Applied Surface Science 546 (2021) 149074

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Applied Surface Science

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

Full Length Article

High-performance photodetector and its optoelectronic mechanism of

MoS2/WS2 vertical heterostructure
Xin Lin a, Fang Wang a, *, Xin Shan a, Yinping Miao a, Xudong Chen b, Meng Yan a, Lifang Zhang a,
Kai Liu c, Jun Luo b, Kailiang Zhang a, *
a
Tianjin Key Laboratory of Film Electronic & Communication Devices, School of Electrical & Electronic Engineering, Tianjin University of Technology, Tianjin 300384,
China
b
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Material Science and
Engineering, Tianjin University of Technology, Tianjin 300384, China
c
Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China

A R T I C L E I N F O A B S T R A C T

Keywords: Two-dimensional heterostructures based on transition metal dichalcogenides (TMDCs) exhibit enhanced elec­
MoS2/WS2 trical and optoelectrical properties, which are promising for next-generation optoelectronics devices. In this
Photodetector work, we demonstrate the preparation of MoS2/WS2 vertical heterostructure and investigate their photoresponse
On/off ratio
properties by fabricating n-type photodetectors with titanium (Ti) as source-drain electrode. Uniform MoS2 and
Photoresponsivity
Response time
WS2 films are synthesized on SiO2/Si substrates by chemical vapor deposition (CVD) method respectively, and
then MoS2/WS2 vertical heterostructures are achieved via transferring MoS2 onto WS2 films. The WS2- and MoS2-
based devices exhibit on/off ratio and electron mobility of 106, 0.03 cm2V-1S-1 and > 106, 2.6 cm2V-1S-1 at Vds =
6 V. Notably, the MoS2/WS2 heterostructure photodetector achieves on/off ratio of near 108 and electron
mobility of 12.6 cm2V-1S-1, which is higher than that of pure WS2 and MoS2 devices. The photodetector based on
MoS2/WS2 heterostructure shows enhanced optoelectronic performance with photoresponsivity of 298 A/W and
specific detectivity of 2.38 × 1011 Jones under 405 nm laser with the power density of 0.09 mW/cm2. Simul­
taneously, fast photoresponse speed of 9 ms is obtained owing to the speed of separating and recombining
electron-hole pairs. The photodetectors exhibit excellent stability and repeatability to laser, which provides more
possibilities for future electronic and optoelectronic applications.

1. Introduction stacking two or more different 2D-layered materials have been created
and studied [13–17]. For instance, Junjie Shan et al built phototransistor
Within the last few years, atomically thin 2D materials, such as using MoS2/WS2 heterojunction as the channel material and demon­
graphene, hexagonal boron-nitride (h-BN) and transition metal dichal­ strated over 50 folds enhanced photoresponsivity of multilayer MoS2
cogenides (TMDCs), have attracted extensive attention from research field-effect transistor [18]. Mengxing Sun et al demonstrated a vertically
scholars for designing next-generation devices [1–5]. As an important integrated phototransistor based on single-layer MoS2/multilayer WSe2
part of two-dimentional materials, TMDCs with the chemical formula heterojunction. Upon visible light illumination (660 nm), the photo­
MX2 (X = S, Se, Te and M = transition metal) show an increasing band detection capabilities reach the optimal values simultaneously with the
gap with the decreasing of their thickness from bulk to monolayer [6,7]. photoresponsivity of 17.8 A/W, photosensivity of 140, and the response
TMDCs materials have adjustable band gap, atomic thickness and speed of < 80 ms [19]. In this way, building a heterojunction can further
moderate electron mobility, which makes it show great potential in the enhance electrical and optoelectrical properties by interlayer coupling
field of widespread applications to serve as field-effect transistors (FETs) resulting in effective charge transfer and band alignments [20,21]. In
[8], photodetectors [9], light-emitting diodes [10], memristors [11], addition, as representative 2D layered materials, MoS2 and WS2 have the
and photovoltaics [12]. same crystal structure which makes it possible to construct tailored
At the same time, van der Waals (vdW) heterostructures formed by heterojunctions without the severe limitation of lattice match compared

* Corresponding authors.
E-mail addresses: [email protected] (F. Wang), [email protected] (K. Zhang).

https://doi.org/10.1016/j.apsusc.2021.149074
Received 28 October 2020; Received in revised form 9 January 2021; Accepted 15 January 2021
Available online 21 January 2021
0169-4332/© 2021 Elsevier B.V. All rights reserved.
X. Lin et al. Applied Surface Science 546 (2021) 149074

to conventional semiconductor heterostructures [22]. Although there 3. Results and discussion

are previous reported several ways to construct a heterojunction,
including CVD one-step or two-step growth, in this work, MoS2 and WS2 3.1. Morphological analysis
sample films were grown separately by CVD methods, which better
ensures crystallinity quality and avoids alloying situation of 2D nano- As schematically shown in Fig. 1a, highly uniform large-area WS2
films. and MoS2 monolayer films were successfully grown separately by CVD
Here, pristine MoS2 and WS2 films are synthesized on the SiO2/Si technique on the SiO2/Si substrates. The specific temperature change
substrates via CVD method by optimizing growth parameters, respec­ curve is shown in Figure S1a during the growth process of MoS2 and WS2
tively. And then MoS2/WS2 vertical heterostructures are achieved via samples. Figure S1b, c gives optical images of pristine MoS2 and WS2
transferring MoS2 onto WS2 films. The surface morphology and structure films, from which we can conclude that the sizes of MoS2 and WS2 are 54
properties of the MoS2/WS2 heterojunctions are characterized by optical and 72 μm, respectively. Follow by, MoS2/WS2 heterojunctions were
microscope (OM), atomic force microscope (AFM), high-resolution constructed by wet transferring method. It is clearly seen in Fig. 1c, the
transmission electron microscope (HRTEM), X-ray photoelectron spec­ overlapping area formed by the bottom WS2 and the upper MoS2 films
troscopy (XPS), Raman and photoluminescence (PL) spectroscopy. After shows an apparent color contrast, which is consistent with the low
structural characterization, photodetectors based on isolated MoS2, WS2 magnification hetorostructure image in Fig. 1b. AFM was further per­
and MoS2/WS2 heterostructure were fabricated. Compared with pure formed to analyze surface topography as well as the thickness of the
WS2 and MoS2 devices, high on/off ratio (near 108) and electron MoS2/WS2 heterostructure, and collected results are shown in Fig. 1d,e.
mobility (12 cm2V-1S-1) of heterostructure photodetector are achieved at The surface morphology of MoS2/WS2 can be clearly seen from Fig. 1d.
Vds = 6 V. The optoelectronic characteristics of the MoS2/WS2 are also In addition, the corresponding AFM height profile measured according
performed with different wavelengths (405, 532 and 635 nm) laser. The to the black line marked in Fig. 1d is shown in the Fig. 1e. The height
heterostructure-based photodetector exhibits low dark current of 4.87 profile provides an average thickness of 0.85 nm and 0.8 nm for upper
× 10-11 A, photoresponsivity of 298 A/W and specific detectivity of 2.38 MoS2 and bottom WS2 films, respectively, which is consistent with the
× 1011 Jones, as well as fast photoresponse speed of 9 ms under 405 nm previously reported thicknesses of single-layer MoS2 and WS2 nano-films
laser. The photodetectors show excellent stability and repeatability, [23–24]. HRTEM measurement was used to characterize the structure
which makes our work play an active role in next-generation photo­ and crystalline quality of pure MoS2 (see Figure S2) and vertically
electronic devices. stacked MoS2/WS2 vdW heterostructure. Fig. 1f shows the low magni­
fication morphology of vertical MoS2/WS2 heterostructure on the Cu
2. Material and methods grids. As shown in Fig. 1g,h, the atomic-resolution HRTEM image and
corresponding selected area electron diffraction (SAED) pattern of
2.1. Preparation of 2D MoS2/WS2 samples MoS2/WS2 vdW heterostructure on the same sample are illustrated.
Based on the above results, we can conclude that the obtained MoS2/
MoS2 films were first synthesized on SiO2 (270 nm)/(P++) Si sub­ WS2 heterojunction has outstanding crystalline quality.
strates via CVD method in a high-temperature two-zone furnace using S
(30 mg, Alfa Aesar, 99.99%) and MoO3 (0.5 mg, Alfa Aesar, 99.97%) 3.2. Structural and optical properties analysis
powders as the precursors. The S and MoO3 powders were located up­
stream zone I and downstream zone II of quartz tube, respectively, with The structural and optical properties of the MoS2/WS2 hetero­
a SiO2/Si substrate placed above the MoO3 powder. Then zone I and II structure were examined by the Raman and PL spectroscopy with the
were heated to 120 ℃ and 780 ℃ respectively and maintained for 30 excitation of the 532 nm laser at room temperature. The corresponding
min at a flow rate of 30 sccm for the growth of MoS2 films. After the results are shown in Fig. 2. Fig. 2b demonstrates the Raman spectra of
growth was completed, the tubular furnace was naturally cooled to room pure monolayer MoS2, monolayer WS2 and stacked MoS2/WS2 hetero­
temperature. The growth conditions of WS2 film are similar to those of structures obtained from the red dots in Fig. 2a. The Raman spectra for
MoS2, using S (30 mg) and WO3 (5 mg, Alfa Aesar, 99.997%), where the pristine MoS2 presents two characteristic peaks at 385 cm− 1 and 404
WO3 powder is heated to 900 ℃. The MoS2/SiO2/Si substrate was spin- cm− 1, corresponding to in-plane (E12g) vibration mode and out-of-plane
coated with polymethacrylate (PMMA), and then baked at 160 ℃ for (A1g) vibration mode (red trace in Fig. 2b). The frequency difference
three and a half minutes. The PMMA/MoS2/SiO2/Si was immersed in a between E12g and A1g is 19 cm− 1, which is consistent with the previous
hydrofluoric acid (HF) solution (HF: DI water = 1:5) and was picked up reported MoS2 monolayer characteristic[25]. We can see that there are
with the WS2/SiO2/Si substrate. Then MoS2 was transferred to the WS2/ two characteristic peaks for pure WS2 locating at 349 cm− 1 and 417
SiO2/Si substrate to form the MoS2/WS2 vertical heterostructure. The cm− 1 respectively with a wavenumber difference of about 68 cm− 1,
prepared heterojunctions were annealed at 400 ℃ for 1 h to facilitate featuring monolayer characteristics[26–27] (blue trace). From the yel­
interlayer coupling. E-beam lithography (EBL, Raith e_LINE plus) is used low curve, it can be found that four Raman characteristic peaks, WS2-
for source-drain electrode exposure, and then 80 nm titanium (Ti) was E12g, MoS2-E12g, MoS2-A1g, and WS2-A1g, appeared in the MoS2/WS2
deposited by e-beam evaporation. heterojunction, and the corresponding peak positions are located at 349
cm− 1, 383 cm− 1, 404 cm− 1 and 415 cm− 1, respectively. The corre­
2.2. Measurements and characterization sponding Raman mapping was then characterized for the marked area of
MoS2/WS2 heterostructure in the Fig. 2a. Fig. 2e,f exhibits Raman in­
Optical microscopy (OM, Olympus DSX510), atomic force micro­ tensity mapping at 350 cm− 1 and 385 cm− 1 for the MoS2/WS2 hetero­
scopy (AFM, Aglient 5600LS) and HRTEM (Talos F200X) were employed structure. From this, the color contrast can be clearly seen, which proves
to prove the morphology and crystallization of the heterojunction. The the formation of MoS2/WS2 vertical heterostructure.
surface elements of MoS2/WS2 film were characterized by the X-ray The PL spectra of pure MoS2, WS2 and MoS2/WS2 heterostructure
photo-electron spectroscopy (XPS, Thermo Scientific Escalab 250Xi). were obtained in Fig. 2c. The binding energy of PL peak collected from
Raman and PL spectra were applied by Raman test system (Renishaw the MoS2 films is located at 1.86 eV (blue curve), corresponding to 667
inVia) under the excitation of the 532 nm laser with a laser power of 5 nm. Moreover, The PL peak position of WS2 is situated at 1.96 eV (636
mW at room temperature. The electrical and photoelectric characteris­ nm), agreeing with the A-exciton emission peak of single-layer WS2[28].
tics were measured by a semiconductor parameter analyser (Agilent However, there are two peaks in the PL spectra of the heterojunction
B1500A) and probe station (JANIS ST-500) with 405, 532 and 635 nm (yellow curve in Fig. 2c), which are derived from MoS2 and WS2
laser at room temperature. respectively by fitting the data, which further implies the formation of

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Fig. 1. Preparation and topography of MoS2/WS2 vertical heterostructure by CVD method. (a) Schematic diagram of CVD growth of pure monolayer MoS2 and WS2
thin films. (b) and (c) Optical microscope images of as-transferred MoS2/WS2 vertical heterojunction at different magnifications. (d) AFM image of MoS2/WS2 film.
(e) The corresponding AFM height profiles at the marked black line from (d), revealing thickness of MoS2 and WS2 film to be ~ 0.85 nm and 0.8 nm. (f) Low-
magnification HRTEM image of the MoS2/WS2 film. (g) HRTEM image at the position framed by a red square in (f). (h) shows the corresponding selected area
electron diffraction (SAED) pattern of heterostructure.

heterostructures. In the MoS2/WS2 heterojunction, compared with the We used a plane-wave basis set with a 500 eV cutoff energy and a 21 ×
corresponding peaks of individual monolayers, the peak of MoS2 slightly 21 × 1 gamma-centered mesh of special K-points for integrations over
red shifts to 1.83 eV, and that of WS2 slightly blue shifts to 1.97 eV. This the Brillouin zone. A cell size and vacuum space region of the con­
energy shifts can be attributed to the interlayer coupling[29,20] be­ structed cell is 3.2 and 15 Å, respectively. Fig. 3a,b,c shows calculated
tween two layers, and the average coupling strength is calculated to be band structures of MoS2, WS2 and MoS2/WS2 heterostructure, respec­
~ 0.045 eV. In addition, the peak intensity of MoS2/WS2 heterojunction tively. In Fig. 3a,b, it is found that calculated monolayer MoS2 and WS2
is lower than that of pure WS2, which can be caused by charge transfer exhibit a direct band gap of 1.64 eV and 1.78 eV, respectively. However,
[29]. As shown in Fig. 2d, the energy band structure of MoS2/WS2 MoS2/WS2 vertical heterostructure has indirect band gap of 1.42 eV (see
heterojunction belongs to type-II[30–31], which is conductive to the Fig. 3c), whose conduction band minimum and valence band maximum
effective separation of electron-hole pairs. The electrons in the con­ are located at K and Γ points in the Brillouin zone, which will lead to a
duction band are transferred from WS2 to MoS2, and the hole transfer type-II band alignment structure. In addition, we notice that compared
path in the valence band is reversed, which would cause the separation with single-layer MoS2 and WS2, the band gap of heterojunction is
of photo-generated electrons and holes. reduced due to the van der Waals coupling between MoS2 and WS2.
To further understand the band structure of these materials, first Fig. 3d displays projected density of states (PDOS) on MoS2 and WS2
principle simulation was implemented in the Vienna Ab-initio Simula­ layer. After photoexcitation, holes photo-generated in MoS2 layer will
tion Package (VASP) based on the plane-wave basis set, and exchan­ have the chance to transfer into the WS2 because its valence band
ge–correlation terms proposed by Perdew-Burke- Ernzerh of generalized maximum is lower than that of WS2, while the electrons photo-
gradient approximation (PBE-GGA) were employed. Projector generated in MoS2 layer will stay in MoS2 since its conduction band
augmented wave (PAW) is used to describe the electron–ion interaction. minimum is also lower than WS2. In addition, holes photo-generated in

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X. Lin et al. Applied Surface Science 546 (2021) 149074

Fig. 2. Structural properties of the MoS2/WS2 heterostructure samples. (a) Optical image of MoS2/WS2 heterojunction. (b) Raman and (c) PL spectra for pure
monolayer WS2, MoS2 and MoS2/WS2 heterostructure, respectively. (d) Schematic diagram of band alignment and charge transfer process for MoS2/WS2 hetero­
junction. The electrons are transferred from WS2 to MoS2, and holes are moved from MoS2 to WS2, leads to built-in electric field. (e) and (f) Frequency-selected
Raman intensity mapping of the MoS2/WS2 heterojunction at 350 and 385 cm− 1, respectively.

WS2 will remain in WS2 film, and electrons may be transferred to MoS2 oxidation of Mo[32–33]. As shown in Fig. 4c, the W 4f spectra involves
layer, so that the effective separation of electron-hole pairs can be W 4f7/2, W 4f5/2, and W 5p3/2 peaks with the binding energies of 33.4,
achieved. 35.5, and 39.6 eV, respectively, while the S 2p3/2 and S 2p1/2 states
correspond to the peaks at the binding energies of 162.8 and 164 eV
respectively in Fig. 4d. All of the XPS measurements suggest that the
3.3. Surface composition and chemical states analysis MoS2/WS2 heterojunction is composed of elements of Mo, W and S
species, which implies the formation of heterostructure [34].
To again more detailed surface composition and chemical states
about the MoS2/WS2-transferred, the surface elemental of hetero­
structure were tested by the XPS spectroscopy, as shown in Fig. 4. From 3.4. Electrical characteristics analysis
the wide-scan spectra (see Fig. 4a), the W 4f, S 2p, Mo 3d, Mo 3p and Si
2p peaks are observed for the heterojunction. High-resolution XPS In order to further investigate the electrical characteristics of MoS2/
spectra of Mo 3d, W 4f and S 2p orbitals peaks were also acquired from WS2 heterostructure, photodetectors based on pristine monolayer WS2,
the MoS2/WS2 films in Fig. 4b-d. In Fig. 4b, the Mo 3d5/2 and Mo 3d3/2 MoS2 and MoS2/WS2 heterojunction were fabricated on SiO2/Si sub­
peaks at 229.9 and 233 eV can be attributed to Mo4+ in MoS2. We note strates. The schematic diagram of the device based on the MoS2/WS2
that there is no peak of 236 eV in this curve, corresponding to the Mo6+ sample is shown in Fig. 5a. Fig. 5b illustrates the output characteristic
3d3/2 orbital peak, suggesting Mo is completely sulfided without curves (Ids − Vds) of the heterostructure-based photodetector with

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X. Lin et al. Applied Surface Science 546 (2021) 149074

Fig. 3. Electronic structures of monolayer MoS2, WS2 and MoS2/WS2 vertical heterojunction in (a) (b) (c), respectively. (d) Projected density of states (PDOS) on
MoS2 and WS2 layer. Photoexcited electron-hole pairs will effectively separate into different layers.

different gate voltages (Vgs), and the inset is optical image of MoS2/WS2 are ~ 108 and 12 cm2V-1S-1 at Vds = 6 V respectively. At the same time,
device. From these curves, we can see that the value of source-drain the electrical performance of pure MoS2 and WS2 photodetectors has
current (Ids) also increases as the Vgs increases from 0 V to 60 V. also been studied, and the results were given in Fig. 5d-f. Fig. 5d,e shows
When MoS2 is in contact with WS2 film, the Fermi levels of MoS2 and output and transfer characteristics curves of the MoS2 device, and on/off
WS2 become equal in order to balance the electric potential. However, ratio of > 106 and electron mobility of 2.6 cm2V-1S-1 are achieved when
the positive gate voltage may increase the Fermi level of MoS2/WS2, Vds = 6 V. For pristine WS2-based photodetector, the transfer curves (in
which will decrease the barrier height and further increase the carrier Fig. 5f), on/off ratio of 106 and electron mobility of 0.03 cm2V-1S-1 are
concentration and hence lead to an increase in current[35]. Moreover, achieved, which is lower than pure MoS2 and MoS2/WS2-based devices.
the corresponding transfer characteristic curve (Ids − Vgs) of this device Generally, the enhanced performance, including on/off ratio and elec­
was displayed in Fig. 5c. It can be clearly shown that the Ids increases tron mobility, suggests that the MoS2/WS2 heterostructures have huge
with Vgs varying from − 60 to 60 V, which reflects a typical n-type potential in future nanoelectronics applications.
characteristics of the heterojunction[36], while both MoS2 and WS2
devices achieved in this study exhibit n-type behavior. When a bias
3.5. Optoelectronic characteristics analysis
voltage is applied to the device, a small current is generated between
source and drain, and a larger bias voltage is conducive to the separation
The optoelectronic properties of photodetectors based on pristine
and transmission of electron-hole pairs[37]. Additionally, according to
MoS2, WS2 and MoS2/WS2 heterostructure were also measured under
this curve, on/off ratio and electron mobility can be calculated, which
the laser wavelength of 405, 532 and 635 nm at room temperature. The

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X. Lin et al. Applied Surface Science 546 (2021) 149074

Raw

Mo 3d5/2
a b

C 1s
S 2s
Mo 3d5/2
Mo 3d3/2

Mo 3d3/2
Mo 3d5/2

Mo 3d3/2
intensity (a.u.)
intensity (a.u.)

S 2p3/2
S 2p1/2
Si 2p

Mo 3p3/2
Mo 3p1/2
W 4f7/2
W 4f5/2

S 2s
0 50 100 150 200 250 300 350 400 450 500 224 228 232 236
Binding energy (eV) Binding energy (eV)

S 2p3/2
W 4f7/2

Raw d Raw
W 4f5/2

W 4f7/2 S 2p3/2
W 4f5/2 S 2p1/2

intensity (a.u.)

S 2p1/2
W 5p3/2
intensity (a.u.)

W 5p3/2

30 32 34 36 38 40 42 158 160 162 164 166 168

Binding energy (eV) Binding energy (eV)
Fig. 4. Surface elemental and chemical states about the transferred-MoS2/WS2 films. (a) Wide-scan XPS spectra obtained from MoS2/WS2 heterostructure for binding
energy ranging from 0 to 500 eV shows the presence of Mo, W and S elements. (b) (c) (d) Detailed XPS spectra of Mo, W and S peaks, respectively.

Ids-Vds curves of devices based on isolated MoS2, WS2 and MoS2/WS2 photocurrent of pure MoS2 and WS2 devices are illustrated in
heterojunction were plotted under the irradiation of 405, 532 and 635 Figure S3d and Figure S4d, further confirming the enhanced photosen­
nm lasers with different incident power density, respectively. As shown sitivity of MoS2/WS2 heterostructure.
in Fig. 6a-c, the values of Ids of MoS2/WS2 device are increased with the Furthermore, responsivity (R) and specific detectivity (D*), two
increasing laser power density regardless of the wavelength of lasers. important parameters for a photodetector, are calculated and displayed
Obviously, the Ids is proportional to the incident power density, indi­ with the wavelength of 405, 532 and 635 nm in Fig. 6e,f. R can be
cating more photo-induced electro-hole pairs will be separated with expressed by R = Iph/PS, where S represents effective illuminated area of
increasing power intensity, which resulted in higher photocurrent[38]. the device. The D* is usually used to evaluate the sensitivity of the de­
In addition, we can notice that the photocurrent excited by the 405 nm vice, which is obtained from the equation D*= RS1/2/(2eIdark)1/2, where
laser is larger than that of 532 and 635 nm laser, which is caused by the e stands for the charge of an electron, and Idark determines the dark
photon energy of the laser. The dark current of MoS2/WS2-based current. According to the equations above, the R and D* of MoS2/WS2
photodetector is 4.8 × 10-11 A, and the current of 3.64 × 10-7 А is photodetector are calculated to be 298 A/W and 2.38 × 1011 Jones, 198
achieved under the irradiation of 405 nm (39.4 mW/cm2) at Vds = 1 V, A/W and 1.59 × 1011 Jones, 124 A/W and 9.9 × 1010 Jones under the
Vgs = 5 V. In addition, pristine MoS2 and WS2 devices were fabricated illumination of 405 nm (0.09 mW/cm2), 532 nm (0.09 mW/cm2) and
and studied with the channel length of 2 μm. From Figure S3 and 635 nm (0.1 mW/cm2), respectively. Besides, we can observe that both R
Figure S4, the Ids of MoS2- and WS2-based photodetector is slightly and D* reduce monotonically when the laser power intensifies, sug­
increased with the increasing laser power density under 405, 532 and gesting highly related to the power intensity. Compared with the laser
635 nm lasers respectively, compared with MoS2/WS2-based intensity-dependent responsivity and detectivity curves of isolated MoS2
photodetector. and WS2 (see Figure S3e,f and S4e,f), it can be clearly seen that the
It is well known that the incident power density plays a significant performance of the heterojunction-based photodetector has been
role in modulating the photocurrent. The photocurrent Iph = Ids - Idark significantly improved, which is attributed to interlayer coupling and
was extracted from the output characteristics of the MoS2/WS2-based charge transfer of the heterojunction. When the laser is irradiated to a
device under dark and illuminated conditions. As shown in Fig. 6d, The single semiconductor material, electrons in the valence band absorb the
Iph shows a strong dependence on laser power intensity under 405, 532 energy of the photon and move to the conduction band to form electron-
and 635 nm when Vds = 1 V. And the experimental data is fitted by the hole pairs, resulting in an increase in conductivity, which is called
following power formula: Iph = APα, in which A is a constant for given photoconductive effect. However, when MoS2 and WS2 samples are
wavelength, P determines laser power density and α is an exponent. binded together to form heterostructures, a type II band alignment
From the fitting data, α is obtained to be 0.77, 0.54 and 0.52 under 405, structure is formed, as shown in Fig. 2d. In order to achieve balance
532 and 635 nm laser, respectively. The laser power intensity-related between electron potential, electrons and holes would separate into

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X. Lin et al. Applied Surface Science 546 (2021) 149074

Fig. 5. Electronic properties of photodetectors based on MoS2/WS2 heterosructure, and pristine single-layer MoS2 and WS2 nano-films. (a) Schematic diagram of the
MoS2/WS2 heterostructure-based photodetector. (b) The output and (c) Transfer characteristics of the device which has n-type behavior. The inset of (b) shows
optical image of MoS2/WS2 photodetector. (d) Ids-Vds and (e) Ids-Vgs characteristics of the MoS2 photodetector, and the inset of (d) shows optical image of MoS2
device. (f) The transfer curve of isolated WS2 device. Both MoS2 and WS2 devices show a typical n-type behavior, indicating that Fermi level lies closer to the
conduction band for each crystals.

Fig. 6. Optoelectronic properties of MoS2/WS2-based device. (a) (b) and (c) show output characteristics curves of photodetector under the irradiation of 405, 532
and 635 nm laser with different power density, respectively. Plots of the photocurrent (d), responsivity (e) and detectivity (f) as a function of power density for device
based on MoS2/WS2 vdW heterojunction under 405 nm (red curve), 532 nm (blue curve) and 635 nm (yellow curve) lasers.

different layers, that is, electrons in the conduction band will be trans­ resulting in an increase of electron concentration in MoS2 channel and
ferred from WS2 to MoS2, and the holes in the valence band will be hole concentration in WS2 channel, which is equivalent to an increase of
transferred from MoS2 to WS2, which leads to the n-doping and p-doping conductance of MoS2 and WS2 at the same time, thereby obtaining a
for MoS2 and WS2 respectively. Under the condition of laser illumination larger photocurrent.
and applied bias, the photo-generated electron-hole pairs are separated, The transient photocurrent response properties of the MoS2/WS2-

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X. Lin et al. Applied Surface Science 546 (2021) 149074

based photodetector are also examined at room temperature. Figure S5 caused by separation and recombination speed of electron-hole pairs far
illustrates time-related current of MoS2/WS2 device using 405, 532 and exceeds the photogating effect. Table 1 lists the R and response time of
635 nm laser with power density of 15 mW/cm2 at Vds = 3 V. The reported photodetectors based on isolated MoS2, WS2 MoS2/WS2 and
semiconductor materials will absorb photons to generate electron-hole other heterostructures [18,39–43]. Through the above data, it is clearly
pairs under laser illumination, and the electron-hole pairs are sepa­ seen that heterostructure-based device shows a recoverable current
rated under the action of a bias voltage[36–37], which increases the response over several on/off laser illumination cycles, which suggests
current. Fig. 7a shows the time-dependent current response of the MoS2/ the well stability and reliability. As a result, the 2D MoS2/WS2
WS2 transistor at different power density when repeatedly switching the
405 nm laser on and off, respectively. As the laser power density in­
creases, the photocurrent performs an increasing trend, which is Table 1
consistent with the previous experimental data. The time-related current Reported optoelectronic performance parameters including responsivity and
response time of the transistors based on pristine MoS2, WS2, MoS2/WS2 and
of MoS2/WS2 device at different positive source–drain voltage Vds is also
other heterostructures.
measured under the illumination of 405 nm (12.2 mW/cm2), as shown
in Fig. 7b. The photocurrent can be significantly increased with Sample Wavelength Responsivity (A/ Response time References
(nm) W) (ms)
increased Vds. Additionally, we can also observe that photocurrent is
equally sensitive with negative Vds, as shown in Fig. 7c. The response MoS2 532 15.6 100 40
WS2 532 18.8 × 10-3 60 41
speed of the MoS2/WS2 photodetector to laser is also our concern,
WSe2/ 532 2700 17 42
therefore the high-resolution time-resolved current is tested under 405 MoS2
laser with a power of 12.2 mW/cm2 in Fig. 7d. From this curve, we can MoS2/ 633 1.42 – 39
obtain that response time is 9 ms, which is superior or comparable to WS2
pristine MoS2 device (see Figure. S6). The semiconductor materials have MoS2/ 532 2.3 120 18
WS2
defects, such as S vacancies, which will cause photogating effect, that is,
WS2/ 450 40 45 43
part of the carriers will be trapped by the defects and cannot participate MoS2
in conduction. This will increase photoresponsivity of the device and MoS2/ 405 298 9 this work
reduce response speed. The fast response speed in this paper may be WS2

Fig. 7. Time-related current of MoS2/WS2-based photodetector with an interval of 5 s with 405 nm laser under different conditions. (a) Time-dependent current
response of heterostructure-based photodetector with increasing power density at the bias of 1 V. (b) Time dependence of current with the laser (12.2 mW/cm2)
switching on/off under positive Vds from 1 to 5 V for MoS2/WS2 device. (c) Photocurrent-time curves during laser (12.2 mW/cm2) on/off switching under operation
of bias (3 V and − 3 V). (d) Photoresponse speed test of photoswitching behavior of MoS2/WS2 photodetector at P = 12.2 mW/cm2, Vds = 3 V.

8
X. Lin et al. Applied Surface Science 546 (2021) 149074

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Acknowledgements [22] L. Samad, S.M. Bladow, Q. Ding, J. Zhuo, R.M. Jacobberger, M.S. Arnold, et al.,
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This work was supported by the Natural Science Foundation of
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Tianjin City (Grant Nos. 18JCZDJC30500, 17JCYBJC16100 and [23] J.Y. Chen, L. Liu, C.X. Li, J.P. Xu, Chemical Vapor Deposition Growth of Large-Area
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China (Grant No.2017YFB0405600) and National Natural Science Lett. 36 (2019), 037301, https://doi.org/10.1088/0256-307X/36/3/037301.
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