[Link].

org Research Article

Gate-Modulated Ultrasensitive Visible and Near-Infrared

Photodetection of Oxygen Plasma-Treated WSe2 Lateral pn-
Homojunctions
Sekhar Babu Mitta, Fida Ali, Zheng Yang, Inyong Moon, Faisal Ahmed, Tae Jin Yoo, Byoung Hun Lee,
and Won Jong Yoo*
Cite This: ACS Appl. Mater. Interfaces 2020, 12, 23261−23271 Read Online
See [Link] for options on how to legitimately share published articles.

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
Downloaded via SUNGKYUNKWAN UNIV on July 16, 2020 at 05:30:28 (UTC).

ABSTRACT: We investigate the development of gate-modulated tungsten diselenide (WSe2)-based lateral pn-homojunctions for
visible and near-infrared photodetector applications via an effective oxygen (O2) plasma treatment. O2 plasma acts to induce the p-
type WSe2 for the otherwise n-type WSe2 by forming a tungsten oxide (WOx) layer upon O2 plasma treatment. The WSe2 lateral pn-
homojunctions displayed an enhanced photoresponse and resulted in open-circuit voltage (VOC) and short-circuit current (ISC)
originating from the pn-junction formed after O2 plasma treatment. We further notice that the amplitude of the photocurrent can be
modulated by different gate biases. The fabricated WSe2 pn-homojunctions exhibit greater photoresponse with photoresponsivities
(ratio of the photocurrent and incident laser power) of 250 and 2000 mA/W, high external quantum efficiency values (%, total
number of charge carriers generated for the number of incident photons on photodetectors) of 97 and 420%, and superior
detectivity values (magnitude of detector sensitivity) of 7.7 × 109 and 7.2 × 1010 Jones upon illumination with visible (520 nm) and
near-infrared lasers (852 nm), respectively, at low bias (Vg = 0 V and Vd = 1 V) at room temperature, demonstrating very high-
performance in the IR region superior to the contending two-dimensional material-based photonic devices. These superior
optoelectronic properties are attributed to the junctions induced by O2 plasma doping, which facilitate the effective carrier
generation and separation of photocarriers with applied external drain bias upon strong light absorption.
KEYWORDS: gate modulation, infrared photodetection, WSe2, O2 plasma doping, lateral pn-homojunctions

■ INTRODUCTION
The two-dimensional (2D) transition-metal dichalcogenides
with tremendous efforts owing to their atomic thinness,
mechanical flexibility, and large-scale development,4−6 whereas
(TMDCs) with a layered semiconducting structure offer a the electrically driven light emission in graphene-based pn-
unique platform to investigate and develop future nanoscale junction photodetectors is challenging and did not show diode-
devices. Indeed, TMDCs are utilized in optoelectronic like rectification behavior due to its zero band gap. Recently,
applications such as photodetectors, solar cells, light-emitting the vdW vertical pn-heterojunctions are developed as a novel
diodes, and photovoltaic cells owing to their tunable band gap section of artificial structures; however, to accomplish this,
controlled by the number of layers.1−3 The pn-junctions are complex processing such as an accurate alignment and
the functional building blocks of various optoelectronic
devices; on the other hand, bulk semiconductor-based pn- Received: December 28, 2019
junctions employed in modern optoelectronic devices hold Accepted: April 29, 2020
certain limitations such as high cost, mechanical rigidity, and Published: April 29, 2020
bandwidth coverage. In recent years, with the advent of
atomically thin van der Waals (vdW) structures, 2D material-
based pn-junction photodetectors have been demonstrated

© 2020 American Chemical Society [Link]

23261 ACS Appl. Mater. Interfaces 2020, 12, 23261−23271
ACS Applied Materials & Interfaces [Link] Research Article

Figure 1. Characterization of multilayered WSe2 on the Si/SiO2 substrate. (a) Schematic representation of as-fabricated bulk WSe2 FET fabricated
on the Si/SiO2 substrate. (b) Optical microscopy (OM) image of the as-fabricated WSe2 FET with Pd contacts indicating five different channels
(1−5). The zoomed part on top right shows an AFM image of a WSe2 flake, and the bottom-right part displays the AFM height profile revealing the
thickness of the ∼10 nm WSe2 flake. (c) Transfer characteristics of as-fabricated WSe2 FET obtained for all the five channels measured at Vd = 1 V
in logarithmic scale and the inset displaying the transfer curves in linear scale. (d) Output curves of WSe2 FET measured at Vg sweep of −60 to +60
V with 10 V step.

multitransfer technology is required and is hard to localize on a exposure.17 Addou et al. also recently reported that the
flake during the device fabrication process, in which the vdW oxidation of chemical vapor deposition-grown WSe2 can be
gaps at the junctions can inhibit the charge transfer and induced by exposure to air.19 These various choices of doping
deteriorate the device performance. Cheng et al. demonstrated techniques are yielding exciting opportunities to WSe2 as a
atomically thin vertical WSe2/MoS2 pn-heterojunction diodes, promising material for future optoelectronic devices by
which resulted in a low quantum efficiency of 12%.7 In rendering high absorption efficiency and responsivity. Among
addition, the pn-junctions are achieved via chemical doping or the doping methodologies, O2 plasma treatment is a semi-
electrical tuning in which the impurities are introduced at the conductor industry-compatible process, which can be easily
interface or require an external electric field.5−11 adapted for doping in the semiconductor manufacturing
Among the various 2D TMDCs, tungsten diselenide (WSe2) process.20−23 In addition, the surface treatment on TMDCs
with a bulk indirect band gap of ∼1.2 eV exhibits an ambipolar by using O2 plasma is investigated for the enhancement of the
behavior when utilized as a channel material for field-effect electrical performances. The monolayered WSe2 p-FETs with
transistors (FETs), while it can be an ideal material for chemically degenerated doped contacts and with surface
optoelectronic applications due to its tunable energy bands, treatment exhibit a high hole mobility of 250 cm2/V·s and
fast charge transfer, and strong optical absorption.12−15 To maximum hole concentration of ∼1019/cm3.24,25
enrich the TMDC optoelectronic device performances, Infrared (IR) photodetectors have been used extensively in
utilization of the appropriate charge doping process becomes diverse applications such as telecommunications, bio-imaging,
noteworthy with either being hole-rich or electron-rich. thermal imaging, military, night vision, etc. Moreover, the 2D
Recently, the functionalization of WSe2 has received significant TMDC materials interact with a wide range of spectra from
attention as a highly efficient technique to enhance the device ultraviolet (UV) to terahertz frequencies and have attracted
performance via electrostatic or chemical doping to achieve pn- great research interest in the field of IR photodetection to
junction photodetectors; however, the devices accomplished demonstrate exceptional optoelectrical properties.26−31 Never-
by electrostatic gating involve complex design as well as the theless, the WSe2-based photodetectors are restricted to IR
stress induced by gating limit the optoelectrical performance light detection and have not been widely demonstrated due to
and stability of pn-junctions.4,16−18 For example, Baugher et al. the direct band gap of 1.6 eV for monolayer WSe2, and also,
reported the electrically tunable pn-junction photodetectors by reports on bulk WSe2 typically focus on visible region
the electrostatic gating of WSe2 flake, and these photodetectors detection.15,17 To circumvent this, here, we demonstrate
demonstrated a photoresponsivity of 210 mA/W and external simple and effective fabrication of O2 plasma-doped multilayer
quantum efficiency of 0.2%.16 Also, Xie et al. demonstrated a WSe2 lateral pn-homojunctions employed for broadband
WSe2 lateral pn-junction with a high rectifying ratio of 106 and (visible and near-infrared) photodetector application with
photoresponsivity of 2.49 A/W by selective N2O plasma different gate voltage tuning. The typical transfer curves exhibit
23262 [Link]
ACS Appl. Mater. Interfaces 2020, 12, 23261−23271
ACS Applied Materials & Interfaces [Link] Research Article

Figure 2. Characterization of the WSe2 FET device after oxygen (O2) plasma treatment. (a) Schematic illustration of O2 plasma treatment to bulk
WSe2 FET with the opened and PMMA-covered regions. (b) OM image of O2 plasma-treated WSe2 FET device showing channels 3, 4, and 5 as p-
WSe2, pn-WSe2, and n-WSe2, respectively. (c) Transfer curves of p-, pn-, and n-WSe2 channels measured at Vd = 1 V after O2 plasma treatment are
represented in logarithmic scale. (d) The output curve of O2 plasma-treated WSe2 FET (pn-WSe2) obtained at Vg = −60 V is represented in both
linear and logarithmic scales. (e−h) The corresponding energy band diagrams depict the carrier transport paths in WSe2 before and after O2 plasma
treatment at applied gate bias.

the n-type and p-type behaviors of WSe2 before and after O2

plasma treatment, respectively, which are attributed to the fact
■ RESULTS AND DISCUSSION
Figure 1a illustrates the schematic of a WSe2 device fabricated
that O2 plasma acts as a p-type dopant by forming a tungsten on a Si/SiO2 substrate. The whole process of exfoliation and
oxide (WOx) layer. We analyzed the Raman spectroscopy and fabrication was performed inside the glove box with a
photoluminescence (PL); nevertheless, the formation of the controlled inert environment. The fabrication process is
tungsten oxide (WOx) layer is scrutinized using X-ray described in Materials and Methods. An optical microscopy
photoelectron spectroscopy (XPS). The WSe2 lateral pn- (OM) image of the as-fabricated WSe2 FET device (with
homojunctions exhibit unique properties like short-circuit channels 1−5) is shown in Figure 1b. The top right side of
current (ISC) and open-circuit voltage (VOC) with an enhanced Figure 1b shows the AFM image of WSe2 channel 5 acquired
photoresponse generated from the pn-junction formed after O2 from the dashed square area, and the bottom right side shows
plasma treatment. The device displays a novel feature in the the AFM height profile, which reveals the thickness of the ∼10
transfer characteristics under gate modulation and reveals nm WSe2 flake. Initially, the electrical characteristics of as-
efficient near-IR photodetecting properties. Upon visible (520 fabricated WSe2 FET were investigated under vacuum
nm) and near-IR laser illuminations (852 nm), the photo- conditions (∼5 mTorr pressure) at room temperature. The
detection properties of pn-WSe2 homojunctions such as transfer characteristics of all the WSe2 channels (1−5)
photoresponsivities, EQE, response time, and detectivity are obtained at Vd = +1 V exemplify an ambipolar behavior with
greatly enhanced compared to those of as-fabricated WSe2. a higher current level at Vg > 0, as shown in Figure 1c. An n-
The scanning photomapping spectroscopy of pn-WSe2 also dominant ambipolar trend unveiled that the electron current
demonstrates the origin of photocurrent generation from the (at Vg = +60 V) was more than 2 orders of magnitude higher
junctions. This promising 2D homojunction induced by the O2 than the hole current (at Vg = −60 V) and showed that the
plasma doping process will facilitate the development of Fermi level lies near to the conduction band of WSe2. This
broadband photodetectors and future electronics applications. might be due to the specific band alignment between Pd and
23263 [Link]
ACS Appl. Mater. Interfaces 2020, 12, 23261−23271
ACS Applied Materials & Interfaces [Link] Research Article

Figure 3. (a) Raman, (b) photoluminescence (PL), and (c) X-ray photoelectron spectroscopy (XPS) spectra of the WSe2 device measured before
and after O2 plasma treatment. The Raman spectra reveal that no change is observed in Raman peaks with O2 plasma treatment. From the PL
analysis, the PL intensities at 1.35 and 1.55 eV were enhanced after O2 plasma doping. The XPS spectra comparison of as-fabricated and O2 plasma-
treated WSe2 flakes clearly shows the existence of two extra peaks at the binding energies of 35.53 and 37.68 eV corresponding to WOx and shift in
binding energies (dashed lines) of W and Se peaks after O2 plasma treatment. The shifts in binding energy are shown with green and red arrows for
both W and Se peaks after O2 plasma treatment.

WSe2, unintentional n-doping by Se vacancies in WSe2, and/or pn-homojunction should be independent of the dielectric
impurities.32 Besides, the output curves of the as-fabricated screening, different from usual electronic carrier transport.
WSe2 FET measured at various gate voltages (Vg = −60 to +60 Therefore, we understood that the photocurrent obtained with
V) are displayed in Figure 1d. Here, we observed a nonlinear bottom SiO2 and top n-side coated with PMMA in this study
trend from the output characteristics at all the applied gating represents accurate photonic performance.
conditions, which suggested the formation of Schottky The effect of O2 plasma doping (p-type doping) on as-
contacts between metal electrodes (Pd) and the WSe2 channel. fabricated WSe2 FET devices was confirmed through the
As observed from the as-fabricated WSe2 FET character- electrical characteristics. The typical transfer curves of three
istics, the electron current is dominated under high positive different channels, i.e., channels 3 (p-WSe2), 4 (pn-WSe2), and
gate bias, and therefore, to achieve the hole-dominated current, 5 (n-Wse2), are compiled in Figure 2c, in which channel 3 and
it is essential to modulate the as-fabricated WSe2 channels with the half-portion of channel 4 resulted in yielding of p-type
O2 plasma, which acts as a p-type dopant upon exposure to the characteristics from n-type. The output curve of channel 4 (pn-
controlled plasma conditions.17,24,25 Figure 2 demonstrates the WSe2) signifying the forward rectifying diode behavior is
electrical performances of O2 plasma-treated WSe2 FET shown in Figure 2d, which implied that the drain current (Id)
devices. The as-fabricated WSe2 devices were covered with under forward bias (Vd > 0 V) is much higher than the Id under
polymethylmethacrylate (PMMA), and a rectangular window reverse bias (Vd < 0 V). The transfer characteristics of as-
was opened on a channel by employing electron-beam fabricated and O2 plasma-doped WSe2 FET for five different
lithography (EBL) followed by O2 plasma treatment. The O2 channels (1−5) and the output curves of pn-WSe2 FET
plasma, generated with the optimized plasma operating measured with respect to Vg sweep are displayed in Figure S3
conditions (see device fabrication), were exposed to the (Supporting Information). The corresponding energy band
WSe2 FET device, as illustrated in Figure 2a. The O2 molecules diagrams depicting the carrier transport paths in WSe2 at
were chemisorbed on top of the WSe2 surface, and applied gate bias are illustrated in Figure 2e−h. The band
consequently, the Se atoms were replaced by O atoms, alignments of Pd and WSe2 for n-dominated (n-WSe2) and p-
which resulted in the formation of a WOx layer on top of the dominated (p-WSe2) WSe2 in the equilibrium state are
WSe2 flake. Figure 2b depicts an OM image of the O2 plasma- illustrated in Figure 2e,f, respectively. At large positive Vg
treated WSe2 FET device. The thickness of WOx generated (Vg > 0 V), more electrons accumulated in the conduction
after O2 plasma treatment is found to be approximately ∼1 nm, band, leading to the increase in electron current level (Figure
which can be analyzed by employing time-of-flight secondary 2g). In contrast, owing to the p-doping effect of O2 plasma
ion mass spectroscopy measurements.23 Here, channel 3 (to (formation of a WOx layer on top of WSe2) and the application
achieve p-type WSe2) and channels 2 and 4 (to achieve WSe2 of large negative Vg (Vg < 0 V), the Schottky barrier width
pn-homojunction) were completely and partially opened with along the Pd/WSe2 interface was thinned, aiding the injection
PMMA, respectively, whereas channels 1 and 5 (n-WSe2) were of hole carriers into the WSe2 channel across the barrier and
covered with PMMA. The WSe2 pn-homojunction used in this thereby resulting in a large hole current, as shown in Figure 2h.
study consists of the n-side coated with PMMA. Initially, we Further characterizations of WSe2 flakes were carried out by
carried out the electronic transport and time-resolved photo- Raman spectroscopy and photoluminescence (PL). Figure 3a
current measurements on the as-fabricated WSe2, comparing displays the characteristic Raman spectra of the WSe2 flake
the results without and with PMMA to investigate the possible with peak position values acquired before and after O2 plasma
dielectric screening effects induced by PMMA, as illustrated in treatment. We observed the typical Raman peaks of WSe2 at
Figure S2 (Supporting Information). Here, we did not observe 247.06 and 255.44 cm−1, which represent in-plane vibrational
noticeable difference in the electronic transport and E2g mode and out-of-plane vibrational A1g mode, respectively,
interpreted that these unchanged electrical properties were and the bulk B2g mode (observed in multilayer and bulk) at
due to short-range scattering, which dominated over long- 306.56 cm−1. We did not observe any characteristic Raman
range scattering. In addition, the photocurrent from the WSe2 peak shift upon O2 plasma treatment compared to the pristine
23264 [Link]
ACS Appl. Mater. Interfaces 2020, 12, 23261−23271
ACS Applied Materials & Interfaces [Link] Research Article

Figure 4. Photoresponse characteristics of pn-WSe2 homojunction FET devices. (a, b) Id−Vd characteristics of pn-WSe2 measured in the dark and
under 532 nm light illumination obtained at Vg = −60 and +60 V, respectively. The inset in (a) shows the OM image of the device and the
measured pn-WSe2 is represented in a white dotted box. (c) Id−Vd characteristics of pn-WSe2 measured in the dark and under 532 and 900 nm
light illuminations demonstrating photovoltaic behavior at Vd = Vg = 0 V, which exhibits a short-circuit current (ISC) and open-circuit voltage
(VOC). (d) Id−Vd characteristics of pn-WSe2 measured in the dark and under various light illuminations.

WSe2 flake, similar to that reported earlier.33 Subsequently, as pn-WSe2 homojunction exhibited short-circuit current values
shown in Figure 3b, the bulk WSe2 device exhibited two main (ISC, photocurrent at zero external bias) of 2.86 nA (for 532
PL peaks at 1.35 and 1.55 eV before O2 plasma treatment; nm) and 1.44 nA (900 nm) and open-circuit voltage values
however, the intensities of PL peaks were enhanced after O2 (VOC, voltage with no current flowing) of 256 mV (532 nm)
plasma doping. To further verify the formation of the WOx and 237 mV (900 nm). Hence, the pn-WSe2 homojunctions
layer on top of WSe2 after O2 plasma treatment, we performed are suggested for the applications of photovoltaic cells. In
XPS for WSe2 before and after O2 plasma treatment, as shown addition, Figure 4d shows the photovoltaic characteristics of
in Figure 3c. The XPS core spectrum of WSe2 showed two the pn-WSe2 homojunction illuminated with different wave-
significant peaks of W (Se) at 32.28 eV (54.53 eV) and 34.43 lengths ranging from 400 to 900 nm.
eV (55.38 eV) corresponding to W 4f7/2 (Se 3d5/2) and W 4f5/2 We explored the optoelectronic properties of three different
(Se 3d3/2), respectively.25 After O2 plasma treatment, two types of WSe2 photodetectors, i.e., n-WSe2 (as-fabricated), p-
additional peaks at the binding energies of 35.53 and 37.68 eV WSe2 (O2 plasma-doped), and pn-WSe2 homojunction FETs,
appeared in the XPS core spectrum corresponding to WOx (x as illustrated in Figure 5 by carrying out electrical measure-
≤ 3).33−35 Moreover, the shifts in the binding energies (0.28 ments in an ambient environment in the dark and laser
and 0.22 eV for W 4f and 0.31 and 0.32 eV for S 3d) were also illuminations. Here, we employed two lasers with wavelengths
observed for both W and Se after O2 plasma treatment (shown (λLaser) of 520 nm (visible) and 852 nm (near-IR) for the
as dashed lines). These results clearly proved that the oxygen illuminations, and the schematic of laser illuminations are
radicals were effectively doped into the WSe2 crystals during depicted in Figure 5a,b, respectively. Initially, the photocurrent
plasma exposure. generated from the as-fabricated WSe2 photodetector was
Next, we investigated the photoresponse of the pn-WSe2 analyzed by illuminating λLaser = 520 nm with various powers,
homojunction by measuring the I−V characteristics with as shown in Figure S4 (Supporting Information). As the power
monochromatic light illumination of different wavelengths, of the laser increased, the photocurrent generated increased
which displayed ideal diode characteristics as shown in Figure monotonically with increasing power and a medium-ranged
4. Figure 4a,b illustrates the photoresponse studies of pn-WSe2 power of 0.31 mW was considered for further investigations of
at Vg = −60 V and +60 V, respectively. In addition, a clear photocurrent analysis to avoid the device heating with high
photovoltaic effect at Vg = 0 V was observed for the pn-WSe2 laser power. Correspondingly, we considered the power of
homojunction, signifying that the spontaneous charge 0.075 mW for λLaser = 852 nm. The typical transfer curves of
separation took place with built-in potential at the junction, three types of WSe2 photodetectors are displayed in Figure
as shown in Figure 4c,d. Figure 4c illustrates the output 5c−e. Figure 5c shows the transfer curves of as-fabricated
characteristics of pn-WSe2 measured in the dark and under 532 WSe2 (n-WSe2) measured in darkness and under λLaser = 520
and 900 nm light illuminations. Under light illumination, the nm (power of 0.31 mW) and λLaser = 852 nm (power of 0.075
23265 [Link]
ACS Appl. Mater. Interfaces 2020, 12, 23261−23271
ACS Applied Materials & Interfaces [Link] Research Article

Figure 5. Optoelectronic characteristics of as-fabricated and O2 plasma-doped WSe2 FET devices. (a, b) Cartoon demonstration of the WSe2
photodetector under 520 and 852 nm laser illuminations, respectively. Typical transfer characteristics of (c) n-WSe2 (before O2 plasma treatment),
(d) p-WSe2, and (e) pn-WSe2 after O2 plasma treatment measured in darkness and under laser illuminations of visible (520 nm) and near-infrared
(852 nm) wavelengths. (f−h) Time-dependent photocurrent measurements of n-WSe2, p-WSe2, and pn-WSe2 achieved under λLaser = 520 nm
(PLaser = 0.31 mW) at applied Vd = 1 V with various Vg’s. (i−k) Time-dependent photocurrent measurements of n-WSe2, p-WSe2, and pn-WSe2
achieved under λLaser = 852 nm (PLaser = 0.075 mW) at applied Vd = 1 V with various Vg’s.

mW) laser illuminations at applied drain bias (Vd = 1 V). As Vg enhancement at Vg = −5 and −8 V, respectively. The
varied, prominent and small variations in photocurrent (Iphoto) minimum Idark observed at Vg = −5 V in p-WSe2 exhibited
were observed at Vg < 0 V and Vg > 0 V, respectively, which substantial increment in Iphoto from 6.62 × 10−12 to 4.1 × 10−6
indicated that the photocurrent was effectively controlled by A for λLaser = 520 nm and 1.5 × 10−7 A for λLaser = 852 nm.
the applied gate bias. It was clearly witnessed that the off-state Similarly, the Idark observed at Vg = −8 V in pn-WSe2 showed
current values measured in the dark exhibited the significant significant increment in Iphoto from 4.35 × 10−13 to 1.08 × 10−6
enhancement in the Iphoto from 3.66 × 10−12 A (Idark) to 6.62 × A and 2.29 × 10−7 A for λLaser = 520 and 852 nm, respectively.
10−7 A (for λLaser = 520 nm) and 3.97 × 10−7 A (for λLaser = This enhancement was mainly ascribed to the strong light
852 nm) after laser illuminations at Vg = 0 V. From Figure absorption in WSe2 photodetectors generating a greater
5d,e, the transfer curves of p- and pn-WSe2 displayed Iphoto number of photoinduced electron−hole pairs and significant
23266 [Link]
ACS Appl. Mater. Interfaces 2020, 12, 23261−23271
ACS Applied Materials & Interfaces [Link] Research Article

Figure 6. Photocurrent analysis of WSe2 photodetectors. (a−c) Photoresponsivity (R), EQE (%), and detectivity (D*) of n-WSe2, p-WSe2, and pn-
WSe2 obtained under λLaser = 520 nm as a function of Vg. (d−f) R, EQE (%), and D* of n-WSe2, p-WSe2, and pn-WSe2 obtained under λLaser = 852
nm as a function of Vg.

reduction in the Schottky barrier that allowed the photo- and pn-WSe2 at Vg = 0 V were 0.27, 1.15, and 13 μA, and the
generated carriers to transmit more effectively along the WSe2/ area-weighted photocurrents were 4.3, 24.5, and 101 nA/μm2,
metal interface with externally applied bias.17,36 To further respectively, resulting in 23.5-fold and 4-fold increments for
investigate the performance of WSe2 photodetectors and to pn-WSe2 compared to n-WSe2 and p-WSe2. This significant
study their photoresponse dynamics, we performed the time- photocurrent enhancement in pn-WSe2 homojunctions after
and gate voltage-dependent photocurrent measurements at the surface modification was attributed to the generation of
fixed drain bias (Vd = +1 V), as demonstrated in Figure 5f−h excess electron−hole pairs with strong light absorption in the
and Figure 5i−k for 520 nm (power of 0.31 mW) and 852 nm junction and reduction of the probability of recombination of
(0.075 mW) laser illuminations, respectively. From the time- the photoactivated charge carriers. This substantial photo-
dependent photocurrent measurements of n-WSe2 shown in current generation at various Vg and positive Vd conditions
Figure 5f for λLaser = 520 nm, as the Vg swept from −60 to +40 resulted from the pn-WSe2 homojunction perhaps used as a
V, the photocurrent enhancement was clearly observed, phototransistor for light detection from visible to near-IR
reached the maximum photocurrent at Vg = −30 V, and spectra.
decreased with a further increase in Vg. For p-WSe2 and pn- We compared the photodetector performances among n-
WSe2, the Vg was swept from −30 to +60 V and −40 to +60 V WSe2, p-WSe2, and pn-WSe2 devices by evaluating the
and exhibited the maximum photocurrent at Vg = +20 and −10 photoresponse figures of merit such as photoresponsivity
V, as illustrated in Figure 5g,h, respectively. Similarly, for the (R), external quantum efficiency (EQE), detectivity (D*), and
time-dependent photocurrent measurements under λLaser = 852 rise (tr) and fall times (tf), as demonstrated in Figure 6 and
nm illuminations for n-WSe2, p-WSe2, and pn-WSe2, the Vg Figure S5 (Supporting Information). The spectral responses of
sweep was applied from −60 to +20 V, −20 to +60 V, and −30 WSe2 photodetectors were expressed through R, which is
to +60 V, and high photoresponses were observed at Vg = −20, defined as the ratio of the photocurrent and incident laser
+30, and + 30 V, respectively, as shown in Figure 5i−k. power, i.e., R = Iphoto/PLaser, where Iphoto = Idark − Ilight. Figure
Interestingly, this similar trend was also witnessed from the 6a,d illustrates the photoresponsivities of WSe2 photodetectors
transfer curves with different applied Vg values (Figure 5c−e). as a function of Vg for 520 and 852 nm laser illumination
The area-weighted photocurrents were compared since the wavelengths, respectively obtained from the time- and voltage-
areas of n-WSe2 (L × W: 4 μm × 16 μm), p-WSe2 (L × W: 3 dependent curves. It was clearly observed that the R of the pn-
μm × 16 μm), and pn-WSe2 (L × W: 8 μm × 16 μm) channels WSe2 homojunction photodetector was higher compared to
are not similar. From Figure 5f−h, the photocurrents observed those of n-WSe2 and p-WSe2 devices. Owing to the formation
at Vg = 0 V for n-WSe2, p-WSe2, and pn-WSe2 with λLaser = 520 of the depletion region in the junction devices, the photon
nm illuminations were 6.35, 13, and 77.9 μA, and the area- collection efficiency was improved and, hence, the responsivity
weighted photocurrents were 0.1, 0.27, and 0.61 μA/μm2, increased. Another crucial figure of merit of photodetector is
respectively, resulting in 6-fold and 2.2-fold increments for pn- EQE, which is stated as the total number of charge carriers
WSe2 compared to n-WSe2 and p-WSe2. Similarly, for λLaser = generated for the number of incident photons on photo-
852 nm, the photocurrent values observed for n-WSe2, p-WSe2, detectors and given by EQE (%) = (hcR/eλ) × 100, where h, c,
23267 [Link]
ACS Appl. Mater. Interfaces 2020, 12, 23261−23271
ACS Applied Materials & Interfaces [Link] Research Article

Table 1. Performance Comparisons of O2 Plasma-Treated WSe2 FET Photodetectors with Reported Intrinsic or Doped Two-
Dimensional Material Photodetectors
operation conditions (wavelength, responsivity EQE detectivity response time
device (method) bias) (mA/W) (%) (Jones) (ms) reference
WSe2 (intrinsic) 532 nm (Vd = 2 V; Vg = −12 V) 7000 40 0.04 15
WSe2 (intrinsic) 635 nm (Vd = 0.2 V) 900 180 900 37
MoS2 (intrinsic) 550 nm (Vd = 0 V; Vg = 1 V) 0.42 38
WSe2 (chemical doping) 650 nm (Vd = 1 V; Vg = −60 V) 360 1 × 109 310 39
WSe2 (chemical doping) 532 nm (Vd = −0.5 V; Vg = 0 V) 20 13 40
WSe2/MoS2 (heterojunction) 500 nm (Vd = −3 V) 170 0.1 41
WSe2/MoS2 (heterojunction) 660 nm (Vd = 2 V; Vg = 10 V) 17,800 80 42
WSe2 (chemical doping) 635 nm (Vd = 5 V; Vg = −40 V) 468 91.2 4 43
MoS2 (chemical doping) 500 nm (Vd = −1.5 V; Vg = 0 V) 330 81 1.6 × 1010 100−200 5
n-WSe2 520 nm (Vd = 1 V; Vg = 0 V) 20 8.7 2.5 × 109 50.2 this work
852 nm (Vd = 1 V; Vg = 0 V) 23 11 2.3 × 1010 68.3
p-WSe2 (O2 plasma doping) 520 nm (Vd = 1 V; Vg = 0 V) 7 2.4 9 × 108 46.5 this work
852 nm (Vd = 1 V; Vg = 0 V) 37.7 15 1 × 1010 61.2
pn-WSe2 homojunction (O2 plasma 520 nm (Vd = 1 V; Vg = 0 V) 250 97 7.7 × 109 41.8 this work
doping) 852 nm (Vd = 1 V; Vg = 0 V) 2000 420 7.2 × 1010 53.7

e, and λ are Planck’s constant (6.63 × 10−34 J·s), the velocity of photodetector device, and therefore, we considered that the
light (3 × 108 m·s−1), the electron charge (1.6 × 10−19 C), and improvement in tr (smaller for pn-WSe2) resulted in a faster
the laser illumination wavelength (λLaser = 520 and 852 nm), response of the device, compared to n- and p-WSe2, and also
respectively. We compared the EQE for pn-WSe2 homo- ascribed to a higher carrier density in the junction devices.
junction photodetectors with n-WSe2 and p-WSe2 devices for Besides, the higher tf (slow decay) indicated the oxygen
520 and 852 nm laser illumination wavelengths, as shown in photochemical absorption and desorption of carriers on WOx
Figure 6b,e, and clearly showed that the homojunction (observed in pn-WSe2) and also ascribed to the excess lifetime
photodetectors resulted in higher EQE at all the applied Vg’s. of trapped carriers even after the termination of light
The EQE values for the pn-WSe2 photodetector at Vg = 0 V illumination. We also expected that due to the higher
were 97% for 520 nm wavelength and 420% for 852 nm photocurrent (in pn-WSe2), a lot of photocarriers generated
wavelength, which were higher than previously reported.7,15,16 need more time to relax. Hence, the tr ’s of pn-WSe 2
Further, the photogain (G) is extracted to quantify the photodetectors were faster than those of n- and p-WSe2,
photosensitivity of the junction, which is proportional to R, while the tf’s were relatively slower.
defined by the equation R = (EQE·G·e)/(hυ), where υ is the Furthermore, we investigated the thickness-dependent WSe2
frequency of the laser. From the above relation, if the EQE is photodetector performances with different thicknesses such as
assumed as 1, then the G values estimated for n-WSe2, p-WSe2, 6 nm (∼8 layers) and 1.8 nm (bilayer) to compare the
and pn-WSe2 are 1, 3, and 10 for 520 nm and 1, 5, and 49 for responsivities under various monochromator wavelengths.
852 nm, respectively, at Vg = 0 V. Figures S6−S8 (Supporting Information) illustrate the
In addition, D* is another figure of merit for photodetector complete optoelectronic characteristics and photoresponsivity
devices that designates the magnitude of detector sensitivity, analysis of thick and thin WSe2 FET devices before and after
given by D* (Jones) = (R·A1/2)/(2e·Idark)1/2, where A = W × L O2 plasma treatment. It was noticed that the O2 plasma
is the area of the device (W is the width and L is the length of treatment converts the bilayer WSe2 (band gap of ∼1.4 eV)
the channel). The areas of n-WSe2, p-WSe2, and pn-WSe2 were into monolayer WSe2 (1.6 eV), similarly observed from a
4 μm × 16 μm, 3 μm × 16 μm, and 8 μm × 16 μm, previous report.33 Hence, it was anticipated from the studies
respectively. The comparisons of D* for WSe2 photodetectors that the O2 plasma-treated bilayer WSe2 FET photodetectors
are displayed in Figure 6c,f. The obtained D* values for the were inadequate for sensing in the IR region. Therefore, our
homojunction photodetector at Vg = 0 were 5.9 × 109 Jones at results depict that the bulk WSe2 can be used for broadband
520 nm wavelength and 2.95 × 1011 Jones at 852 nm photodetector applications, which ranged from visible (400
wavelength. In addition, we evaluated the rise time (tr) and fall nm) to near-IR (900 nm) regions. Additionally, we have
time (tf) to determine the speed of the device by plotting a determined the optoelectrical characteristics of as-fabricated
single ON/OFF photocurrent cycle (Vd = 1 V; Vg = 0 V) and WSe2 channels covered with and without PMMA to observe
compared them as shown in Figure S5 (Supporting the dielectric screening effect, as shown in Figure S2
Information). The times taken to increase the saturation (Supporting Information). From the results, it was shown
photocurrent from 10 to 90% and decrease it from 90 to 10% that PMMA does not influence the electrical properties; rather,
are designated as tr and tf, respectively. The tr and tf obtained similar results were seen in photodetection for both channels
under λLaser = 520 nm were 50 and 70 ms for the n-WSe2 without and with PMMA under 532 and 700 nm illuminations.
photodetector, 45.6 and 302.9 ms for the p-WSe2 photo- To compare the performance of our fabricated WSe2 pn-
detector, and 41.8 and 2289.8 ms for the pn-WSe2 photo- homojunction photodetector to the literature, we have
detector. Likewise, the tr and tf obtained for n-, p-, and pn- summarized the figures of merit in Table 1.
WSe2 photodetectors under λLaser = 852 nm were 59.3 and 89.3 To further confirm that the enhanced photocurrent
ms, 57 and 100.84 ms, and 53.7 ms and 1027.5 ms, generation was actually from the junction created from p-
respectively. Here, the tr indicated the speed of the WSe2 and n-WSe2, we used scanning photocurrent microscopy
23268 [Link]
ACS Appl. Mater. Interfaces 2020, 12, 23261−23271
ACS Applied Materials & Interfaces [Link] Research Article

Figure 7. Photocurrent mapping studies. (a) OM image of the O2 plasma-treated WSe2 FET photodetector used for photocurrent mapping. The
area to be measured is represented in a rectangular box. (b, c) Scanning photocurrent mapping results of the pn-WSe2 FET photodetector taken at
Vg = 0 V and Vd = 1 V under λLaser = 520 and 852 nm illuminations, respectively. (d−f) Energy band diagrams of n-WSe2, p-WSe2, and pn-WSe2
represented under light illuminations.

(SPCM) to map the photocurrent. Figure 7a displays an OM plasma treatment was performed by an O2 plasma source under the
of the pn-WSe2 device with a rectangular portion designating following operating conditions: 13.56 MHz RF, 50 W power, 8.0 ×
the scanned area. The photocurrent mapping images of the pn- 10−6 Torr base pressure, 30 mTorr working pressure, 30 SCCM O2
WSe2 photodetector illuminated under λLaser = 520 and 852 flow rate, and 200 s plasma generation time.
Fabrication of WSe2 Lateral pn-Homojunctions. Subse-
nm at Vd = 1 V and Vg = 0 V are demonstrated in Figure 7b,c,
quently, we developed the WSe2 lateral pn-homojunctions from the
respectively. The electrodes were represented with dashed lines as-fabricated WSe2 FETs as follows. The as-fabricated WSe2 devices
to distinguish the photocurrent generated in the channel. It (as shown in Figure 1b) were spin-coated with PMMA A4 495
was clearly observed that the photocurrent generated mostly (Microchem) at a speed of 4000 rpm for 60 s followed by annealing
from the pn-junction region of WSe2 at zero gate bias. A video on a hot plate at 180 °C for 90 s. Consecutively, PMMA A6 950
captured during the photocurrent mapping measurement for (Microchem) was also spin-coated on top of PMMA A4 with the
pn-WSe2 under 852 nm laser illumination is shown in Video S1 same procedure as above. To achieve pn-homojunctions, we opened a
(Supporting Information). The photocurrent characteristics of portion of a channel near the electrode using EBL followed by
the junction can be further understood through the energy development with a developer (a mixture of isopropyl alcohol (IPA)
band diagrams, as shown in Figure 7d−f. When the energy of and deionized water in a 3:1 ratio) for a few seconds, rinsed with IPA,
illuminated light is greater than the band gap of the material, and then dried using N2 gas blowing. Subsequently, the opened
channels were doped with O2 plasma (procedure as in above section)
the electrons are excited from the valence band to the
to achieve lateral pn-homojunctions from WSe2 (as shown in Figure
conduction band, and the photon absorptions produce more 2b).
electron−hole pairs, which were then separated by a built-in Device Characterization. Atomic Force Microscopy (AFM).
electric field and external drain bias (Vd), and reduces the AFM was performed by placing the sample on a metal puck, which
recombination of electron−hole pairs to generate a high was connected to the ground. All the AFM images were taken at room
photocurrent. When the channel is modified with O2 plasma to temperature under atmospheric pressure and dehumidification
achieve a junction and as the laser is illuminated, the condition (<25%) under noncontact mode.
generation of electron−hole pairs takes place near the Optical, Raman, and Photoluminescence (PL) Measurements.
depletion region and the photoexcited carriers are swept All the optical images of the devices were acquired from an Olympus
from the junction in opposite directions by externally applied BX51 microscope with an attached video camera. The Raman and PL
bias, resulting in a net increase in photocurrent. measurements were conducted with a micro-Raman spectroscopy
system equipped with 532 nm laser wavelength (spot size, ∼2 μm)

■ MATERIALS AND METHODS

Fabrication of n-Type and O2 Plasma-Treated (p-Type)
operated at 0.2 mW laser power and a Xe-arc lamp-equipped
fluorometer with a power of 0.2 mW, respectively.
X-ray Photoelectron Spectroscopy (XPS) Measurement. XPS
WSe2 FETs. The WSe2 crystals were obtained from HQ Graphene, analysis was executed for as-fabricated WSe2 and O2 plasma-treated
the Netherlands. Prior to device fabrication, the heavily doped p-type WSe2 samples fabricated on Si/SiO2 substrates with an ESCALAB
Si substrates coated with a thermally oxidized SiO2 layer (with a 250Xi spectrometer (Thermo Scientific, UK). A monochromatic Al
thickness of 285 nm, which was used as a backgate oxide layer) were Kα (1486.6 eV) X-ray source was used to irradiate the device with a
cleaned thoroughly in acetone, isopropyl alcohol (IPA), and ethanol 600 μm-diameter spot size. The complete survey and the high-
using ultrasonication for 15 min followed by drying with N2 blow. resolution deconvoluted spectra were measured for as-fabricated and
The few-layer-thick WSe2 were mechanically exfoliated using Scotch O2 plasma-treated WSe2 devices.
tape on the p-type Si/SiO2 substrate. The WSe2 flakes were scanned Electrical (I−V) and Photocurrent Measurements. All the
and chosen selectively by an optical microscope. The source and drain electrical and photocurrent measurements were performed using a
electrodes were patterned by electron beam lithography (EBL), and semiconductor parameter analyzer (Keithley 4200) in ambient
the metal electrode Pd (50 nm) was deposited using electron beam conditions at room temperature. For the measurements of photo-
deposition. Later, the p-type WSe2 devices were achieved by treating response characteristics, solid-state laser diodes with different
the as-fabricated WSe2 channel with O2 plasma (p-type dopant). The wavelengths, i.e., 520 and 852 nm, were used as an illumination

23269 [Link]
ACS Appl. Mater. Interfaces 2020, 12, 23261−23271
ACS Applied Materials & Interfaces [Link] Research Article

source. The incident power of the lasers was measured with an optical Fida Ali − SKKU Advanced Institute of Nano Technology
power meter (Newport model 1918-C) and thermopile sensor (919P- (SAINT), Sungkyunkwan University, Suwon, Gyeonggi-do
003-10). The detailed experimental setup is illustrated in Figure S1 16419, Republic of Korea
(Supporting Information). We also measured the photoresponse Zheng Yang − SKKU Advanced Institute of Nano Technology
characteristics with a monochromator light source producing different
wavelengths ranging from 400 to 900 nm. The power value varies on
(SAINT), Sungkyunkwan University, Suwon, Gyeonggi-do
the power level of mW and μW for laser and monochromator light 16419, Republic of Korea
source illuminations, respectively. Inyong Moon − SKKU Advanced Institute of Nano Technology

■
(SAINT), Sungkyunkwan University, Suwon, Gyeonggi-do
CONCLUSIONS 16419, Republic of Korea
Faisal Ahmed − Department of Mechanical Engineering, College
We developed lateral pn-homojunctions formed from bulk of Electrical and Mechanical Engineering, National University of
WSe2 via oxygen plasma doping, and these pn-homojunctions Science and Technology, Islamabad 44000, Pakistan
demonstrated gate-modulated broadband photodetector appli- Tae Jin Yoo − School of Materials Science and Engineering,
cations. The polarity change from n-type to p-type was clearly Center for Emerging Electronic Devices and Systems, Gwangju
observed from transfer curves after O2 plasma doping, and this Institute of Science and Technology, Gwangju 61005, Republic
enabled us to develop a WSe2 lateral pn-homojunction. The of Korea
WSe2 lateral pn-homojunctions exhibited an increase in Byoung Hun Lee − School of Materials Science and Engineering,
photoresponse for various wavelengths, which resulted in Center for Emerging Electronic Devices and Systems, Gwangju
VOC and ISC originating from the pn-junction formed after O2 Institute of Science and Technology, Gwangju 61005, Republic
plasma treatment. We executed the gate-dependent photo- of Korea; [Link]/0000-0002-4540-7731
response properties of WSe2 photodetector FETs before and
after O2 plasma treatment upon visible (520 nm) and near- Complete contact information is available at:
infrared laser (852 nm) illuminations, which led to the [Link]
significant enhancement in photoresponse for the homojunc-
tion devices at Vg = 0 V and Vd = +1 V. The devices exhibited Notes
excellent photoresponsivity, EQE (%), and detectivity with a The authors declare no competing financial interest.

■
short response time at room temperature. We confirmed by
scanning photocurrent microscopy that the prominent photo- ACKNOWLEDGMENTS
response originated from the junctions. Hence, this work
furnishes an industry-compatible plasma doping technique to This work was supported by the Global Research Laboratory
fabricate pn-homojunctions to improve the optoelectronic (GRL) Program (2016K1A1A2912707) and Global Frontier
properties of 2D materials. R&D Program (2013M3A6B1078873), both funded by the

■
National Research Foundation of Korea (NRF).
ASSOCIATED CONTENT
* Supporting Information
sı

The Supporting Information is available free of charge at

■ REFERENCES
(1) Wang, Q. H.; Kalantar-Zadeh, K.; Kis, A.; Coleman, J. N.;
Strano, M. S. Electronics and Optoelectronics of Two-Dimensional
[Link] Transition Metal Dichalcogenides. Nat. Nanotechnol. 2012, 7, 699−
Schematic diagram of the SPCM measurement setup, 712.
photocurrent comparisons of WSe2 without and with (2) Zhang, W.; Chiu, M. H.; Chen, C. H.; Chen, W.; Li, L. J.; Wee,
PMMA, time-dependent photocurrent measurements of A. T. S. Role of Metal Contacts in High-Performance Phototransistors
Based on WSe2 Monolayers. ACS Nano 2014, 8, 8653−8661.
n-WSe2 measured under λLaser = 520 nm with various (3) Luo, X.; Andrews, K.; Wang, T.; Bowman, A.; Zhou, Z.; Xu, Y.
laser powers (mW), response time comparisons, and Q. Reversible Photo-Induced Doping in WSe2 Field Effect
optoelectronic characteristics and photoresponsivity Transistors. Nanoscale 2019, 11, 7358−7363.
comparisons of as-fabricated and O2 plasma-doped (4) Ross, J. S.; Klement, P.; Jones, A. M.; Ghimire, N. J.; Yan, J.;
thick and thin WSe2 FET devices (PDF) Mandrus, D. G.; Taniguchi, T.; Watanabe, K.; Kitamura, K.; Yao, W.;
Cobden, D. H.; Xu, X. Electrically Tunable Excitonic Light-Emitting
Scanning photocurrent mapping video of pn-WSe2 Diodes Based on Monolayer WSe2 p-n Junctions. Nat. Nanotechnol.
under 852 nm laser illumination displaying the photo- 2014, 9, 268−272.
current generation in the junction part (MP4) (5) Choi, M. S.; Qu, D.; Lee, D.; Liu, X.; Watanabe, K.; Taniguchi,

■
T.; Yoo, W. J. Lateral MoS2 p−n Junction Formed by Chemical
Doping for Use in High-Performance Optoelectronics. ACS Nano
AUTHOR INFORMATION 2014, 8, 9332−9340.
Corresponding Author (6) Li, H. M.; Lee, D.; Qu, D.; Liu, X.; Ryu, J.; Seabaugh, A.; Yoo,
Won Jong Yoo − SKKU Advanced Institute of Nano Technology W. J. Ultimate Thin Vertical p-n Junction Composed of Two-
(SAINT), Sungkyunkwan University, Suwon, Gyeonggi-do Dimensional Layered Molybdenum Disulfide. Nat. Commun. 2015, 6,
6564.
16419, Republic of Korea; [Link]/0000-0002-3767- (7) Cheng, R.; Li, D.; Zhou, H.; Wang, C.; Yin, A.; Jiang, S.; Liu, Y.;
7969; Email: yoowj@[Link] Chen, Y.; Huang, Y.; Duan, X. Electroluminescence and Photocurrent
Generation from Atomically Sharp WSe2/MoS2 Heterojunction p-n
Authors
Diodes. Nano Lett. 2014, 14, 5590−5597.
Sekhar Babu Mitta − SKKU Advanced Institute of Nano (8) Lee, C. H.; Lee, G. H.; Van Der Zande, A. M.; Chen, W.; Li, Y.;
Technology (SAINT), Sungkyunkwan University, Suwon, Han, M.; Cui, X.; Arefe, G.; Nuckolls, C.; Heinz, T. F.; Guo, J.; Hone,
Gyeonggi-do 16419, Republic of Korea; [Link]/0000- J.; Kim, P. Atomically Thin p-n Junctions with van Der Waals
0002-8011-5291 Heterointerfaces. Nat. Nanotechnol. 2014, 9, 676−681.

23270 [Link]
ACS Appl. Mater. Interfaces 2020, 12, 23261−23271
ACS Applied Materials & Interfaces [Link] Research Article

(9) Deng, Y.; Luo, Z.; Conrad, N. J.; Liu, H.; Gong, Y.; Najmaei, S.; Two-Dimensional Materials and Hybrid Systems. Nat. Nanotechnol.
Ajayan, P. M.; Lou, J.; Xu, X.; Ye, P. D. Black Phosphorus-Monolayer 2014, 9, 780−793.
MoS2 van Der Waals Heterojunction p-n Diode. ACS Nano 2014, 8, (27) Long, M.; Liu, E.; Wang, P.; Gao, A.; Xia, H.; Luo, W.; Wang,
8292−8299. B.; Zeng, J.; Fu, Y.; Xu, K.; et al. Broadband Photovoltaic Detectors
(10) Groenendijk, D. J.; Buscema, M.; Steele, G. A.; Michaelis De Based on an Atomically Thin Heterostructure. Nano Lett. 2016, 16,
Vasconcellos, S.; Bratschitsch, R.; Van Der Zant, H. S. J.; Castellanos- 2254−2259.
Gomez, A. Photovoltaic and Photothermoelectric Effect in a Double- (28) Liu, Y.; Shivananju, B. N.; Wang, Y.; Zhang, Y.; Yu, W.; Xiao,
Gated WSe2 Device. Nano Lett. 2014, 14, 5846−5852. S.; Sun, T.; Ma, W.; Mu, H.; Lin, S.; Zhang, H.; Lu, Y.; Qiu, C.-W.; Li,
(11) Jariwala, D.; Howell, S. L.; Chen, K. S.; Kang, J.; Sangwan, V. S.; Bao, Q. Highly Efficient and Air-Stable Infrared Photodetector
K.; Filippone, S. A.; Turrisi, R.; Marks, T. J.; Lauhon, L. J.; Hersam, Based on 2D Layered Graphene−Black Phosphorus Heterostructure.
M. C. Hybrid, Gate-Tunable, van der Waals p−n Heterojunctions ACS Appl. Mater. Interfaces 2017, 9, 36137−36145.
from Pentacene and MoS2. Nano Lett. 2016, 16, 497−503. (29) Yu, W.; Li, S.; Zhang, Y.; Ma, W.; Sun, T.; Yuan, J.; Fu, K.; Bao,
(12) Das, S.; Appenzeller, J. WSe2 Field Effect Transistors with Q. Near-Infrared Photodetectors Based on MoTe2/Graphene
Enhanced Ambipolar Characteristics. Appl. Phys. Lett. 2013, 103, Heterostructure with High Responsivity and Flexibility. Small 2017,
103501. 13, 1−8.
(13) Tosun, M.; Chuang, S.; Fang, H.; Sachid, A. B.; Hettick, M.; (30) Deng, W.; Chen, Y.; You, C.; An, B.; Liu, B.; Li, S.; Zhang, Y.;
Lin, Y.; Zeng, Y.; Javey, A. High-Gain Inverters Based on WSe2 Yan, H.; Sun, L. Visible-Infrared Dual-Mode MoS2-Graphene-MoS2
Complementary Field-Effect Transistors. ACS Nano 2014, 8, 4948− Phototransistor with High Ratio of the Iph/Idark. 2D Mater. 2018, 5,
4953. No. 045027.
(14) Chuang, H. J.; Tan, X.; Ghimire, N. J.; Perera, M. M.; (31) Wei, X.; Yan, F.-G.; Shen, C.; Lv, Q.-S.; Wang, K.-Y.
Photodetectors Based on Junctions of Two-Dimensional Transition
Chamlagain, B.; Cheng, M. M. C.; Yan, J.; Mandrus, D.; Tománek, D.;
Metal Dichalcogenides. Chin. Phys. B 2017, 26, No. 038504.
Zhou, Z. High Mobility WSe2 p- and n- Type Field-Effect Transistors
(32) Tosun, M.; Chan, L.; Amani, M.; Roy, T.; Ahn, G. H.; Taheri,
Contacted by Highly Doped Graphene for Low-Resistance Contacts.
P.; Carraro, C.; Ager, J. W.; Maboudian, R.; Javey, A. Air-Stable n-
Nano Lett. 2014, 14, 3594−3601. Doping of WSe2 by Anion Vacancy Formation with Mild Plasma
(15) Pradhan, N. R.; Ludwig, J.; Lu, Z.; Rhodes, D.; Bishop, M. M.; Treatment. ACS Nano 2016, 10, 6853−6860.
Thirunavukkuarasu, K.; McGill, S. A.; Smirnov, D.; Balicas, L. High (33) Li, Z.; Yang, S.; Dhall, R.; Kosmowska, E.; Shi, H.; Chatzakis, I.;
Photoresponsivity and Short Photoresponse Times in Few-Layered Cronin, S. B. Layer Control of WSe2 via Selective Surface Layer
WSe2 Transistors. ACS Appl. Mater. Interfaces 2015, 7, 12080−12088. Oxidation. ACS Nano 2016, 10, 6836−6842.
(16) Baugher, B. W. H.; Churchill, H. O. H.; Yang, Y.; Jarillo- (34) Biloen, P.; Pott, G. T. X-Ray Photoelectron Spectroscopy Study
Herrero, P. Optoelectronic Devices Based on Electrically Tunable p-n of Supported Tungsten Oxide. J. Catal. 1973, 30, 169−174.
Diodes in a Monolayer Dichalcogenide. Nat. Nanotechnol. 2014, 9, (35) Jaegermann, W.; Schmeisser, D. Reactivity of Layer Type
262−267. Transition Metal Chalcogenides towards Oxidation. Surf. Sci. 1986,
(17) Xie, Y.; Wu, E.; Hu, R.; Qian, S.; Feng, Z.; Chen, X.; Zhang, H.; 165, 143−160.
Xu, L.; Hu, X.; Liu, J.; Zhang, D. Enhancing Electronic and (36) Jo, S. H.; Kang, D. H.; Shim, J.; Jeon, J.; Jeon, M. H.; Yoo, G.;
Optoelectronic Performances of Tungsten Diselenide by Plasma Kim, J.; Lee, J.; Yeom, G. Y.; Lee, S.; Yu, H.-Y.; Choi, C.; Park, J.-H. A
Treatment. Nanoscale 2018, 10, 12436−12444. High-Performance WSe2/h-BN Photodetector Using a Triphenyl-
(18) Lee, D. S.; Kim, J. Y.; Shin, D. Y.; Lee, Y.; Kim, J.; Lee, S. J.; phosphine (PPh3)-Based n-Doping Technique. Adv. Mater. 2016, 28,
Joo, J. Significantly Increased Photoresponsivity of WSe2-Based 4824−4831.
Transistors through Hybridization with Gold-Tetraphenylporphyrin (37) Zheng, Z.; Zhang, T.; Yao, J.; Zhang, Y.; Xu, J.; Yang, G.
as Efficient n-Type Dopant. Adv. Electron. Mater. 2019, 5, 1800802. Flexible, Transparent and Ultra-Broadband Photodetector Based on
(19) Addou, R.; Smyth, C. M.; Noh, J.-Y.; Lin, Y.-C.; Pan, Y.; Large-Area WSe2 Film for Wearable Devices. Nanotechnology 2016,
Eichfeld, S. M.; Fölsch, S.; Robinson, J. A.; Cho, K.; Feenstra, R. M.; 27, 225501.
Wallace, R. M. One Dimensional Metallic Edges in Atomically Thin (38) Yin, Z.; Li, H.; Li, H.; Jiang, L.; Shi, Y.; Sun, Y.; Lu, G.; Zhang,
WSe2 Induced by Air Exposure. 2D Mater. 2018, 5, No. 025017. Q.; Chen, X.; Zhang, H. Single-Layer MoS2 Phototransistors. ACS
(20) Yamamoto, M.; Dutta, S.; Aikawa, S.; Nakaharai, S.; Nano 2012, 6, 74−80.
Wakabayashi, K.; Fuhrer, M. S.; Ueno, K.; Tsukagoshi, K. Self- (39) Hu, C.; Dong, D.; Yang, X.; Qiao, K.; Yang, D.; Deng, H.;
Limiting Layer-by-Layer Oxidation of Atomically Thin WSe2. Nano Yuan, S.; Khan, J.; Lan, Y.; Song, H.; Tang, J. Synergistic Effect of
Lett. 2015, 15, 2067−2073. Hybrid PbS Quantum Dots/2D-WSe2 Toward High Performance and
(21) Wang, S.; Zhao, W.; Giustiniano, F.; Eda, G. Effect of Oxygen Broadband Phototransistors. Adv. Funct. Mater. 2017, 27, 1603605.
and Ozone on p-Type Doping of Ultra-Thin WSe2 and MoSe2 Field (40) Ko, S.; Na, J.; Moon, Y. S.; Zschieschang, U.; Acharya, R.;
Effect Transistors. Phys. Chem. Chem. Phys. 2016, 18, 4304−4309. Klauk, H.; Kim, G. T.; Burghard, M.; Kern, K. Few-Layer WSe2
(22) Yamamoto, M.; Nakaharai, S.; Ueno, K.; Tsukagoshi, K. Self- Schottky Junction-Based Photovoltaic Devices through Site-Selective
Limiting Oxides on WSe2 as Controlled Surface Acceptors and Low- Dual Doping. ACS Appl. Mater. Interfaces 2017, 9, 42912−42918.
Resistance Hole Contacts. Nano Lett. 2016, 16, 2720−2727. (41) Lee, H. S.; Ahn, J.; Shim, W.; Im, S.; Hwang, D. K. 2D WSe2/
(23) Moon, I.; Lee, S.; Lee, M.; Kim, C.; Seol, D.; Kim, Y.; Kim, K. MoS2van Der Waals Heterojunction Photodiode for Visible-near
H.; Yeom, G. Y.; Teherani, J. T.; Hone, J.; Yoo, W. J. The Device Infrared Broadband Detection. Appl. Phys. Lett. 2018, 113, 163102.
Level Modulation of Carrier Transport in a 2D WSe2 Field Effect (42) Sun, M.; Fang, Q.; Xie, D.; Sun, Y.; Xu, J.; Teng, C.; Dai, R.;
Transistor via a Plasma Treatment. Nanoscale 2019, 11, 17368− Yang, P.; Li, Z.; Li, W.; Zhang, Y. Novel Transfer Behaviors in 2D
17375. MoS2/WSe2 Heterotransistor and Its Applications in Visible-Near
(24) Fang, H.; Chuang, S.; Chang, T. C.; Takei, K.; Takahashi, T.; Infrared Photodetection. Adv. Electron. Mater. 2017, 3, 1600502.
Javey, A. High-Performance Single Layered WSe2 p-FETs with (43) Yang, Y.; Huo, N.; Li, J. Gate-Tunable and High
Optoelectronic Performance in Multilayer WSe2p−n Diode. J.
Chemically Doped Contacts. Nano Lett. 2012, 12, 3788−3792.
Mater. Chem. C 2018, 6, 11673−11678.
(25) Zhao, P.; Kiriya, D.; Azcatl, A.; Zhang, C.; Tosun, M.; Liu, Y.
S.; Hettick, M.; Kang, J. S.; McDonnell, S.; Kc, S.; Guo, J.; Cho, K.;
Wallace, R. M.; Javey, A. Air Stable p-Doping of WSe2 by Covalent
Functionalization. ACS Nano 2014, 8, 10808−10814.
(26) Koppens, F. H. L.; Mueller, T.; Avouris, P.; Ferrari, A. C.;
Vitiello, M. S.; Polini, M. Photodetectors Based on Graphene, Other

23271 [Link]
ACS Appl. Mater. Interfaces 2020, 12, 23261−23271