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Surface-Modified Ultrathin InSe Nanosheets

with Enhanced Stability and
Photoluminescence for High-Performance
Optoelectronics
Qiaoyan Hao,# Jidong Liu,# Gang Wang, Jiewei Chen, Haibo Gan, Jiaqi Zhu, Yuxuan Ke, Yang Chai,
Junhao Lin, and Wenjing Zhang*
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sı Supporting Information

ABSTRACT: Indium selenide (InSe) has become a research hotspot

because of its favorable carrier mobility and thickness-tunable band
gap, showing great application potential in high-performance
optoelectronic devices. The trend of miniaturization in optoelec-
tronics has forced the feature sizes of the electronic components to
shrink accordingly. Therefore, atomically thin InSe crystals may play
an important role in future optoelectronics. Given the instability and
ultralow photoluminescent (PL) emission of mechanically exfoliated
ultrathin InSe, synthesis of highly stable mono- and few-layer InSe
nanosheets with high PL efficiency has become crucial. Herein,
ultrathin InSe nanosheets were prepared via thermal annealing of
electrochemically intercalated products from bulk InSe. The size and yield of the as-prepared nanosheets were up to ∼160 μm
and ∼70%, respectively, and ∼80% of the nanosheets were less than five layer. Impressively, the as-prepared nanosheets
showed greatly enhanced stability and PL emission because of surface modification by carbon species. Efficient
photoresponsivity of 2 A/W was achieved in the as-prepared nanosheet-based devices. These nanosheets were further
assembled into large-area thin films with photoresponsivity of 16 A/W and an average Hall mobility of about 5 cm2 V−1 s−1.
Finally, one-dimensional (1D) InSe nanoscrolls with a length up to 90 μm were constructed by solvent-assisted self-assembly
of the exfoliated nanosheets.
KEYWORDS: indium selenide, photoluminescence, ultrathin, large area, optoelectronics

quantum efficiency for next-generation flexible optoelectronics

T wo-dimensional (2D) layered InSe has recently

attracted tremendous research interest due to its
tunable electronic structure with thickness, promising
optoelectronic properties, and excellent nonlinear effect.1−3
Unlike layered transition metal dichalcogenides (TMDs),
whose monolayer form has a direct band gap, indirect band
gap InSe in the monolayer form transforms to a direct band
gap when the layer number N is more than 7.4 Thus, mono-
and few-layer (N = 1−5) InSe have ultralow PL efficiencies
because of their indirect band gaps. In addition, mono- and
few-layer InSe are not stable in the presence of ambient oxygen
and moisture and are very difficult to mechanically exfoliate
from bulk crystal layers bound by the strong interlayer
interaction.5,6 However, the trend of miniaturization in future
optoelectronics means that mono- and few-layer InSe are
attractive for their atomically thin nature. Therefore, it is highly
desirable to synthesize ultrathin InSe with high stability and PL
based on 2D materials.
A number of strategies have been developed to attempt to
synthesize mono- and few-layer InSe flakes or films. For
example, mono- and few-layer InSe have been produced by
direct growth, including pulsed laser deposition,7 physical
vapor deposition,8 chemical vapor deposition,9 and colloidal
growth,10 but these methods largely rely on harsh growth
conditions, as well as complicated craftsmanship. Liquid-phase
exfoliation (LPE) has also been performed to produce an InSe
Received: April 28, 2020
Accepted: August 18, 2020
Published: August 18, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsnano.0c03556

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Figure 1. (a) Schematic illustration of the electrochemical exfoliation process of InSe. (b) Photograph of InSe single crystals. (c, d) OM
images of the exfoliated InSe nanosheets on the SiO2/Si substrates. The inset of (c) shows a photograph of uniformly dispersed nanosheets
in NMP. (e) AFM image of a folded monolayer M-InSe along with the corresponding OM image with a scale bar of 3 μm (inset). (f, g)
Statistical analysis of the thicknesses and lateral sizes of M-InSe nanosheets. (h) XRD patterns of the as-synthesized samples.

nanosheet dispersion for solid-state devices.11,12 However,
challenges remain with this approach, such as small sizes of the
exfoliated flakes and limited dispersion concentration in the
range of 0.1 mg/mL.13 In contrast, electrochemical exfoliation
has been shown to be an efficient method for scalable
production of 2D material nanosheets, which involves
intercalation of guest species into the crystal lattices by
applying an appropriate voltage and mild sonication to
exfoliate and isolate the 2D nanosheets.14−16 Various 2D
material sheets, including TMDs (such as MoS2, NbSe2, and
VSe2),17,18 In2Se3,19 and black phosphorus,20 have been
reported with different molecules as the intercalant agents.
Thus, despite the strong interlayer interaction in InSe,
electrochemical exfoliation could be an efficient way for
scalable synthesis of mono- and few-layer InSe nanosheets
from bulk InSe crystals.
In this study, we produced solution-processable InSe
nanosheets by using cetyltrimethylammonium bromide
(CTAB) as an intercalant to enlarge the interlayer spacing of
bulk InSe, of which ∼80% of the nanosheets were mono- and
few-layer (N = 1−5) nanosheets with sizes of up to 160 μm
and exfoliation yield of 70%. More importantly, after post-
annealing of the exfoliated InSe nanosheets at 300 °C, the
CTAB molecules escaped from the interlayer, and the mono-
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and few-layer InSe nanosheets showed greatly enhanced
stability and photoluminescence emission because of surface
modification by carbon species, which was verified exper-
imentally with various characterization techniques, such as
Raman spectra, X-ray photoelectron spectroscopy (XPS), and
PL spectra. In addition, the photodetectors fabricated with the
as-prepared nanosheets achieved an efficient photoresponsivity
of 2 A/W. These nanosheets were further assembled into large-
area thin films, exhibiting a photoresponsivity of 16 A/W and
an average Hall mobility of about 5 cm2 V−1 s−1 at room
temperature. Finally, 1D InSe nanoscrolls with a length of up
to 90 μm were produced from the exfoliated nanosheets via
solvent-assisted self-assembly.
RESULTS AND DISCUSSION
A schematic illustration of the electrochemical exfoliation
process of InSe is shown in Figure 1a. The experimental
process started with reaction between bulk InSe and the
intercalant CTAB in a two-electrode system to obtain the
intercalated sample CTAB-InSe (see Figure S1, Supporting
Information). After simple sonication, the exfoliated nano-
sheets were thoroughly cleaned with N-methyl-2-pyrrolidone
(NMP), followed by post-annealing at 300 °C to obtain
carbon-modified InSe (M-InSe, see Methods for details).
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Figure 2. (a) Three-dimensional (3D) schematic model of ε-InSe. (b) High-angle annular dark-field (HAADF) image and corresponding
EDS maps of pristine InSe. Scale bars, 1 μm. (c) Planar and (d) cross-sectional HRTEM images of InSe. (e) HAADF image and
corresponding EDS maps of M-InSe. Scale bars, 500 nm. (f) Planar and (g) cross-sectional HRTEM images of M-InSe.

Electrochemical exfoliation resulted in a high exfoliation yield
of ∼70% according to gravimetric analysis. Figure 1b shows a
photograph of InSe single crystals with lateral sizes of ∼8 mm,
which is a prerequisite for producing large nanosheets. Figure
1c and d show the optical microscopy (OM) images of the
exfoliated InSe nanosheets, whose sizes ranged from tens of
micrometers to ∼160 μm (Figure S2, Supporting Informa-
tion). An atomic force microscopy (AFM) image of a smooth
monolayer M-InSe (Figure 1e) indicated the thickness of ∼1.1
nm, which was larger than the theoretical interlayer distance of
each atomic layer (0.83 nm) probably because of substrate
effects.17,21 Statistical analysis revealed that ∼80% of the as-
prepared nanosheets were less than five layer, and all of the
specimens achieved a mean lateral size of ∼28 μm (Figure
1f,g). Intriguingly, diverse microscopic structures, such as
butterflies and leaves, formed during the exfoliation process
owing to strain-induced cracks on the crystal surface (Figure
S3, Supporting Information).22 Structural evolution of InSe
was verified by powder X-ray diffraction (XRD) (Figure 1h).
The XRD pattern of pristine InSe showed a hexagonal
structure with lattice parameters of a = 0.400 nm and c =
1.656 nm, consistent with a previous study.2 The 002 peak
shifted to a lower angle of 4.8° (d = 1.851 nm) for CTAB-InSe,
suggesting that the interlayer distance increased by 123%
during the intercalation process. Finally, each reflection in the
XRD pattern of M-InSe coincided with that of pristine InSe,
indicating the escape of CTAB molecules from the interlayer
and preservation of the crystal phase of InSe.
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The InSe crystal consists of covalently bonded Se−In−In−
Se atomic sheets in a honeycomb lattice. These sheets are held
together by van der Waals interactions as depicted in Figure 2a.
To further evaluate the crystalline quality, the as-prepared
samples were characterized by high-resolution transmission
electron microscopy (HRTEM) and energy dispersive X-ray
spectrometry (EDS) mapping. For pristine InSe, EDS maps
(Figure 2b) confirmed the homogeneous distribution of In and
Se at a ratio of ∼1:1 with a trace amount of carbon over the
crystal (Figure S4, Supporting Information). The measured
distance between the lattice fringes was 0.344 nm viewed along
the [001] zone axis, which agreed with the (100)/(010) plane
of InSe (Figure 2c).23 The cross-sectional HRTEM image
indicated an average interlayer distance of 0.828 nm,
corresponding to the (002) plane of InSe (Figure 2d). In
contrast, the intercalated sample CTAB-InSe was sensitive to
electron irradiation, and it decomposed even under low-dose
and low-voltage imaging, presumably because of the instability
of the intercalant CTAB organic molecules. This was
evidenced by the fading of the electron diffraction spots of
the CTAB-InSe specimen upon exposure to electron
irradiation, which indicated loss of its crystallinity. Never-
theless, structural integrity of hexagonal ε-phase was still
confirmed in CTAB-InSe (see more discussions in Figure S5,
Supporting Information). Finally, EDS maps of the M-InSe
specimen (Figure 2e) revealed clear In, Se, and C signals
throughout the crystal, which is an indication of successive
intercalation. The amount of carbon for M-InSe was further
quantified by elemental analysis to be ∼2.58 wt %, as listed in
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Figure 3. (a) Representative Raman spectra of InSe and M-InSe samples using 532 nm laser excitation. XPS spectra of InSe and M-InSe in
(b) the In 3d core level, (c) the Se 3d core level, (d) the C 1s core level, and (e) the O 1s core level regions, respectively. (f) FTIR spectra of
InSe and M-InSe.
Table S1 (Supporting Information), indicating that there was a
considerable increase of carbon in M-InSe after the
experimental process. Moreover, the basal plane of M-InSe
resembled much of pristine InSe, evidenced by the (100)/
(010) lattice fringes of 0.349 nm (Figure 2f). The interlayer
distance slightly expanded to 0.842 nm in M-InSe (Figure 2g),
possibly because of variations in interlayer coupling and strain-
induced lattice expansion after intercalation/release of CTAB
in/from the interlayer.24 All of these results demonstrated
successive intercalation of InSe and high quality of the as-
prepared M-InSe samples, which is consistent with the XRD
results.
Raman spectroscopy was further performed to probe the
local structure change of the samples. In Figure 3a, the Raman
spectrum of 13-layer InSe showed three peaks corresponding
to the A11g (114 cm−1), E12g (177 cm−1), and A21g (227 cm−1)
vibrational modes, consistent with a previous report.2 Mean-
while, 13-layer M-InSe solely exhibited the A21g peak around
253 cm−1, and the other two Raman modes (A11g and E12g) were
suppressed, suggesting the perturbation of its intralayer
bonding. The Raman modes were not observed in few-layer
InSe and M-InSe samples (N = 1−5). We note that there were
two additional peaks at around 1385 and 1590 cm−1 for M-
InSe, which correspond to the typical D and G bands of
graphitized carbon trapped on the surface of InSe.25,26
Compared with pristine InSe, the blue-shift of 26 cm−1 for
the A21g mode and suppression of other two Raman modes in
13-layer M-InSe could be explained by p-type doping of InSe
owing to the surface carbon species as well as variations in
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interlayer stacking and coupling.27,28 To shed light on the
charge transfer between InSe and carbon species, XPS surface
analyses were performed on the samples. In Figure 3b,c, the In
3d and Se 3d peaks in M-InSe exhibited significant red-shift
compared with InSe. Specifically, In 3d3/2 shifted from 452.8 to
452.3 eV, and In 3d5/2 shifted from 445.2 to 444.7 eV. Se 3d3/2
shifted from 55.4 to 55.0 eV, and Se 3d5/2 shifted from 54.6 to
54.1 eV. We note that XPS did not detect obvious oxidation
associated with SeOx in M-InSe, suggesting a higher stability
for the exfoliated nanosheets after post-annealing (see
characterization of CTAB-InSe in Figure S6, Supporting
Information). The C 1s spectra in Figure 3d can be assigned
to C−C (284.8 eV), C−O (285.7 eV), and CO (287.8 eV),
respectively.29 In Figure 3e, the weak but discernible O 1s peak
for InSe was due to the unavoidable oxidation in the process of
sample preparation. For M-InSe, the O 1s peak was
comparable to that in graphene oxide, suggesting the formation
of carbon functional groups through chemical reaction
between CTAB molecules and oxygen attachments upon
post-annealing treatment.29 Moreover, Fourier-transform infra-
red (FTIR) spectroscopy shown in Figure 3f was performed to
verify the presence of these carbon functional groups, including
carboxyl (COOH), hydroxyl (C−OH), and ketonic species
(CO).30,31 Consequently, these results suggest that the
surface carbon species serve as the electron-withdrawing
groups and thus lead to p-type doping in InSe.
The optical properties of the as-synthesized samples were
investigated by PL spectra. The PL spectra obtained from
mechanically exfoliated 13-layer InSe showed a clear peak at
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Figure 4. (a) Thickness-dependent PL spectra of InSe and M-InSe using 532 nm laser excitation. (b) PL map integrated over the spectral
range 572−580 nm of a typical M-InSe flake with variant thicknesses. Inset shows the corresponding OM image. Evolution of PL spectra for
(c) 13-layer and (d) monolayer M-InSe after four months of ambient exposure, respectively. (e) OM image of the as-prepared M-InSe flakes.
(f) AFM image of the M-InSe flake marked with a yellow square in (e) after four months of ambient exposure.

930 nm (1.33 eV), which exhibited a significant blue-shift to
800 nm (1.55 eV) and an emission intensity reduction by
∼67% in five-layer InSe because of a direct-to-indirect band
gap crossover (Figure 4a).3,4 Concurrently, the PL spectrum of
13-layer M-InSe showed a prominent peak at around 590 nm
(2.10 eV), consistent with the optical band gap of monolayer
InSe.32 The peaks at 572 and 580 nm were attributed to the
Raman signal from carbon species.27,33 The PL emission peaks
from typical M-InSe samples (13 layer, five layer, and
monolayer) did not show evident shifts, which should be
attributed to the presence of stacking misalignment and
variations in interlayer coupling (see Figure S7 for details,
Supporting Information). Moreover, the PL emission intensity
from monolayer M-InSe was equivalent to that from 13-layer
InSe, which is much higher than that expected from mono- and
few-layer InSe. Figure 4b shows the PL map of a typical M-
InSe flake with variant thicknesses (1−8 L), yielding spatially
homogeneous intensity with respect to the layer number over
the whole flake. These results suggested that the PL emission
of few-layer InSe was significantly enhanced as a result of
CTAB intercalation and post-annealing treatment (see detailed
discussions in Figure S8, Supporting Information). Figure 4c,d
show the PL emission evolution for 13-layer and monolayer
M-InSe flakes upon ambient exposure, respectively. After four
months of ambient exposure, 13-layer M-InSe demonstrated
almost no decay in PL emission intensity, while monolayer M-
InSe exhibited a small attenuation in PL emission, which was
in stark contrast to the dramatic decrease in PL emission for
mechanically exfoliated few-layer InSe within several days
(Figure S9, Supporting Information). Meanwhile, the
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morphology of a few-layer M-InSe flake measured by AFM
remained smooth with no discernible surface protrusions after
four months of ambient exposure, as shown in Figure 4e,f. In
contrast, few-layer InSe prepared by mechanical exfoliation
exhibited significantly degraded morphological stability within
a week (Figure S9, Supporting Information). Thus, we
concluded that the as-prepared M-InSe nanosheets exhibited
greatly improved PL emission and morphological stability,
which should be attributed to the inserted CTAB-induced p-
doping as well as variations in interlayer stacking and coupling
upon post-annealing.34,35
The optoelectronic performance of electrochemically
exfoliated InSe was investigated by fabricating field-effect
transistor (FET) devices using individual M-InSe nanosheets.
Figure 5a illustrates the 3D schematics of the FETs made of
few-layer M-InSe and Ti/Au (10/50 nm) electrodes. The
typical output characteristics (Ids−Vds) of the device based on a
M-InSe nanosheet with a moderate thickness of ∼7 nm as a
function of gate voltage are shown in Figure 5b, indicating
near-ohmic conduction according to the linearity of the curves.
In contrast, the CTAB-InSe-based FET showed Schottky-like
contact between the channel and electrodes, suggesting
improved electrical contact after post-annealing (Figure S10,
Supporting Information). Figure 5c shows the output
characteristics of M-InSe nanosheet devices in the dark and
under 532 nm laser illumination at zero gate voltage. The
illuminated current (Ilight) gradually increased with increasing
light intensity, and the photocurrent (Iph = Ilight − Idark) of the
device was extracted under various excitation intensities as
shown in Figure 5d. Photoresponsivity (R = Iph/PS) is one of
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Figure 5. (a) Three-dimensional schematic structure of the M-InSe device. The upper left shows an optical image of a typical device. (b)
Output characteristics of the device based on the M-InSe flakes as a function of gate voltage. Inset shows an AFM image of the device along
with the height profile. (c) Output characteristics of the device in the dark and under illumination with various excitation intensities (Vg = 0
V, λ = 532 nm). (d) Measured photocurrent and photoresponsivity as a function of the illumination intensity. (e) OM image of large-area M-
InSe thin film devices with a zoomed-in image of a device and AFM image of the thin film. (f) Measured photocurrent and photoresponsivity
of the thin film devices as a function of the illumination intensity.

the most important figures of merit for determining the
photodetector performance, which is defined as the photo-
current (Iph) generated by the light power density (P) on the
effective area of a photodetector (S). The photoresponsivity as
a function of the light power intensity of the device was also
plotted in Figure 5d. At a relatively low illumination density of
12.5 μW/cm2, the M-InSe device achieved a maximum
photoresponsivity of 2 A/W, which exceeds that of few-layer
GaSe crystals grown by vapor-phase mass transport.36
Additionally, M-InSe thin films were readily assembled over
a large-area substrate by drop coating thanks to the high
concentration of the obtained suspensions (5 mg/mL in
NMP). The film thickness can be varied depending on the
concentration or droplet volume of the suspensions. Figure
S11 shows the AFM images of representative M-InSe thin films
with different thicknesses. These films were compact and
continuous because of the ultrathin feature of 2D nanosheet
building blocks. Figure 5e shows an OM image of a large-area
M-InSe thin-film device with a thickness of ∼60 nm. Its output
characteristics in the dark and under 532 nm laser illumination
are shown in Figure S12, exhibiting near-ohmic conduction in
the film. The dependence of photocurrent as well as
photoresponsivity of the thin film devices on light power
density is shown in Figure 5f, achieving a maximum
responsivity of ∼16 A/W. This performance is comparable
to that of LPE InSe thin films, indicating a high quality of the
resulting M-InSe nanosheets and their potential use in large-
area optoelectronics.12 Furthermore, we performed Hall effect
measurements on the assembled thin films with millimeter-
scale lateral size and nanoscale thickness by using the van der
Pauw four-point probe technique. M-InSe thin films of 4 mm
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× 4 mm showed an average Hall mobility of 5.2 cm2 V−1 s−1 at
room temperature from repeated measurements, which could
be enhanced by improving the nanosheets’ connectivity and
optimizing the distribution of thickness.37
The high flexibility of the exfoliated InSe nanosheets makes
them promising building blocks for constructing 1D
architectures, which has been demonstrated by a class of 2D
nanosheets, such as TMDs, graphene, and graphene
oxide.38−41 As expected, distinct M-InSe nanoscrolls were
produced from the as-prepared nanosheets, showing a hollow
tube-like structure with diameters of 0.5−6.4 μm and lengths
of 20−90 μm (Figure S13). A schematic illustration of the
nanoscroll preparation process is shown in Figure 6a, following
the solvent-assisted self-assembly.42,43 An ultrathin nanosheet
in the act of rolling was confirmed to be a monolayer according
to the thickness of ∼1.1 nm extracted from the AFM image
(Figure 6b). Figure 6c magnifies the spiral structure of an
isolated M-InSe nanoscroll with a height of 10.5 nm in the
central part. It was found that a higher drying temperature of
80 °C resulted in the formation of significant amounts of
nanoscrolls (Figure 6d), while a much smaller degree of rolling
was observed at 60 °C, which can be attributed to slower fluid
flow at lower temperature (Figure S14). The M-InSe
nanoscrolls also showed high PL emission because of carbon
modification, as indicated by the Raman and PL spectra
(Figure 6e−g). As a proof of concept, the M-InSe nanoscrolls
were integrated into FET devices to evaluate their optoelec-
tronic properties. The output characteristics of the device
based on a single M-InSe nanoscroll in the dark and under
laser illumination (Vds = 5 V, P = 4.5 mW/cm2) are shown in
Figure 6h. An AFM image of the device (Figure 6i) indicated
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Figure 6. (a) Schematic illustration of the nanoscroll preparation process. (b) AFM image of a partially rolled monolayer nanosheet. (c)
AFM image of a complete nanoscroll and magnified open end (yellow box). (d) OM image of a large amount of M-InSe nanoscrolls. (e)
Raman mapping image of the outlined area in the inset for a partially rolled M-InSe nanosheet. (f, g) Raman and PL spectra taken from the
two marked positions in the inset of (e). (h) Output characteristics of the M-InSe nanoscroll device in the dark and under illumination with
a 532 nm laser (Vg = 0 V). The lower right inset shows an OM image of the device. (i) AFM image of the device (left) and its corresponding
peak force error image (right). (j) Time response characteristics of the device.

an average height of 13 nm and length of ∼46 μm of the
nanoscroll. The photocurrent trace of the device under laser
illumination showed efficient switching behavior, suggesting
that the M-InSe nanoscrolls possessed good stability and
photodetection capability (Figure 6j).
CONCLUSION
In summary, we have demonstrated the synthesis of mono- and
few-layer InSe nanosheets via thermal annealing of electro-
chemically intercalated products from bulk InSe crystals. The
exfoliation yield of the as-prepared nanosheets, with sizes of up
to ∼160 μm, was ∼70%, and ∼80% of the nanosheets were less
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than five layer. Impressively, the ultrathin nanosheets showed
greatly improved PL emission and morphological stability due
to surface carbon species induced p-doping as well as variations
in interlayer stacking and coupling. In addition, photodetectors
based on the as-prepared nanosheets achieved efficient
photoresponsivity of 2 A/W, and the assembled millimeter-
scale M-InSe thin films exhibited a photoresponsivity of 16 A/
W and an average Hall mobility of about 5 cm2 V−1 s−1 at room
temperature. Finally, 1D InSe nanoscrolls were produced by
solvent-assisted self-assembly of the exfoliated nanosheets.
This work provides an efficient approach to synthesize highly
crystalline and ultrathin InSe nanosheets with enhanced
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stability and PL emission, offering more opportunities for their
potential applications in optoelectronics.
METHODS
Growth of InSe Single Crystals. InSe single crystals were
synthesized using a mixture of In (Macklin, 99.99%) and Se (Aladdin,
99.99%) with the molar ratio of 1:1 in evacuated silica ampules (Φinner
= 11 mm). The mixture was heated to 730 °C within 6 h, held at this
temperature for 3 days, and then slowly cooled to room temperature
within 5 days.
Intercalation of InSe with CTAB. The intercalation procedure
was carried out using a two-electrode electrochemical cell. A thinly
cleaved InSe flake and a 15 mm/15 mm Pt foil were placed as the
cathode and anode, respectively. Typically, a 20 mg InSe flake was
immersed into the electrolyte of 0.01 M CTAB (Aladdin, 99%)
solution in 40 mL of NMP (Aladdin, 99.5%). The applied voltage was
set to be −5 V, and the intercalation process was allowed to proceed
for 2−4 h. Completion of the intercalation reaction was proved by the
dramatic volume expansion of bulk InSe and the electrolyte changing
from colorless to yellowish. Then, the electrochemically intercalated
CTAB-InSe products were collected, washed four times with
isopropanol, and dried in a vacuum oven overnight at 60 °C for
further characterization.
Exfoliation and Thermal Annealing of CTAB-InSe. The
obtained CTAB-InSe flakes were sonicated in NMP at 2 mg/mL
for 10−30 s. Afterward, the dispersion was centrifuged at 8000 rpm
for 10 min. The supernatant was carefully removed by a pipet, and the
sediment was washed with NMP four times to remove unreacted
species. After the final cycle, the precipitate was redispersed in NMP
and centrifuged at 800 rpm for 5 min to get rid of the unexfoliated
crystal or thick flakes. The top 90% of the supernatant was centrifuged
and collected for further characterization. The dispersion of exfoliated
nanosheets was deposited on the SiO2/Si substrates and dried in a
vacuum oven overnight at 60 °C. Then, the substrates were post-
annealed in a tube furnace at 300 °C for 2 h with a flow of 150 sccm
argon gas to produce the resultant M-InSe nanosheets or thin films.
To produce the M-InSe nanoscrolls, the exfoliated nanosheets
deposited on the SiO2/Si substrates was dried and post-annealed
following the same protocol except that the drying temperature was
increased to 80 °C or even higher.
TEM Specimen Preparation. To prepare the InSe specimen, the
flakes were mechanically exfoliated from bulk InSe and transferred
onto the SiO2/Si substrates. The substrates were then sonicated in
absolute ethanol to collect the exfoliated InSe flakes. Finally, the
dispersion was dipped onto holey carbon grids for further character-
ization. To prepare the specimens of CTAB-InSe and M-InSe, the
powders were dispersed in absolute isopropanol by sonication for
several minutes; then each dispersion was dipped onto holey carbon
grids for further characterization.
Characterization. Powder XRD patterns were recorded on a
Rigaku SmartLab X-ray diffractometer with Cu Kα radiation (λ =
1.5406 Å). HAADF-STEM and EDS mapping images were collected
by transmission electron microscope (Titan Cubed Themis G2 300,
FEI) with an accelerating voltage of 300 kV for pristine InSe and the
resultant M-InSe samples and 80 kV for the intercalated sample
CTAB-InSe, respectively. XPS measurements were performed using a
PHI 5000 VersaProbe II equipped with a monochromatic Al Kα X-ray
source. All of the binding energies were calibrated with the C 1s peak
located at 284.8 eV. XPS peak fitting was carried out using a fixed
Lorentzian/Gaussian ratio of 0.3 after a linear background
subtraction. Raman and PL spectra were recorded at room
temperature using a WITec (alpha 300) Raman microscope with
laser excitation of 532 nm and a laser power of 500 μW. Atomic force
microscopy was performed using a Bruker Dimension ICON system.
The content of carbon was measured with a CNS analyzer (Elementar
Vario EL cube). FTIR spectra were collected on a Thermo Nicolet
6700 instrument. The film thickness was measured using a Dektak XT
surface profilometer.
11380
Article
Device Fabrication and Characterization of the Electrical
and Optoelectronic Performance. The devices were fabricated on
highly doped p-type silicon substrates capped with 300 nm of SiO2.
The metal electrodes were patterned by a copper grid shadow mask.
To improve contacts between electrodes and the channel, the devices
were annealed at 150 °C for 2 h with a flow of 100 sccm argon gas. All
of the electrical and optoelectronic measurements were performed
using a Keithley 4200 semiconductor characterization system under
ambient conditions. A homemade four-point probe system was
designed to measure the Hall effect using a Nanometrics HL5500 Hall
system. To produce a continuous and reasonable film, a high
concentration of 5 mg/mL dispersion was deposited onto the quartz
substrates and dried in a vacuum oven overnight at 60 °C, followed by
post-annealing treatment. Finally, silver paste was used to make the
electrodes.
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsnano.0c03556.
Photographs of bulk InSe before and after intercalation;
optical images of exfoliated nanosheets; EDS spectrum
of pristine InSe; TEM and spectral characterization and
optoelectronic performance of CTAB-InSe; elemental
analysis results; stacking misalignment and moiré
patterns in restacked M-InSe nanosheets; effect of
CTAB intercalation and post-annealing on PL emission
of few-layer InSe; PL and morphological stability of few-
layer InSe; characterization of M-InSe thin films; optical
images of M-InSe nanoscrolls (PDF)
AUTHOR INFORMATION
Corresponding Author
Wenjing Zhang − International Collaborative Laboratory of 2D
Materials for Optoelectronics Science and Technology, Shenzhen
University, Shenzhen 518060, China; orcid.org/0000-
0001-6931-900X; Email: wjzhang@szu.edu.cn
Authors
Qiaoyan Hao − International Collaborative Laboratory of 2D
Materials for Optoelectronics Science and Technology, Shenzhen
University, Shenzhen 518060, China
Jidong Liu − International Collaborative Laboratory of 2D
Materials for Optoelectronics Science and Technology, Shenzhen
University, Shenzhen 518060, China
Gang Wang − Department of Physics, Southern University of
Science and Technology, Shenzhen 518055, China
Jiewei Chen − Department of Applied Physics, Hong Kong
Polytechnic University, Hong Kong 999077, China;
orcid.org/0000-0002-9756-742X
Haibo Gan − International Collaborative Laboratory of 2D
Materials for Optoelectronics Science and Technology, Shenzhen
University, Shenzhen 518060, China
Jiaqi Zhu − International Collaborative Laboratory of 2D
Materials for Optoelectronics Science and Technology, Shenzhen
University, Shenzhen 518060, China
Yuxuan Ke − International Collaborative Laboratory of 2D
Materials for Optoelectronics Science and Technology, Shenzhen
University, Shenzhen 518060, China
Yang Chai − Department of Applied Physics, Hong Kong
Polytechnic University, Hong Kong 999077, China;
orcid.org/0000-0002-8943-0861
https://dx.doi.org/10.1021/acsnano.0c03556
ACS Nano 2020, 14, 11373−11382
ACS Nano
Junhao Lin − Department of Physics, Southern University of
Science and Technology, Shenzhen 518055, China;
orcid.org/0000-0002-2195-2823
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsnano.0c03556
Author Contributions
# (8) Zhou, J.; Shi, J.; Zeng, Q.; Chen, Y.; Niu, L.; Liu, F.; Yu, T.;
Q.Y.H. and J.D.L. contributed equally.
Author Contributions
W.J.Z. supervised and conceptualized the research. Q.Y.H. and
J.D.L. performed most of the experiments, including the
material synthesis, characterizations, and device measurements.
G.W. and J.H.L. performed the HRTEM measurement. J.W.C.
and Y.C. offered valuable discussions about the Hall measure-
ment. J.Q.Z. and Y.X.K. performed the optical and AFM
measurements. Q.Y.H., J.D.L., and H.B.G. wrote the manu-
script. All of the authors discussed the results and commented
on the manuscript.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The work at Shenzhen University was supported by the
Shenzhen Peacock Plan (grant number
KQTD2016053112042971), the Educational Commission of
Guangdong Province (grant number 2016KCXTD006), and
the Science and Technology Planning Project of Guangdong
Province (grant number 2016B050501005). G.W. and J.H.L.
would like to acknowledge support from the National Natural
Science Foundation of China (grant number 11974156) and
the Guangdong International Science Collaboration Project
(grant number 2019A050510001) and also assistance from
SUSTech Core Research Facilities, especially technical support
from the Pico-Centre. Q.Y.H., J.D.L., and W.J.Z. would like to
acknowledge assistance with HRTEM observation from the
Electron Microscope Center of Shenzhen University. The
authors thank Prof. Kaibin Tang for helpful discussions.
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11382 https://dx.doi.org/10.1021/acsnano.0c03556
ACS Nano 2020, 14, 11373−11382