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Sulfur-Vacancy-Enriched MoS2 Nanosheets Based Heterostructures

for Near-Infrared Optoelectronic NO2 Sensing
Yi Xia, Chenyu Hu, Shenghui Guo, Libo Zhang, Mingjun Wang, Jinhui Peng, Lei Xu,* and Jing Wang*
Cite This: ACS Appl. Nano Mater. 2020, 3, 665−673 Read Online

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ABSTRACT: Transition metal dichalcogenide nanostructures

especially MoS2 have emerged as novel gas sensing materials.
Particularly, MoS2-based optoelectronic devices activated by UV or
visible light have been demonstrated as promising candidates for
room temperature NO2 sensors. Here, we propose a novel room-
temperature optoelectronic NO2 sensor based on sulfur-vacancy-
enriched MoS2 (SV-MoS2). SV-MoS2 nanosheets were efficiently
fabricated by a microwave-hydrothermal method, and their
enhanced optical absorption and optoelectronic properties in the
near-infrared (NIR) light region were experimentally and
theoretically investigated. The optoelectronic gas sensors based on SV-MoS2 exhibited enhanced performance to ppb level of
NO2 under NIR light illumination at room temperature. In addition, through functionalization with ZnO quantum dots, the SV-
MoS2/ZnO nanocomposites exhibited a further enhancement in responses with fast response/recovery rates, full reversibility, and
sub-ppb detection limit to NO2 at room temperature. The significant NO2 sensing improvement was due to the improved charge
generation and transfer induced by sulfur vacancy under NIR light illumination. In addition, the sensor shows satisfied stability,
reliable selectivity, and humidity resistance at room temperature. Therefore, this work provides an alternative approach to high-
performance, low-power-consumption optoelectronic NO2 gas sensors working at room temperature, which can also be applied to
other transition metal dichalcogenides for optoelectronic devices.
KEYWORDS: MoS2, sulfur vacancy, optoelectronic gas sensing, NO2, near-infrared light, 2D/0D heteostructures

1. INTRODUCTION
As a dangerous air pollutant, even nitrogen dioxide (NO2) with
ppb concentration will have adverse effects on human health
and ecosystem.1 Developing real-time operating NO2 gas
sensors has received continuous attention. Employing metal
oxide nanostructures at high temperatures (>150 °C) has been
proved to improve the performance of NO2 sensors.2
Considering that the NO2 sensors working at room temper-
ature should have the characteristics of security, low power
consumption, and being easy to combine with wearable
devices3 has been focused in many research. However, most of
the NO2 sensors composed of nanostructured metal oxides do
not perform well at room temperature in practical applications.
Recently, transition metal dichalcogenide (TMDs) nanostruc-
tures, especially MoS2 nanosheets, have emerged as novel NO2
gas sensing materials.4−7 Moreover, various techniques such as
morphology and defects engineering, noble metal functional-
ization, and nanocomposite design have been utilized to
further enhance the room-temperature sensing performances
of MoS2.8,9 According to the previous studies, most MoS2-
based room temperature NO2 sensors still have the problems
of slow response/recovery rate, low sensitivity, or poor room
temperature reversibility.
Compared with the thermally activated gas sensor, the one
using light illumination is cheaper and simpler, which can
significantly improve the performance of the sensor and
become the research hotspot at present.10−12 Under the action
of light illumination, the separation of electrons and holes is
produced and strengthened. Photoinduced free electrons
transfer to the electrophilic NO2 to obtain NO2−, which
promotes the surface adsorption and electron transfer. That is
to say, the photocurrent here can be used for NO2 detection,
realizing the replacement of dark current in semiconductor.
Accordingly, MoS2-based optoelectronic NO2 sensors activated
by UV and visible light have been recently developed and
showed improved room-temperature sensing perform-
ance.13−16 However, the illuminating efficiency of UV and
visible light would sometimes be limited due to their poor
penetration into film and the light scattering by the film
surface.17,18 Moreover, the utilization of UV and visible light
would also be a high-power consumption. Therefore, the NIR-
Received: November 6, 2019
Accepted: December 27, 2019
Published: December 27, 2019

© 2019 American Chemical Society https://dx.doi.org/10.1021/acsanm.9b02180

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Scheme 1. Construction of NIR Light Active SV-MoS2 Based Nanostructures
activated optoelectronic NO2 sensors would be highly
attractive for practical applications due to their low power
consumption, effective illumination, wide applicability, and
improved device integration. So far, near-infrared (NIR) light
has seldom been utilized by room temperature optoelectronic
gas sensors. Some recent studies suggested that the rich sulfur
vacancies in MoS2 nanostructures would lead to their
enhanced optical absorption and optoelectronic properties in
the NIR light region.19,20
Inspired by these previous findings, herein, we proposed a
novel optoelectronic gas sensor based on sulfur-vacancy-
enriched MoS2 (SV-MoS2), which exhibited highly enhanced
NO2 sensing performance under NIR light illumination at
room temperature (Scheme 1). To further enhance the sensing
performance of SV-MoS2, ZnO quantum dots (QDs) were
used to construct heterostructures with SV-MoS2 due to their
ultrafine particle size, unique physical and chemical properties,
and good sensitivity to NO2.21,22 The functionalization of SV-
MoS2 with ZnO quantum dots further improved the sensor
sensitivity, response rates, and reversibility due to the
enhanced charge separation. Therefore, this work provides an
alternative approach to high-performance, low-power-con-
sumption optoelectronic NO2 gas sensors working at room
temperature, and such a strategy can also be applied to other
transition metal dichalcogenides for optoelectronic devices.
2. EXPERIMENTAL SECTION
2.1. Materials Synthesis. For synthesis of sulfur-vacancy-
enriched MoS2 nanosheets (SV-MoS2), Na2MoO4·2H2O and thiourea
(molar ratio = 1:5) were added in 40 mL of distilled water and
subsequently hydrothermally treated under microwave irradiation
(SpeedWave Xpert, 2450 MHz, up to 2000 W, Berghof, the heating
rate is 25 °C/min) at 210 °C for 10 min. The black precipitate was
washed, filtered, and dried at 80 °C overnight. For comparison, the
experiment was also carried out under conventional hydrothermal
treatment at 210 °C for 24 h to obtain conventional MoS2 nanosheets
(C-MoS2). ZnO QDs were prepared by dropwise adding 65 mL of
0.03 mol/L KOH ethanol solution to 125 mL of 1 mol/L Zn(AC)2·
2H2O ethanol solution at 60 °C for 120 min under stirring, followed
by centrifuging at 10 000 rpm and drying at room temperature
overnight. The SV-MoS2/ZnO (the mass ratio of ZnO = 2%, 5%,
10%, and 20%) was obtained by mixing SV-MoS2 and ZnO QDs in
ethanol for 120 min at room temperature and then washing and
drying at room temperature overnight.
2.2. Characterization. The microstructures of the specimens
were investigated by FESEM (Nova NanoSEM 630, FEI, USA),
HRTEM, and infrared spectroscopy (FT-IR, Shimadzu, Japan)
(Tecnai G2 TF30, FEI, USA). The defect structures of the specimens
were studied by a powder XRD spectrometer (Rigaku Dmax-2200,
Japan, λ = 0.154 178 nm), an electron paramagnetic resonance
spectrometer (EPR, JEOL-TE300), and an XPS equipment (PHI-
5300, PHI, USA). The I−V responses and photoresponse properties
of the devices fabricated by different samples were analyzed by a
Keithley 2614B equipment with an applied voltage of 1 V at 25 °C.
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2.3. Computational Method. All the calculations are conducted
based on the reported density functional theory methods.23,24 The
DFT-D3 approach is employed to describe the van der Waals
interaction of long range.25 400 eV is designated as the cutoff energy
for plane wave, and 10−5 eV is chosen as the energy criterion in
iterative solution of the Kohn−Sham equation. The electronic
properties of the perfect structure and defective structure with an S
vacancy are investigated in 4 × 4 × 1 supercells. The Brillouin zone
integration is performed using a 2 × 2 × 2 k-mesh. All the structures
remain relaxed until the residual forces on the atoms are smaller than
0.03 eV/Å.
2.4. Gas Sensor Fabrication and Tests. In this study, we
selected (100) n-type silicon wafers as the sensing substrates, and
there was a thermal growth of SiO2 substrates (the thickness is 300
nm) on the surfaces. The interdigital electrode of Ti/Au (finger
width, gap width = 10 μm) was constructed by photolithography. To
prepare the sensing film, the obtained MoS2 based materials were
added into deionized water/ethanol mixing solution (the volume ratio
= 1:1) to form a 3.0 mg·mL−1 suspension. Then, the suspensions were
spun on the interdigital electrodes, respectively, followed by drying at
the temperature of 90 °C for the duration of 2 h. The obtained
sensors were put into a homemade chamber with gas inlet and outlet.
The carrier gas is dry air, and the airflow is 200 mL/min (the
humidity is adjusted from 0−80%). A xenon lamp with a Y-43 cutoff
filter (λ > 780 nm, light intensity = 0.71 mW·cm−2) was employed as
the UV source. The resistance variation of sensors was analyzed by a
Keithley 2700 equipment at room temperature of 25 °C. The
response of the sensor for oxidizing gas and reducing gas is defined as
Ra − Rg Rg − Ra
Rg
× 100 (%) and Ra
× 100 (%), respectively, where Rg and
Ra represent the film resistance in target gases and in air, respectively.
The time required for resistance to reach 90% in the process of
response/recovery is defined as the response/recovery time.
3. RESULTS AND DISCUSSION
3.1. Sulfur-Vacancy-Enriched MoS2 with Near-Infra-
red Adsorption. Conventional MoS2 (C-MoS2) and sulfur-
vacancy-enriched MoS2 (SV-MoS2) were obtained by conven-
tional- and microwave-hydrothermal treatment of the
precursor solution containing Na2MoO4·2H2O and thiourea.
As shown in Figure 1a and Figure 1b, both samples exhibited
nanosheet-assembled flower-like morphology; however, the
SV-MoS2 sample showed smaller assembly size due to the fast
nucleation rate under microwave-hydrothermal condition. The
HRTEM images (Figure 1c,d) clearly display the few-layer
stacked structures of the nanosheets with estimated interplanar
spacings of 0.63 and 0.67 nm for C-MoS2 and SV-MoS2,
respectively. In addition, more distortions and kinks could be
observed in the slabs of SV-MoS2 nanosheets, indicating the
higher concentration of defects in the SV-MoS2 sample.
The nature of the defects in the MoS2 nanosheets was
identified by using X-ray diffraction (XRD), electron para-
magnetic resonance (EPR), and X-ray photoelectron spectros-
copy (XPS). Both samples (C-MoS2 and SV-MoS2) could be
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Figure 1. SEM images (a, b) and HRTEM images (c, d) of C-MoS2
(a, c) and SV-MoS2 (b, d) samples.
indexed to pure hexagonal MoS2 (JCPDS No. 37-1492) in
XRD patterns (Figure 2a). The typical (002) peak of SV-MoS2
(2θ = 13.4°, d = 0.670 nm) showed an obvious shift compared
to that of C-MoS2 (2θ = 14.2°, d = 0.629 nm), consistent with
the TEM observations. The enlarged (002) d-spacing in SV-
MoS2 may be attributed to the lattice expansion induced by
sulfur vacancy defects according to some previous reports.26 In
addition, different peaks were observed in C-MoS2 and SV-
MoS2. The different peaks displayed in XRD may be attributed
to the different defective structures of C-MoS2 and SV-MoS2.
The sulfur-vacancy-enriched structures of SV-MoS2 may
induce the peak shift and the change of peak intensity.
Therefore, C-MoS2 and SV-MoS2 exhibit different XRD peaks.
In the EPR spectra (Figure 2b), the signal detected around
∼3505 G could be assigned to the dangling bonds from the
sulfur vacancies in the MoS2. The stronger EPR signal of SV-
MoS2 suggested its enriched sulfur vacancy defects.27 XPS was
used to further investigate the defect-related surface species in
the MoS2 samples. The Mo 3d XPS spectra of both samples
consisted of two sets of peaks corresponding to intrinsic
Mo(+IV) and undercoordinated Mo(UC) (Figure 2c). The
deconvoluted peaks at 232.7 and 229.6 eV, and 231.7 and
228.5 eV correspond to the Mo 3d5/2 and Mo 3d3/2 of intrinsic
Mo(+IV) and undercoordinated Mo(UC), respectively.
Obviously, the contribution of the undercoordinated Mo(UC)
increased in the SV-MoS2 sample. As a result, the doublets
Figure 2. XRD (a), EPR (b), and Mo 3d XPS (c) spectra of C-MoS2 and SV-MoS2 samples.
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were shifted to the lower binding energy side. This confirmed
that the density of sulfur vacancies was highly enriched in the
microwave-produced SV-MoS2 sample, since the XPS peak
area ratio of Mo(UC)/Mo(+IV) was reported to be directly
associated with the sulfur vacancies.28 As shown in Figure S1, a
long time (>720 min) is required to produce MoS2 nanosheets
under conventional hydrothermal treatment (Figure S1a),
while about 120 mg of MoS2 could be obtained only in 10 min
via microwave heating (Figure S1b). Therefore, the formation
of the sulfur-vacancy-enriched structure may be attributed to
reduced barrier of nucleation and ultrafast crystallization of
MoS2 induced by microwave irradiation (the reaction time
needs only 10 min),27 leading to the decreased number of
sulfurs that can be incorporated with Mo. FT-IR spectra of the
two samples (Figure S2) indicated that SV-MoS2 displayed
strong absorption bands associated with CS, C−N, and N−
H,26 which were very weak for C-MoS2, implying that more
unreacted thiourea remained during the rapid microwave
hydrothermal process. The Mo:S ratios of SV-MoS2 and C-
MoS2 are calculated from the peak areas of the XPS patterns as
1:1.57 and 1:1.84, respectively, indicating the sulfur-vacancy-
enriched structures of SV-MoS2. Therefore, the microwave-
assisted hydrothermal method provides a simple and efficient
(reaction time: 10 min) route for the production of MoS2
nanosheets with rich sulfur vacancies.
The optical performance of the C-MoS2 and SV-MoS2 based
devices was recorded via UV−vis−NIR absorbance spectra
(Figure 3). The absorption peak of C-MoS2 appeared at
Figure 3. UV−vis−NIR absorbance spectra of C-MoS2 and SV-MoS2
samples.
around 490 nm, while the SV-MoS2 sample exhibited an
obvious red shift and broad absorption in the wavelength range
of 750−1100 nm. The enhanced near-infrared (NIR)
absorption of SV-MoS2 suggested that the apparent band gap
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of MoS2 was narrowed, which should be attributed to the
possible formation of sulfur-vacancy-induced new energy levels
between conduction band and valence band of MoS2.
The mechanism for sulfur-vacancy-induced NIR absorption
of MoS2 was investigated through band structures and density
of states (DOS) within the DFT-PBE approach. The band
structures of MoS2 without and with sulfur vacancy were
studied in 4 × 4 × 1 supercells, and the results are displayed in
Figure 4a and Figure 4b. Evidently the presence of S-vacancy
Figure 4. Band structures of MoS2 without (a) and with (b) S-
vacancies; corresponding density of electronic states (DOS) for MoS2
without and with S-vacancies (c); (d) schematic illustration of the
transition process of the exciton corresponding to NIR absorption of
MoS2 with S-vacancies.
modifies the band structure and introduces three extra
localized states within the MoS2 band gap (Figure 4b).
There are two unoccupied states at about 0.63 eV below the
conduction band (CB), while the other shallow state is around
the valence band (VB), which may be related to the broken
trigonal crystal field around molybdenum atoms. As a result, a
new defect level appears within the band gap as indicated by
the DOS results (Figure 4c and Figure S3), causing the band
gap narrowing compared to that of S-vacancy-free MoS2.
Therefore, the NIR absorption mechanism of SV-MoS2 can be
schematically illustrated in Figure 4d. The NIR light induced
exciton in SV-MoS2 mostly corresponds to the optical
transitions in the VB and S-vacancy states of SV-MoS2. On
Figure 5. I−V responses of the C-MoS2 (a) and SV-MoS2 (b) devices analyzed in the dark and under NIR light illumination; (c) single pulse
photocurrents of C-MoS2 and SV-MoS2 devices measured under NIR light illumination.
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the basis of the above calculation results, the enhanced optical
absorption of SV-MoS2 in the NIR region can be attributed to
the generation of a defect energy level induced by S-vacancy.
3.2. Near-Infrared Optoelectronic NO2 Gas Sensor
Based on SV-MoS2. The C-MoS2 and SV-MoS2 samples were
incorporated into optoelectronic devices, and their photo-
response properties under NIR light illumination (λ > 780 nm,
light intensity of 0.71 mW·cm−2) were first investigated. Figure
5a and Figure 5b show the I−V curves of C-MoS2 and SV-
MoS2 based devices measured in the dark and under NIR
illumination. Under NIR illumination, the current across the
C-MoS2 based device was almost unchanged, while the current
across the SV-MoS2 based device increased from 0.10 to 0.55
μA at an applied bias of 1.0 V, indicating that the S-vacancy-
enriched MoS2 was optically active to NIR light. Figure 5c
shows the single pulse photocurrents of C-MoS2 and SV-MoS2
based devices measured under NIR light illumination. No
photocurrent could be observed for the C-MoS2 device, while
the SV-MoS2 device showed a dramatic NIR-to-dark current
ratio of ∼18. The optoelectronic measurements further
demonstrated the enhanced optoelectronic property of SV-
MoS2 in the NIR light region. These results also suggested the
potential application of S-vacancy-enriched MoS2 in novel NIR
photodetector and optoelectronic gas sensors.
The optoelectronic gas sensing performance of C-MoS2 and
SV-MoS2 sensors to ppb level of NO2 was then evaluated at
room temperature under NIR light illumination. Although
MoS2-based optoelectronic gas sensors working under UV or
visible light illumination have been previously reported, here,
we presented for the first time, a NIR light-activated gas sensor
based on S-vacancy-enriched MoS2. Figure 6a and Figure 6b
show the dynamics NO2 sensing curves of the C-MoS2 and SV-
MoS2 based sensors in the dark and under NIR illumination;
the corresponding gas responses achieved in these tests were
summarized in Figure 6c. It was observed that the C-MoS2
sensor showed a low response of 0.6% to 200 ppb of NO2 in
the dark, and the response only slightly increased to 0.9%
under NIR illumination, since C-MoS2 exhibited almost no
NIR activity. The SV-MoS2 sensor showed a higher response
of 3.9% to 200 ppb of NO2 in the dark compared to the C-
MoS2 sensor. The enhanced gas sensing by S-vacancy in the
dark could be connected with the possible role of surface S-
vacancies as the active centers for NO2 adsorption. A previous
study demonstrated that sulfur vacancy could reduce the Gibbs
free energy of gas adsorption.29 Moreover, the degree of
electron transfer from MoS2 to NO2 would also increase in the
presence of S-vacancies. Therefore, the SV-MoS2 also showed
better sensing performance in the dark than that of the C-
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Figure 6. Dynamics response curve of C-MoS2 (a) and SV-MoS2 (b) sensors to 200 ppb of NO2 in the dark and under NIR illumination at 25 °C;
(c) summarized gas responses of C-MoS2 and SV-MoS2 sensors in the dark and under NIR illumination; (d) dynamics response curve of SV-MoS2
sensors to 10−200 ppb of NO2 under NIR illumination at 25 °C.

Figure 7. (a) SEM, (b) TEM, and (c) HRTEM images of SV-MoS2 functionalized by ZnO QDs (denoted as SV-MoS2/ZnO); (d) I−V response of
SV-MoS2/ZnO based device analyzed in the dark and under NIR illumination; (e) periodic photoresponse on/off cycle tests of SV-MoS2/ZnO and
SV-MoS2 under NIR illumination; (f) schematic diagram of the charge generation and separation mechanism in the SV-MoS2/ZnO heterojunction
under NIR illumination.

MoS2. By introduction of NIR light illumination, the sensitivity
of the SV-MoS2 device to 200 ppb of NO2 significantly
increased to 45%, indicating that the abundant S-vacancies in
SV-MoS2 play a major role in its improved NO2 sensing
performance under NIR illumination. In combination with the
optical and optoelectronic measurements in Figure 3 and
Figure 4, the S-vacancy enhanced NIR optoelectronic NO2
sensing properties may be closely related to the enhanced light
absorption and optoelectronic properties in the NIR light
region. In other words, the S-vacancy-induced photocurrent
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generated in SV-MoS2 sensor under NIR light could be
employed instead of dark current for the highly effective
sensing of NO2 at room temperature.
The concentration-dependent sensing property of SV-MoS2
based NO2 sensor was also investigated under NIR light at
room temperature. As can be seen in Figure 6d, upon exposure
to NO2 in the range of 10−200 ppb, the SV-MoS2 sensor
exhibited good responses ranging from 9.2% to 45%,
suggesting the high sensitivity of the sensor toward ppb-level
of NO2. Unfortunately, the reversibility and reproducibility of
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Figure 8. (a) Dynamic response curves of the sensors based on SV-MoS2 and SV-MoS2/ZnO to 200 ppb of NO2 under NIR illumination; (b)
dynamic response curves of the sensors based on SV-MoS2/ZnO to 10−200 ppb of NO2. Three gas on−off cycles were performed for 200 ppb of
NO2. Variation of responses (c) and response/recovery times (d) of the SV-MoS2/ZnO sensor with ZnO loading amount (200 ppb of NO2).
the sensor were still unsatisfied due to the continuous baseline
drift, suggesting the insufficient long-term stability of the SV-
MoS2 sensor. Such behavior should result from the high
electron−hole recombination rate in MoS2 as well as the
insufficient desorption of NO2 from MoS2 surface.
3.3. Further Enhanced Gas Sensing Performance by
ZnO QDs Functionalization. Generally, the efficient charge
separation can be realized by construction of heterostructures.
It has been reported that the integration of TMDs with metal
oxides (MO) led to multiple benefits such as improving
optoelectronic electronic property as well as gas sensitivity,
selectivity, and stability issues.4,30−37 However, the application
of the TMD/MO heterostructures in an optoelectronic gas
sensor has not been addressed until now. Since ZnO
nanostructures have been widely demonstrated as an excellent
NO2 gas sensing material, the present work tried to further
enhance the NIR optoelectronic gas sensor performance by
functionalization of p-type SV-MoS2 with n-type ZnO
quantum dots (QDs). Moreover, the formation of 2D/0D
heterostructured SV-MoS2/ZnO nanocomposites was realized
by simply mixing the two components in solution. Such
colloidal self-assembly should be attributable to the strong van
der Waals interactions between 2D/0D nanoscale building
blocks.38−40 Figure 7a shows the morphology of the SV-MoS2/
ZnO nanocomposites containing 10 wt % of ZnO QDs. The
SV-MoS2 nanosheets became rather rough after covering with
ZnO QDs. TEM and HRTEM observations further demon-
strated the successful decoration of 4−8 nm ZnO QDs onto
the MoS2 nanosheet surface (Figure 7b,c). As shown in the
HRTEM image of SV-MoS2/ZnO, the nanoparticles showed a
d-space of 0.26 nm corresponding to the (001) planes of ZnO,
and the clear lattice fingers indicated the high crystallinity of
the nanoparticles (Figure S4a). In addition, the EDS pattern
also demonstrated the presence of Zn and O elements in SV-
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MoS2 (Figure S4b). Moreover, the XPS survey and Zn 2p, O
1s spectra of SV-MoS2/ZnO (Figure S5a−c) further confirmed
the successful deposition of ZnO QDs on the surface of SV-
MoS2. I−V measurement (Figure 7d) indicated that the SV-
MoS2/ZnO device exhibited an enlarged photocurrent of 1.3
μA under NIR illumination at an applied bias of 1 V, and the
dark current was declined to 0.028 μA due to the formation of
heterojunctions with localized depletion regions. In the
periodic photoresponse on/off cycle tests (Figure 7e), the
SV-MoS2/ZnO device exhibited a highly enhanced NIR-to-
dark current ratio of ∼59, being over 3 times higher than that
of the SV-MoS2 device (INIR/Idark ∼ 18). In addition, the SV-
MoS2/ZnO device exhibited a more stable photoresponse as
the maximum photocurrent remained almost unchanged for
each cycle. The enhanced NIR optoelectronic property of SV-
MoS2/ZnO could be explained by the schematic illustration in
Figure 7f. When MoS2 and ZnO are brought into contact, their
Fermi energy levels (EF) become the same due to the band
alignment, and an internal electrostatic field is established at
the heterojunction interface. According to the work functions
of MoS2 (Φ(MoS2) = 5.2 eV) and ZnO (Φ(ZnO) = 4.5 eV),
the conduction band of MoS2 locates above that of ZnO.13,41
Under NIR light illumination, electrons will be photoexcited to
the SV level and further to the conduction band of SV-MoS2.
Because of the effect of the internal electrostatic field, these
NIR light-induced electrons on the conduction band of SV-
MoS2 could then be transferred to those of ZnO. Therefore,
the formation of MoS2−ZnO heterojunction would improve
the charge separation under NIR light illumination, leading to
the enhanced NIR optoelectronic properties of the nano-
composites.
The enhanced optoelectronic property of the SV-MoS2/
ZnO nanocomposites should lead to their further enhanced
NO2 sensing performance under NIR light illumination. As
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Table 1. Comparison of the Developed Presently and Reported TMD Based Sensors for NO2 Sensing at Room Temperature
sensitive material NO2 (ppm) response (%)
WS2−carbon nanofiber 1 15
WS2/ZnS heterostructures 5 32.5
MoS2@WS2 heterojunction 50 27
MoS2/ZnO heterostructures 5 3050
MoS2/SnO2 10 28
MoS2−Pt NPs 1.2 16
thin-layered MoS2 100 54
MoS2 nanosheet−ZnO nanowire (UV light) 0.2 188
MoS2 (UV light) 100 35.16
mixed MoS2 flakes (UV light) 10 −21.78
MoS2 (red light) 0.2 ∼1100
SV-MoS2/ZnO (NIR light) 0.2 226
shown in Figure 8a, the SV-MoS2/ZnO sensor showed a
response of 226% to 200 ppb of NO2 at room temperature,
being much higher than that of the SV-MoS2 sensor (45%).
Moreover, the SV-MoS2/ZnO sensor exhibited a significantly
reduced response and recovery time (75 and 111 s) as
compared to the SV-MoS2 sensor (201 and 247 s). In addition,
the SV-MoS2/ZnO sensor could be fully recovered after
releasing the NO2 gas. Although the functionalization of ZnO
improved the recovery of baseline, the reason is still unclear
until now. In our opinion, with the introduction of ZnO, the
heterojunctions will be formed at the interface between SV-
MoS2 and ZnO, which could act as additional reaction sites to
improve the gas adsorption and desorption. In addition, the
internal electric field built at the SV-MoS2/ZnO interface
enhanced the further oxygen adsorption and charge carrier
transportation. Furthermore, the ZnO layer could act as a
passivation layer to inhibit the interaction among SV-MoS2 and
atmospheric oxygen. Therefore, the baseline of SV-MoS2/ZnO
sensor could be well recovered. The impact of light intensity
ranging from 0.33 to 1.04 mW·cm−2 was investigated for SV-
MoS2/ZnO sensor (Figure S6). The response tended to
saturate at high light intensity, implying that excessive
photogenerated carrier may hinder the gas adsorption.42
Upon exposure to 10−200 ppb of NO2, the SV-MoS2/ZnO
sensor exhibited responses ranging from 36% to 226% (Figure
8b). Excellent reversibility without observable baseline drift
was achieved by the sensor in gas exposure cycles. Also, the
stable responses (224−227%) achieved in three cycles to 200
ppb of NO 2 further confirmed a good repeatability.
Furthermore, the sensor presented an apparently observable
response of 0.7% to 0.1 ppb of NO2 (Figure S7), indicating the
sub-ppb detection limit of macro/mesoporous film at room
temperature. The fabrication of SV-MoS2/ZnO nanocompo-
sites was also optimized by adjusting the content of ZnO QDs
in the range of 2−20 wt %, and the TEM images for typical
samples were displayed in Figure S8. Gas sensing test results
revealed that the maximum response and fastest response and
recovery rates could be achieved at a ZnO loading amount of
10 wt %, as shown in Figure 8c,d. These results suggested that
an optimized coverage of ZnO QDs on MoS2 surface was
critical for achieving the highest sensing performance.
The NO2 sensing performance results of the TMD
nanostructures or nanocomposites based sensors reported in
the present work and the previous studies were listed in Table
1. It was demonstrated that the prepared SV-MoS2/ZnO
sensor had high responses when compared with sensors in
most reports. Although some optoelectronic gas sensors
671
www.acsanm.org Article
response/recovery time detection limit ref
>300 s/>900 s 200 ppb 43
4 s/1000 s 10 ppb 44
1.6 s /27.7 s 10 ppb 7
40 s/>300 s 50 ppb 5
408 s/162 s 500 ppb 45
>20 min/− 500 ppb 46
180 s/600 s not reported 47
about 20 s/20 s 50 ppb 13
29 s/350 s 5 ppm 14
6 s/149 s 10 ppm 15
>500 s/>500 s 25 ppb 16
75 s/111 s 0.1 ppb this work
exhibited higher responses, our sensor showed faster
response/recovery rates. Taking both response and sensing
rate properties into consideration, the presently developed
sensors represented the best room-temperature performance of
TMD-based sensing materials. Notably, our sensors possessed
advantages of their full reversibility and sub-ppb detection
limit. The long-term stability tests also showed that the sensing
response decreased very slightly during the 60 days’ storage in
air (Figure S9). Moreover, the SV-MoS2/ZnO sensor showed
enhanced NO2 selectivity over other gases in comparison to
that of SV-MoS2 sensor, which should be attributed to the
favorable adsorption of NO2 by ZnO QDs (Figure S10). As it
was reported, the surface of ZnO could produce O2− at room
temperature. Owing to the low oxidation ability of O2−, the
reducing gases such as CO, CH4, H2S are hard to interact with
O2−, leading to the low sensitivities of the sensors. Never-
theless, the surface reaction among O2− of the ZnO surface and
the highly electrophilic NO2 gas can be directly achieved even
at room temperature (O2− + e− + NO2 → NO3−), leading to
the improved selectivity of SV-MoS2/ZnO. Furthermore, the
effect of relatively humidity (RH) on the SV-MoS2/ZnO
sensor was also investigated (Figure S11). Although sensor
response decreased at high RH, a response above 150% could
still be obtained to fulfill the requirements of NO2 detection.
Generally, when SV-MoS2/ZnO is in the humid atmosphere,
the interface of the sensing materials will interact with the
water vapor and thus decrease transportation of charge carriers.
In addition, the existence of water molecules could partially
cover the reaction sites of SV-MoS2/ZnO. Therefore, the
increased humidity leads to the decreased NO2 sensing
performance. However, the sensors still show high sensitivity
of 150% at high humidity (80%), indicating that the
photogenerated carriers induced by NIR light may improve
the decomposition and desorption of adsorbed water and thus
increase the tolerance of the sensor to humidity.48 On the basis
of the above results, this work introduces a NIR optoelectronic
NO2 sensor based on sulfur-vacancy-enriched MoS2 nano-
structures, which provides an alternative approach to high-
performance, low-power-consumption gas sensors working at
room temperature.
4. CONCLUSION
In summary, sulfur-vacancy-enriched MoS2 (SV-MoS2) was
fabricated by a microwave-hydrothermal method and incorpo-
rated into a novel room-temperature optoelectronic NO2
sensor. The sulfur-vacancy-enriched structures were studied
by multiple spectroscopy characterizations and density of states
https://dx.doi.org/10.1021/acsanm.9b02180
ACS Appl. Nano Mater. 2020, 3, 665−673
ACS Applied Nano Materials
(DOS) theory calculation. The optoelectronic gas sensor based
on SV-MoS2 exhibited enhanced performance to ppb level of
NO2 at room temperature owing to the sulfur-vacancy-induced
photocurrent generation under near-infrared light illumination.
Moreover, the functionalization of SV-MoS2 with ZnO
quantum dots further improved the sensor sensitivity, response
rates, and reversibility due to the enhanced charge separation.
This work provides an alternative approach to high-perform-
ance, low-power-consumption gas sensors working at room
temperature.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsanm.9b02180.
FT-IR patterns, corresponding density of electronic
states of C-MoS2 and SV-MoS2, HRTEM image, EDX
pattern, Zn 2p and O 1s XPS patterns of SV-MoS2/ZnO,
sensing responses of SV-MoS2/ZnO based sensor under
different light intensity, responses of SV-MoS2/ZnO-
based sensor upon exposure to 0.1 ppb of NO2, TEM
images of SV-MoS2/ZnO composites with different ZnO
content, sensing response of the sensor versus storage
time, NO2 selectivity over other typical gases of the
sensor, and sensing response of SV-MoS2/ZnO under
different humidity under NIR illumination (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Lei Xu − Kunming University of Science and Technolog,
Kunming, China; orcid.org/0000-0001-7130-8625;
Email: xu_lei@kust.edu.cn
Jing Wang − Jiangnan University, Wuxi, China;
orcid.org/0000-0002-4185-1421; Email: jingwang@
jiangnan.edu.cn
Other Authors
Yi Xia − Kunming University of Science and Technology,
and Analytic & Testing Research Center of Yunnan,
Kunming, China
Chenyu Hu − Jiangnan University, Wuxi, China
Shenghui Guo − Kunming University of Science and
Technolog, Kunming, China
Libo Zhang − Kunming University of Science and
Technolog, Kunming, China
Mingjun Wang − Kunming University of Science and
Technology, and Analytic & Testing Research Center of
Yunnan, Kunming, China
Jinhui Peng − Kunming University of Science and
Technolog, Kunming, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsanm.9b02180
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by National Natural Science
Foundation of China (Grants 51802123, 51522405,
51864030), Scientific Research Fund of Yunnan Education
672
www.acsanm.org Article
Department (Grant 2019J0034), Scientific Research Fund of
Kunming University of Science and Technology (Grants
KKSY201732033 and KKZ3201752046), Analysis and Testing
Foundation of Kunming University of Science and Technology
(Grant 2018T20110222), the Natural Science Foundation of
Jiangsu Province (Grant BK20180630), and the Fundamental
Research Funds for the Central Universities (Grant
JUSRP11816).
■
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