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Gas Sensors

Stabilizing MoS2 Nanosheets through SnO2 Nanocrystal
Decoration for High-Performance Gas Sensing in Air
Shumao Cui, Zhenhai Wen, Xingkang Huang, Jingbo Chang, and Junhong Chen*

The unique properties of MoS2 nanosheets make them a promising candidate for
high-performance room temperature sensing. However, the properties of pristine
MoS2 nanosheets are strongly influenced by the significant adsorption of oxygen
in an air environment, which leads to instability of the MoS2 sensing device, and
all sensing results on MoS2 reported to date were exclusively obtained in an inert
atmosphere. This significantly limits the practical sensor application of MoS2 in an
air environment. Herein, a novel nanohybrid of SnO2 nanocrystal (NC)-decorated
crumpled MoS2 nanosheet (MoS2/SnO2) and its exciting air-stable property for room
temperature sensing of NO2 are reported. Interestingly, the SnO2 NCs serve as strong
p-type dopants for MoS2, leading to p-type channels in the MoS2 nanosheets. The
SnO2 NCs also significantly enhance the stability of MoS2 nanosheets in dry air. As a
result, unlike other MoS2 sensors operated in an inert gas (e.g. N2), the nanohybrids
exhibit high sensitivity, excellent selectivity, and repeatability to NO2 under a practical
dry air environment. This work suggests that NC decoration significantly tunes the
properties of MoS2 nanosheets for various applications.

1. Introduction attention because of its significant direct band gap (1.8 eV),
large surface-to-volume ratio, and outstanding field-effect
Recently, 2D-layered materials have attracted extensive transistor (FET) behavior.[10,13,14] For example, single-layered
interest due to their unique structures and properties as MoS2 showed unique FET properties with a high current on/
well as various applications, which include sensors, solar off ratio of 1 × 108 and a mobility of about 200 cm2 V−1 s−1 at
cells, water splitting, electrocatalysis, lithium-ion batteries, room temperature.[10] Consequently, significant research has
and supercapacitors.[1–9] As a model of 2D nanomaterials, been devoted to the demonstration of pure MoS2 nanosheets
graphene-based materials have been widely reported for for various potential applications, such as sensors,[15,16] catal-
electronic devices;[10,11] however, the lack of a band gap in gra- ysis,[17] photonics,[18,19] and energy storage.[20] However, there
phene significantly limits its application in transistor devices are still ample opportunities in tuning the properties of MoS2
because it cannot reach a low off-state current.[12] In addition nanosheets for advanced applications.
to graphene, molybdenum disulfide (MoS2), which is a tran- The unique properties of MoS2 nanosheets make them
sition metal dichalcogenide, has been attracting increasing a promising candidate for high-performance room tempera-
ture sensing materials. Both single- and few-layered MoS2
nanosheets have been demonstrated for the detection of
Dr. S. M. Cui, Dr. Z. H. Wen, Dr. X. K. Huang, various gases, such as NO,[15] NO2,[21–23] NH3,[16,22,23] and
Dr. J. B. Chang, Prof. J. H. Chen triethylamine.[24] However, the properties of pristine MoS2
Department of Mechanical Engineering nanosheets are strongly influenced by the significant adsorp-
University of Wisconsin-Milwaukee tion of oxygen in an air environment; the on-state current, car-
Milwaukee, WI 53211, USA
rier concentration, and carrier mobility dramatically degrade
E-mail: jhchen@uwm.edu
with the accumulative exposure to ambient oxygen.[25,26] This
DOI: 10.1002/smll.201402923 fact at least partially explains our observation that all sensing

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results on MoS2 reported to date were exclusively obtained properties in dry air. We confirmed this result by measuring
in an inert atmosphere (e.g., N2), which significantly limits the the sensing performance of pure MoS2 nanosheets and the
practical sensor application of MoS2 in an air environment. MoS2/SnO2 nanohybrids in a dry air environment. Unlike
Coupling graphene with nanocrystals (NCs) has opened pure MoS2 nanosheets, lack of stability, the sensors based on
up new frontiers in science and technology and significantly the MoS2/SnO2 nanohybrids show outstanding stable sensing
expanded the application of graphene.[2] While maintaining performance for room temperature detection of NO2 in a dry
the unique properties of NCs and those of graphene, novel air environment with high sensitivity, excellent reversibility,
properties emerge due to the interaction between the NCs and selectivity. Our results indicate that the properties of
and the nanosheets. Coupling MoS2 nanosheets with NCs to MoS2 nanosheets can be effectively engineered through the
form nanohybrids is also a promising strategy for designing decoration of MoS2 nanosheets with carefully selected NCs.
novel properties, overcoming the limitations and expanding
the applications of MoS2 nanosheets. For example, it was
previously reported that the Pt–MoS2 nanohybrids exhibited 2. Results and Discussion
much higher electrocatalytic activity toward the hydrogen
evolution reaction compared with the commercial Pt catalysts Figure 1a illustrates the synthesis procedure for crumpled 2D
having the same Pt loading.[27] Nevertheless, most studies to MoS2/SnO2 nanohybrids. First, an MoS2 suspension in water
date have focused on decorating MoS2 nanosheets with noble was prepared based on a lithium exfoliation method.[32] The
metal nanoparticles (e.g., Pt, Pd, Ag, and Au).[27,28] Currently, MoS2 nanosheets were negatively charged due to the electron
there is very limited research on MoS2 nanosheets function- transfer between the lithium compound and the MoS2.[17] The
alized with other nanomaterials, such as metal oxides. Tin resulting suspension showed a uniform yellow color. Then, an
oxide (SnO2) is an n-type semiconducting sensing material SnCl4 solution was added dropwise into the MoS2 suspen-
with unique gas adsorption properties and typically oper- sion under strong stirring; the yellow suspension gradually
ates at elevated temperatures (>200 °C).[29,30] SnO2 is also a changed into a water mixture containing a large number of
promising material to tune the room temperature properties black precipitates. During this process, tin ions were depos-
of 2D nanomaterials, such as graphene.[31] ited on the MoS2 surface due to the electrostatic interaction
Herein, we report for the first time that nanohybrids of between positively charged tin ions and negatively charged
SnO2 NC-decorated MoS2 nanosheets (MoS2/SnO2) can be MoS2 nanosheets. Finally, the MoS2/SnO2 nanohybrids were
facilely prepared through a wet chemistry method. Surpris- obtained by annealing the black precipitate in a tube furnace
ingly, the MoS2/SnO2 hybrids show p-type semiconducting at 300 °C for 2 h in an argon (Ar) environment.
behavior that is different from MoS2 (n-type) and SnO2 After the chemical exfoliation, a large fraction of the
(n-type). More importantly, the nanohybrids showed stable MoS2 nanosheets were in an octahedral phase (1T-MoS2),

Figure 1. a) Schematic illustration of the preparation process for MoS2/SnO2 nanohybrids. The inset photographs show the MoS2 suspension in
water before and after adding the SnCl4 solution. b) An SEM image of the 2H-MoS2 nanosheets. c–g) SEM images of the MoS2/SnO2 nanohybrids:
c) overview of a MoS2/SnO2 film, d) magnified image in the center, e) magnified image in the edge, and f,g) high-resolution SEM images showing
that SnO2 NCs decorate on the MoS2 nanosheets.

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which is metallic.[32] Annealing the 1T- MoS2 at 300 °C for
1 h in Ar led to the transformation from the metallic octa-
hedral phase to a semiconducting trigonal prismatic phase
(2H-MoS2), which is consistent with previous studies.[32]
Figure 1b shows a scanning electron spectroscopy (SEM)
image of the 2H-MoS2 nanosheets on a silicon wafer. The
nanosheets exhibit a 2D-layered structure, and the wrinkles
demonstrate the flexibility of the nanosheets. To reveal the
number of layers in the 2H-MoS2 nanosheets, atomic force
microscopy (AFM) imaging and thickness measurements
were carried out (Figure S1, Supporting Information). Based
on the height profiles, the nanosheets have a thickness of
2–3 nm. Because the thickness of a monolayer MoS2 is about
1 nm,[32] our MoS2 nanosheets consist of ≈2–3 layers. The
thickness of MoS2 nanosheet is an important factor influ-
encing the sensing sensitivity. A previous study showed that
the sensitivity of the MoS2 thin film decreased dramatically
with the increasing thickness (2–16 nm).[21] This is because
the thickness increase lowers the surface-to-volume ratio of
the MoS2, resulting in the decrease of sensitivity.
The morphology of the as-prepared MoS2/SnO2 nano-
hybrids was examined through SEM imaging (Figures 1c-g).
Unlike the flat MoS2 nanosheets, the MoS2/SnO2 nanohy-
brids exhibit a distinct crumpled structure (Figure 1c). The
magnified images (Figure 1d,e) reveal that the MoS2/SnO2
nanohybrids still maintain the 2D structure of MoS2, but with
a large number of wrinkles on their surfaces. The crumpled
surface can be observed more clearly with a high-resolu-
tion SEM image (Figure 1f). The SnO2 NCs are also clearly
observed and uniformly distributed on the crumpled MoS2
surface (Figure 1g). For comparison, the morphology of the
MoS2 nanosheets coated with tin ions was also captured Figure 2. a–c) TEM images, d) SAED pattern, and e, f) HRTEM images
(Figure S2, Supporting Information), and a similar crumpled of the MoS2/SnO2 nanohybrids. The inset of (f) shows a typical SnO2
structure was observed likely due to the adsorption of tin nanocrystal on the MoS2 surface.
ions. The nanohybrids were further characterized by energy
dispersive X-ray spectroscopy (EDX) (Figure S3, Supporting spacings of 0.27 and 0.16 nm, respectively. Because the lat-
Information). The EDX spectrum indicates that there is only tice spacings of the SnO2 (101) plane and the 2H-MoS2 (100)
Mo, S, Sn, and O in the structure (Figure S3b, Supporting plane are very similar, the SAED rings overlap each other,
Information). The elemental mapping results show that all leading to a sharper ring than the rest. Nevertheless, the well-
of the elements are uniformly distributed, which further con- defined rings indicate both 2H-MoS2 and SnO2 are crystalline
firms the uniform dispersion of SnO2 NCs in the MoS2/SnO2 instead of amorphous. The nanostructure of the MoS2/SnO2
nanohybrids. nanohybrids was further confirmed using HRTEM images
To obtain further information about the MoS2/SnO2 (Figure 2e,f). Crystalline SnO2 NCs on MoS2 nanosheets with
nanohybrids, transmission electron microscopy (TEM) and clear lattice fringes can be observed. The sizes of the NCs
high-resolution transmission electron microscopy (HRTEM) are very small, about 2–5 nm. The labeled lattice spacing of
were used to investigate the nanostructure. TEM images 0.34 nm is indexed to the (110) plane of the rutile SnO2. The
(Figure 2a,b) reveal that the MoS2/SnO2 nanohybrids show a folded edges of MoS2 nanosheets allow the observation of
crumpled fabric-like structure with obvious wrinkles over the the number of layers (1–3) in the MoS2 nanosheets with a
entire thin film. A typical magnified TEM image is shown in spacing of 0.62 nm between layers (Figure 2f), which is con-
Figure 2c, clearly demonstrating the curved MoS2 nanosheets sistent with the AFM data discussed above.
coated with a thin layer of SnO2 NCs. The selected area elec- The MoS2/SnO2 nanohybrids were also investigated using
tron diffraction (SAED) pattern of the MoS2/SnO2 nano- resonance Raman (RR) spectroscopy and compared with
hybrids with well-defined rings is composed of two parts pure MoS2 nanosheets (Figure 3a). The RR spectra show
(Figure 2d). The rings marked with solid straight lines (from that both the pure MoS2 nanosheets and the MoS2/SnO2
inside to outside) are indexed to rutile SnO2 (110), (101), nanohybrids show typical peaks from the 2H-MoS2, which is
and (211) planes, corresponding to the lattice spacings of consistent with a previous report.[33] The surface composition
0.34, 0.27, and 0.18 nm, respectively. The rings marked with of the MoS2/SnO2 was characterized by X-ray photoelectron
dashed straight lines (from inside to outside) are indexed to spectroscopy (XPS). Figure S4 (Supporting Information)
semiconducting 2H-MoS2 (100) and (110) planes with lattice shows the entire survey spectra, illustrating the presence of

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a 403
452
Si
b Mo4+ 3d5/2
Mo4+ 3d3/2

Intensity (a.u.)

Counts (a.u.)
379
Mo6+ 3d5/2
597 632
184 225 564
MoS2 Mo6+ 3d3/2
S 2s
MoS2/SnO2

200 400 600 800 240 236 232 228 224
Raman shift (cm-1) Binding energy (eV)

c S2- 2p3/2 d Sn 3d5/2

S2- 2p1/2 Sn 3d3/2

Counts (a.u.)
Counts (a.u.)

S 2p3/2
S 2p1/2

168 164 160 156 500 496 492 488 484
Binding energy (eV) Binding energy (eV)

Figure 3. a) RR spectra of MoS2 nanosheets and MoS2/SnO2 nanohybrids. The peak at 520 cm−1 is from the Si wafer that served as the sample
support. b–d) High-resolution XPS spectra of Mo 3d, S 2p, and Sn 3d, respectively.

Mo, S, Sn, and O in the nanohybrids, which is consistent with oxygen in air, which traps electrons.[25,26] We have observed
the EDX results. Figures 3b-d show the high-resolution XPS the same phenomenon in this work with our 2H-MoS2
spectra of Mo 3d, S 2p, and Sn 3d, respectively. Most of the nanosheets. The current versus voltage (I–V) curve of the
Mo signal is from its +4 oxidation state at the peak positions pure 2H-MoS2 nanosheets (Figure S5a, Supporting Informa-
around 229.2 and 232.3 eV, corresponding to Mo4+ 3d5/2 and tion) obtained immediately after the annealing shows a non-
Mo4+ 3d3/2, respectively (Figure 3b). linear curve with a resistance of ≈21 MΩ, indicating a strong
Meanwhile, the peaks centered at about 232.9 and 235.9 eV Schottky barrier at the interface between the 2H-MoS2
are attributed to the +6 oxidation state of the Mo, which nanosheets and the gold electrodes consistent with the pre-
is likely due to partial oxidation of the MoS2[34] and was vious report.[16] However, with 12 h exposure to the dry air,
also observed in the S 2p region of the spectra (Figure 3c). the resistance of the device increased to ≈200 MΩ (inset of
Besides the two dominant doublet peaks of 2H-MoS2 in the S Figure S5a, Supporting Information). The FET behavior
2p region (S 2p3/2 and S 2p1/2) centered at 162.0 and 163.0 eV, clearly shows that the pure 2H-MoS2 obtained immediately
additional peaks located at higher binding energies were after the annealing is an n-type semiconductor (Figure S5b,
observed, which further confirms the +6 oxidation state of Supporting Information). Nevertheless, the transfer curve
the Mo.[34] However, we did not find any diffraction ring from shows a bipolar characteristic with a Dirac point at about
the crystalline MoO3 (corresponding to the +6 oxidation +5 V of gate (inset of Figure S5b, Supporting Information)
state of the Mo) in the SAED pattern nor any NC assigned after 12 h exposure to the dry air, indicating a significant
to MoO3 in the HRTEM images (Figures 2d-f). A previous p-doping effect through the oxygen adsorption in the dry air.
study showed that MoS2 nanosheets were stable even under This cumulative oxygen adsorption would cause the device to
thermal annealing at 300 °C in air.[35] However, since the fail in a short time due to the significant electron trapping.
defects and edges of MoS2 are highly reactive with oxygen,[36] For the FET of MoS2 nanosheets, the Schottky barrier
some oxygen was likely bonded to defects and edges of the at the electrode interface suppresses the electron transport
MoS2 nanosheets in the nanohybrids.[26] Figure 3d presents between the electrode and the MoS2, which may cause a low
the Sn 3d region of the spectra, showing two typical sym- carrier mobility of the MoS2 nanosheets.[37] In contrast, a low-
metric peaks of SnO2 with binding energies of 486.5 and resistance ohmic contact provides a direct injection channel
495.1 eV for Sn 3d5/2 and Sn 3d3/2, respectively. at the interface that minimizes the interface's influence on
It has been reported that the on-state current of pristine intrinsic properties of MoS2 nanosheets. With the deposition
2H-MoS2 significantly degrades due to the adsorption of of SnO2 NCs on the MoS2 nanosheets, a straight line of the

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150
a 100 MoS2/SnO2
b 122
MoS2/SnO2
120
50
118

Ids (nA)
Ids (nA) 0

-50 116

-100 114

-150 112
-4 -2 0 2 4 -40 -20 0 20 40
Vds (V) Vg (V)

c 30 1.0 0.5 ppm
10 ppm 10 d 30 100
Δ G/G0(%)

log10(ΔG/G0)
0.5 10
0.0
20 0 500 1000 20 1

Δ G/G0(%)
Δ G/G0(%)

Time (s) 8
0.1
0 2 4 6 8 10
7 Concen tration (ppm)
10 10
5
0.5 1 2
0
0
0 3000 6000 9000 0 2 4 6 8 10
Time (s) Concentration (ppm)

e 30 10 10 10 ppm f 30
NO2
H2
20 CO
20 H2S
ΔG/G0(%)
ΔG/G0(%)

NH3
10
10

0
0
0 2000 4000 0 500 1000 1500
Time (s) Time (s)

Figure 4. a) I–V and b) Transfer curve of MoS2/SnO2 nanohybrids. c) Dynamic sensing response of the MoS2/SnO2 nanohybrids toward different
NO2 concentrations. The inset is the enlarged sensing response curve for 0.5 ppm NO2. d) Sensitivity variation of the MoS2/SnO2 sensor as a
function of NO2 concentration. The inset is a linear fitting of log10 (ΔG/G0) versus concentration. e) Three successive sensing cycles of the MoS2/
SnO2 nanohybrid sensor. f) Sensing response of the MoS2/SnO2 nanohybrid to various gases at a concentration of 10 ppm.

I–V curve for the nanohybrids was observed (Figure 4a), indi- after the oxygen adsorption in the dry air (Figure S5b, Sup-
cating an ohmic contact between the MoS2/SnO2 and the gold porting Information), the p-type transport characteristic of
electrode. Interestingly, the transfer curve (Figure 4b) shows the MoS2 nanosheets was relatively weak. The work func-
a p-type behavior for the nanohybrids, which is dramatically tion of SnO2 is about 5.7 eV,[38] which is larger than that of
different from the n-type of pure 2H-MoS2 (Figure S5b). MoS2 (5.2 eV),[37] leading to electron transfer from the MoS2
Zhang and co-workers[35] first reported the conversion of nanosheets into the SnO2 NCs in the nanohybrids. Thus, the
MoS2 from an n-type to a p-type by the thermal annealing of discrete SnO2 NCs layer acts as a thin layer of hole injection,
few-layer MoS2 nanosheets in air. The MoO3 fragments that leading to p-type channels in the MoS2 nanosheets. There-
formed on the top layers of the MoS2 acted as p-type dopants, fore, we believe that the large number of SnO2 NCs served
leading to a p-type channel in the annealed MoS2 nanosheets. as strong p-type dopants for the MoS2 nanosheets, which
In this work, two possible mechanisms are responsible for the was the dominant mechanism for the p-type behavior of the
p-type semiconducting MoS2 nanosheets, the oxygen chem- nanohybrids.
isorption and the decoration of the SnO2 NCs. However, pre- The sensing performance of the MoS2/SnO2 nanohybrid
vious studies have shown that the MoS2 nanosheet retains an was evaluated through the electrical conductance change
n-type semiconducting behavior after heavy oxygen adsorp- upon exposure to low concentration NO2. It should be noted
tion (both chemical and physical adsorption).[25,26] Although that all sensing tests were performed under a dry air envi-
we observed the Dirac point at about +5 V of gate voltage ronment at room temperature, and the NO2 was diluted in

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air. Figure 4c illustrates the dynamic sensing response of the However, our MoS2/SnO2 nanohybrid sensor did not show
sensor against various NO2 concentrations. The sensor sen- enhancement in the sensing performance to NO2 under a
sitivity was defined as S = ΔG/G0, where ΔG is the sensor positive gate voltage, likely due to the relatively weak gate
conductance change before and after the NO2 exposure, and dependence of the hybrid. Further investigation on this phe-
G0 is the sensor electrical conductance in the dry air. It is nomenon is underway.
obvious that the sensor conductance increased upon expo- To further demonstrate repeatable sensor responses, the
sure to NO2. Based on our previous experimental and theo- same sensor was exposed to 10 ppm NO2 for three succes-
retical studies, the SnO2 NC surfaces were reactive for NO2 sive cycles (Figure 4e). Consistent sensing responses with
adsorption, forming a NO3 complex on the surface.[31,39] In excellent recovery characteristics were observed with a sen-
this work, the surfaces of MoS2 nanosheets were decorated sitivity of 28%, indicating the excellent repeatability of our
with a layer of SnO2 NCs that likely served as the major sensor. Based on the analysis of the sensing response, the
gas adsorption centers. When the NO2, which is an electron response time of the sensors, which is defined as the time
acceptor, was adsorbed by the SnO2 surface, electron transfer required for achieving 90% of the entire sensing response,
occurred from the SnO2 to the NO2.[31] Since the MoS2 is about 6.8 min for 10 ppm NO2, which is comparable with
nanosheets in the MoS2/SnO2 nanohybrids acted as the con- that of other high performance NO2 gas sensors as well as
ductance channels with p-type semiconducting behavior, the recent reports on MoS2 sensors.[23,40,44] The surface binding
electron transfer significantly shifted the Fermi level to the energy of SnO2 and the NCs loading density on MoS2
valance band, leading to a decrease in resistance. could be key factors influencing the response speed, which
The sensing response increased with the increasing con- could be enhanced by doping SnO2 by other elements and
centration of NO2 from 0.5 to 10 ppm, and the sensor had increasing the loading density of SnO2. The average recovery
the same response under the same NO2 concentration time (defined as the time for recovering 90% of the sensing
(e.g., 10 ppm) as shown in Figure 4c. The sensing signal response) was about 2.7 min. It is worth noting that our
experienced low noise; although the sensitivity (≈0.6%) for sensor completely recovered in a dry air flow, which is unlike
0.5 ppm NO2 is relatively small (inset of Figure 4c), it still can other graphene-based or carbon nanotube-based NO2 sen-
be defined as the lower detection limit of the sensor based on sors that require thermal annealing, inert gas, or UV light
a signal (S)-to-noise (N) ratio (S/N > 3). This is comparable to facilitate recovery,[40,44,45] likely due to the relatively weak
with or lower than the experimental lower detection limits binding between the sensing material and the gas molecules.
of other high-performance NO2 sensors as well as recent The same sensor was measured after storage in the air at
reports on MoS2-based sensors, such as chemically modi- room environment for 11 months (Figure S7, Supporting
fied graphene (1 ppm),[40] reduced graphene oxide (rGO)- Information). Compared with the original sensing perfor-
conjugated Cu2O nanowire mesocrystals (0.4 ppm),[41] and mance, the sensor still responded well to NO2 with slight
Pt-decorated MoS2 (0.5 ppm).[15] The lower detection limit of degradation of sensitivity.
our sensor is much lower than the permissible exposure limit To illustrate the important role of SnO2 NCs on the
(5 ppm) of NO2 recommended by Occupational Safety and stability of MoS2 nanosheets, a sensor device using pure
Health Administration, and meets the detection requirement 2H-MoS2 was prepared and characterized against 10 ppm
of recommended exposure limit (1 ppm) by National Insti- NO2 diluted in a dry air environment. Compared with
tute for Occupational Safety and Health. The lower detection MoS2/SnO2, the MoS2 sensor was unstable because of the
limit also can be further improved by several methods, such oxygen adsorption in the dry air, and the conductance
as using one single-layer MoS2 nanosheet as the conduct- of the device kept shifting negatively under a constant
ance channel and increasing the SnO2 NC density on the bias (Figure 5a). The conductance decrease in the diluted
MoS2 nanosheet. The exposure time to NO2 in each sensing NO2 gas was attributed to both NO2 and oxygen adsorp-
cycle was 10 min. Most of the responses did not reach the tion. Therefore, we can conclude that the thin layer of
saturated state, indicating that our nanohybrids had a strong SnO2 NCs on the surface of the MoS2 nanosheets greatly
ability to adsorb NO2 molecules and that a higher sensitivity enhanced the stability of the MoS2/SnO2 nanohybrid sensor
can be obtained with a longer exposure time. The sensor also in dry air. On one hand, the work function of the MoS2
responded well to a higher concentration of NO2, such as 100 nanosheets can be well tuned by a p- or n-type-doping
ppm (Figure S6, Supporting Information), indicating a wide treatment, and the p-type dopants increase the work func-
detection range. tion of the MoS2 nanosheets due to the electron transfer
Figure 4d shows the sensitivity variation as a function of from the MoS2 nanosheets to the p-type dopants.[46] In
NO2 concentration. The log10(ΔG/G0) linearly increased with this work, SnO2 NCs act as the strong p-type dopants for
the increasing NO2 concentrations (inset of Figure 4d), which the MoS2 nanosheets, which is evidenced by the change
will facilitate the determination of gas concentrations in of transfer curve (Supporting Information Figure S5b
practical applications. Since the conductivity of FET devices and Figure 4b). Therefore, the work function of the MoS2
can be tuned by varying the gate voltage, this may provide likely increased after the p-doping of SnO2 NCs due to the
an effective route to obtain a better sensitivity of FET sen- electron transfer from the MoS2 nanosheets to SnO2 NCs,
sors.[42] For example, the sensitivity of rGO FET sensor was leading to an increase in hole concentration in the MoS2
greatly enhanced for NH3 sensing by applying a positive gate nanosheets. This increase in holes would degrade the elec-
voltage.[43] Similarly, MoS2 FET sensors also had a higher tron-donating ability of the MoS2 nanosheets when oxygen
sensitivity to NO2 by applying a gate voltage of 30 V.[23] (electron accepter) approaches the surface, which means

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to SnO2, and the Schottky barrier, ΦB, is generally influ-
enced by the electronic state of SnO2. These electron deple-
tion zones may connect with each other on the surface of
MoS2 nanosheets and could serve as a passivation layer to
prevent the interaction between the oxygen and the MoS2,
thereby leading to significantly improved stability of MoS2/
SnO2 nanohybrids in dry air (Figure 5c). To further demon-
strate the role of SnO2 NCs, we measured the stability of
MoS2 functionalized with different loadings of SnO2 NCs
in dry air (Figure S8, Supporting Information). It is obvious
the stability was gradually enhanced with the increasing
NC loading.
The MoS2 nanosheet sensors are usually responsive to
multiple gases, which suggests inadequate selectivity similar
to pristine graphene sensors.[15,16,21,24] For example, MoS2
sensors are sensitive to both NO2 and NH3. Fortunately, the
sensor with MoS2/SnO2 nanohybrids showed excellent selec-
tivity for NO2 (Figure 4f). To investigate the selectivity of
the nanohybrids, the same sensor was measured against sev-
eral other gases (i.e., H2, CO, H2S, and NH3) under the same
concentration (10 ppm) in a dry air environment. Figure 4f
demonstrates the dynamic sensing responses, showing very
weak responses to all gases except NO2. The good selectivity
for NO2 is likely attributed to the deposited SnO2 NCs. Our
previous experimental and theoretical studies demonstrated
that SnO2 NCs selectively enhanced the sensing performance
of rGO and carbon nanotubes to NO2 at room tempera-
ture.[31,39,47] Similarly, the uniformly dispersed SnO2 NC thin
layer on the MoS2 surface could be dominant in the sensing
interaction between the nanohybrid and gas molecules,
which greatly enhanced the selectivity of the MoS2/SnO2
nanohybrids.
Compared with graphene, MoS2 could be a better choice
for FET-based sensors, due to its proper band gap and high
on/off current ratio. In general, sensing materials with better
semiconducting properties show a higher sensing response,
because the charge carrier density can be substantially
affected by the small charge transfer between the gas and
the semiconducting material.[48] A previous study showed
that a p-type MoS2 had a better sensing performance to
NO2 than rGO in an N2 environment, which was attributed
to the better switching behavior of MoS2.[21] To prove that
Figure 5. a) The room temperature dynamic sensing response of MoS2 the MoS2/SnO2 is better than rGO/SnO2 for NO2 detec-
nanosheets with and without SnO2 NC decoration against 10 ppm NO2
tion, rGO/SnO2 nanohybrids were prepared using a simple
in a dry air environment, indicating the SnO2 NCs significantly enhanced
the stability of MoS2 in the dry air. b) Band diagram of the MoS2/SnO2 wet chemical method.[49] The nanostructure was studied by
nanohybrid. The EF,SnO2 and EF,MoS2 are Fermi levels of SnO2 and MoS2, HRTEM (Figure S9, Supporting Information). Because the
respectively. The CB and VB are the conductance and valance band SnO2 NCs serve as the adsorption centers, the loading den-
edges of MoS2, respectively. d is the thickness of the electron depletion sity likely affects the sensor sensitivity, which increases with
zone, and ΦB is the Schottky barrier height. c) Schematic of the MoS2/ increasing NC coverage. The coverage of SnO2 NC was meas-
SnO2 nanohybrid structure and the electron depletion zone formed at
ured by counting the NCs in the HRTEM images, and it is
the interface.
about 3 and 7 NCs 100 nm–2 for MoS2/SnO2 and rGO/SnO2,
respectively. The sensing responses of MoS2/SnO2 and rGO/
MoS2 nanosheets have a lower reactivity with oxygen. On SnO2 nanohybrids were measured upon exposure to 10 ppm
the other hand, electron depletion zones, d, formed at the NO2 at room temperature (Figure S10, Supporting Informa-
interface between the n-type SnO2 NCs and the p-type tion). Although the rGO/SnO2 has higher NC coverage, the
MoS2 nanosheets due to the electron transfer induced by sensor based on MoS2/SnO2 had a higher sensitivity, a faster
the work function difference between SnO2 and MoS2 as recovery, and a lower signal noise than the sensor based on
mentioned above (Figure 5b). The electron transfer also rGO/SnO2 nanohybrids, indicating that MoS2 is superior to
caused a built-in electric field directed from MoS2 toward rGO as the conductance channel in an FET sensor.

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DOI: 10.1002/smll.201402923
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3. Conclusions followed by drying in air. Then the sensor device was annealed in
a tube furnace at 300 °C in Ar for 2 h to form MoS2/SnO2 nanohy-
In summary, we have demonstrated a novel nanohybrid of brids to bridge the electrode gap.
SnO2 NCs decorated on MoS2 nanosheets and their high-per- Sensing Tests: The sensing tests were carried out in an air-
formance practical gas detection in a dry air. The SnO2 NCs tight chamber with electrical feedthroughs. A constant voltage
served as the strong p-type dopants on top of MoS2, leading to was applied to the device and the variation of conductance was
p-type channels in the MoS2 nanosheets. The SnO2 NCs also monitored and recorded with the changes in the gas environment
significantly enhanced the stability of the MoS2 nanosheets in using a Keithley 2602 source meter. In a typical test for this work, a
dry air by increasing their work function and creating a pas- sensing measurement cycle has three continuous steps: (1) intro-
sivation layer to prevent the interaction between the oxygen ducing a dry air (dew point –62 °C) flow as a background, then
and the MoS2. Thus, our sensors based on MoS2/SnO2 nano- (2) injecting NO2 gas balanced with dry air (0.5–10 ppm) to reg-
hybrids operated in a practical dry air environment instead of ister a sensing signal, and (3) introducing a dry air flow again
under protection by an inert gas. Moreover, this new sensing for sensor recovery. All gas flows were precisely controlled using
platform shows a high sensitivity, excellent repeatability, and mass-flow controllers.
selectivity to NO2 with a low signal noise. The lower detec- Material Characterization: SEM and EDX (Noran Si:Li detector)
tion limit can reach a concentration of 0.5 ppm. This work were carried out with a Hitachi S-4800 electron microscope. AFM
indicates that NCs decoration significantly tunes the proper- was performed using an Agilent Technology 5420 AFM with a can-
ties of MoS2 nanosheets. The MoS2/NC nanohybrid structures tilever (Nanosensors PPP-NCH). The structure of the as-produced
can potentially open up a new avenue for various applica- nanohybrids was characterized by TEM (Hitachi H-9000-NAR),
tions, such as sensors, catalysis, and energy storage. HRTEM, and SAED (at an acceleration voltage of 300 kV). The
surface chemical composition was characterized using XPS (HP
5950A). RR spectra were taken using a Raman spectrometer (Ren-
4. Experimental Section ishaw 1000B) with a 633 nm laser excitation.

Material Synthesis: The MoS2 nanosheets were prepared
using a chemical exfoliation method.[32] Typically, 0.5 g of natural
MoS2 crystals (Sigma-Aldrich) were immersed in 10 mL of 1.6 m
n-Butyllithium solution in hexane (Sigma-Aldrich) for 7 d in a flask Supporting Information
filled with argon gas. Li-intercalated MoS2 (LixMoS2) was retrieved
by centrifugation and washed with hexane three times under the Supporting Information is available from the Wiley Online Library
protection of argon to remove the excess lithium and organic resi- or from the author.
dues. Then 200 mL deionized water was added into the flask con-
taining the LixMoS2 and sonicated for 1 h. The MoS2 nanosheets
were retrieved and washed with water several times by filtering Acknowledgements
the mixture through a mixed cellulose ester membrane with 25 nm
pores (Millipore). The suspension of MoS2 nanosheets was pre- Financial support for this work was provided by the U.S. National
pared by sonicating the retrieved MoS2 with a sonicator horn in Science Foundation (IIP-1128158) and the University of Wisconsin-
deionized water for 10 min. Milwaukee Research Foundation Bradley Catalyst Grant.
In a typical process to prepare MoS2/SnO2 nanohybrids, 2.5 mL
of SnCl4 (0.01 m) solution was added dropwise into a 40 mL MoS2
suspension (0.2 mg mL–1) with magnetic stirring (600 rpm). The
black precipitate was collected by centrifugation and dried in air
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DOI: 10.1002/smll.201402923