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Asymmetric 2D MoS2 for Scalable and High-Performance

Piezoelectric Sensors
Wonbong Choi,* Junyoung Kim, Eunho Lee, Gayatri Mehta, and Vish Prasad
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ABSTRACT: Piezoelectricity in two-dimensional (2D) transition-metal dichalcogenides

Downloaded via UNIV PRESBITERIANA MACKENZIE on August 11, 2021 at 18:59:49 (UTC).

(TMDs) has attracted significant attention due to their unique crystal structure and the
lack of inversion centers when the bulk TMDs thin down to monolayers. Although the
piezoelectric effect in atomic-thickness TMDs has been reported earlier, they are
exfoliated 2D TMDs and are therefore not scalable. Here, we demonstrate a superior
piezoelectric effect from large-scale sputtered, asymmetric 2D MoS2 using meticulous
defect engineering based on the thermal-solvent annealing of the MoS2 layer. This yields
an output peak current and voltage of 20 pA and 700 mV (after annealing at 450 °C),
respectively, which is the highest piezoelectric strength ever reported in 2D MoS2.
Indeed, the piezoelectric strength increases with the defect density (sulfur vacancies),
which, in turn, increases with the annealing temperature at least up to 450 °C. Moreover,
our piezoelectric MoS2 device array shows an exceptional piezoelectric sensitivity of 262
mV/kPa with a high level of uniformity and excellent performance under ambient
conditions. A detailed study of the sulfur vacancy-dependent property and its resultant asymmetric structure-induced piezoelectricity
is reported. The proposed approach is scalable and can produce advanced materials for flexible piezoelectric devices to be used in
emerging bioinspired robotics and biomedical applications.
KEYWORDS: TMDs, MoS2, piezoelectric sensors, asymmetric, defects

1. INTRODUCTION coefficient. This membrane is packed in a hexagonal lattice

The piezoelectricity of thin films, nanowires, and bulk crystals
has been extensively studied for its applications in sensors,
electronics, nanogenerators, and energy conversion.1,2 Con-
sequently, two-dimensional (2D) materials have attracted
considerable interest due to their high crystallinity as well as
ability to withstand tremendous strain while presenting their
piezoelectric properties at the atomic level. Indeed, two-
dimensional (2D) transition-metal dichalcogenides (TMDs)
have been the subject of intense research due to their unique
structural features of thin atomic layers held together via van
der Waals (vdW) interactions.3,4 Any qualitative change in
their atomic layer of 2D TMDs can affect their physical and
chemical properties because of the large surface-area-to-
thickness ratio.5−8
Interestingly, bulk TMDs, including MoS2, do not possess a
piezoelectric effect due to the opposite orientations of adjacent
atomic layers, centrosymmetric in their bulk. However, when
the same 2D TMDs are thinned down to a few layers,
inversion symmetry disappears and the piezoelectric effect
appears.8−10 In free-standing MoS2 membranes, it has been
found that piezoelectricity exists when there are odd number
layers in the 2D crystal because the inversion symmetry breaks
down.11 The monolayer of MoS2 has a D3h crystalline
symmetry, which can adequately describe the anisotropic
electromechanical coupling by the single piezoelectric
with one atomic layer of Mo sandwiched between two S layers.
Two S atoms asymmetrically order this unit cell between Mo
atoms, such that an external electric field is generated from the
S to the Mo site in the hexagonal lattice. This enables the
generation of internal piezoelectricity of the 2D MoS2
membrane when it is strained.11,12 On the other hand, the
piezoelectricity from alternating layers is canceled out when
the membranes are even-layered. Evidently, the piezoelectric
effect of 2D MoS2 is a number of layer-dependent.
As is well established, a conventional flexible piezoelectric
sensor measures the dipole moment to obtain its strain-
induced piezoelectric field.12−14 The internal electric dipoles of
piezoelectric materials are coupled to the material lattice;
therefore, any changes in the lattice, such as point defects,
impurities, and vacancies, can result in a change in the
spontaneous polarization.15−17 Prezhdo et al. have observed
that the defects introduce charge traps and accelerate
electron−hole recombination by a factor of 1.7 since the
Received: January 12, 2021
Accepted: March 3, 2021
Published: March 12, 2021

© 2021 American Chemical Society https://dx.doi.org/10.1021/acsami.1c00650

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Figure 1. Thermal-solvent annealing process and characterization of MoS2. (a) Schematic illustration for the thermal-solvent annealing process
(top diagram) and its microstructure change. (b) Cross-sectional high-resolution transmission electron microscope (HRTEM) image of MoS2,
which confirms three layers of MoS2. (c) Intensity profile of HRTEM analysis that confirms the interlayer spacing of the layer as 0.65 nm. (d)
atomic force microscope (AFM) analysis of the MoS2 device; thickness of the device is 1.32 nm. (e) Raman spectra of pristine (magenta) and
thermal-solvent annealed MoS2 at 350 °C (blue), 400 °C (black), and 450 °C (red). (f) XPS analysis of MoS2, pristine (bottom) and annealed at
450 °C (top); the nonstoichiometric area fraction of the MoxSy peak appeared due to the sulfur-deficient MoS2. (g) Calculated interdefect areal
fractions of the MoxSy; the areal fraction gradually increases from 0 to 31.51% for 450-MoS2.

sulfur vacancy in MoS2 creates a deep electron trap and a
shallow hole trap that couple to the free hole.18 Moreover, a
sulfur vacancy with unsaturated chemical bonds at the Mo
atoms attempts to interact with the adjacent S atoms, resulting
in a perturbed MoS2 symmetry.
As reported by Wu et al., the strain-induced polarization
charges in MoS2 can modulate charge carrier transport at the
MoS2 interface and enhance its strain-sensing property. The
undoped MoS2 possesses a relatively finite intrinsic charge
carrier density with a limited piezoelectric response.12
Therefore, if the distribution of free carriers in MoS2 is
modified, an additional polarization effect may arise by the
asymmetrical charge distribution and can result in higher
piezoelectricity.11,19,20 The additional doping in the MoS2
structure can further improve the sensitivity of strain-induced
polarization in the MoS2 membrane and enhance its
piezoelectric effect.9,10,21,22 Nakamura et al. have reported
that based on the density functional theory (DFT), a p-type
MoS2 monolayer possesses high longitudinal gauge factors of
94.2 (armchair) and 87.4 (zigzag) at room temperature,23
which are 800 times higher than those of the n-type MoS2
monolayer. Moreover, upon uniaxial tensile strain, the carrier
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redistribution occurs in conduction- or valence bands, which
can cause an asymmetrical modulation of carrier transport and
higher piezoelectric response from the p-type MoS2 monolayer.
It has also been shown that the intrinsic p- or n-type dopants
can be introduced by generating structural defects during the
sample fabrication process.24,25 Indeed, these defects can be
presented as the chalcogenide vacancies or surface in the
structure, resulting in the local nonstoichiometry as well as
varying doping regions.26−28 This inhomogeneous electronic
landscape plays a critical role in electron transport in these
materials.
Interestingly, by creating defects in the graphene nanoribbon
of the proper symmetry, Sharma et al. have found that even
centrosymmetric graphene nanoribbon can act as a piezo-
electric material.29 The implication, therefore, is that the
precise control of the defects in the 2D MoS2 structure can
lead to fine-tuning of the piezoelectrical property. The
difference in atomic bonding lengths gives rise to inequivalent
charge distribution, resulting in a broken reflection symmetry
along the vertical direction and vertical piezoelectric polar-
ization. In the same manner, sulfur-deficient MoS2 exhibits
similar characteristics due to the lack of inversion symmetry. In
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this regard, conventional etching methods such as plasma or
electron irradiation etching suffer from severe limitations due
to their complexity and limited controllability. To control
precise defects over large-scale 2D TMDs, a new technique
needed to be devised.26,30−32
Recently, the authors have developed a facile and precise
defect-engineering process, using a thermal-solvent etching
method, to fabricate large-scale asymmetrically engineered 2D
WS2 piezoelectric structures/devices.33 These 2D WS2-based
devices have demonstrated a 3-fold higher piezoelectric
response voltage (96.74 mV) than the pristine WS2 under a
3 kPa compression. In this paper, we extend the thermal-
solvent method to synthesize an asymmetrical 2D MoS2. This
defect-engineered MoS2 shows an exceptional piezoelectric
output of current and voltage of 20 pA and 700 mV,
respectively, which is 20 times higher than that of the pristine
MoS2 device and much higher than that of the WS2-based
devices.33 Furthermore, it shows excellent uniformity and
piezoelectric sensitivity, 262 mV/kPa, in an ambient
atmosphere. Note that unlike plasma or irradiation etching
techniques, the thermal-solvent etching method uses a
temperature-controlled organic solvent vapor to etch the sulfur
with atomic precision and with no damage to the sample.
Moreover, the produced sulfur vacancies lead to excessive
holes in MoS2, rendering strong piezoelectric properties.
Consequently, we have established a scalable process for the
synthesis of precise, defect-engineered 2D MoS2 that can
provide a comprehensive methodology/guidance for the
design of future flexible piezoelectronics of high capacities.
2. RESULTS AND DISCUSSION
A large-scale polycrystalline MoS2 was grown by the two-step
process developed by Choi and co-workers,3,4 the details of
which can be found in the Experimental Section. Essentially,
Mo was sputtered for 2 s on top of the bottom electrode, Ti/
Au, followed by its sulfurization at 600 °C in a low-pressure
chemical vapor deposition system. A schematic illustration of
the two-step process and its scalability is described in Figure
S1.
By devising this process, we have established a novel
thermal-solvent etching method to synthesize the non-
stoichiometric 2D MoS2 by controlling the sulfur defect
density.33 An illustration of the thermal-solvent etching process
is presented in Figure 1a. Briefly, the vaporized organic solvent
partially dissolves the sulfur of MoS2 to create sulfur defects on
MoS2. This process was repeated at three different temper-
atures, 350, 400, and 450 °C, to vary the etched sulfur
concentration. The samples were termed as 350-MoS2, 400-
MoS2, and 450-MoS2 corresponding hereafter to different
annealing temperatures used. An X-ray photoelectron spec-
troscopy-energy dispersive spectroscopy (XPS-EDX) mapping
confirmed the uniform film surface before and after the
thermal-solvent annealing, as shown in Figure S2.
The usefulness of a solvent for etching TMD materials can
be determined by the Hansen solubility parameter (HSP), as
presented in the previous paper on WS2-based piezoelectric
sensors.33 A nonpolar circularity feature and high density of π-
bonds of the solvent molecule facilitate the dissolution of a
cyclic crown-shaped sulfur of the MoS2 surface.34 A semi-
empirical correlation explaining the dissolution behavior of
sulfur in etchant can be expressed using the Hansen solubility
parameter (HSP).35 Each solubility parameter represents the
character of a solvent or solute by δD, δP, and δH,
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corresponding to a dispersive, polar, and hydrogen-bonding
parameter, respectively36,37
δ T = (δ D2 + δ P2 + δ H2)1/2
The close predicted values of a total parameter, δT, for MoS2,
18.54−24.02, and toluene, 18.16, using HSP calculations
suggest that the sulfur can be efficiently etched on the MoS2
surface using toluene. The full parameter values for MoS2 and
toluene are summarized in Table S1.
A cross-sectional high-resolution transmission electron
microscope (HRTEM) was used to determine the number of
layers of MoS2 as well as the interlayer distance to confirm its
uniformity at the atomic scale. As shown in Figure 1b, the
trilayered MoS2 was uniformly synthesized onto the SiO2/Si
substrate. Moreover, its intensity profile confirms that the
interlayer distance was 0.65 nm, as shown in Figure 1c.
Additionally, the thickness of the MoS2 device was measured
using an atomic force microscope (AFM), as shown in Figure
1d. The pristine MoS2 possessed a thickness of 1.32 nm, which
after thermal-solvent annealing did not change in any
significant manner.
Raman spectroscopy was used to determine the sulfur-
deficient MoS2 crystal structure after thermal-solvent anneal-
ing. Sulfur deficiencies created during this process lead to the
formation of defects in the MoS2 structure. The two-vibration
mode difference, Δk, was linearly increased from 20.47 to
23.95 cm−1, indicating a systematic decrease in the out-of-
plane binding energy due to the generation of defects.38,39 The
density functional theory analysis suggests that the sulfur-
deficient structure weakens the restoring force constant and
allows the static Mo atom to vibrate out-of-plane.38,39 This
behavior was clearly observed in the present case, where the
out-of-plane phonon vibration mode, A1g, was blue-shifted, as
shown in Figure 1e. The observation further supports the
hypothesis that the generated defects in the present samples
are sulfur vacancies, and their density can be increased with the
annealing temperature to generate more asymmetry in the
MoS2 structure.
In addition, the surface film quality and scalable uniformity
were measured using Raman mapping and XPS-EDX. The two
major phonon vibration mode differences, Δk, for pristine,
350-MoS2, 400-MoS2, and 450-MoS2 were mapped, as shown
in Figure S3. The Mo and S distributions of five randomly
selected different zones were mapped using XPS-EDX to
confirm the scalable uniformity of the film surface, as shown in
Figure S4. This Raman mapping and XPS-EDX analysis
confirm that the thermal-solvent annealing process gradually
etches the sulfur while it maintains its scalable uniform film
surface.
The details of sulfur vacancies on electronic and chemical
states of MoS2 were further characterized by X-ray photo-
electron spectroscopy (XPS). As compared to other vacancies,
sulfur vacancies have low formation energy, and their
formation is more favored during the thermal-solvent
annealing.26,27 As shown in Figure 1f, the two major Mo 3d
peaks were observed for the pristine and 450-MoS2 samples.
The most intense binding energy peaks were observed in the
pristine sample at 232.06 (Mo 3d3/2) and 228.95 eV (Mo
3d5/2), corresponding to the Mo4+ state.1,2 In contrast, the
thermal-solvent-annealed-MoS2 sample shows the blue-shifted
Mo4+ state at 232.13 (Mo 3d3/2) and 229.07 eV (Mo 3d5/2)
corresponding to the Mo4+ state.39 In addition, nonstoichio-
metric MoxSy peaks with lower binding energy in the Mo 3d
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Figure 2. Electrical characterization of MoS2. (a) Relative potential peak shift in MoS2, pristine (black) and thermal-solvent annealed at 350 °C
(red), 400 °C (blue), and 450 °C (magenta). (b) KPFM image of the pristine MoS2 (left) and thermal-solvent-annealed MoS2 (right). (c)
Illustration of the field-effect transistor (FET) device and a top-view optical image of the FET device. (d) Threshold voltage shift of MoS2 devices;
the initial threshold voltage of 1.2 V was shifted to 12 V, which demonstrates the enhanced p-type behavior after thermal-solvent annealing due to
the deep electron trap. (e) Summary plot of the threshold voltage and electron mobility of the MoS2 device.

Figure 3. Piezoelectric characterization of MoS2. (a, d) Output voltage of the pristine MoS2, 350-MoS2, 400-MoS2, and 450-MoS2 samples; the
thermal-solvent-annealed-MoS2 sample shows 35 times higher output voltage and 20 times higher output current than the pristine device. (b, e)
Output voltage and current data of 450-MoS2. (c) Output voltage of pristine and 10 different samples annealed between 350 and 450 °C, indicating
that the systematically controlled sulfur vacancy has an output voltage enhancement. (f) Output current of pristine and 10 samples annealed
between 350 and 450 °C indicates that the systematically controlled sulfur vacancy has an output current enhancement.

were observed near 230.81 and 227.98 eV, representing
intermediate defect states.40−43
The areal fraction of MoxSy indicates that the density of
sulfur vacancies increases with the annealing temperature. A
detailed XPS analysis of different temperature samples, 350-
MoS2 and 400-MoS2, is summarized in Figure S5. As the
annealing temperature was increased, the areal fraction of
nonstoichiometric MoxSy peaks gradually increased from 0 to
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31.51%, as shown in Figure 1g. Likewise, the ratio of Mo and S
significantly decreased from 1:2 to 1:1.45 with increased
annealing temperature. The ratio of Mo vs S, i.e., S defect
concentration, with annealing temperature variation, is
summarized in Table S2. Their Raman and XPS analyses
confirm that the sulfur defects can be efficiently generated to
create asymmetry in the MoS2 structure, which can then be
used for piezoelectric applications. In HRTEM images (Figure
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Figure 4. Large-area array and stability demonstration. (a) Schematic illustration of the piezoelectricity measurement setup and tested device. (b)
Durability test data from the 450-MoS2 device showing excellent stability over 1000 s. (c) Voltage output map measured on 5 cm × 5 cm. MoS2
piezoelectric sensor showing the uniform distribution of piezoelectricity with a value of 0.659 ± 0.17 V under a compression pressure at 3 kPa. (d)
Piezoelectric sensitivity of pristine (black) MoS2 and thermal-solvent-annealed at 350 °C (red), 400 °C (blue), and 450 °C (pink); the sensitivity
increases gradually from 7.72 to 262 mV/kPa. (e) Stability of the MoS2 piezoelectric sensor; our device shows good stability in an ambient
atmosphere of 23 ± 1 °C and 33.4 ± 3% humidities for a month.

S6), sulfur defects are clearly seen from the thermal-solvent-
annealed sample, and the atomic structure with defects is not
centrosymmetric. Therefore, it can be concluded that the
defects generated by the present thermal-solvent annealing
method result in asymmetric MoS2 structures.
To understand the electron trapping during the thermal
release process and differentiate the role of the defects in active
MoS2, the surface potential and carrier density before and after
the thermal-solvent annealing were analyzed using Kelvin
probe force microscopy (KPFM). The relative surface
potential of pristine MoS2 was set to zero to compare the
surface potential with thermal-solvent-annealed MoS2. As a
result, the relative potential of 450-MoS2 decreased by 0.175
eV, indicating a Fermi level shift toward the intrinsic Fermi
level, as shown in Figure 2a. The binding energy shift observed
in XPS results in Figure 1g corresponds to the Fermi level of
the system, where the shift of 0.15 eV to lower binding energy
can be attributed to the shift in the Fermi level.44,45 A KPFM
image of the pristine and 450-MoS2, as shown in Figure 2b,
confirms the uniformity of the defect-engineered MoS2 surface
and its surface potential change with thermal-solvent annealing
temperature.
Furthermore, we fabricated the MoS2 field-effect transistor
(FET) device to characterize the carrier density before and
after the thermal-solvent annealing, as shown in Figure 2c. Ids−
Vgs curves of the pristine and annealed-MoS2 film-based FET
are p-type, as presented in Figure 2d,e. They revealed that after
annealing, the threshold voltage (Vth) of the MoS2 device
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shifted from 0.8 to 12.42 V and the drain−source current (Ids)
decreased from 1.298 to 0.017 nA. Also, the mobility decreased
from 1.36 × 10−3 to 2.24 × 10−5 cm2/(V s). Evidently, the
annealed-MoS2 samples exhibit a p-type characteristic with an
increase in positive charges in the MoS2 crystal structure.24,46,47
A behavior as demonstrated by the threshold voltage, Vth, in
Figure 2e was also followed by the carrier density, n2D, which
was calculated to compare the doping levels of the pristine and
thermal-solvent-annealed MoS2 using the following equation47
n2D = (IDSL)/(qWVDSμ)
where q is the electron charge, L is the channel length, W is the
channel width, and μ is the mobility at VDS = −1 V. The
detailed calculation is provided in the Supporting data (Figure
S8). The carrier (electron) density of the pristine MoS2 device
was 1.83 × 1011 cm−2. However, the carrier density of the
annealed device decreased to 6.69 × 1010 cm−2, about a 2.73
times reduction after the annealing. Note that the hole density
did not decrease as much as the electron density during the
annealing process.
The piezoelectric performance of the pristine sample and
thermal-solvent-annealed samples is shown in Figure 3. The
piezoelectric output voltage responses of pristine and 450-
MoS2 were measured under an applied compressive force of 3
kPa. Interestingly, the piezoelectric output voltage and current
increased with thermal-solvent annealing temperature (Figure
3a,d). It is noted that the pristine MoS2 device generated an
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output voltage of around 40 mV. Notably, 450-MoS2 generated
an output voltage of around 700 mV, which is over 18 times
higher than that of the pristine MoS2 device and the highest
output voltage reported from 2D MoS2 thus far. In the case of
the output current, the 450-MoS2 device generated 20 pA,
which is about 20 times higher than that of the pristine MoS2
device, as shown in Figure 3d. It is evident that the level of the
holes is similar in all types of MoS2 devices, as shown in Figure
2c. However, an electron density in 450-MoS2 was significantly
more suppressed than that of any other types of MoS2 devices,
which resulted in limiting the charge carrier recombination.
This allows excessive holes to behave as free carriers for
current transport in a device consistent with the previously
reported data.18,25,46
Indeed, Inoue et al. have found that the MoS2 device
behaves as a relatively metallic-like feature due to the sulfur
defects, as predicted by the DFT calculations.48 By removing
sulfur atoms from a MoS2 surface, electronic states are formed
in a mid-gap state assigned to the Mo d-orbital under the sulfur
vacancy.49 Therefore, a high density of surface vacancy is found
to increase the electronic density of states in the band gap,
resulting in a metallic feature. Moreover, these defects provide
low-resistance conduction paths in MoS2-based nanodevi-
ces.44,48 The difference in atomic bonding lengths gives rise to
inequivalent charge distribution, resulting in a broken
reflection symmetry in vertical piezoelectric polarization.50 In
the same manner, sulfur-deficient MoS2 exhibits piezoelectric
characteristics due to the lack of inversion symmetry. A
summary of the piezoelectric output voltage and current is
presented in Figure 3c,f, respectively; the piezoelectric
performance of other samples is described in Figure S7.
From these experiments, we can conclude that the precise
defect control in 2D MoS2 enhances its piezoelectric strength
by creating local asymmetry and increasing p-type dopants
within the MoS2 structure. Here, the piezoelectric coefficient
was calculated using the method of Lefki and Dormans51
Q method to engineer piezoelectricity in atomic-thickness MoS2
d33 =
F
= ∫ I dt / F
The piezoelectric coefficient, d33, was calculated to be 16.6 pC/
N (pristine MoS2), 49.8 pC/N (350-MoS2), 83 pC/N (400-
MoS2), and 332 pC/N (450-MoS2); evidently, piezoelectric
coefficients increase with the thermal-solvent annealing
temperature. Further studies will be carried out using
piezoresponse force microscopy (PFM) to visualize the
electrochemical motion of the dipole moment to provide an
insight into switchable electric polarization.52
Figure 4a shows the fabricated scalable MoS2 piezoelectric
sensor and its schematic with the measurement setup. A
representative voltage durability data from the 450-MoS2
device shows exceptional reliability over 1000 s, as shown in
Figure 4b. A large-area, 5 cm × 5 cm piezoelectric mapping
taken from the fabricated MoS 2 piezoelectric sensor
undoubtedly shows the outstanding film uniformity and
sensitivity on the entire surface area, as shown in Figure 4c.
The output voltage average, measured at 3 kPa, was 0.659 ±
0.17 V. The sensitivity of the pristine and thermal-solvent-
annealed samples with respect to the pressure variation from 1
to 5 kPa was also investigated and is presented in Figure 4d.
The pristine MoS2 device had 7.72 mV/kPa of sensitivity, and
this gradually increased to 262 mV/kPa for the 450 °C
annealed sample. This sensitivity data shows that our thermal-
solvent-annealed device can generate 34 times higher
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sensitivity than that by the pristine MoS2 regardless of the
pressure, which makes it extremely suitable for its use as an
effective piezoelectric sensor in bioinspired robots and
biomedical applications.
Finally, all of the MoS2 devices were exposed to the ambient
temperature for 1 month to investigate their stability in normal
operating conditions for a long time; the temperature and
humidity were maintained at 23 ± 1 °C and 33.4 ± 3%,
respectively. Indeed, all of the devices showed environmental
stability in the atmosphere even after a month within a 5%
deviation, which is comparable to other reported values.22
These results demonstrate that the present thermal-solvent
annealing process can be an effective method to engineer
defect concentrations in 2D MoS2 layers, thereby facilitating
the fabrication of large-scale stable MoS2 piezoelectric sensors
with excellent performance.
3. CONCLUSIONS
We have demonstrated that the sulfur-deficient 2D MoS2,
synthesized using a thermal-solvent etching method, can
produce a precisely defect-engineered structure with a p-type
characteristic and provide a synergistic effect toward piezo-
electricity. This can lead to the piezoelectric output current
and voltage of the defect-controlled MoS2 device by more than
20 times compared to a pristine device, a phenomenon
attributed to the formation of the local asymmetric structure by
the created defects and abundance of p-type dopants within
the MoS2 structure. Our results also demonstrate that the
piezoelectricity increases with the defect density, increasing
with the thermal-solvent annealing temperature within the
range of present experiments (≤450 °C). Indeed, the MoS2
device created by us shows an outstanding piezoelectric
sensitivity of 262 mV/kPa while retaining its performance in an
ambient atmosphere for a long time, over a month in the
present experiment. This work also establishes that the
thermal-solvent etching method is a facile and effective
layers by precisely creating an asymmetrical charge distribu-
tion.
4. EXPERIMENTAL SECTION
4.1. Synthesis of MoS2. For piezoelectric device fabrication, a
bottom electrode was patterned and sputtered on a SiO2/Si substrate
by using titanium (99.99%, Plasmaterials) and gold (99.99%,
Plasmaterials) targets. Then, the 2D MoS2 film was synthesized via
a two-step synthesis method.1,2 First, the bottom electrode-patterned
substrate was transferred to a radiofrequency magnetron plasma
sputtering system. Molybdenum (Mo) (99.99%, Plasmaterials) was
sputtered under Ar plasma (99.99% Airgas) at a deposition of 60 W
for 2 s. Then, the Mo-sputtered sample was transferred to the low
pressure chemical vapor deposition (LPCVD) chamber for sulfuriza-
tion at 600 °C for 1 h. Finally, a top electrode, Cu (99.99%
Plasmaterials), was patterned and deposited on top of the MoS2 layer.
4.2. Thermal-Solvent Annealing Method. The defect-engi-
neered MoS2 was processed via LPCVD with organic solvent vapor.
First, the as-deposited MoS2 film on top of the quartz sample was
placed in the middle of the LPCVD furnace connected to an attached
supplementary chamber filled with toluene. Second, once the vacuum
level and the annealing temperature were reached, the supplementary
chamber was opened for 7 min to allow the toluene vapors to etch the
sulfur of the MoS2 surface. This process was repeated at three
different temperatures to vary the concentration of the etched sulfur:
350, 400, and 450 °C.
4.3. Field-Effect Transistor (FET) Fabrication. An electrical
property of defect-engineered MoS2 was characterized by the MoS2-
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FET device. First, a 300 nm thickness of SiO2/Si was prepared and
cleaned. A few-layered MoS2 was prepared by the aforementioned
method on top of SiO2/Si, followed by the thermal-solvent annealing
process. Second, a patterned shadow mask was placed on top of the
MoS2 layer, and then gold (99.99%, Plasmaterials) was sputtered and
used as an electrode.
4.4. Microscopic and Electrical Characterization. The
crystalline property of the MoS2 was analyzed by Raman spectroscopy
(WiTec Alpha 300R) with an excitation wavelength of 532 nm. The
thickness of the MoS2 film was confirmed by atomic force microscopy
(Parks NX-10). The structural composition of the MoS2 was
determined by X-ray photoelectron spectroscopy (PHI 5000
VersaProbe Scanning XPS) at 15 KV under an ultrahigh vacuum
(10−8 Torr). The electrochemical properties were analyzed by a
Kelvin probe force microscope (Bruker MultiMode 8). The
piezoelectricity was measured using an automated tapping machine,
ESM-303 (Mark-10); the compressive force was applied vertically
from 1 to 5 kPa. ESM-303 was connected directly with the computer
and precision source/measure unit electrometer (Agilent B2912A) to
read the piezoelectric responses. TEM analysis was performed using a
JSM-7800F Prime instrument (JEOL Ltd.) at an operational voltage
of 200 kV, fitted with a Cs corrector (CEOS GmbH) FEG-STEM/
TEM unit. The images were reconstructed using a Gatan Digital
Micrograph computational package.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.1c00650.
Schematic illustration of our two-step process of MoS2
synthesis (Figure S1); XPS-EDX mapping confirmed the
uniform film surface (Figure S2); Raman mapping
analysis of peak differences (Figure S3); XPS-EDX
analysis of Mo and S atomic distributions (Figure S4);
XPS analysis of MoS2 (Figure S5); high-resolution TEM
images (Figure S6); temperature-dependent piezo-
electric output current−voltage (Figure S7); carrier
density calculations (Figure S8); Hansen solubility
parameters (Table S1); and summarized Mo and S
ratios (Table S2) (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Wonbong Choi − Department of Materials Science and
Engineering and Department of Mechanical Engineering,
University of North Texas, Denton, Texas 76203, Unites
States; orcid.org/0000-0002-7896-7655;
Email: Wonbong.choi@unt.edu
Authors
Junyoung Kim − Department of Materials Science and
Engineering, University of North Texas, Denton, Texas
76203, Unites States; orcid.org/0000-0001-5023-4030
Eunho Lee − Department of Mechanical Engineering,
University of North Texas, Denton, Texas 76203, United
States; orcid.org/0000-0002-8564-6999
Gayatri Mehta − Department of Electrical Engineering,
University of North Texas, Denton, Texas 76203, United
States
Vish Prasad − Department of Mechanical Engineering,
University of North Texas, Denton, Texas 76203, United
States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.1c00650
13602
www.acsami.org Research Article
Author Contributions
All of the work was designed and performed under the
supervision of W.C. J.K. performed material synthesis and
characterizations, and E.L performed device characterization.
W.C. and V.P. wrote the manuscript. G.M. analyzed data and
edited the manuscript. All authors have discussed the results,
read the manuscript, and agreed with its content.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Science Foundation
(grant No. CBET-1936255).
■
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