesized MoS2/graphene heterostructure shows superior
photoresponse activities under the illumination of sunlight in contrast with bare MoS2 and graphene.
The improved photoresponsivity can be attributed to the enhanced light absorption, strong light–
matter interaction and the extremely efficient charge separation of the heterostructure. The structure
and performances of the MoS2/graphene heterostructure suggest promising applications in the field of
photonics and optoelectronics.

1. Introduction Moreover, MoS2 exhibits strong light absorption in

Graphene and graphene-like two-dimensional (2D)
materials have drawn substantial attention in the last
few years owing to their exotic properties inherited
from the ultrathin planar structures [1–7]. Recently,
molybdenum disulfide (2H−MoS2, space group P6_3/
mmc), consisting of weakly van der Waals-bonded S
−Mo−S slabs, has generated tremendous advances due
to its inspiring semiconducting characteristics and
wide applications in the fields of electronics [8],
photonics [9, 10] and optoelectronics [11–14]. Inter-
estingly, the band structure of MoS2 sensitively
depends on the layer number and the indirect-to-
direct gap transition of MoS2 occurs when the thick-
ness is reduced down to a monolayer [15, 16]. Benefit-
ting from its thickness-modulated optical energy gap,
graphene-like MoS2 possesses a broad spectral
response ranging from ultraviolet to near infrared
[17–19], making these materials advantageous for a
variety of photo-detection applications [17, 20].
association with Van Hove singularities in the density
of states [21] and in addition photodetectors based on
MoS2 thin layers have been reported to have reason-
ably good photo-response activities [17, 18, 22–26].
Most recently, the creation of 2D heterostructures
assembled by graphene and other graphene-like 2D
crystals have been proposed to be an important mile-
stone [27] and have already proven fruitful for the
realization of novel 2D electronic and optoelectronic
applications. Accompanied with the robust interface, a
modulated Schottky contact [28–30] and strong light–
matter interaction [21, 31] between MoS2 and gra-
phene, the MoS2/graphene heterostructure was
demonstrated to work as a phototransistor with
exceptionally high photoresponsivities [32–37]. How-
ever, most of the investigated photodetectors are
constructed in thin-film transistor configurations that
need to be driven by external bias voltage, which is
usually provided by extra energy storage/supply sys-
tems. In the meantime, the currently available 2D

© 2015 IOP Publishing Ltd

2D Mater. 2 (2015) 035011
Figure 1. A schematic diagram of the photoelectrochemical-type photodetector with a model of the MoS2/graphene heterostructure
coated on the working electrode.
heterostructures are fabricated by chemical vapor
deposition methods or mechanically exfoliated routes,
making them unsuitable for large-scale preparation.
The photoelectrochemical (PEC)-type photo-
detector is a newly developed photoresponsive device
which can be used to detect signals without external
power sources [38]. Due to its advantages such as low
cost and a simple manufacturing process, large
amounts of PEC-type photodetectors have been built
based on various materials [38–40] including a semi-
conductor, P-N junction, Schottky junction and semi-
conductor/graphene hybrid. In the present work, by
taking the combined advantages of strong optical
absorption and the broad spectral response of MoS2
and the excellent carrier transportation of graphene,
we have fabricated a sunlight photodetector based on a
MoS2/graphene heterostructure synthesized by a facile
hydrothermal method plus a subsequent annealing
process. The mutual coupling between MoS2 and gra-
phene could improve the light–matter interaction and
the photo-induced charge separation. The experi-
mental results of the photo-response performed in the
PEC measurement system reveal that the as-prepared
MoS2/graphene heterostructure has superior sunlight
photoresponsivity. Our work proposes that the PEC-
type MoS2/graphene heterostructure might be devel-
oped as a prototype for low-cost and high-efficiency
sunlight photodetectors.
2. Experimental
2.1. Synthesis
Initially, graphene oxide (GO) precursor was synthe-
sized from graphite powder by a modified Hummer’s
method using a mixture of H2SO4, NaNO3 and
KMnO4. The MoS2/graphene heterostructure was
obtained via a typical hydrothermal method as
reported previously [41]. In detail, 30 mg of solution-
processed GO was dissolved in 30 mL distilled H2O
2
Z Huang et al
followed by dropping 20 mL of 70 mM cationic
surfactant (dodecyltrimethylammonium bromide)
into GO aqueous under vigorous stirring for 12 h at
room temperature. After adding 20 mL solution of
1.5 mmol Na2MoO4 · 2H2O and 7.5 mmol L-cysteine
(Lcys), the mixture was transferred into the 100 mL
Teflon-lined stainless steel autoclave and hermetically
sealed at 240 °C for 24 h. The black solid product was
collected and annealed in Ar/H2 (10% H2) atmosphere
at 800 °C for 2 h in order to form the MoS2/graphene
composites. For comparison, bare MoS2 and graphene
was also prepared under the same procedure as a
control sample for further testing experiments.
2.2. Characterization
The crystal structures of the as-prepared samples were
determined by x-ray diffraction (XRD) by Cu/Ka
radiation. Raman spectra were collected using the
Renishaw inVia Raman microscope, excited at room
temperature with an excitation laser wavelength of
532 nm. The morphologies and microstructures of the
samples were characterized by means of scanning
electron microscopy (SEM; VEGA3 SBH, Tescan) and
transmission electron microscopy (TEM; JEM2100).
The UV–vis absorption spectra were measured under
the diffuse reflection mode with the aid of Shimadzu
2550 UV–visible spectrometer equipped with an
integrating sphere (ISR-2200, Shimadzu). Fine BaSO4
powder was used as a standard for baseline measure-
ments and the spectra were recorded within the range
of 200−800 nm.
2.3. Photoresponse performance
Photoresponse activities were evaluated based on a
photoelectrochemical measurement system com-
posed of a CHI660D (ChenHua, China) electrochem-
istry workstation, an illumination source and a
homemade three-electrode cell. Figure 1 is a schematic
diagram for the PEC-type photodetector. The
2D Mater. 2 (2015) 035011
Figure 2. (a) XRD patterns of the MoS2/graphene heterostructure and bare MoS2, (b) Raman spectra of the GO precursor, bare MoS2
and the MoS2/graphene heterostructure.
indium–tin oxide (ITO) conductor glass coated with
the as-prepared MoS2/graphene heterostructure was
used as the working electrode with Pt foil and saturated
calomel electrode as the counter and reference electro-
des, respectively. Typically, a total of 10 mg as-
prepared samples mixed with 2 mL deionized water
was ultrasonicated for 1 h to yield a stable MoS2/
graphene suspension. The Na2SO4 aqueous solution
(0.5 M, 98.0%) was used as the electrolyte and the light
source was a 150 W high-pressure Xenon lamp (CHF-
XM150W) with AM 1.5 filter. The sweep voltammo-
grams of the samples under light illumination were
recorded at a scanning rate of 10 mV s−1. All the
experiments were carried out in the same conditions.
Electrochemical impedance spectroscopy (EIS) mea-
surements were carried out in the frequency range of
0.01 Hz to 100 kHz at open-circuit voltage with a
potential pulse of 10 mV in amplitude.
3. Results and discussion
XRD and Raman measurements have been performed
to explore the structural characterization of the as-
prepared samples. Figure 2(a) shows the typical XRD
spectra of the as-prepared MoS2/graphene hetero-
structure and the bare MoS2. The diffractions peaks at
13.9°, 33.1°, 39.5°, 49.3°, 58.7°, 59.9° and 69.1°
observed in both XRD patterns can be indexed as the
(002), (100), (103), (105), (110), (008) and (201)
crystal planes, in accordance with 2H−MoS2 phase
(JCPDF card no. 37-1492). However, no diffraction
signal for graphene can be discerned in the present
XRD pattern of the MoS2/graphene heterostructure,
which probably resulted from the relatively low
diffraction intensity of graphene. Figure 2(b) shows
the representative Raman spectra of the graphene
oxide precursor, as-prepared MoS2 and the MoS2/
graphene heterostructure. The peaks observed at 282,
336, 378, 402 and 449 cm−1 in the Raman spectra of
the bare MoS2 and the MoS2/graphene heterostructure
3
Z Huang et al
can be indexed to the E11g, LA, E12g, A1g and 2LA(M)
vibration of 2H−MoS2 [41, 42]. As expected, the
Raman spectra of the GO precursor displays a
prominent G-band (graphite carbon band) as the only
feature at 1602 cm−1, corresponding to the in-plane
vibration of sp2 carbon atoms. The D-band (disor-
dered carbon band) at 1353 cm−1 is attributed to the
first-order zone boundary phonons in defective gra-
phene [43]. Interestingly, the D-band and G-band of
the MoS2/graphene heterostructure are still present at
1593 cm−1 and 1366 cm−1, which strongly indicates
the presence of graphene.
The morphologies and microstructures of the het-
erostructure are further investigated by SEM and
TEM. Figure 3(a) is an SEM image of as-prepared
sample; it can be clearly observed that the highly wrin-
kled 2D nanosheets are widespread, indicating that the
MoS2 flake is well anchored on the plain graphene
platform. Owing to the significance of the attractive
substrate-induced high selective nucleation and
growth mechanism for the graphene oxide precursor
during the synthesis process [44], graphene-like 2D
MoS2 flakes can be well supported on the surface of
graphene to form the vertical hetero-layered structure.
Figure 3(b) is a TEM image of the MoS2/graphene het-
erostructure, it indicates that the graphene-like 2D
structure has been inherited well. Further HRTEM
characterization (insert image in figure 3(b)) clearly
depicts the well-stacked layered structures of the MoS2
with a lattice spacing of 6.02 Å, corresponding to the
(002) plane of hexagonal atomic lattices, which is con-
sistent with the above XRD analysis. Figure 4 is the
typical UV–vis spectra of the MoS2/graphene hetero-
structure and the bare MoS2. It was found that there
are two broad peaks around 597 nm (2.07 eV) and
665 nm (1.86 eV), which are related to A1 and B1 via
direct transition with energy separation, arising from
the energy split from the valence band and spin–orbit
coupling [15, 45]. Compared with that of bare MoS2,
the characteristic absorption of the heterostructure
shows a significant improvement in absorption
2D Mater. 2 (2015) 035011
Figure 3. (a) Scanning electron microscope image and (b) transmission electron microscopy image and high-resolution TEM image
(insert in (b)) of the MoS2/graphene heterostructure.
Figure 4. UV–vis diffuse reflectance spectra (DRS) of the
MoS2/graphene heterostructure and bare MoS2.
intensity from 320 to 800 nm. The obvious red shift
found in the absorption edge is attributed to the spe-
cial hetero-layer structure and the positive synergetic
effects between MoS2 and graphene. The relatively
broad and powerful absorption of the MoS2/graphene
heterostructure implies that the as-prepared hetero-
structure would possess excellent photoresponse
performances.
To gain insight into the photoresponse activity of
the MoS2/graphene heterostructure, linear sweep vol-
tammograms and time responses of photocurrent are
carried out based on the photoelectrochemical mea-
surement system under sunlight irradiation (the aver-
age light intensity was 40 mW cm−2). Figure 5(a)
displays the linear sweep voltammograms of the
MoS2/graphene heterostructure, bare MoS2 and gra-
phene, respectively. It is discerned that the short-cir-
cuit current density and open-circuit voltage of bare
MoS2 increases from 0.729 mA cm−2 and −1.228 V in
dark to 1.310 mA cm−2 and −1.06 V under irradiation
of sunlight with 40 mW cm−2 powder intensity. While
those of the bare graphene electrode have almost no
4
Z Huang et al
obvious change under sunlight irradiation. In com-
parison, the short-circuit current density of the MoS2/
graphene heterostructure sharply increases from
0.868 mA cm−2 to 3.127 mA cm−2 and the open-cir-
cuit voltage also has an obvious increase from −1.102
to −1.04 V. In addition, when a bias voltage beyond
−1.0 V is applied, a significant improvement in cur-
rent density is observed and the heterostructure elec-
trode shows the higher photocurrent density of
approximately −5.654 mA cm−2 at −1.3 V bias, which
is observed to be about 2 fold compared to the bare
MoS2 (−2.998 mA cm−2) electrode. The introduction
of graphene is proposed to improve the sensitivity to
sunlight significantly.
In order to gain clear knowledge about the stabi-
lity and responsivity of the Sunlight photodetector,
we have measured the photoresponse switching
behavior of the electrodes without bias voltage. As
shown in figure 5(b), the signal of current density can
be reproducibly switched from the ‘ON’ state to the
‘OFF’ state by periodically turning the Sunlight on
and off with a power density of 40 mW cm−2 for the
MoS2/graphene heterostructure, the bare MoS2 and
the graphene electrodes. In contrast to the mono-
tonous ‘on−off’ switching behavior of the bare gra-
phene electrode, that of both the sole MoS2 and the
MoS2/graphene heterostructure electrodes exhibits
preferable performance. It is noteworthy that the
photocurrent of the heterostructure electrode is
about 2.5 times more than that of the bare MoS2 elec-
trode and the photocurrent is very stable without any
obvious photocurrent decay.
The dependence of current density on incident
light intensity is another key factor in evaluating the
performance of a photodetector. As shown in
figure 5(c), photocurrent linearly increases with the
increasing intensity of sunlight in a wide variation
range from 0 mW cm−2 to 40 mW cm−2. Figure 5(d)
2D Mater. 2 (2015) 035011 Z Huang et al

Figure 5. (a) Linear sweep voltammograms of the MoS2/graphene heterostructure, bare MoS2 and graphene electrodes under sunlight
irradiation with 40 mW cm−2 power intensity. (b) The photocurrent transient response of the MoS2/graphene heterostructure, bare
MoS2 and graphene electrodes under sunlight irradiation (40 mW cm−2) with zero bias voltage. (c) Current density (J) as a function of
incident sunlight intensity in a wide range from 0 mW cm−2 to 40 mW cm−2 (black points are the experimental results and red lines
are the linear fitting data). (d) Photosensitivity linearity and photoresponse switching behaviors under low light intensity from
5 μW cm−2 to 40 mW cm−2.

indicates the fast and uniform photocurrent responses

for each switch-on and switch-off operation even with
a relatively low light intensity of 40 μW cm−2, suggest-
ing a superior sunlight detection behavior of the as-
prepared MoS2/graphene heterostructure electrode
under low light intensity.
Electrochemical impedance measurements
under irradiation of sunlight are conducted to evalu-
ate the interface charge separation efficiency of the
photo-excited electrons and holes of the MoS2/gra-
phene heterostructure and the bare MoS2 electrodes,
as shown in figure 6. The radius of the arc on the EIS
spectra mirrors the interface layer resistance occur-
ring at the surface of the electrode in which the smal- Figure 6. (a) EIS Nynquist plots of the MoS2/graphene
heterostructure and bare MoS2 electrodes in sulfide−sulfite
ler arc radius indicates the higher efficiency of charge electrolyte and under irradiation of simulated sunlight with
transfer. It is observed that the arc radius of the 40 mW cm−2 power intensity.
MoS2/graphene heterostructure is much smaller than
that of the bare MoS2, which is proposed to deter-
mine the presence of graphene and can benefit the
transport of photo-induced electrons for the excel-
lent conductivity of graphene. Therefore, the super- for splitting the photo-generated electron–hole pairs
ior photoresponse performance of the present MoS2/ by significantly reducing the photoluminescence
graphene heterostructure is believed to be attributed [46]; (ii) the introduction of graphene could facilitate
to the following factors: (i) the Schottky barrier in the the charge transfer due to the ultrahigh carrier mobi-
MoS2/graphene junction, which could be beneficial lity of graphene [29].

5
2D Mater. 2 (2015) 035011
4. Conclusions
In this study, a MoS2/graphene heterostructure has
been successfully synthesized by a facile hydrothermal
method along with a subsequent annealing process.
The obtained materials are used as electrodes to
fabricate photoelectrochemical-type photodetectors
and the MoS2/graphene heterostructure exhibits pre-
ferable photoresponse activity under the irradiation of
sunlight which is proposed to be derived from
excellent broad light absorption, strong light–matter
interaction, high charge separation and transport as
well as the superior durability of this type of material.
The unique structure and superior photoresponsivity
of the MoS2/graphene heterostructure suggests that it
holds great promise as a building block for optoelec-
tronic devices. We also believe that the as-prepared
MoS2/graphene heterostructure is extendable to other
applications based on photoelectrochemical effects,
such as dye-sensitized solar cells and photoelectro-
chemical hydrogen production.
Acknowledgments
This work is partially supported by the MOE grant
(grant no. NCET 11-0135), the National Natural
Science Foundation of China (grant no. 61222505,
61435010), the Hunan Provincial Natural Science
Foundation of China (grant no. 13JJ1012) and the Key
Laboratory of Optoelectronic Devices and Systems of
the Ministry of Education and Guangdong Province
Fund (grant no. GD201404).
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