RESEARCH ARTICLE | AUGUST 13 2014

MoS2@ZnO nano-heterojunctions with enhanced

photocatalysis and field emission properties 
Ying-Hua Tan; Ke Yu; Jin-Zhu Li; ... et. al

Journal of Applied Physics 116, 064305 (2014)

https://doi.org/10.1063/1.4893020

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 JOURNAL OF APPLIED PHYSICS 116, 064305 (2014)

MoS2@ZnO nano-heterojunctions with enhanced photocatalysis

and field emission properties
Ying-Hua Tan, Ke Yu,a) Jin-Zhu Li, Hao Fu, and Zi-Qiang Zhu
Key Laboratory of Polar Materials and Devices (Ministry of Education of China), Department of Electronic
Engineering, East China Normal University, Shanghai 200241, People’s Republic of China
(Received 29 June 2014; accepted 3 August 2014; published online 13 August 2014)
The molybdenum disulfide (MoS2)@ZnO nano-heterojunctions were successfully fabricated
through a facile three-step synthetic process: prefabrication of the ZnO nanoparticles, the synthesis
of MoS2 nanoflowers, and the fabrication of MoS2@ZnO heterojunctions, in which ZnO nanopar-
ticles were uniformly self-assembled on the MoS2 nanoflowers by utilizing polyethyleneimine as a
binding agent. The photocatalytic activities of the composite samples were evaluated by monitoring
the photodegradation of methylene blue (MB). Compared with pure MoS2 nanoflowers, the compo-
sites show higher adsorption capability in dark and better photocatalytic efficiency due to the
increased specific surface area and improved electron-hole pair separation. After irradiation for
100 min, the remaining MB in solution is about 7.3%. Moreover, the MoS2@ZnO heterojunctions

Downloaded from http://pubs.aip.org/aip/jap/article-pdf/doi/10.1063/1.4893020/15143367/064305_1_online.pdf

possess enhanced field emission properties with lower turn-on field of 3.08 V lm1and lower
threshold field of 6.9 V lm1 relative to pure MoS2 with turn-on field of 3.65 V lm1 and threshold
field of 9.03 V lm1. V C 2014 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4893020]

I. INTRODUCTION H2 evolution and MoS2@WS2 heterostructures with good

electronic and photovoltaic performances have also been
After the discovery and applications of graphene nano-
reported in recent years.15,22 However, much less research
sheets, the two-dimensional (2D) layered nanomaterials have
has been carried out on the MoS2@ZnO nanoheterjunctions.
attracted great attention because of their unique properties
ZnO, as one of the most successful n-type semiconduc-
and wide potential applications.1–4 Molybdenum disulfide
tors, has been widely applied in photocatalysis,23 sensors,24
(MoS2), a typical 2D layered material, composes of Mo
and field emission fields.25 Due to its wide band gap
atoms sandwiched between two layers of hexagonally close-
(3.37 eV), ZnO has been combined with other semiconduc-
packed sulfur atoms.5 Due to its unique layered structure and
tors with narrower band gaps, including Cu2S,26 Cu2O,27
relatively narrow band gap, MoS2 has been particularly im-
CdS,28 CdSe,29 etc., to enhance various performances. Based
portant for lithium battery,6 solid lubricant,7 sensor,8–10
on this point, the MoS2@ZnO heterojunctions may have val-
hydrogen production,11,12 field emission (FE),13 and photoca-
uable applications in electric, optoelectronic and many other
talysis applications.14 However, the intrinsic defects for the
nanotechnology fields. The combination of MoS2 nano-
MoS2, as a kind of single semiconductor, limit its practical
flowers, a narrow band gap p-type semiconductor, and ZnO
applications in many fields, such as photocatalysis and field
nanoparticles, a n-type semiconductor with a wide band gap
emission.15,16 By combining the individual constituents,
and small sizes will enhance light absorption from UV to
some new properties which are difficult to achieve in a single
visible, increase the separation and lifetime of charge car-
system can be presented. Hence, it is highly desirable to de-
riers, and have more tips, which can provide potential appli-
velop MoS2-based composites and unique structures, aiming
cations in photocatalytic and field emission fields.
to overcome inherent defects, such as the high recombination
In this paper, MoS2@ZnO nano-heterojunctions were
rate of the photographed electron-hole pairs and the lack of
fabricated via low-temperature hydrothermal method and
effective emission sites. Combining MoS2 with graphene or
thermal annealing process. In the process of synthesis, polye-
TiO2 can enhance electrochemical performance for lithium
thyleneimine (PEI) was selected as the middle auxiliary to
ion batteries.17–19 MoS2/carbon hybrid possesses high effi-
control the aggregation of nanomaterials and made ZnO
cient platinum-free counter electrode for dye-sensitized solar
nanoparticles uniformly disperse on the MoS2 nanoflowers.
cells.20 Meanwhile, the peculiar heterostructures obtained by
PEI was removed by thermal annealing method. The influ-
coupling two semiconductors with matched energy levels
ence of different S sources on the morphology was dis-
have been extensively studied.21 Because of the enhancement
cussed. In addition, the photocatalytic and field emission
of sunlight absorption and high transfer efficiency of photo-
performances of the as-prepared heterojunctions were meas-
generated carriers, various MoS2-based heterostructures have
ured. The results indicate that MoS2@ZnO heterojunctions
also been fabricated as promising nanomaterials. MoS2@CdS
possess stronger absorption abilities, enhanced photocata-
heterojunctions with high photoelectrochemical activities for
lytic activities, and much better field emission performance
compared with pure MoS2 nanoflowers. Furthermore, corre-
a)
Author to whom correspondence should be addressed. Electronic mail: sponding theoretical explanations of the measured properties
yk5188@263.net. Tel.: þ86 021 54345198. Fax: þ86 021 54345198. were given in detail.

0021-8979/2014/116(6)/064305/9/$30.00 116, 064305-1 C 2014 AIP Publishing LLC

V
064305-2 Tan et al.
II. EXPERIMENTAL SECTION
A. Synthesis of layered MoS2 nanoflowers
All the chemical reagents in our experiment were ana-
lytical graded and used directly without further purification.
The layered MoS2 nanoflowers were synthesized through a
simple hydrothermal method. In a typical reaction, 0.5 g of
sodium molybdate (Na2MoO4.2H2O) powder and 0.7 g of
thiocarbamide (CH4N2S) powder were mixed and dissolved
in 70 ml deionized water. After stirring the solution for
25 min, 0.47 g of citric acid (C6H8O7) was added into the
foregoing mixed solution to adjust the PH value. After mag-
netically stirring for 10 min, the homogeneous solution was
obtained and transferred to a 100 ml Teflon-lined stainless
steel autoclave. The autoclave was sealed and maintained at
200  C for 21 h. Then the autoclave was cooled down to
room temperature. Black precipitates were collected and
washed several times with deionized water and ethanol,
respectively. After drying at 60  C for 6 h, the black powders
were obtained. To improve MoS2 crystallinity, the as-
prepared samples were annealed under an atmosphere of Ar
at 800  C for 1 h in a conventional tube furnace.
B. Synthesis of ZnO nanoparticles
ZnO nanoparticles were also fabricated via the hydro-
thermal route. 10 ml urea solution (2 M) was added into
10 ml zinc chloride solution (0.5 M), which was dissolved in
80 ml deionized water. The solution was magnetically stirred
for 30 min and then transferred to an autoclave, which was
maintained at 140  C for 6 h. After the reaction, the precipi-
tates were collected and washed several times in a centrifuge
(6500 rpm) with deionized water and ethanol to remove any
impurities. Finally, the ZnO nanoparticles were obtained and
kept in deionized water.
C. Synthesis of MoS2@ZnO nano-heterojunctions
A small amount of the as-prepared MoS2 nanoflowers
was dissolved in deionized water and maintained for 30 min
in the presence of PEI solution (2 gl1). The PEI layer gradu-
ally self-assembled on the surface of the MoS2 nanoflowers
to form MoS2-PEI hybrid, which was washed several times
with deionized water. For comparison, different amounts of
the as-synthesized ZnO nanoparticles were added to the
MoS2-PEI solutions. The suspensions were sonicated for
30 min to form the MoS2-PEI-ZnO heterostructures. Then
the mixtures were washed several times with ethanol and
deionized water, dried at 60  C for 4 h and then annealed
under an atmosphere of argon at 600  C for 5 min, which can
remove the PEI and other impurities, meanwhile further
facilitating the combination and growth of the MoS2 and
ZnO to obtain MoS2@ZnO nano-heterojunctions. Based on
many experiments under different amounts of ZnO nanopar-
ticles, the optimal molar ratio of MoS2 to ZnO is 2:1.
D. Characterization
The crystal structure of the products was characterized by
X-ray diffraction (XRD, Bruker D8 Advance diffractometer)
J. Appl. Phys. 116, 064305 (2014)
with Cu Ka radiation (k ¼ 1.5418 Å). The diffraction patterns
were collected in the 2h scanning range of 10–80 with 0.02
per step. The morphologies and structures of the MoS2@ZnO
were characterized by field emission scanning electron mi-
croscopy (FESEM, JEOL-JSM-6700F) at an accelerating volt-
age of 20 kV and transmission electron microscopy (TEM,
Jeol, JEM-2100F) at an accelerating voltage of 200 kV.
E. Photocatalytic measurement
To investigate the photocatalytic properties, methylene
blue (MB) was chosen to examine the photodegradation of the
samples due to its excellent stability under various pH condi-
tions. The concentration of the MB solution was estimated by
monitoring the intensity of the maximum absorption peak
(663 nm). The evaluation of the photocatalytic activity was
performed at room temperature. Prior to light irradiation, the
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photocatalysts (0.02 g) were dispersed into 100 ml MB aque-
ous solution (20 mg l1). The suspensions were magnetically
stirred in the dark for 20 min to ensure the establishment of the
adsorption/desorption equilibrium and estimate the adsorption
ability. Then the clarified solution was analysed by a UV-vis
spectrophotometer (UNICO 2802). The remainder suspension
was illuminated by an 18 W daylight lamp (20 cm above the
reactor) used as a solar-simulated light source. To minimize
the heat effect, the reactor was fixed in a big glass container
and cooled by flowing water at room temperature. The MB
concentration was analysed by the UV-vis spectrophotometer
every 20 min during the total irradiation time of 100 min.
F. Field-emission measurement
The field emission properties of the nanomaterials were
measured using a simple diode configuration in the vacuum
chamber under a pressure of about 2  105 Pa at the room
temperature. We used Si substrates for field emission investi-
gation. The as-prepared MoS2 nanoflowers and MoS2@ZnO
nano-heterojunctions were painted on the Si substrates (as
cathodes) via a screen-printing method, respectively. After
drying at 60  C for 6 h, the Si substrates with nanomaterials
were separated from a phosphor-indium tin oxide (ITO)/glass
anode by two Teflon spacers with a maintained distance of
400 lm. The measured emission area was about 1 cm  1 cm.
In our measurement, the turn-on field is defined as the field
needed to produce a current density of 10 lA cm2 and the
threshold field is the field needed to produce a current density
of 1 mA cm2.
III. RESULTS AND DISCUSSION
A. X-ray diffractogram of the as-fabricated samples
Fig. 1(a) shows the XRD patterns of MoS2 nanoflowers
and MoS2@ZnO composites. It is obvious that all the peaks
in Fig. 1(a-B) (black curve) can be clearly indexed to the
pure hexagonal phase of MoS2 (Molybdenite, JCPDS car
no.37–1492) with lattice constants of a ¼ b ¼ 3.16 Å,
c ¼ 12.29 Å. The observed peaks can be assigned to the (002),
(100), (103), (006), (105), (110) and (008) planes of the hexag-
onal phase MoS2. The most strong peak at 2h ¼ 14.42 indi-
cates a well-stacked layered structure along the c axis. There
064305-3 Tan et al.
FIG. 1. (a) X-ray diffraction patterns of the MoS2 nanoflowers (B, black
curve) and MoS2@ZnO nano-heterojunctions (A, red curve). (b) Nitrogen
adsorption-desorption isotherms of the MoS2 nanoflowers and MoS2@ZnO
heterojunctions. The table in the inset is the SBET for the MoS2 and
MoS2@ZnO samples.
is no characteristic peak for other impurities, indicating the
pure crystalline MoS2 nanoflowers were obtained. Fig. 1(a-A)
shows the XRD pattern of the MoS2@ZnO nanocomposite.
The ZnO diffraction peaks are clearly observed and corre-
spond to the wurtzite structure of ZnO (JCPDS 36–1451). In
the nanocomposites diffractogram, distinct lattice planes cor-
responding to the ZnO nanoparticles and MoS2 nanoflowers
reveal the presence of individual components of ZnO and
MoS2. The N2 adsorption-desorption isotherms for MoS2 and
MoS2@ZnO nanocomposites are observed in Fig. 1(b). Two
distinct hysteresis loops are identified at a relative pressure of
0.1–0.9, which indicates the presence of a mesoporous struc-
ture. The Brunauer-Emmett-Teller (BET) surface area of
MoS2 nanoflowers is 26.1 m2g1. MoS2@ZnO composite is
48.7 m2 g1, which shows the larger specific surface area.
B. Morphology of the MoS2 nanoflowers
The morphology and nanostructure of the MoS2 nano-
flowers were characterized by scanning electron microscopy
J. Appl. Phys. 116, 064305 (2014)
(SEM) and TEM under different magnifications. A set of
SEM images is illustrated in Figs. 2(a) and 2(b). It can be
seen that the as-prepared MoS2 products are actually flower-
like nanospheres with the diameters of about 400–900 nm in
Fig. 2(a), so called nanoflowers. These nanoflowers easily
stick together during hydrothermal process. As shown by
Fig. 2(b), every nanoflower is composed of many irregular
nanopetals, which point toward a common inner centre and
are aligned to the spherical surface in the inset of Fig. 2(b).
To further investigate the morphology and crystallographic
feature of the MoS2 product, TEM and HTEM measurements
were performed by Figs. 2(c) and 2(d). Fig. 2(c) shows the
TEM of a typical MoS2 nanoflower with the diameter of
550 nm. It is clearly observed that these nanopetals are
extremely thin and overlapped each other. The high-
resolution TEM and the corresponding selected area electron
diffraction (SAED) pattern of a typical nanopetal are shown
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in Fig. 2(d). It is obviously that many stripes are at the edges
of nanopetals, which indicates that the MoS2 is the layered
structure. Moreover, the interlayer distance is 0.62 nm, which
is consistent with the theoretical spacing for (002) planes of
the hexagonal MoS2 structure. The inset in Fig. 2(d) illus-
trates that the corresponding SAED rings arise from stacking
MoS2 with different crystallographic orientations.
C. Morphology of the MoS2@ZnO
nano-heterojunctions
Fig. 3 presents the representative SEM and TEM images
of the MoS2@ZnO nanocomposites. As shown by Figs. 3(a)
and 3(b), the nano-heterojunctions consist of the MoS2 nano-
flowers and ZnO nanoparticles. It is clearly observed that
ZnO nanoparticles with diameters of about 16–25 nm dis-
persedly distribute on the MoS2 nanoflowers. From the inset
of Fig. 3(b), the high magnification SEM image illustrates
ZnO nanoparticles tightly adhered to the upper surfaces,
lower surfaces, the edges and inner space of the nanopetals,
which leads to the increased specific surface area and more
cusps on the surface of the composites. Fig. 3(c) is the TEM
image of a typical MoS2 nanopetal inlayed with several dis-
persive ZnO nanoparticles. It can be seen that the sizes of the
ZnO nanoparticles are within the range of 16–25 nm, which
is in accord with the results of TEM images. Fig. 3(d) illus-
trates the HRTEM image of the MoS2@ZnO nano-
heterojunctions, where several ZnO nanoparticles adhered to
the MoS2 nanopetal. The upper inset of Fig. 3(d) presents the
HRTEM image of the ZnO nanoparticles. The lattice fringes
of 0.52 nm correspond to the (002) planes of the wurtzite-
structured ZnO. The SAED pattern reveals that the nanopar-
ticles are single crystal with preferred growth along the
[0001] in the lower inset of Fig. 3(d).
D. Effect of different S sources
It is proposed that the formation of nanomaterials with
different morphologies may be related to the characteristics
of complex precursors synthesized in different reaction con-
ditions.30 In this paper, the S source in the hydrothermal
reaction is supposed to be a significant factor for the synthe-
sis of the MoS2 nanoflowers. Therefore, experiments with
064305-4 Tan et al.
various chemicals instead of CH4N2S as S sources were per-
formed and the morphologies of the obtained products are
monitored by SEM. When the selected S source was
(NH4)2S and other reaction conditions were kept constant,
the product is MoS2 nanoparticle with the size of 10–40 nm
and indefinite shape in Fig. 4(a). These nanoparticles are dis-
organized and separated from each other. Using C2H5NS
instead of CH4N2S, a large amount of uniform MoS2
J. Appl. Phys. 116, 064305 (2014)
FIG. 2. (a) Low magnification SEM
image of the MoS2 nanoflowers. (b)
Medium magnification SEM image of
the MoS2 nanoflowers. The inset is the
high magnification SEM image. (c)
The TEM image of a typical nano-
flower. (d) The high magnification
TEM image of a nanopetal. Lower inset
is the corresponding SAED pattern.
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nanospheres with diameters of approximately 255 nm were
obtained in Fig. 4(b). As shown by the inset of Fig. 4(b), the
surfaces of these nanospheres are highly wrinkled. For com-
parison, Fig. 4(c) is the SEM image of MoS2 nanoflowers
with the CH4N2S. When Na2S is selected as S source, the
products are also two-dimensional nanoflowers with uniform
morphology composed of the thin nanosheets clustering to-
gether in Fig. 4(d). Compared with the nanoflowers in Fig.
FIG. 3. (a) Low magnification SEM
image of the MoS2@ZnO nanocompo-
sites. (b) Medium magnification SEM
image of the MoS2@ZnO samples.
The inset is the high magnification
SEM image. (c) The TEM image of
the MoS2@ZnO samples. (d) High
magnification TEM image. The red
circle exhibits a MoS2@ZnO nano-
heterojunction. The upper inset is the
HRTEM image corresponding to a
ZnO nanoparticle from the area
marked with a red rectangle. The lower
inset is the corresponding SAED pat-
tern. Upper inset is the HRTEM image
corresponding to a ZnO nanoparticle
from the area marked with a red rec-
tangle. The lower inset is the corre-
sponding SAED pattern.
064305-5 Tan et al.
4(c), these hierarchical nanopetals are not serried but narrow
sheet, so called nanosheets to be distinguished from the
nanoflowers in Fig. 4(c). The XRD patterns of MoS2 nano-
particles, nanospheres, nanoflowers, and nanosheets are
shown in Fig. 5, corresponding to the samples in Figs.
4(a)–4(d), respectively. It can be seen that the XRD patterns
of these samples are similar, except for the relative peak in-
tensity due to the different growth orientations. All XRD pat-
terns can be well indexed to the hexagonal phase of MoS2
(JCPDS No. 37–1492). For the nanoparticles, the (002) peak
exhibits extremely strong diffraction intensity, indicating the
better-stacked layered structure along the c axis than other
nanomaterials. Moreover, the enhanced (006) peak of the
nanoparticles indicates the more exposed [006] faces.
FIG. 5. The XRD patterns of MoS2 (a) nanoparticles, (b) nanospheres, (c)
nanoflowers, and (d) nanosheets, which correspond to the samples in Figs.
4(a)–4(d), respectively.
J. Appl. Phys. 116, 064305 (2014)
FIG. 4. SEM images of MoS2 nanoma-
terials with different chemicals as S
source. (a) (NH4)2S, (b) C2H5NS, (c)
CH4N2S, and (d) Na2S.
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E. Photocatalytic activities
To the best of our knowledge, ZnO has been explored as
an effective photocatalyst in the ultraviolet region.
Meanwhile, MoS2 nanomaterials have photocatalytic proper-
ties in the visible region. Therefore, there is a great hope that
the MoS2@ZnO nanocomposites would possess enhanced
photocatalytic properties across the whole UV-vis light region
of the sunlight to improve sunlight utilizing efficiency. The
photocatalytic activities of the catalysts were evaluated by the
photodegradation of MB under UV-vis light irradiation in an
aqueous solution. The changes in the absorption spectra of
MB at 663 nm were used to monitor the photocatalytic degra-
dation process. UV-vis absorption spectrum of MB solution in
the presence of MoS2 nanoflowers and MoS2@ZnO nanocom-
posites under various irradiation times are presented in Figs.
6(a) and 6(b), respectively. It can be seen that the intensity of
main absorption peak continues to decrease with the irradia-
tion time. Correspondingly, the colour of the MB solution
continually becomes lighter and almost completely colourless
after irradiating for 100 min, especially in Fig. 6(b). It is
known that the decrease in the intensity of main absorption
peak and the change in colour can be explained by two ways:
(1) the decolorization of MB due to the existence of colourless
MB and (2) decomposition of MB. The decolorization of MB
can only occur in absence of oxygen.31 However, our experi-
ments were operated in the air. Therefore, the aforementioned
changes in the intensity of main absorption peak and colour
indicate that the MB molecules were gradually decomposed
during irradiation process. For comparison, the dependencies
of the degradation efficiency on irradiation time of the MoS2
nanoflowers and MoS2@ZnO nano-heterojunctions are shown
in Fig. 6(c) through monitoring the concentrations of the MB
solution at 663 nm. The degradation efficiency is defined as
064305-6 Tan et al. J. Appl. Phys. 116, 064305 (2014)

nanoflowers, the remaining MB in solution is about 58.3%

before light irradiation. Nevertheless, the remaining MB for
the MoS2@ZnO nanocomposites is about 41.3%, exhibiting
the higher adsorption ability. The high adsorption ability
should be mainly attributed to the larger specific surface area
of the MoS2@ZnO heterojunctions. Fig. 6(c) shows the photo-
degradation rates of MB with photocatalysts as the function of
irradiation time. After irradiation for 100 min, the C/C0 is
about 23.7% for the MoS2 nanoflowers and rapidly dropped
to 7.3% for the MoS2@ZnO heterojunctions, indicating that
the MoS2@ZnO nano-heterojunctions possess better photoca-
talytic performances.
The enhanced photodegradation activities of the compos-
ite samples may be attributed to two main reasons: increased
specific surface area and improved electron-hole pair separa-
tions. It is generally accepted that the photocatalytic process
is mainly related to the adsorption and desorption processes

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on the surface of the photocatalyst.26 Thus the large surface
area of the MoS2@ZnO nanocomposites can improve adsorp-
tion capacity for dye molecules and result in more unsaturated
surface coordination sites exposed to the MB solution and
interacting with positively charged MB molecules.30 Besides,
the presence of the heterojunction improves electron-hole pair
separation and promotes the photocatalytic performance. As
shown by Fig. 7, UV light can excite electron-hole pairs in
the ZnO nanoparticles. Meanwhile, the electron-hole pairs in
the MoS2 nanoflowers are excited by visible light, which
improve the sunlight utilizing efficiency. These photogener-
ated electrons with high energy obtained from the sunlight
transfer to the conduction band from the valence. As the het-
erojunction forms, the electrons in the ZnO nanoparticles dif-
fuse to the MoS2 at the interface due to the presence of the
carrier density gradient, forming the positive charges region.
Likewise, the holes diffuse to the ZnO from the MoS2, which
results in the negative charges region. The positive and nega-
tive charge regions lead to the form of an internal electrostatic
field and band bending at contact. Moreover, the MoS2 and
ZnO have the same Fermi energy level (EF) in the heterojunc-
tion. Due to the different work functions of the MoS2 and
ZnO, the conduction band and the valence band of ZnO lie
below the energy band of MoS2 after forming the same EF.

FIG. 6. UV-vis absorption spectra of MB solution in the presence of (a)

MoS2 nanoflowers and (b) MOS2@ZnO nano-heterojunctions. (c) The pho-
todegradation rates of MB with photocatalysts as the function of irradiation
time.

C/C0, where C and C0 correspond to the remnants and initial

concentration of MB, respectively. Prior to light irradiation,
the suspension containing MB and photocatalyst was stirred
for 20 min in dark to establish the adsorption/desorption equi-
librium of MB on the photocatalyst surface. Due to the
adsorption of photocatalyst for MB molecules, a certain FIG. 7. Schematic diagram of the charge generation and transfer process
decrease in the MB concentration was observed. For MoS2 under the UV-vis light in MOS2@ZnO nano-heterojunctions.
064305-7 Tan et al. J. Appl. Phys. 116, 064305 (2014)

Therefore, the photoexcited electrons on the conduction band

of the MoS2 can easily transfer to that of ZnO under the inter-
nal electrostatic field. Similarly, the excited holes on the va-
lence band of ZnO transfer to that of MoS2. Thus, the
photogenerated electrons and holes can be separated effi-
ciently at the interface, which can increase the lifetime of the
charge carriers, hinder the recombination of electron and hole
pairs, and finally improve the photocatalytic abilities. After
the separation of the electrons and holes, chemical reactions
involved for the formation of OH• radicals can be written as
follows:5

hþ þ H2 O ! Hþ þ OH• ;
e þ O 2 ! • O 
2;
•
O • 
2 þ H2 O ! HO2 þ OH ;

Downloaded from http://pubs.aip.org/aip/jap/article-pdf/doi/10.1063/1.4893020/15143367/064305_1_online.pdf

HO•2 þ H2 O ! H2 O2 þ OH• ;

H2 O2 þ e ! OH• þ OH :

F. Field emission properties

It is widely known that FE is a quantum mechanical
tunnelling phenomenon, where electrons emit to vacuum
from the tips on solid surface due to the presence of an
external electric field.31 The tip morphology and the pinna-
cle density are very crucial factors for the field emission in-
tensity. If the cathode material surfaces have sharp edges or
protrusions, electrons are extracted at these sharp edges and
tips with considerably stronger applied electric field and
easily emitted to the ITO/glass anode with phosphor under
the presence of an external electric field. This can be
explained by the lines of force converge at the sharp points
of the cathode material. Hence, the physical geometry of the
sharp edges and tips can provide improved field enhance-
ment.32 The MoS2@ZnO nanocomposites consist of many
petals with sharp edges and nanoparticles which can
increase the pinnacles on the surface. Therefore, the sam-
ples are supposed to have good field emission properties.
The field emission properties of the as-synthesized samples
were measured by the method described in the experimental
section. The schematic illustration for FE measurement is
presented by the inset of Fig. 8(a). The dependencies of the
field emission current density on the applied electric field
(J-E) are shown in Fig. 8(a). The turn-on field is defined as
the field needed to produce a current density of 10 lAcm2
and the threshold field is the field with the current density of
1 mA cm2. The turn-on and threshold fields for the MoS2
nanoflowers are 3.65 and 9.03 Vlm1, respectively. The
MoS2@ZnO heterojunctions are 3.08 and 6.9 Vlm1,
respectively. It is clear that the MoS2@ZnO heterojunctions
have better field emission properties with lower turn-on and
threshold field comparing with that of the MoS2 nano- FIG. 8. (a) The dependence of the FE current density (J) on the applied elec-
flowers. The corresponding Fowler-Nordheim (F-N) plots tric field strength (E) of MoS2 nanoflowers and MoS2@ZnO heterojunctions.
are presented in Fig. 8(b). The straight lines indicate that the The inset is the schematic illustration for FE measurement. (b) The corre-
sponding Fowler-Nordheim (F-N) plots. The inset is the field emission pho-
emitting electrons mainly result from field emission. The tos for the MoS2 nanoflowers (left) and MoS2 nanoflowers (right). (c)
field emission characteristic can be analyzed by the Fowler- Schematic energy band diagram of the as-grown MoS2@ZnO heterojunc-
Nordheim equation:33 tions with an applied electric field.
064305-8 Tan et al.
lnðJ=E2 Þ ¼ lnðAb2 =uÞ  Bu3=2 =bE; (1)
where A and B are constants with the values of 1.56  1010
(AV2 eV) and 6.830  103 (eV3/2Vlm1), u is the work
function of the emitter material, and b is the field enhance-
ment factor. According to Eq. (1), the field enhancement fac-
tor b has an inverse ration to the slope and can be described
as follows:
B ¼ Bu3=2 = kslope : (2)
Assuming that the work function of the MoS2 is
5.96 eV.34 The field enhancement factor of the MoS2 nano-
flowers is estimated to be about 2839. It is known that the
work function, band gap, material density, surface morphol-
ogy, and tip radius are main factors for field emission proper-
ties. Therefore, the difference of b may be attributed to the
surface morphology, the tip radius, and different screening
effects. The inset of Fig. 8(b) shows the field emission
images of these two emitters operated at an electric field of
8.25 Vlm1. The light spots on the fluorescent screen for the
MoS2@ZnO nanocomposite emitters are obviously more
uniform and denser than those of the MoS2, which illustrates
its higher emission electron density.
For MoS2@ZnO heterojunctions, the significantly
enhanced field emission properties may be attributed to two
reasons: more emission sites on the surface of the composites
and the decrease in potential energy barrier because of band
bending and inevitable interfacial defects at the interface
between MoS2 and ZnO. Due to the small sizes, ZnO nano-
particles on the MoS2 nanoflowers can provide enough nano-
protrusions acting as extra emission sites beside the thin
edges of the MoS2 nanopetals and increase in number of
emission dots. Thus, the unique morphology with higher tip
density can effectively improve the field emission properties.
In addition, Schematic energy band diagram of the
MoS2@ZnO heterojunction with an applied electric field is
shown in Fig. 8(c). The bending band is beneficial to the
movement of electrons from the MoS2 to ZnO and holes
from ZnO to MoS2, which effectively reduces the recombi-
nation of electron-hole pairs.35 The interfacial vacancies and
defects can induce defect energy bands (Edefects) between the
original energy bands. The electrons on the MoS2 conduction
band can easily jump into these defect energy bands and then
jump into the ZnO nanoparticles. Hence, a large number of
electrons gather on the surface of ZnO nanoparticles and are
easily emitted into the vacuum through subsequent F–N tun-
neling under strong local electric field. The free electrons
move to the phosphor-ITO/glass anode.
IV. CONCLUSIONS
In summary, MoS2@ZnO nano-heterojunctions were
successfully fabricated via low-temperature hydrothermal
method and thermal annealing process. The influence of
different S sources on the morphologies was discussed.
Compared with pure MoS2 nanoflowers, the composite sam-
ples demonstrate stronger adsorption capabilities in dark and
enhanced photocatalytic activities. The high photodegradation
J. Appl. Phys. 116, 064305 (2014)
activity is attributed to the increased specific surface area and
improved electron-hole pair separations. The field emission
properties of MoS2@ZnO heterojunctions were measured.
The results indicate the significantly enhanced field emission
properties than those of pure MoS2, because of more emission
sites on the surface of the composites and the decrease in
potential energy barrier. It can be demonstrated that the ZnO
nanoparticles play important roles in improving these proper-
ties due to their small sizes and n-type semiconductor with a
wide band gap. We believe this kind of attractive materials
will have promising application in the water treatment to
remove toxic heavy metal ions, degradation of dye pollutants,
and future field emission devices.
ACKNOWLEDGMENTS
The authors acknowledge financial support from the NSF
Downloaded from http://pubs.aip.org/aip/jap/article-pdf/doi/10.1063/1.4893020/15143367/064305_1_online.pdf
of China (Grant Nos. 61204018, 61274014) and Innovation
Research Project of Shanghai Education Commission (Grant
No. 13zz033).
1
A. K. Geim and K. S. Novoselov, Nature Mater. 6, 183 (2007).
2
A. K. Geim, Science 324, 1530 (2009).
3
R. Mas-Balleste, C. Gomez-Navarro, J. Gomez-Herrero, and F. Zamora,
Nanoscale 3, 20 (2011).
4
A. H. Castro Neto, N. M. R. Peres, K. S. Novoselov, and A. K. Geim, Rev.
5
Mod. Phys. 81, 109 (2009).
Y. Tan, K. Yu, T. Yang, Q. Zhang, W. Cong, H. Yin, Z. Zhang, Y. Chen,
and Z. Zhu, J. Mater. Chem. C 2, 5422 (2014).
6
P. Sun, W. Zhang, X. Hu, L. Yuan, and Y. Huang, J. Mater. Chem. A 2,
3498 (2014).
7
M. H. Cho, J. Ju, S. J. Kim, and H. Jang, Wear 260, 855 (2006).
8
B. Miremadi, R. Singh, S. R. Morrison, and K. Colbow, Appl. Phys. A 63,
271 (1996).
9
Q. Yue, Z. Shao, S. Chang, and J. Li, Nanoscale Res. Lett. 8, 425-1 (2013).
10
F. K. Perkins, A. L. Friedman, E. Cobas, P. M. Campbell, G. G. Jernigan,
and B. T. Jonker, Nano Lett. 13, 668 (2013).
11
H. I. Karunadasa, E. Montalvo, Y. Sun, M. Majda, J. R. Long, and C. J.
Chang, Science 335, 698 (2012).
12
D. Voiry, M. Salehi, R. Silva, T. Fujita, M. Chen, T. Asefa, V. B. Shenoy,
G. Eda, and M. Chhowalla, Nano Lett. 13, 6222 (2013).
13
Y. B. Li, Y. Bando, and D. Golberg, Appl. Phys. Lett. 82, 1962 (2003).
14
K. H. Hu, X. G. Hu, Y. F. Xu, and X. Z. Pan, React. Kinet., Mech. Catal.
100, 153 (2010).
15
Y. Liu, Y.-X. Yu, and W.-D. Zhang, J. Phys. Chem. C 117, 12949 (2013).
16
W. Zhou, Z. Yin, Y. Du, X. Huang, Z. Zeng, Z. Fan, H. Liu, J. Wang, and
H. Zhang, Small 9, 140 (2013).
17
K. Chang and W. Chen, ACS Nano 5, 4720 (2011).
18
X. Xu, Z. Fan, S. Ding, D. Yu, and Y. Du, Nanoscale 6, 5245 (2014).
19
K. Chang and W. Chen, Chem. Commun. 47, 4252 (2011).
20
G. Yue, J. Wu, Y. Xiao, M. Huang, J. Lin, and J.-Y. Lin, J. Mater. Chem.
A 1, 1495 (2013).
21
J. Kang, S. Tongay, J. Zhou, J. Li, and J. Wu, Appl. Phys. Lett. 102,
012111 (2013).
22
L.-Y. Gan, Q. Zhang, Y. Cheng, and U. Schwingenschl€ ogl, J. Phys. Chem.
Lett. 5, 1445 (2014).
23
S. Chakrabarti and B. K. Dutta, J. Hazard. Mater. 112, 269 (2004).
24
T. Santhaveesuk, D. Wongratanaphisan, and S. Choopun, Sens. Actuators,
B 147, 502 (2010).
25
R. Zou, G. He, K. Xu, Q. Liu, Z. Zhang, and J. Hu, J. Mater. Chem. A 1,
8445 (2013).
26
S. Li, K. Yu, Y. Wang, Z. Zhang, C. Song, H. Yin, Q. Ren, and Z. Zhu,
CrystEngComm 15, 1753 (2013).
27
Y. Wang, S. Li, H. Shi, and K. Yu, Nanoscale 4, 7817 (2012).
28
S. Yan, D. Hu, J. Wu, X. Xu, J. Wang, and Z. Xiao, J. Alloys Compd. 509,
L239 (2011).
29
G. Shan, X. Kong, X. Wang, and Y. Liu, Surf. Sci. 582, 61 (2005).
30
H. Shi, K. Yu, F. Sun, and Z. Zhu, CrystEngComm 14, 278 (2012).
064305-9 Tan et al. J. Appl. Phys. 116, 064305 (2014)

31 34
M. Basu, A. K. Sinha, M. Pradhan, S. Sarkar, Y. Negishi, Govind, and T. Q. Zhang, K. Yu, B. Zhao, Y. Wang, C. Song, S. Li, H. Yin, Z. Zhang, and
Pal, Environ. Sci. Technol. 44, 6313 (2010). Z. Zhu, RSC Adv. 3, 10994 (2013).
32 35
N. S. Xu and S. E. Hug, Mater. Sci. Eng., R 48, 47 (2005). Y. Wang, K. Yu, H. Yin, C. Song, Z. Zhang, S. Li, H. Shi, Q. Zhang,
33
C. Song, K. Yu, H. Yin, H. Fu, Z. Zhang, N. Zhang, and Z. Zhu, J. Mater. B. Zhao, Y. Zhang, and Z. Zhu, J. Phys. D: Appl. Phys. 46, 175303
Chem. C 2, 4196 (2014). (2013).

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