Optical Materials 98 (2019) 109429

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Optical Materials
journal homepage: http://www.elsevier.com/locate/optmat

Studying of photo-excitation dynamics and photodetector based on

MoSe2 nanosheet
Lianfei Yao a, Xue Lou a, Ning Sui a, Qinghui Liu a, Ye Zhang a, Xiaochun Chi a, **, Zhihui Kang a,
Qiang Zhou b, Hanzhuang Zhang a, Yinghui Wang a, *
a
Femtosecond Laser Laboratory, Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics, Jilin University,
Changchun, 130012, PR China
b
State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun, 130012, PR China

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

Keywords: The photo-excitation dynamics occurring in the nanosheet of MoSe2 have been studied by employing the tran­
MoSe2 nanosheet sient absorption. We find that four types of dynamic behaviors participate in the relaxation of excited MoSe2
Photo-excitation dynamics nanosheet by global fitting, which corresponds to the exciton-exciton interaction, exciton capture by trapping
Photodetector
state, exciton dissociation and free charge movement. Since many free charge has generated after photo-
Transient absorption
excitation, the photo-detector based on MoSe2 nanosheet is fabricated and the period- and voltage-dependent
photocurrent is further clarified. In addition, nanosecond transient photocurrent test probes the dynamics of
carrier and confirms that illumination intensity would accelerate the lifetime of carrier recombination to 1 μs at
high intensity and enhance the corresponding loss of carrier. Moreover, it is also found that the bias voltage
would linearly facilitate the yield of free carriers in photo-detector and the lifetime of carrier recombination
would decrease to 4 μs at 60 V. The final results could help people to further understand the photo-physical
property of MoSe2 nanosheet and facilitate its application in the opto-electronic devices.

1. Introduction
Two-dimensional (2D) layered materials, which exhibit novel and
intriguing properties with potential applications in field effect transis­
tors [1], optoelectronic devices [2], topological insulators [3], electro­
catalysts [4], and so on, have attracted a great deal of attention since the
recently successful preparation and characterization of graphene [5]. As
part of 2D materials, layered transition metal dichalcogenides (TMDs),
which have unique crystal structures, wide range of chemical compo­
sitions and variety of chemical properties, have attracted many funda­
mental research and accessed technological applications [6]. Transition
metals ranging from group Ⅳ to group Ⅹ have different numbers of
d-electrons, which fill up the non-bonding d bands to different levels,
resulting in varied electronic properties including insulating [7], semi­
conducting [8], metallic [9], and superconducting [10]. TMDs have a
common structural formula MeX2, where Me stands for transition metals
(Mo, W, Ti, etc.) and X for chalcogens (S, Se, Te) [11]. In particular,
molybdenum and tungsten based TMDs are semiconductors with band
gaps ranging from the visible to the near-infrared [12]. Besides Mo and
W, chalcogenides of Ti, Sn, and Zr are also predicted to be semi­
conducting but little to no experimental evidence exists on their isola­
tion in monolayer form, stability, or performance in devices [13]. Thus,
Mo and W chalcogenides have been investigated heavily among the
post-graphene two-dimensional materials [14].
The TMDs nanosheets can also be further processed via inkjet
printing [15], spray-coating [16] and doctor blading [17] to fabricate
thin-film heterostructure devices such as batteries, sensors, and solar
cells. Moreover, the performance of TMDs nanosheets for many appli­
cations is depending on the physical behavior of photogenerated
charges. However, the recent research works largely focus on TMDs
samples formed via mechanical exfoliation [18] or chemical vapor
deposition (CVD) [19]. The photo-physical property of nanosheet re­
mains unclear, which restricts its further application in opto-electronic
device. Recently, MoSe2 nanosheet has been synthesized, which helps
people to further understand the physical property of TMDs nanosheet
and broaden their application.

* Corresponding author.
** Corresponding author.
E-mail addresses: chixc@jlu.edu.cn (X. Chi), yinghui_wang@jlu.edu.cn (Y. Wang).

https://doi.org/10.1016/j.optmat.2019.109429
Received 3 June 2019; Received in revised form 25 September 2019; Accepted 27 September 2019
Available online 4 October 2019
0925-3467/© 2019 Elsevier B.V. All rights reserved.
L. Yao et al. Optical Materials 98 (2019) 109429

In this paper, we study the photo-excitation dynamics of monolayer

MoSe2 nanosheet with transient absorption technique, which exhibits
that exciton-exciton interaction, exciton capture by trapping state,
exciton dissociation, free carrier movement would participate in the
relaxation of excited MoSe2 nanosheet. According to this result, we
fabricate a simple photodetector based on monolayer MoSe2 nanosheet.
The corresponding performance and working mechanism are scanned by
illumination intensity-dependent I–V test and the time-dependent
photocurrent measurements. The nanosecond transient photocurrent
offers the information about the illumination intensity and bias voltage
dependent on carrier dynamics. The final results help us to further un­
derstand the photo-physical property of MoSe2 nanosheet.

2. Experimental section

The MoSe2 nanosheet is synthesized according to the previous report

[20]. Selenourea (0.25 g, 0.2 mmol) is weighed into a three-neck
round-bottom flask and diluted with oleylamine (10 mL, 21.4 mmol).
The mixture is stirred and heated at 120 � C for 30 min under N2 flow,
then the solution is heated at 200 � C until completely dissolved. In a
typical synthesis, molybdenum (II) acetate dimer (0.04 g, 0.1 mmol),
stearic acid (0.32 g, 1.0 mmol), octadecanamine (2 g, 6.77 mmol), tri­
octylphosphine oxide (2 g, 5.07 mmol), and squalene (4.0 mL,
7.51 mmol) are added to a 25 mL three-neck round-bottom flask under
N2 atmosphere. The mixture is heated to 330 � C at a heating rate of
8.0 � C min 1 under N2 flow. Then the mixture is stirred at 330 � C for
3 min after 0.4 mL of selenourea solution is injected into the reaction
solution subsequently. Then cool it down to room temperature.
Extracting the sample into centrifuge tube which has hex­
ane/isopropanol (Vh:Vi ¼ 1:2), centrifuge and decant. The resulting
nanosheet is dispersed in 8 mL of toluene, then adds 16 mL methanol.
Then, the resulting nanosheet is separated by centrifugation and
decantation, which is dried under a flow of N2. The sample, which is
dissolved into toluene, forms the film on the glass substrate with the ITO
(indium-tin-oxide) electrode by spin-coating method, where the dis­
tance between two ITO electrodes is about 25 μm. And then, the sample
layer is immediately transferred to a nitrogen-filled glove box.
Steady-state absorption measurements are carried out with UV–Vis
absorption spectrometer (Purkinje, TU-1810PC). The femtosecond
transient absorption (TA) technique is reported in the previous report
[21]. We use an OPO module (MagicPRISM VIS) to obtain the light pulse
with a wavelength of 400 nm. The illumination intensity dependent I–V
test is employed by CHI760E potentiostat (CH Instruments, China)
accompanied with a continuum laser with wavelength of 532 nm. The
nanosecond transient photocurrent is reported in the previous work
[22], which is composed of nanosecond laser (Quantel, QS450-2W3W)
and oscilloscope (Tektronix TDS 3032C). TEM (transmission eletron
microscope) images are taken on a JEM-2200FS transmission electron
microscope with an acceleration voltage of 200 kV. The Raman spectra
is recorded using a Renishaw in Via Raman Microscopic instrument.
Laser excitation at 514.5 nm is obtained with a Spectra-Physics 160 M
argon ion laser and the instrument is calibrated using the 521 cm 1
silicon peak.
Fig. 1. (A)The UV–vis absorption spectra of MoSe2 nanosheet; (B) Low-
magnification TEM image of monolayer MoSe2 nanosheet. (C) High-
resolution TEM image of the basal plane and the standing edge of the nano­
sheet shows nanodomains. Inset: Raman spectra of MoSe2 nanosheet under
514 nm excitation.
grids. It is facile to observe the dark contrast line in the image, which
represents the standing edge of MoSe2 nanosheet. The corresponding
high resolution TEM (HR-TEM) image given in Fig. 1(C) exhibits the
polycrystalline feature of the basal plane of MoSe2 nanosheet, and the
measured lattice distance is about 0.3 nm.
Fig. 2(A-D) exhibit the time-dependent transient absorption spec­
trum of the MoSe2 nanosheet excited by 400 nm laser, which track the
evolution of photo-generated transient species. The femtosecond ΔT/T
spectra shows photobleaching at the excitonic resonances (located at
450 nm) superimposed on a structured photo-induced absorption
(located at 550 nm) that covers the spectral range. During the first 4 ps,
the bleaching signal undergoes a monotonical decay as seen in Fig. 2(A),
while the photo-induced absorption features show a rise behavior. Fig. 2
(B) points out that the signal of bleaching and photo-induced absorption
both decreases, which should be attributed to the capture process of
exciton by trapping state. As seen in Fig. 2(C), the signal of bleaching is
invariable, while the photo-induced absorption exhibits an obvious rise,
implying that the exciton dissociation process may be responsible for
this evolution of spectral feature, since the population of electron would
be invariable during the exciton dissociation. After 393 ps, the TA

3. Results and discussion

The optical and structure properties of the colloidal monolayer

MoSe2 nanosheet are well characterized by UV–vis absorption and TEM.
As seen in Fig. 1(A), there are two absorption peaks in absorption
spectrum of monolayer MoSe2 nanosheet, which are located at 780 and
680 nm, respectively. They are consistent with the previous report [23]
and correspond to A and B excitonic transitions of the TMDs. The Raman
spectrum shown in the inset of Fig. 1(A) gives the A1g mode and E12g Fig. 2. Time-dependent TA spectra of monolayer MoSe2 nanosheet in toluene
mode, which are located at 241.8 and 288.5 cm 1, indicating that the solution (A-D). Global analysis of the transient absorption spectra. Note: EEI:
MoSe2 we have prepared is single layer structure [24]. Fig. 1(B) offers exciton-exciton interaction; TP: capture process of exciton by trapping state;
the TEM image of the MoSe2 nanosheet by preparing on Qunatifoil gold EDP: exciton dissociation process; FDC: free diffusion of carrier.

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L. Yao et al. Optical Materials 98 (2019) 109429

spectral feature would decrease with time, which corresponds to the

annihilation of transient species as seen in Fig. 2(D).
Global analysis is further employed to extract the time-independent
correlations as the evolution-associated difference spectra (EADS) from
these transient absorption data. As shown in Fig. 3(A), four components
(0.7, 53, 171 and 3380 ps) are required to obtain the best fitting from the
global analysis. The concentration kinetics are extracted and plotted in
Fig. 3(B). It is clear to see that the rise and decay of the EADS in MoSe2
follow a sequential model in the relaxation process. It can be seen from
Fig. 3(B) that the first component (exciton-exciton interaction as seen
inset of Fig. 2(A)) with lifetime 0.7 ps and the second component
(capture process of exciton by trapping state, as seen inset of Fig. 2(B))
with lifetime of 53 ps occur simultaneously. The above concentration
kinetics indicate that exciton-exciton interaction appears immediately
after photo-excitation, since the illumination intensity is estimated to be
4.46 mW mm 2, which is high enough to induce the exciton-exciton
interaction. During the relaxation of the second component, the con­
centrations of the third component (exciton dissociation process, as seen
inset of Fig. 2(C)) with lifetime of 171 ps and the long lifetime state (>1
ns), which corresponds to the free carrier movement (as seen inset of
Fig. 2(D)) both increasing. And the rising process of the free diffusion of
carrier and the bound exciton relaxation is accompanied with the decay
process of exciton dissociation process.
Many free carriers would be generated after photo-excitation, owing
to the dissociation of exciton, suggesting that the MoSe2 nanosheet has Fig. 4. (A) The experimental principle of I–V test; (B) I–V curves of photode­
potential in the opto-electronic device. Therefore, we fabricate a simple tector based on MoSe2 nanosheet under different illumination intensity, where
photodetector based on MoSe2 nanosheet, whose structure is given in the illumination intensity is ranged from 0 to 235 mW mm 2 respectively. Inset:
the corresponding photocurrent as a function of illumination intensity.
Fig. 4(A). Fig. 4(B) offers the I–V curves of photodetector as a function of
illumination intensity [25]. The dark current of photodetector is about
1 nA under the bias voltage of 3 V, indicating that there are many free [26], which is excited by 532 nm laser and the illumination intensity is
charges exist, which are easy to move under electric field. When the estimated to be 70 mW mm 2. Apparently, the evolution progress of the
illumination intensity increases from 0 to 235 mW mm 2, the current photocurrent can be seen during repetitive switching of light illumina­
enhances from 1 to 211 nA, indicating that the number of free carriers tion, or on/off switching, in five different electric tension. There are
increases with the illumination enhancing, which can attribute to the obvious photo-responses curves when the laser is irradiated on the de­
dissociation of exciton under illumination. The photocurrent as a func­ vices. It is worth noted that there is no obvious degradation during
tion of illumination intensity is given the inset of Fig. 4(B), which fol­ scores of cycles, which suggests the excellent stability and repeatability
lows a linear enhancement behavior, suggesting that this detector is a of the photodetector device. The bias voltage dependent photocurrent of
linear detector and the yield of free charge carrier is invariable during photodetector is given in Fig. 5(B), which almost linearly increases with
the experiment. bias voltage. Moreover, it is found that there is a threshold for photo­
The bias voltage dependent I–V curve of photodetector based on current response of photodetector. The intercept at the x-axis approxi­
MoSe2 nanosheet by linear sweep polarography is given in Fig. 5(A) mate is estimated to be 2 V through linear fitting. This phenomenon
should be assigned to two factors. Firstly, the generation of photocurrent
in the device depends on the free carriers, which are driven by bias
voltage. On the other hand, a large number of exciton is generated by
laser. These excitons would dissociate into free carrier under the

Fig. 3. Global analysis of the transient absorption spectra. EADS obtained using Fig. 5. (A) Photocurrent of MoSe2 nanosheet based on ITO at different voltage
a sequential relaxation model for MoSe2 nanosheet dissolved in toluene solution under 532 nm excitation and the illumination intensity is 70 mW mm 2. (B)
(A); concentrations of the EADS components in MoSe2 nanosheet (B) as a Photocurrent as a function of voltage; (C) Plot of photocurrent with different
function of time in toluene solution. period at the same voltage of 10 V; (D) Photocurrent as a function of period.

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L. Yao et al. Optical Materials 98 (2019) 109429

interaction of bias voltage and the corresponding yield of exciton

dissociation would also enhance with bias voltage. In order to further
understand the performance of photodetector, the cycle period of
photodetector is changed and the corresponding data are summarized in
Fig. 5(C). The photocurrent gradually increases with period and their
relationship is given in Fig. 5(D). Apparently, it is not a linear
enhancement relationship. The relationship between photocurrent and
the half of period follows an exponential enhancement behavior. It is
reasonable to employ the function of I0 þ A⋅expð t =τÞ to analyze the
evolution of photocurrent at different period. According to the fitting
results, it is interesting to find that the initial I0 is estimated to be
12.0 nA. The photocurrent would finally reach a maximum of 16.5 nA
with time.
In order to further investigate the carrier dynamic behavior, the
nanosecond transient photocurrent is employed to test carrier dynamic
behavior of photodetector based on MoSe2 nanosheet. With the bias
voltage applying to the photodetector, the carriers would transport from
one electrode to another one. Fig. 6(A) offers the illumination intensity
(0.01–4.07 mW) dependent photocurrent (I0) at the bias voltage of 60 V.
Note that the decay curve of I0 exhibits an exponential behavior at low
illumination intensity, which should depend on the factors involving the
diffusion, migration, and recombination of carriers. After that, a fast
relaxation component gradually appears in the curve of I0, which leads
to a non-exponential relaxation behavior. The percentage of rapid
relaxation component obviously enhances with illumination intensity, Fig. 6. The illumination intensity (A) and bias voltage (B) dependent the
which should be assigned to the recombination originated from multi- photo-current of light witch based on MoSe2 nanosheet; the corresponding
lifetime and amplitude as a function of illumination intensity (C) and bias
body interaction of carrier at high concentration. Moreover, the
voltage (D).
enhancement of illumination intensity would increase the initial
amplitude of I0 and accelerate its relaxation velocity at the same time.
These data are summarized in Fig. 6(C). The lifetime of I0 decreases with nanosheet has a potential in the opto-electronic device. The illumination
illumination intensity and gradually reaches a minimum of 0.62 μs, intensity dependent I–V test confirms that this device owns a good
when the illumination intensity increases to 1.77 mW. After that, the performance, whose photocurrent would linearly enhance with illumi­
lifetime would be insensitive to the illumination intensity. In addition, nation intensity. Moreover, the nanosecond transient photocurrent
the initial amplitude of I0 also exhibits a nonlinear enhancement further clarifies the carrier dynamics occurring in photo-detector, which
behavior with illumination intensity and the corresponding increase is is sensitive to the illumination intensity and bias voltage.
getting smaller and smaller. Apparently, this should be attributed to the Although historically, emphasis has been placed on transition metal
rapid recombination of carriers. sulfides due to the abundance and popularity of sulfur compounds, in
The bias voltage (0–60 V) dependent I0 is given in Fig. 6(B). An various applications, particularly in electrochemical and photovoltaic
exponential relaxation behavior also appears at 10 V. It is interesting to systems, this attention is shifting to transition metal selenides. On the
find that a rapid relaxation component also appears in the curve of I0 at other hand, the first row of transition metals is not the dominant cations
different bias voltage, which is also attributed to the rapid recombina­ in dichalcogenides because heavier elements such as Mo and W have
tion of carriers. Considering the number of photo-generated exciton shown promising properties. MoSe2 is a rising star in the family and a
which is invariable in this experiment, two factors would be responsible promising candidate for a variety of applications.
for this phenomenon. Firstly, the dissociation yield of exciton would
improve apparently, which creates many free carriers. Secondly, the Declaration of competing interest
carriers driven by bias voltage also enhance with bias voltage. Finally,
they create an environment with a high concentration of free carriers The authors declare that they have no known competing financial
together, which leads to the rapid recombination of carriers. The initial interests or personal relationships that could have appeared to influence
amplitude and the corresponding lifetime of I0 as a function of bias the work reported in this paper.
voltage are summarized in Fig. 6(D). It is interesting to find that the
lifetime of I0 also reaches a minimum with voltage and is insensitive to Acknowledgements
the value of bias voltage. However, the minimum of lifetime is closed to
be about 3.5 μs, which is longer than that (~1.0 μs) in Fig. 6(C). In This work was supported by the National Natural Science Foundation
addition, the initial amplitude almost linearly increases with bias of China (No. 21573094), the National Science Fund for Young Scholars
voltage, suggesting that the carriers driven by bias voltage should play (No. 11904123), the National Natural Science Foundation of China (No.
an important role in the experiment in comparison with that induced by 51502109, 11774122, 11574112, and 11474131) and the National
dissociation of photo-generated exciton. Found for Fostering Talents of Basic Science (No. J1103202).

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