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Japanese Journal of Applied Physics 57, 060309 (2018) RAPID COMMUNICATION
https://doi.org/10.7567/JJAP.57.060309

Low-temperature study of neutral and charged excitons

in the large-area monolayer WS2
Hong Gu1,2, Le Chen1, Youming Lu1, Feifei Tian3, Zhiqiang Zhang3, Ke Xu3,
Jing Wu4, V. Divakar Botcha1,2, Kuilong Li1,2, and Xinke Liu1*
1
College of Materials Science and Engineering, Guangdong Research Center for Interfacial Engineering of Functional Materials, Shenzhen Key
Laboratory of Special Functional Materials, Chinese Engineering and Research Institute of Microelectronics, Shenzhen University,
Shenzhen 518060, P. R. China
2
Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering,
Shenzhen University, Shenzhen 518060, P. R. China
3
Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences, Suzhou 215123, P. R. China
4
Institute of Materials Research and Engineering (IMRE), 138634, Singapore
*E-mail: xkliu@szu.edu.cn
Received February 21, 2018; accepted March 23, 2018; published online May 11, 2018

We present a low-temperature optical study of the large-area monolayer WS2 grown by chemical vapor deposition (CVD). Power-dependent
photoluminescence (PL) measurements were conducted, and temperature-dependent PL spectra were measured in the range of 3 to 300 K. With
the comparative PL bands obtained, a stronger trion emission in the edge region was detected to be the key difference. Sulfur vacancies (SVs)
were observed to increase in density along the growth direction and found to be the main source of the large population of local charge carriers.
The monolayer WS2 exhibited an upper bound for the trion binding energy of 18 meV in the edge region.
© 2018 The Japan Society of Applied Physics

R
ecently, as a typical of a transition metal dichalco-
genide (TMD) material, WS2 has gained wide
interest, owing to the great potential related to its
lower dimensionality.1–7) Analogous to other TMDs, WS2
layers are composed of a slab S–W–S sandwich that crys-
tallizes in a van der Waals layered structure and shows
bandgap-layer dependent properties,8) offering WS2 a higher
possibility in various applications, such as nanoelectronics,
optoelectronics, electronics, and energy harvesting.9) Corre-
spondingly, significant attempts have been made to grow the
monolayer WS2 by different methods, these being mainly
mechanical or chemical exfoliation and chemical vapor
deposition (CVD). The monolayer allows researchers to
better understand unique physicochemical properties under
simple conditions, as in bilayers and thicker multilayers,
where interlayer interaction, geometrical confinement, and
crystal symmetry will play a collective role in defining their
electronic structures.10–12)
Special attention is focused on the optical properties of
WS2, the monolayer of which is known for strong excitonic
effects that entirely account for its photoluminescence (PL)
emission.13) It is also believed that the monolayer WS2 has a
stronger PL than other TMDs such as MoS2 and WSe2.14)
These properties are not only fundamentally interesting but
also technically important for novel semiconductor devices.
As a large exciton binding energy of 0.5 eV has been
reported, the room-temperature PL spectrum of the mono-
layer WS2 is characterized by two exciton peaks (A and B
peaks), arising from vertical transitions at the K point of
the Brillouin zone.15) At lower temperatures, both neutral
excitons (X0) and charged excitons [including two electrons
and one hole (X−) or one electron and two holes (X+)] have
been observed in the PL spectrum. Moreover, the behavior
of excitons and trions has been reported to be sensitive to
the preparation method, as the monolayers grown by CVD
always show PL emission at energies lower than those in the
case of mechanical exfoliation. Although the creation of a
single-crystalline structure of the monolayer WS2 has been
realized and related studies have been performed,16–20) there
060309-1
are still several challenges to control the large-area CVD
growth of the monolayer WS2 with intrinsic defects con-
sidered the main factor affecting material properties.21,22)
Thus, to further improve the performance of monolayer
growth and supplement experimental data for practical appli-
cation, there is much to be investigated with regard to the
characteristics of excitons and trions and related properties of
WS2, especially for large-area monolayers.
In this paper, we present a low-temperature optical study
of the large-area monolayer WS2 grown by CVD. In this
study, both neutral and charged exciton emissions were
observed in the PL spectrum, and the stronger trion emission
was detected to be the key difference between the edge and
inner regions. By detailed comparison and analysis, sulfur
vacancies were proved to play a significant role in both the
luminescence performance and the CVD growth. As there
are fewer works on the behavior of excitons and trions in the
low-temperature PL spectrum, our results may serve as
reference for further exploration of the optical mechanism
and material properties of the monolayer WS2.
WS2 samples were grown on SiO2 (300 nm)=Si substrates
by CVD under an atmospheric pressure. Tungsten oxide
(WO3) powder, sulfur (S) powder, and argon (Ar) gas were
used as the wolfram source, sulfur source and carrier gas,
respectively, with the deposition taking place at 1000 °C for
10 min. In this work, Raman and PL measurements were
carried out using a Jobin Yvon LabRAM HR 800UV system
with a 532 nm laser, and the laser power was maintained
below 20 µW to reduce local laser heating. Temperature-
dependent PL measurements were conducted in the range of
3 to 300 K using a customized experimental setup with a
Montana Instrument Cryostation. Power-dependent PL meas-
urements were also performed, as the spectrum was obtained
under the maximum laser power P0 that was then gradually
reduced to 1=2P0, 1=4P0, and 1=10P0, with an optical atten-
uator. All the PL spectra were measured in a vacuum
environment.
Figure 1(a) shows an optical microscopy image of an
individual WS2 triangle marked as A with a lateral dimension
© 2018 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 57, 060309 (2018)
(b)
(d)
Fig. 1. (Color online) (a) Optical microscopy image of small triangular
2D clusters of WS2 layers; (b) room-temperature Raman spectra for the
monolayer WS2 (triangle A) and multilayer (triangle B); (c, d) AFM image
and height profile of triangle A.
of ∼50 µm and of a multilayer triangle marked as B for com-
parison. Room-temperature Raman scattering was conducted
to determine the number of layers. As shown in Fig. 1(b),
for triangle A, the spectrum was dominated by three Raman
modes: 2LA (M) mode at 350 cm−1, E12g mode at 355 cm−1,
and A1g mode at 417 cm−1. The intensity of the strongest 2LA
(M) mode was approximately twice that of the A1g mode,
which is different from that of the multilayer triangle B. This
behavior of the Raman mode for the monolayer WS2 is con-
sistent with that observed in a previous study23) and indi-
cates the single-layer nature of triangle A. The thickness of
triangle A was further confirmed using a Dimension 3100
atomic force microscopy (AFM) system. The AFM image
and corresponding height profile are shown in Figs. 1(c) and
1(d), respectively, and presenting a typical thickness (∼1 nm)
of 1L-WS2. Thus, we could focus on triangle A as the target
of the monolayer WS2 in this study. However, it is also
clearly observed in the AFM image that a considerably large
number of particles distribute in the edge region. Corre-
spondingly, a high level of corrugation in the edge region is
presented in the height profile, while the inner region appears
much smoother. Furthermore, this distribution was also
observed in the other monolayer triangles. As the growth
direction of WS2 was from the center to the edge,19) this
particle distribution in the edge region appears to be a
characteristic of the CVD growth of the monolayer, which
may well be associated with the intrinsic defects.
Figure 2 shows the comparative 3 K PL bands obtained in
the edge and inner regions of monolayer triangle A [marked
in Fig. 1(a)]. Compared with that observed in the inner
region, the PL band obtained in the edge region shows a
redshift in peak position and an increase in intensity. On the
basis of the results of peak-differentation-imitating analysis,
the edge-region PL bands can be divided into 4 groups: a
deep-defect-related exciton peak XD at 1.944 eV, a charged
060309-2
H. Gu et al.
Fig. 2. (Color online) 3 K PL spectra of the monolayer WS2 in the edge
and inner regions, with peak-differentation-imitating analysis performed.
exciton X− at 1.971 eV, and a neutral exciton X0 at 1.992 eV
with the shallow state XS at 2.016 eV.13,15,24) For the inner
region, the following peaks were derived: XD at 1.945 eV,
X− at 1.974 eV, X0 at 1.996 eV, and XS at 2.020 eV. Here,
it is clear that the X− peak intensity is the key difference
between these two spectra.
In fact, the PL intensities of the exciton X0 and trion X− (IX0
and IX−) were reported to be proportional to their respective
population densities, which can be expressed as25) IX−=IX0 =
NX−=NX0, where NX0 and NX− are the exciton and trion
concentrations, respectively. Thus, it can be noted from Fig. 2
that, the Ratio (IX−=IX0) is 0.45 in the inner region and that in
the edge region increases to 0.96, indicating a considerable
increase in the number of trions. As the neutral exciton is the
ground state of a charge neutral system, trions are believed
to be formed only in the presence of excess charge,13) which
ends up controlling the trion emission intensity. Conse-
quently, the trion emission is often observed weakly in
exfoliated WS2 samples.26,27) On these understanding, the
strong trion emission in the edge region is thought to result
from the large population of local charge carriers (here
electrons), which will contribute to the formation of trions.
3 K Raman spectra were further measured in monolayer
triangle A for the edge and inner regions, respectively. As
shown in Fig. 3, compared with that in the inner region, the
strain-related E12g mode in the edge region presents a redshift
(∼0.3 cm−1) showing a tensile-strain effect, which is also con-
sistent with the shift in the PL spectrum. A redshift (∼0.2
cm−1) for the doping-related A1g mode is also observed in the
edge region, indicating an increase in the number of elec-
trons. Here, these Raman results also indicate the abundance
of sulfur vacancies (SVs) in the edge region, a behavior
similar to that observed in previous studies.22,28) In fact,
during the CVD growth, it is believed that SVs will be
generated gradually and will further result in the tensile-strain
effect and hydrogen or particle adsorption,29,30) which also
corresponds to the considerably large number of particles
observed in the AFM image. Meanwhile, in this study, with
© 2018 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 57, 060309 (2018)
Fig. 3. (Color online) 3 K Raman spectra of the monolayer WS2 in the
edge and inner regions, with peak-differentation-imitating analysis
performed. The inset is the Raman frequencies obtained in the edge and inner
regions, respectively.
(a) (b)
(c)
Fig. 4. (Color online) (a) Power-dependent PL spectra of the monolayer
WS2 at 3 K; (b) the ratio of (IX−=IX0) as a function of laser power for the edge
region at 3 K; (c) the ΔE obtained from the edge (black square) and the inner
(red circle) regions, with the value obtained from the exfoliated WS2 (blue
pentagram) shown for comparison.
no other impurities introduced in our CVD growth process,
the SV with shallow donor states could also be a reasonable
source of background charge, which facilitates the formation
of trions.
To obtain further insight into the exciton emission
discussed here, power-dependent PL spectra were also
investigated in the edge region at a temperature of 3 K. As
shown in Fig. 4(a), the lower energy shoulder for the X−
peak was observed to rise gradually. The Ratio (IX−=IX0)
exhibited an upward trend, increasing from 0.86 to 0.96,
because more charge carriers would be created with steadily
increasing laser power, as shown in Fig. 4(b). This result is in
good agreement with that of the above analysis of the trion
emission. Meanwhile, the energy difference ΔE between the
X0 and X− peaks could also be described as20)
E ¼ EX0  EX ¼ Eb,X þ EF ;
H. Gu et al.
Fig. 5. (Color online) Temperature-dependent PL spectra of the
monolayer WS2. The inset is the peak positions of the exciton (X0) and trion
(X−) as a function of temperature. The solid lines represent the fits to the
experimental data following the Varshni equation.
where EX0 and EX− are the exciton and trion peak energies,
respectively, Eb,X− is the trion binding energy, and EF is the
Fermi energy. Here, our monolayer WS2 grown by CVD
exhibits an upper bound for the trion binding energy of
18 meV with 2 µW excitation in the edge region. The ΔE
values obtained from the edge (black square) and inner (red
circle) regions were also plotted in Fig. 4(c) with the value
of the exfoliated WS2 (blue pentagram)20) presented for
comparison. This figure shows that the ΔE of the inner region
for the CVD-grown WS2 is close to that of the exfoliated WS2,
but much larger than that of the edge region. As it is believed
that with increasing SV density, the bands will move closer to
the Fermi level and increase the number of gap states,30) these
results of the ΔE also confirm the change in SV density. Thus,
with the SV density observed to increase along the growth
direction, the edge region with the highest SV density presents
the smallest ΔE. Likewise, in the photoluminescence process,
with many charge carriers provided by the SVs, more trions
are formed and a stronger trion emission is finally observed in
the edge region. Meanwhile, as the large number of SVs and
particles were discovered in the edge region, this abundance
may also be responsible for the suppressed triangle growth.
Temperature-dependent PL spectra were further measured
in the edge region from 3 to 300 K. Figure 5 shows the
normalized PL spectra of the monolayer WS2 at various
temperatures. It is clearly observed that each PL band shifts
towards the low-energy side and broadens gradually with the
increase in temperature as the direct electronic transition
energy decreases with increasing temperature owing to the
shift in the K point. Accordingly, both the X− and X0 peaks
shift with the temperature. These changes are plotted in the
inset and can be well described using the Varshni equation:
T 2
ð1Þ Eg ðTÞ ¼ Eg ð0Þ  ; ð2Þ
Tþ
060309-3 © 2018 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 57, 060309 (2018)
where Eg(0) is the bandgap at 0 K, and α and β are
phenomenological fit parameters. For the X0 peaks, the fit
matches with α = 3.33 × 10−4 eV=K, β = 263 K, and Eg(0) =
1.995 eV. The parameters are comparable to those obtained in
previous studies of the monolayer WS2, and reconfirm the
identification of the X0 and X− peaks.24)
In summary, we presented a low-temperature optical study
of monolayer WS2 grown by CVD and focused especially on
the characteristics of excitons and trions and related optical
properties. By a detailed comparison between the edge and
inner regions, a stronger trion emission was observed in the
edge region. Moreover, SVs were found to be the main
source of the large population of local charge carriers that
contributed to the trion emission. With the abundance of SVs,
the monolayer WS2 also exhibited an upper bound for the
trion binding energy of 18 meV in the edge region. These
results indicate that SVs should play an important role in
the optical properties and large-area CVD growth of the
monolayer WS2.
Acknowledgments This work was supported by the National Natural
Science Foundation of China (61504083), Public Welfare Capacity Building in
Guangdong Province (2015A010103016), Natural Science Foundation of SZU
(Grant No. 000062201501), Science and Technology Foundation of Shenzhen
(JCYJ20160226192033020), National Key Research and Development Program
of China (2017YFB0404100 and 2017YFB0403000), Ph.D. Start-up Fund of
Natural Science Foundation of Guangdong Province (2017A030310424), Natural
Science Foundation of Guangdong Province (2016A030313060), and A+STAR
IMRE=15-2C0111.
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© 2018 The Japan Society of Applied Physics