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An Ultrafast WSe2 Photodiode Based on a

Lateral p‑i‑n Homojunction
Youwei Zhang,# Kankan Ma,# Chun Zhao, Wei Hong, Changjiang Nie, Zhi-Jun Qiu,* and Shun Wang*
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ABSTRACT: High-quality homogeneous junctions are of great

significance for developing transition metal dichalcogenides
(TMDs) based electronic and optoelectronic devices. Here, we
demonstrate a lateral p-type/intrinsic/n-type (p-i-n) homojunc-
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tion based multilayer WSe2 diode. The photodiode is formed

through selective doping, more specifically by utilizing self-
aligning surface plasma treatment at the contact regions, while
keeping the WSe2 channel intrinsic. Electrical measurements of
such a diode reveal an ideal rectifying behavior with a current
on/off ratio as high as 1.2 × 106 and an ideality factor of 1.14.
While operating in the photovoltaic mode, the diode presents
an excellent photodetecting performance under 450 nm light illumination, including an open-circuit voltage of 340 mV, a
responsivity of 0.1 A W−1, and a specific detectivity of 2.2 × 1013 Jones. Furthermore, benefiting from the lateral p-i-n
configuration, the slow photoresponse dynamics including the photocarrier diffusion in undepleted regions and photocarrier
trapping/detrapping due to dopants or doping process induced defect states are significantly suppressed. Consequently, a
record-breaking response time of 264 ns and a 3 dB bandwidth of 1.9 MHz are realized, compared with the previously
reported TMDs based photodetectors. The above-mentioned desirable properties, together with CMOS compatible processes,
make this WSe2 p-i-n junction diode promising for future applications in self-powered high-frequency weak signal
photodetection.
KEYWORDS: tungsten diselenide, photodetector, selective doping, plasma treatment, p-i-n diode, lateral homojunction

T wo dimensional materials have plenty of appealing

electronic and optical properties, rendering them
promising candidates for high-performance photo-
detectors.1,2 Among them, transition metal dichalcogenides
(TMDs) are of particular interest in developing optoelectronic
devices, thanks to their strong light−matter interaction
properties, tunable band gap within visible/near-infrared
spectral range, and relatively high mobilities.3 In the field of
optoelectronic devices, p-/n-type (p-n) junctions are widely
employed, particularly in the form of p-n junction photodiodes.
A typical p-n junction photodiode offers the advantages of
quick response speed, high photoresponse linearity, low noise,
and low power consumption.4 Recently, various types of
vertical heterogeneous TMDs based p-n junctions have been
constructed by transfer technology.5 In some reports, the
performance of such heterogeneous devices were limited by
defects and nonuniformity at the junction interfaces produced
during the transfer process. So far, some progress has been
made to eliminate defects and to gain atomically clean
interfaces.6,7 As an alternative, high-performance TMDs
based p-n diode can be constructed using the seamless
junction. Among them, p-type/intrinsic/n-type (p-i-n) junc-
tions, where an intrinsic layer is sandwiched between the n-
type and p-type regions of a p-n junction, can significantly
reduce the junction capacitance. Therefore, in practice, p-i-n
junctions, are widely employed to achieve a high-speed
response.
The realization of high-performance diodes depends
crucially on high-quality p-n junctions and low resistance
Ohmic contacts. To create TMDs based homogeneous p-n
junction, a variety of doping techniques have been adopted in
pioneering studies, including the electrostatic doping with local
gate or ferroelectric polarization,8−12 substitutional doping13,14
and surface charge transfer doping by using a range of chemical
dopants.15−17 On the other hand, a balanced yet highly
efficient carrier injection through low resistance contact is
required to enhance drive currents for real application of
Received: September 25, 2020
Accepted: February 11, 2021
Published: February 15, 2021

© 2021 American Chemical Society https://dx.doi.org/10.1021/acsnano.0c08075

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Figure 1. (a) Three-dimensional schematic illustration of process flow. (b) Optical image of the device. The scale bar represents 10 μm.
TMDs based p-n diodes. However, this is rarely demonstrated
in aforementioned reports. Such low resistance contacts are
normally obtained by doping the contact region into the
degenerate level for conventional bulk semiconductor diodes.
Therefore, a simple and practical doping approach with a
complete compatibility with existing semiconductor processes
is demanded in producing the TMDs based p-n junction with
low metal contact resistance. For the past few years, the plasma
treatment has been proven to be effective in fine-tuning the
electrical properties of TMDs by means of plasma-induced
structural defects or surface reaction.18−24
Inspired by the surface plasma treatment approach, self-
aligned argon (Ar) and oxygen (O2) plasma treatments with
photoresist mask were performed prior to contact metal
deposition. This allows for doping the multilayer WSe2 at
different contact regions into n-type and p-type, respectively.
As a result, the intrinsic WSe2 channel is laterally sandwiched
between n-type and p-type doped WSe2 at the contact regions,
yielding a complete p-i-n structure. Compared with previously
reported TMDs based homogeneous p-n junctions, the use of
this lateral p-i-n architecture is conductive to (i) boost carrier
injection/extraction by lowering contact resistance, (ii)
increase photoactive volume by extending the depletion region
through adding the intrinsic layer, (iii) suppress the slow
photocarrier diffusion process by avoiding photon absorption
at the undepleted regions with intentional doping, (iv)
diminish the possible undesired effects of doping, such as the
trapping/detrapping of photocarriers, (v) improve the stability
of doping by isolating the doped area from air with metal
electrodes serving as protection layers. With this approach,
substantial n-type and p-type doping of WSe2 are enabled by
plasma-induced interfacial layers, that is, anion (Se) vacancies-
abundant tungsten selenide (WSe2−y) and substoichiometric
tungsten oxide (WOx). In this way, an excellent polarity
control and low resistance Ohmic contacts are obtained both
for electron and hole injection in the multilayer WSe2 back-
gated field effect transistors (FETs). For the diode
configuration, a good current-rectifying behavior with an
ideality factor close to unity (1.14) and high current
rectification ratio (1.2 × 106) are realized, indicating a high-
quality built-in potential. Upon illumination, the p-i-n diode
exhibits high photodetection performance, possessing a linear
dynamic range of 48 dB, a responsivity of 0.1 A W−1, a specific
detectivity of 2.2 × 1013 Jones, a response speed of 264 ns, and
a 3 dB bandwidth of 1.9 MHz. We believe this work manifests
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the TMDs based lateral p-i-n homojunction diodes as a
promising building block for the next-generation optoelec-
tronic application.
RESULTS AND DISCUSSION
The fabrication process of the devices started with the
mechanical exfoliation of WSe2 flakes on heavily p-doped Si
substrate covered by 90 nm-thick SiO2. Then the multilayer
WSe2 samples were picked out through optical inspection via
the thickness-dependent optical contrast. Accurate thickness
characteristics of WSe2 flakes were obtained by further
characterization using an atomic force microscope (AFM), as
shown in Figure S1. To guarantee sufficient light absorption
and thus high photoresponsivity, multilayer WSe2 flakes with
thicknesses ranging from 10 to 20 nm were selected for our
experiments.17 Based on the absorption efficiency of 5% per
layer,25 a total absorption efficiency more than 60% is expected
for the 20-layer (∼13 nm) WSe2 flake assuming minimal
reflection. A two-step photolithography process was employed
in device fabrications, where the photoresist was not only used
to define the metal electrodes but also serves as a mask during
plasma treatment, as depicted in the process flow diagram
(Figure 1a). Prior to metallization, the O2 and Ar plasma were
adopted to introduce p-type and n-type doping, independently.
The detailed doping mechanism of such plasma treatment is
discussed in the Methods section.
After the plasma treatment, the metal contacts were
deposited by electron beam evaporation. We selected the
high work function Pd/Au metal stack (5/50 nm) and low
work function Ti/Au metal stack (5/50 nm) for p-type and n-
type metal contacts, respectively.26 For this device config-
uration, the WSe2 at contact regions beneath the metal
electrodes has been intentionally doped to p-type and n-type
by a two-step plasma treatment, and meanwhile, the middle
WSe2 channel is kept intact under the protection of
photoresist. A doping distribution with the deliberately p-
type and n-type doped WSe2 regions separated by intrinsic
WSe2 (defined as “i” region) was formed in WSe2, rendering a
complete lateral p-i-n homogeneous junction architecture. A
three-dimensional structure of the final fabricated device is
schematically illustrated in Figure 1a.
Before the electrical characterization of the WSe2 based
diodes, the surface plasma-treatment-induced doping and
corresponding carrier type control were first characterized.
For this purpose, two pairs of metal electrodes were fabricated
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Figure 2. Transfer characteristics of multilayer WSe2 FETs measured at Vds of 1 V (a) using p2-p1 metal electrodes, (b) using n1-n2 metal
electrodes. The insets show the corresponding output characteristics taken at various Vg.

Figure 3. Electrical properties of multilayer WSe2 device with p1-n1 contact configuration in the dark. (a) Transfer characteristic on the
linear (red line) and semilogarithmic (blue line) scale measured at Vds of 1 V. (b) Semilogarithmic plot of the output characteristic (black
solid circles) with the fitted curve (red line) measured at zero gate bias. (c) Schematic cross-sectional illustration of the doping distribution.
(d) Schematic energy band structure of lateral WSe2 p-i-n junction diode under equilibrium state.

on one multilayer WSe2 flake, comprising two Ti/Au metal
contacts with WSe2−y interfacial layer and two Pd/Au metal
contacts with WOx interfacial layer. The top-view optical
micrograph of a typical device is displayed in Figure 1b, where
the two Pd/Au metal contacts are labeled as p1 and p2, and the
two Ti/Au metal contacts are labeled as n1 and n2,
respectively. Therefore, three kinds of contact configurations
can be obtained, namely, p2-p1, p1-n1, n1-n2 from left side to
right side. When the p2-p1 contact configuration is adopted, a
back-gated FET architecture is available, with the SiO2 and
heavily doped silicon substrate serving as dielectric and
electrode, respectively. In Figure 2a, the measured transfer
characteristic shows clear unipolar hole transport over a wide
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back gate voltage (Vg) range, where the current is strongly
modulated with Vg sweeping from negative to positive values.
Under the negative Vg of −36 V, a maximal on-state current of
28.7 μA is measured. The drain current versus drain bias
characteristics display near-perfect linearity in the applied bias
voltage range of 100 mV (Figure 2a, inset), indicating the
formation of good p-type Ohmic contact. Meanwhile, the
electron injection is significantly suppressed even for large
positive gate voltage biasing, exhibiting a trivial off-state
current of 164 pA and giving a current on/off ratio (Ion/Ioff) of
1.8 × 105. In contrast, a typical n-type conduction behavior
with high current on/off ratio exceeding 4 × 104 and output
characteristics with good linearity are observed for n1-n2
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Figure 4. (a) Output characteristics of the WSe2 p-i-n junction diode under 450 nm illumination with changing the incident power density.
(b) Isc (red solid circles) and Voc (blue solid squares) of the device as a function of incident power density. The red line shows a linear fit to
the light density dependence of Isc. The blue line is drawn to guide the eye. (c) R and D* as a function of incident light power density under
photovoltaic mode and photoconductive mode with reverse bias voltage of −1 V. The solid lines are only guide for the eye. (d) Short-circuit
SPCM image using a 488 nm focused laser with power of 0.16 μW.

contact configuration (Figure 2b). This demonstrates an
effective electron doping of WSe2 region beneath the metal
contacts by the WSe2−y interfacial layer, which dramatically
reduces the tunneling barrier thickness of electron and leads to
the low resistance n-type Ohmic contact.27 A qualitative
analysis on plasma treatment induced doping level in WSe2 is
presented in Figure S2.
To rule out the presence of considerable Schottky barrier
(ΦB) for carrier injection, the temperature-dependent transfer
curves of n-type (n1-n2 configuration) and p-type (p1-p2
configuration) FETs were measured independently in temper-
atures ranging from 200 to 300 K. As shown in Figure S3, the
on-state Ids of both n-type and p-type FETs is found to be a
weak function of temperature, implying that the main carrier
injection mechanism at metal contact is associated with
tunneling rather than thermionic emission. To make a
quantitative analysis on effective ΦB, the Arrhenius plots for
Ids at different Vg were generated according to temperature-
dependent transfer curves (see Figure S4). Consequently, the
true Schottky barrier value can be extracted in the flat band
condition, as presented in Figure S5, where ΦB starts to deviate
from the linear trend in the ΦB versus Vg curve.28 The rather
insignificant, if not negligible, hole injection barrier of ∼45
meV and electron injection barrier of ∼39 meV are confirmed
in the p-type and n-type multilayer WSe2 FETs, respectively,
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giving rise to not only good electrical contacts, but also
outstanding polarity control. Therefore, an ambipolar transport
behavior should be anticipated for p1-n1 contact configuration.
As expected, an ambipolar transfer characteristic with well-
balanced n-type conduction and p-type conduction is realized,
as presented in Figure 3a. To be noted, the charge neutrality
point in the middle of the electron branch and the hole branch
is located at about −5 V, implying a naturally occurring light n-
type doping in multilayer WSe2 sample, in accordance with the
previously extracted carrier concentration in pristine WSe2
channel.
Distinct from the above-discussed WSe2 devices with
symmetric contacts, the intrinsic WSe2 channel is laterally
sandwiched between n-type and p-type doped WSe2 at the
contact region in this asymmetric device with p1-n1 contact
configuration, forming a p-i-n structure. Consequently, such
ambipolar transistor could function as a diode naturally,
making a unidirectional conductivity. Without any assistance of
gate biasing, the output characteristic exhibits a strong
rectifying behavior, as demonstrated in Figure 3b. A minuscule
reverse saturation current of 2.2 × 10−11 A (−1.5 V) along with
a high forward current of 2.7 × 10−5 A (1.5 V) is achieved. The
rectifying ratio is up to 1.2 × 106, which is comparable to those
highest values obtained on TMDs based homojunction diode
in the literatures.9,29,30 With Ohmic contacts being confirmed
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for both electron and hole injections, we ascribe this excellent
current-rectifying characteristic to the establishment of a high-
quality homogeneous junction, which stems from the apparent
carrier concentration gradient in our p-i-n diode.
To extract the physical parameters of the WSe2 p-i-n diode, a
modified form of Shockley equation in terms of the Lambert W
ÄÅ ÉÑ
function9,31 was utilized to fit the forward current data:
nVT ÅÅÅÅ I0R s ijj VKs + I0R s yzzÑÑÑÑ
expjj zzzÑÑ − I0
WÅ
R s ÅÅÅÅÇ nVT j nV
k {ÑÑÖ
Ñ
Ids =
T
where the I0, VT, n, and W denote the reverse saturation
current, the thermal voltage, the junction ideality factor, and
the Lambert W function, respectively. As shown in the Figure
3b, the forward current trace is fitted quite well by the above
equation, with the series resistance (Rs) taken into account.
The curve fitting suggests a n of 1.14 along with a Rs of 7.2 ×
104 Ω. Apparently, the n value of our diode is very close to the
ideal value of 1, indicating that the current flow in WSe2 p-i-n
junction follows the ideal diode equation very well.
Considering the forward current is predominantly governed
by majority carrier diffusion, rather than carrier recombination
at the space charge region via trap states within the band gap,
the ideality factor implies a high perfection of diode with few
trap states in its junction region.29,32
To better understand the working mechanism of the lateral
WSe2 p-i-n junction, a cross-sectional schematic of the doping
distribution and the corresponding energy band diagram is
illustrated in Figure 3c,d, respectively. After the notable carrier
injection barriers have been significantly reduced, we put
emphasis on the energy potential within the multilayer WSe2
channel. Since the selective doping creates a significant lateral
carrier concentration gradient, a built-in potential barrier is
established under the equilibrium condition by charge carrier
diffusion at p-i-n interface, as shown in Figure 3d, thus leading
to a complete in-plane intramolecular X-ray photoelectron
spectroscopy (XPS) homogeneous junction. Under the biasing
condition, the applied voltage primarily dropped across the
high-resistance space charge region, yielding the width of the
space charge region as a function of the applied voltage. As a
consequence, the built-in potential barrier would be reduced
under forward bias and enlarged under reverse bias. This
ensures the superior rectification behavior characteristics, just
like a classic diode, as manifested by tiny reverse current and
high forward current.
In addition to the above-mentioned rectifying behavior, the
in-plane lateral p-i-n structure with intentional doping of WSe2
strictly confined to contact regions is expected to possess some
appealing optoelectrical properties compared with the mostly
adopted p-n type junctions. The photoresponse is studied by
shining 450 nm light onto the WSe2 p-i-n junction diode with
variable power density (defined as P) while measuring output
characteristics. The whole device area was illuminated by a
uniform circular light spot with a diameter of 2 mm. The
output curves show an obvious current increase under
illumination as shown in the Figure 4a. Compared with the
dark condition curve, the output characteristics present a
striking nonzero current at zero bias voltage, namely short-
circuit current (Isc), under illumination, and the highest value
of 0.57 μA is achieved under 3.3 mW·cm−2 light illumination.
In conjunction with ultralow dark current under short-circuit
mode, this prominent Isc leads to an ultrahigh photoswitching
ratio exceeding ∼4 × 105 (Figure S6). Figure 4b displays the Isc
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against power density P in detail, extracted from the data in
Figure 4a. As can be observed, the Isc follows a clear linear
dependence on the light power. On other hand, the open
circuit voltage (Voc) exhibits a nonlinear relation with P, which
initially increases with the increase of P and then tends to be
saturated to around 340 mV with a further increase in P. The
apparent Voc and Isc are clear evidence of photovoltaic effect in
WSe2 p-i-n junctions. Now that the photovoltaic effect induced
maximal Voc is theoretically limited by the built-in potential
(Vbi) under low-level injection condition for the ideal p-n
junction diode.33 To quantitatively analyze the potential
barrier height across the junction, temperature-dependent
output curves of the WSe2 p-i-n junction diode were taken at
several temperatures to generate the Arrhenius plots (ln(Ids/
T3/2) versus 1/T plot), as shown in Figure S7. Because the
slope extracted from the Arrhenius plots follows a linear
dependence with Vds, the Vbi can be simply evaluated from the
extrapolated value of the slope at zero Vds34 as displayed in
Figure S7c. The Vbi is found to be 430 mV, which is slightly
larger than the Voc value.
Usually, the illumination power dependence of photocurrent
is often described as power-law relationship, that is, IPC ∝ Pα.
For an ideal p-n junction photodiode, the photocurrent is
expected to depend linearly on the illumination power density,
namely α = 1. However, because the introduced midgap states
related to disorder, defects, or impurities may serve as traps or
recombination centers, a sublinear (0 < α < 1) power
dependence is ubiquitous for previously reported low dimen-
sional photodetectors, known as photoconductive gain.35 As a
result, the responsivity of those photodetectors always shows a
decreasing trend with the increase of light intensity, as the trap
states will be filled gradually with the increase of light power.
By fitting the experimental data in Figure 4b according to the
power-law relationship, a near-unity exponent value of 1.06 is
obtained, which means that the photocurrent shows a good
linear behavior upon altering the irradiation power density
over 3 orders of magnitude from 12.5 μW·cm−2 to 3.3 mW·
cm−2, corresponding to a linear dynamic range (LDR) of 48
dB.36 Since no deviation of photocurrent from linear behavior
occurs at maximum illumination power applied in this work,
the LDR could be further extended. Clearly, the large LDR in
our WSe2 p-i-n diode represents a significant advantage for
practical application in the future.
Figure 4c shows the dependence of responsivity (R) as well
as specific detectivity (D*) on illumination intensity. Since the
photocurrent depends linearly on light power, the responsivity
maintains almost constant with increasing incident light power
density for different bias voltage condition. Note that this
constant responsivity can be taken as one of the characterizing
attributes of photovoltaic effect; thus, the photoconductive
gain can be excluded as the major working mechanism.
Besides, owing to the overwhelming dominance of photo-
voltaic effect at our p-i-n junction, no clear contribution of
photothermoelectric effect can be discerned. This is evidenced
by the fixed polarity of photocurrent when the majority carrier
changed from electron to hole under gate modulation, as
shown in Figure S8. Moreover, the application of reverse bias
voltage (−1 V) can only bring very limited improvement
(∼30%) on photocurrent compared with that at zero bias
condition but could result in orders of magnitude increase in
the dark current noise. This is because of the good collection
efficiency of photogenerated carriers under photovoltaic mode.
Notably, such good collection efficiency of photogenerated
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Figure 5. (a) Response time measured by oscilloscope under zero bias using an electrically modulated 450 nm LED as light source at
frequency of 20 kHz. (b) Enlarged photoresponse curve at 20 kHz showing the rise time (τr) and fall time (τf). (c) Broadband frequency
response of the WSe2 p-i-n junction diode. (d) A plot of specific detectivity vs response time for photodetectors based on TMDs and
comparison with commercial Si (Thorlabs FDS015), InGaAs (Thorlabs FGA01), and Ge (Thorlabs FDG05) photodiodes. PD = photodiode,
FET = field effect transistor.

carriers under photovoltaic mode is the prerequisite for high-
performance, self-powered photodetection. In addition to
responsivity, D* is another key parameter of photodetectors,
which represents their ability in weak signal detection.
Assuming that the dark current, Idark, is the major contributor
of noise floor, D* can be given by RA1/2/(2qIdark)1/2, where A
is the effective area and q is the electronic charge.37 With this
relationship, D* can be calculated, as displayed in Figure 4c.
Similar to responsivity, D* also exhibits power-independency.
A higher D* of around 2.2 × 1013 Jones is achieved in unbiased
mode irrespective of the light power, which is comparable with
the commercially available silicon and InGaAs based photo-
diodes (D* ∼ 1012 Jones). Given the little difference in R for
the two type of operation modes, the higher D* in unbiased
mode can be attributed to the ultralow thermal noise, which
overtakes shot noise as the major contribution in total noise at
zero bias condition.
Figure 4d presents the spatially resolved photocurrent
mapping (SPCM) of the device under zero bias condition.
During this measurement, short-circuit current was recorded as
a function of position by utilizing a 488 nm focused laser spot
scanning. Unlike the Schottky barrier induced photovoltaic
effect at metal/TMDs contact, where the photocurrent
generation is mostly localized in a rather small region near
contact edge,38,39 the SPCM image shows that the photo-
current originates from the entire WSe2 channel. Thus, it is
verified that the intrinsic WSe2 region between two metal
electrodes is fully depleted. As a consequence, the photo-
4410
responsive area covers the whole WSe2 channel, rendering a
good collection efficiency of photogenerated carriers and
corresponding strong photovoltaic effect.
The response time, which directly relates to the bandwidth
of a photodetector, is also a key performance indicator. The
time-resolved photoresponse behavior was characterized by
illuminating the device with a pulsed 450 nm LED at a
frequency of 20 kHz under short-circuit mode. The rise time
(τr) and fall time (τf), are defined as the time for the
photocurrent to rise from 10% to 90% or fall from 90% to 10%
of the peak. As presented in Figure 5a,b, the τr and τf are 264
and 552 ns, respectively. Figure 5c shows the normalized
response of the photodetector to a sine wave-modulated light
emitted from the laser diode (450 nm) over a broad frequency
range from 1 kHz to 5 MHz, measured using a lock-in
amplifier. The cutoff frequency is defined as the frequency at
which the output signal drops by 3 dB as the sine wave
frequency is increased. A 3 dB bandwidth f−3 dB = 1.9 MHz is
obtained for our WSe2 p-i-n junction diode, which is consistent
with the above response time. To the best of our knowledge,
an operating speed on the hundreds of nanosecond-scale in the
repeated photoswitching characteristics has been rarely
reported for a TMDs based photodetector, despite that
ultrafast carrier dynamics and the corresponding fastest
response component of photogenerated carriers has been
revealed to be the order of picosecond in monolayer and
multilayer MoS2 film by using the special optical/THz pump−
probe or two-pulse photovoltage correlation measurements.40
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Table 1. Performance Comparison of TMDs Based Homogeneous p-n Junction Photodiodes

doping strategy response time
active rectification ideality light source responsivity detectivity ratio
material n-type p-type ratio factor (nm) (mA W−1) (Jones) rise fall ref
monolayer local gating local gating  2.14 532 0.7  10.4 ms 9.8 ms 8
WSe2
monolayer local gating local gating 105
1.9 532 210    9
WSe2
few-layer substitutional substitutional  ∼2.5 660 25  80 ms 80 ms 12
MoS2 Fe Nb
few-layer N2H4  ∼103  470 30 6.18 × 108 2 ms 2 ms 15
WSe2
few-layer BV AuCl3 100 1.6 655 30    16
MoS2
multilayer PEI global gating 103 1.66 520 80 1011 200 μs 16 μs 17
WSe2
multilayer N2H4  105 1.1 635 468 2.5 × 109 4 ms 4 ms 29
WSe2
multilayer global gating surface oxide 106 3.1 520 1 × 108 9.6 × 1012 2 ms 10 ms 30
WSe2 layer
few-layer CTAB  103 1.64 450 3 × 104 1011 7.8 ms 7.7 ms 32
WSe2
multilayer global gating WOx   633 800  136 μs 39 μs 52
WSe2
multilayer WSe2‑y WOx 106 1.14 450 105 2.2 × 1013 264 ns 552 ns this
WSe2 work

By comparison, the previously reported works on photo-
dectector with TMDs serving exclusively as photosensing
active material show response times from 10−5 s to 102 s.2,41
Generally, these relatively long response times are associated
with the structure defects, disorder, nearby impurities, or
absorbed molecules which act as minority carrier trap
centers.41 Hence, these trap centers would greatly deteriorate
the response speed, albeit with the improved responsivity,
manifesting as photoconductive gain.35,42 Clearly, this fast
response reveals a negligible role of the photoconductive gain
effect on photoresponse mechanism, indicating a low density
of trap states in photoactive region of our device.35 It is worth
pointing out that during plasma treatment, ion bombardment
will lead to plenty of structural damage and defects, which may
serve as minority carrier trap centers. Fortunately, the
photogenerated electrons (or holes) within the untreated
WSe2 channel would drift to the respective undepleted n-type
(or p-type) doped region under the action of the built-in
electric field, where the photogenerated carriers are the
majority carriers. It is thus evident that the influence of
minority carrier trapping at these plasma-treated regions on the
diode photoresponse is of little importance.
In the next section, we analyze the causes of the fast
response speed of multilayer WSe2 p-i-n junction photodiode
in detail. Because the photoconductive gain needs to work
under a nonzero bias voltage condition,35 the response time of
a photodiode under photovoltaic mode is generally determined
by three factors: RC time constant (τRC), carrier drift time
(τDrift) across the depletion region, and carrier diffusion time
(τDiffusion) in the undepleted region. The τRC is the most
common limiting factor of the response time for the
commercially available photodiode with vertical-junction
configuration based on conventional bulk semiconductor.
However, because the capacitance area for the lateral junction
configuration is defined by the greatly reduced cross sectional
area of the multilayer WSe2 flake, τRC could be greatly reduced.
To verify such prediction, τRC is calculated as τRC = RL × C,
4411
where RL is the load resistance43 and C is junction capacitances
of p-i-n diode. We use the following formula,
εtW
C=
4πkL
to calculate the value of C, where ε is the in-plane dielectric
constant (8.5),44 k is the electrostatic force constant (8.99 ×
109 N·m2/C2), W and L represent the width and length of
WSe2 channel, respectively. C is calculated to be about 6 ×
10−6 pF. Combined with the load resistance value (50 Ω) used
in our time- and frequency-dependent response measurements,
a τRC = 3 × 10−4 ps is obtained. This calculated value of τRC is
extremely small, indicating that τRC is no longer a response-
time limitation factor. Considering that the depletion width
extended completely through the entire intrinsic WSe2 channel
owing to its low carrier concentration, as demonstrated in the
SPCM, the undepleted regions in our p-i-n structure
photodiode can be simply regarded as the intentionally n-
and p-doped regions located underneath the metal contact. In
this case, τDiffusion would not contribute to response time as no
photoabsorption can occur within those undepleted WSe2.
Finally, the τDrift becomes the only decisive factor in
determining response speed. When the “i” region is fully
depleted, a maximum built-in electric field strength of 1.7 kV/
cm is concluded for the 2 μm WSe2 channel under zero bias
condition, assuming that the photogenerated Voc mainly drops
across the high-resistance depletion region. After the extraction
of electron and hole mobility (10 cm2 V−1 s−1 and 8 cm2 V−1
s−1 for electron and hole, respectively) based on the ambipolar
transfer characteristic shown in Figure 3a, the transit time for
electron and hole across the depleted channel can be made as
small as 11.8 and 14.7 ns, respectively. These calculated transit
times are approximately an order of magnitude smaller than
the measured response time value. We speculate that the
reason for this discrepancy could be the larger contribution of
the relatively slow interlayer transport of photogenerated
carriers due to anisotropic layered structure of multilayer
WSe2,45 which was not taken into account. Therefore, to
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ACS Nano 2021, 15, 4405−4415
ACS Nano
evaluate the transit time more accurately, further work is
necessary to develop another model with considering the
structure formed by layers of WSe2 and van der Waals gaps.
Table 1 lists the corresponding performance indexes of the
recently reported TMDs based homogeneous p-n junction
photodiodes. As can be seen from the table, the response speed
achieved by multilayer WSe2 p-i-n junction diode is far superior
to those demonstrated in the existing literature. Additionally,
the rectifying ratio, ideality factor, and specific detectivity of
our WSe2 p-i-n diode are comparable with or better than that
of the state-of-the-art TMDs based homogeneous p-n diodes,
demonstrating a significant advantage of this work. Because the
responsivity is not normalized with the active area, the
detectivity is thus used to compare the sensitivity to weak light
signal of different photodetectors with varied sizes. Figure 5d
summarizes the specific detectivity versus response time for the
photodetectors based on TMDs15,17,29,32,46−51 and the
comparison with commercial Si (Thorlabs FDS015), InGaAs
(Thorlabs FGA01), and Ge (Thorlabs FDG05) photodiodes.
Although the multilayer WSe2 p-i-n photodiode exhibits the
best performance among TMDs based photodetectors, with
both high sensitivity and high response speed simultaneously,
there is still room for improvement in response speed
compared with the Si and InGaAs photodiodes.
CONCLUSIONS
In conclusion, we constructed a multilayer WSe2 based
homogeneous p-i-n lateral junction photodiode, which shows
excellent performances far superior to those previous reported
photodetectors based on TMDs. The devices reported in this
paper utilized the WOx and WSe2−y interfacial layers as p-type
and n-type dopant independently, through self-aligned surface
plasma treatment prior metal contact deposition. Through the
establishment of high-quality homogeneous potential barrier,
the diode shows near-ideal rectifying behavior with an ideality
factor of 1.14 and a rectification ratio of 1.2 × 106. By the same
token, the diode presents apparent open-circuit-voltage of 340
mV and photocurrent with good linearity under visible light
illumination at zero bias condition, demonstrating a strong
photovoltaic effect. This leads to an outstanding responsivity
and specific detectivity of 0.1 A W−1 and 2.2 × 1013 Jones,
respectively, irrespective of the incident light power density.
Thanks to the appealing configuration of our device and
negligible trap states introduced into the intrinsic WSe2
channel during the device fabrication process, an ultrafast
response speed of hundreds of nanosecond-scale (264 ns) and
a 3 dB bandwidth of 1.9 MHz are obtained. These excellent
performances promise great prospects for our WSe2 p-i-n
photodiode in self-powered high-frequency weak signal light
detection applications. Finally, we believe this study reveals a
promising route to create p-i-n junction diode and ambipolar
transistor for the other TMDs, by achieving selective doping
via an easily implemented plasma treatment technique.
METHODS
Exfoliation and Characterization of WSe2 Flakes. The WSe2
flakes were peeled by mechanical exfoliation using Scotch tape from
bulk WSe2 crystal (HQ graphene) at room temperature and
transferred to a heavily doped p-type Si substrate with 90 nm-thick
SiO2 grown by dry thermal oxidation. Prior to the mechanical
exfoliation, the substrate was precleaned by sonication in acetone,
isopropyl alcohol, and deionized water, separately, for 5 min. After the
transfer procedure, the WSe2 samples were identified by using an
www.acsnano.org Article
optical microscope. The accurate thickness of WSe2 flakes was
acquired through atomic force microscopy (AFM, Shimadzu,
SPM9700) measurements operated in the tapping mode. X-ray
photoelectron spectroscopy (XPS) analysis was carried out using an
Axis Ultra DLD-600W spectrometer (Shimadzu-Kratos, Japan) using
Thermo Al Kα radiation. The obtained XPS spectra were corrected
with the C 1s peak at 285 eV as a reference.46−48
Device Fabrication. A two-step photolithography was used to
define the p-type and n-type metal contact separately, by means of
laser direct writing using PMGI/S1805 bilayer photoresist stack. After
development, the different plasma treatments on the exposed WSe2
surface were performed at room temperature with photoresist as the
mask prior to metal deposition at each step, to achieve local doping of
contact regions. Specifically, a 60 W oxygen (O2) plasma exposure for
130 s at the pressure of 12 mTorr was adopted for hole doping after
the first development. In this work, a remote O2 plasma was adopted
to promote surface oxidation reaction while inhibiting etching effect
by direct ion impact. Then sample was transferred into electron beam
evaporation chamber immediately to deposit Pd/Au metal stack (5/
50 nm) for p-type contact. After lift-off, a second photolithography
process was employed to pattern n-type electrode. In comparison, an
argon (Ar) plasma treatment was carried out at a pressure of 8 mTorr,
a power of 100 W, and a duration time of 50 s to achieve electron
doping. Subsequently, a Ti/Au metal stack (5/50 nm) was evaporated
as n-type metal contact.
Plasma Treatment Induced p-Type and n-Type Doping.
When the WSe2 surface was exposed to O2 plasma, the topmost WSe2
layers would be oxidized to form a substoichiometric tungsten oxide
(WOx) layer and the underlying WSe2 layers are kept intact because
of the self-limiting layer-by-layer oxidation process.53,54 Owing to the
oxygen-vacancy-induced abundant gap states close to the conduction
band, the oxygen-deficient WOx is a high conductive n-type
semiconductor with very deep work function (>6 eV). For this
reason, WOx has been extensively used as a hole transporting layer for
efficient hole injection and extraction in organic semiconductor
devices such as light emitting diodes and photovoltaic cells.55 By the
oxidation of WSe2 surface via O2 plasma or O3 exposure, the greatly
improved hole-injection contact has been realized.18,22,56 Moreover,
WOx has a low-lying Fermi level and thus a strong electron-
withdrawing ability, making it as an efficient p-type dopant.55 When
the WOx interfacial layer was formed between metal electrode and
WSe2, a mass of electrons would transfer from the underlying WSe2 to
high-electron-affinity WOx. This process pushes the Fermi level of
WSe2 toward the valence band and provides the p-type doping of
WSe2 around the metal contact even to the heavy doping level.20,56,57
Therefore, the interface WOx layer works both as a hole transporting
layer and as a hole dopant for the underlying WSe2. The formation of
WOx and the hole doping on the underlying WSe2 are also
demonstrated in the XPS results (Figure S9a,b).
Unlike p-type doping, another doping strategy is utilized to obtain
the desired n-type doping in WSe2. Apart from the most commonly
used substitutional doping methods, defect engineering (e.g.,
formation of anion or cation vacancies) is regarded as a promising
alternative scheme to control the carrier concentration in compound
semiconductors.58−60 Since the vacancy formation energy for the
chalcogen vacancy is much lower than that for metal vacancy,61 plenty
of anion (Se) vacancies can be created in the exposed top few WSe2
layers under Ar plasma bombardment, forming a substoichiometric
WSe2, namely WSe2−y. These abundant Se vacancies endow the
interfacial WSe2−y layer with a good electron donor capacity, thus
rendering an electron doping of WSe2 at the contact region even up to
the degenerate level via the electron transfer between WSe2‑y and
WSe2.21 In XPS spectra, the core-level W 4f and Se 3d binding
energies after Ar plasma treatment increase clearly compared with
pristine WSe2, indicating a Fermi level shift toward the conduction
band edge as shown in Figure S9c,d. Apparently, owing to the doping
induced thinning of the Schottky barrier width, the electron tunneling
at metal/WSe2‑y/WSe2 interface would be significantly enhanced,
leading to a low resistance n-type contact. To ensure the reliability of
the plasma treatment process, more than 10 devices were fabricated.
4412 https://dx.doi.org/10.1021/acsnano.0c08075
ACS Nano 2021, 15, 4405−4415
ACS Nano www.acsnano.org
Table S1 summarizes the electrical properties of n- and p-type WSe2
FETs with Ar and O2 plasma treatment, respectively. Moreover, the
improvement of contact resistance after Ar or O2 plasma treatment is
further confirmed by transmission line method (TLM) measurements
shown in Figure S10.
Electrical Characterization. Electrical and photoelectrical
characterizations of fabricated WSe2 devices were carried out with a
Keysight B1500A semiconductor parameter analyzer in the vacuum
probe station chamber under the base pressure of 10−3 Torr at room
temperature, unless otherwise noted. Photoresponse measurements
were performed using a 450 nm light-emitting-diode (LED) as light
source. The light beam diameter is ∼2 mm. The scanning
photocurrent microscopy (SPCM) was accomplished by scanning
over the device with a 488 nm focus laser beam (<1 μm) on a Raman
spectrometer equipped with computer controlled XY mapping stage
and the spatial resolved photocurrent was acquired by utilizing the
semiconductor parameter analyzer at the same time. To analyze the
response time of our multilayer WSe2 based p-i-n photodiode, the 450
nm LED was electrically modulated by a function generator (RIGOL
DG1062Z) and an oscilloscope (Keysight, DSOZ634A Infiniium)
equipped with transimpedance amplifier (Thorlabs, TIA60) was
employed to record the time-dependent photocurrent signal. For
frequency response analyzing, a lock-in amplifier (Zurich Instruments
HF2LI) equipped with current amplifier (Zurich Instruments
HF2TA) was used to generate a sine wave-modulated light emitted
from the laser diode (450 nm) at various frequencies and meanwhile
monitor the amplitude of the photoresponse. For the time and
frequency response measurements of the multilayer WSe2 based p-i-n
photodiode, the heavily doped Si substrate was grounded to minimize
any parasitic capacitance induced by the SiO2 layer. The spectral
photoresponsivity of the WSe2 p-i-n junction diode is shown in Figure
S11.
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsnano.0c08075.
Experimental data of AFM (S1), the impact of plasma
treatment induced WSe2 channel doping after source/
drain contact metallization (S2), extraction of the
Schottky barrier value in the flat band condition (S3−
S5), photoswitching behavior of WSe2 p-i-n junction
diode (S6), extraction of the built-in potential (Vbi)
(S7), photocurrent as a function of Vg operated under
zero bias mode (S8), XPS spectra of WSe2 samples
with/without O2(Ar) plasma treatment (S9), extracted
of contact resistance (S10), spectral photoresponsivity of
the WSe2 p-i-n junction diode (S11), and performance
statistics of n- and p-type WSe2 FETs (Table S1) (PDF)
AUTHOR INFORMATION
Corresponding Authors
Shun Wang − MOE Key Laboratory of Fundamental Physical
Quantities Measurement & Hubei Key Laboratory of
Gravitation and Quantum Physics, PGMF and School of
Physics, Huazhong University of Science and Technology,
Wuhan 430074, P. R. China; Shenzhen Huazhong
University of Science and Technology Research Institute,
Shenzhen 518057, China; orcid.org/0000-0001-6890-
8371; Email: shun@hust.edu.cn
Zhi-Jun Qiu − State Key Laboratory of ASIC and System,
School of Information Science and Technology, Fudan
University, Shanghai 200433, China; Email: zjqiu@
fudan.edu.cn
4413
Article
Authors
Youwei Zhang − MOE Key Laboratory of Fundamental
Physical Quantities Measurement & Hubei Key Laboratory of
Gravitation and Quantum Physics, PGMF and School of
Physics, Huazhong University of Science and Technology,
Wuhan 430074, P. R. China; Shenzhen Huazhong
University of Science and Technology Research Institute,
Shenzhen 518057, China
Kankan Ma − MOE Key Laboratory of Fundamental Physical
Quantities Measurement & Hubei Key Laboratory of
Gravitation and Quantum Physics, PGMF and School of
Physics, Huazhong University of Science and Technology,
Wuhan 430074, P. R. China
Chun Zhao − MOE Key Laboratory of Fundamental Physical
Quantities Measurement & Hubei Key Laboratory of
Gravitation and Quantum Physics, PGMF and School of
Physics, Huazhong University of Science and Technology,
Wuhan 430074, P. R. China
Wei Hong − MOE Key Laboratory of Fundamental Physical
Quantities Measurement & Hubei Key Laboratory of
Gravitation and Quantum Physics, PGMF and School of
Physics, Huazhong University of Science and Technology,
Wuhan 430074, P. R. China
Changjiang Nie − MOE Key Laboratory of Fundamental
Physical Quantities Measurement & Hubei Key Laboratory of
Gravitation and Quantum Physics, PGMF and School of
Physics, Huazhong University of Science and Technology,
Wuhan 430074, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsnano.0c08075
Author Contributions
#
Y.Z. and K.M. contributed equally to this work. Y.Z.
conceived the research. Y.Z. and S.W. designed the experi-
ments. K.M. contributed to the device fabrication and electrical
characterizations in dark and illuminated condition. C.N. and
K.M. performed AFM analysis and SPCM characterizations.
C.Z. and W.H. performed response time measurement. Y.Z.
and Z.Q. analyzed the data. Y.Z. and S.W. cowrote the
manuscript. All authors discussed the results and contributed
to the preparation of the manuscript.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We acknowledge the support from the National Natural
Science Foundation of China (12074134 and 61774042),
Shenzhen Science and Technology Project
(JCYJ20180507183904841), and the Analysis and Testing
Center of Huazhong University of Science and Technology.
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