Highly Efficient Van Der Waals Heterojunction on Graphdiyne toward the High-Performance Photodetector.

Graphdiyne (GDY), a new 2D material, has recently proven excellent performance in photodetector applications due to its direct bandgap and high mobility. Different from the zero-gap of graphene, these preeminent properties made GDY emerge as a rising star for solving the bottleneck of graphene-based inefficient heterojunction. Herein, a highly effective graphdiyne/molybdenum (GDY/MoS2 ) type-II heterojunction in a charge separation is reported toward a high-performance photodetector. Characterized by robust electron repulsion of alkyne-rich skeleton, the GDY based junction facilitates the effective electron-hole pairs separation and transfer. This results in significant suppression of Auger recombination up to six times at the GDY/MoS2 interface compared with the pristine materials owing to an ultrafast hot hole transfer from MoS2 to GDY. GDY/MoS2 device demonstrates notable photovoltaic behavior with a short-circuit current of -1.3 × 10-5 A and a large open-circuit voltage of 0.23 V under visible irradiation. As a positive-charge-attracting magnet, under illumination, alkyne-rich framework induces positive photogating effect on the neighboring MoS2 , further enhancing photocurrent. Consequently, the device exhibits broadband detection (453-1064 nm) with a maximum responsivity of 78.5 A W-1 and a high speed of 50 µs. Results open up a new promising strategy using GDY toward effective junction for future optoelectronic applications.

Multi-neuron connection using multi-terminal floating-gate memristor for unsupervised learning.

Multi-terminal memristor and memtransistor (MT-MEMs) has successfully performed complex functions of heterosynaptic plasticity in synapse. However, theses MT-MEMs lack the ability to emulate membrane potential of neuron in multiple neuronal connections. Here, we demonstrate multi-neuron connection using a multi-terminal floating-gate memristor (MT-FGMEM). The variable Fermi level (EF) in graphene allows charging and discharging of MT-FGMEM using horizontally distant multiple electrodes. Our MT-FGMEM demonstrates high on/off ratio over 105 at 1000 s retention about ~10,000 times higher than other MT-MEMs. The linear behavior between current (ID) and floating gate potential (VFG) in triode region of MT-FGMEM allows for accurate spike integration at the neuron membrane. The MT-FGMEM fully mimics the temporal and spatial summation of multi-neuron connections based on leaky-integrate-and-fire (LIF) functionality. Our artificial neuron (150 pJ) significantly reduces the energy consumption by 100,000 times compared to conventional neurons based on silicon integrated circuits (11.7 µJ). By integrating neurons and synapses using MT-FGMEMs, a spiking neurosynaptic training and classification of directional lines functioned in visual area one (V1) is successfully emulated based on neuron's LIF and synapse's spike-timing-dependent plasticity (STDP) functions. Simulation of unsupervised learning based on our artificial neuron and synapse achieves a learning accuracy of 83.08% on the unlabeled MNIST handwritten dataset.

A Polymorphic Memtransistor with Tunable Metallic and Semiconducting Channel.

Modulating semiconducting channel potential has been used for electrical switching in transistors without biological plasticity operations that are critical for energy-efficient neuromorphic computing. To achieve efficient data processing, alternative transport mechanisms, such as tunneling and thermionic emission, have been introduced with 2D materials. Here, a polymorphic memtransistor based on atomically thin Mo0.91 W0.09 Te2 is presented, where the lattice and electronic structures of the lateral device channel can be tuned as either metallic (1T') or semiconducting (2H) phases by electrical gating. The structural and electronic phase change of the channel material, optimized in Mo0.91 W0.09 Te2 , is explored using transport and optical measurements at the device scale. Based on the phase transition, the polymorphic memtransistor demonstrates a high on/off ratio (up to 105 ), low subthreshold swing (down to 80 mV dec-1 ), and various memristive behaviors, which are distinguished from traditional phase-change memory, transistors, and passive memristors for diverse neuromorphic and in-memory computing.

CNT-molecule-CNT (1D-0D-1D) van der Waals integration ferroelectric memory with 1-nm2 junction area.

The device's integration of molecular electronics is limited regarding the large-scale fabrication of gap electrodes on a molecular scale. The van der Waals integration (vdWI) of a vertically aligned molecular layer (0D) with 2D or 3D electrodes indicates the possibility of device's integration; however, the active junction area of 0D-2D and 0D-3D vdWIs remains at a microscale size. Here, we introduce the robust fabrication of a vertical 1D-0D-1D vdWI device with the ultra-small junction area of 1 nm2 achieved by cross-stacking top carbon nanotubes (CNTs) on molecularly assembled bottom CNTs. 1D-0D-1D vdWI memories are demonstrated through ferroelectric switching of azobenzene molecules owing to the cis-trans transformation combined with the permanent dipole moment of the end-tail -CF3 group. In this work, our 1D-0D-1D vdWI memory exhibits a retention performance above 2000 s, over 300 cycles with an on/off ratio of approximately 105 and record current density (3.4 × 108 A/cm2), which is 100 times higher than previous study through the smallest junction area achieved in a vdWI. The simple stacking of aligned CNTs (4 × 4) allows integration of memory arrays (16 junctions) with high device operational yield (100%), offering integration guidelines for future molecular electronics.

Synthesis of a Selectively Nb-Doped WS2-MoS2 Lateral Heterostructure for a High-Detectivity PN Photodiode.

In this study, selective Nb doping (P-type) at the WS2 layer in a WS2-MoS2 lateral heterostructure via a chemical vapor deposition (CVD) method using a solution-phase precursor containing W, Mo, and Nb atoms is proposed. The different chemical activity reactivity (MoO3 > WO3 > Nb2O5) enable the separation of the growth temperature of intrinsic MoS2 to 700 °C (first grown inner layer) and Nb-doped WS2 to 800 °C (second grown outer layer). By controlling the Nb/(W+Nb) molar ratio in the solution precursor, the hole carrier density in the p-type WS2 layer is selectively controlled from approximately 1.87 × 107/cm2 at 1.5 at.% Nb to approximately 1.16 × 1013/cm2 at 8.1 at.% Nb, while the electron carrier density in n-type MoS2 shows negligible change with variation of the Nb molar ratio. As a result, the electrical behavior of the WS2-MoS2 heterostructure transforms from the N-N junction (0 at.% Nb) to the P-N junction (4.5 at.% Nb) and the P-N tunnel junction (8.1 at.% Nb). The band-to-band tunneling at the P-N tunnel junction (8.1 at.% Nb) is eliminated by applying negative gate bias, resulting in a maximum rectification ratio (105) and a minimum channel resistance (108 Ω). With this optimized photodiode (8.1 at.% Nb at Vg = -30 V), an Iphoto/Idark ratio of 6000 and a detectivity of 1.1 × 1014 Jones are achieved, which are approximately 20 and 3 times higher, respectively, than the previously reported highest values for CVD-grown transition-metal dichalcogenide P-N junctions.

One-Step Synthesis of NbSe2/Nb-Doped-WSe2 Metal/Doped-Semiconductor van der Waals Heterostructures for Doping Controlled Ohmic Contact.

van der Waals heterostructures (vdWHs) of metallic (m-) and semiconducting (s-) transition-metal dichalcogenides (TMDs) exhibit an ideal metal/semiconductor (M/S) contact in a field-effect transistor. However, in the current two-step chemical vapor deposition process, the synthesis of m-TMD on pregrown s-TMD contaminates the van der Waals (vdW) interface and hinders the doping of s-TMD. Here, NbSe2/Nb-doped-WSe2 metal-doped-semiconductor (M/d-S) vdWHs are created via a one-step synthesis approach using a niobium molar ratio-controlled solution-phase precursor. The one-step growth approach synthesizes Nb-doped WSe2 with a controllable doping concentration and metal/doped-semiconductor vdWHs. The hole carrier concentration can be precisely controlled by controlling the Nb/(W + Nb) molar ratio in the precursor solution from ∼3 × 1011/cm2 at Nb-0% to ∼1.38 × 1012/cm2 at Nb-60%; correspondingly, the contact resistance RC value decreases from 10 888.78 at Nb-0% to 70.60 kΩ.µm at Nb-60%. The Schottky barrier height measurement in the Arrhenius plots of ln(Isat/T2) versus q/KBT demonstrated an ohmic contact in the NbSe2/WxNb1-xSe2 vdWHs. Combining p-doping in WSe2 and M/d-S vdWHs, the mobility (27.24 cm2 V-1 s-1) and on/off ratio (2.2 × 107) are increased 1238 and 4400 times, respectively, compared to that using the Cr/pure-WSe2 contact (0.022 cm2 V-1 s-1 and 5 × 103, respectively). Together, the RC value using the NbSe2 contact shows 2.46 kΩ.µm, which is ∼29 times lower than that of using a metal contact. This method is expected to guide the synthesis of various M/d-S vdWHs and applications in future high-performance integrated circuits.

In-sensor reservoir computing for language learning via two-dimensional memristors.

The dynamic processing of optoelectronic signals carrying temporal and sequential information is critical to various machine learning applications including language processing and computer vision. Despite extensive efforts to emulate the visual cortex of human brain, large energy/time overhead and extra hardware costs are incurred by the physically separated sensing, memory, and processing units. The challenge is further intensified by the tedious training of conventional recurrent neural networks for edge deployment. Here, we report in-sensor reservoir computing for language learning. High dimensionality, nonlinearity, and fading memory for the in-sensor reservoir were achieved via two-dimensional memristors based on tin sulfide (SnS), uniquely having dual-type defect states associated with Sn and S vacancies. Our in-sensor reservoir computing demonstrates an accuracy of 91% to classify short sentences of language, thus shedding light on a low training cost and the real-time solution for processing temporal and sequential signals for machine learning applications at the edge.

Selective Pattern Growth of Atomically Thin MoSe2 Films via a Surface-Mediated Liquid-Phase Promoter.

Two-dimensional transition metal dichalcogenides (TMDs) offer numerous advantages over silicon-based application in terms of atomically thin geometry, excellent opto-electrical properties, layer-number dependence, band gap variability, and lack of dangling bonds. The production of high-quality and large-scale TMD films is required with consideration of practical technology. However, the performance of scalable devices is affected by problems such as contamination and patterning arising from device processing; this is followed by an etching step, which normally damages the TMD film. Herein, we report the direct growth of MoSe2 films on selective pattern areas via a surface-mediated liquid-phase promoter using a solution-based approach. Our growth process utilizes the promoter on the selective pattern area by enhancing wettability, resulting in a highly uniform MoSe2 film. Moreover, our approach can produce other TMD films such as WSe2 films as well as control various pattern shapes, sizes, and large-scale areas, thus improving their applicability in various devices in the future. Our patterned MoSe2 field-effect transistor device exhibits a p-type dominant conduction behavior with a high on/off current ratio of ∼106. Thus, our study provides general guidance for direct selective pattern growth via a solution-based approach and the future design of integrated devices for a large-scale application.

Photoinduced Tuning of Schottky Barrier Height in Graphene/MoS2 Heterojunction for Ultrahigh Performance Short Channel Phototransistor.

Two-dimensional (2D) layered materials with properties such as a large surface-to-volume ratio, strong light interaction, and transparency are expected to be used in future optoelectronic applications. Many studies have focused on ways to increase absorption of 2D-layered materials for use in photodetectors. In this work, we demonstrate another strategy for improving photodetector performance using a graphene/MoS2 heterojunction phototransistor with a short channel length and a tunable Schottky barrier. The channel length of sub-30 nm, shorter than the diffusion length, decreases carrier recombination and carrier transit time in the channel and improves phototransistor performance. Furthermore, our graphene/MoS2 heterojunction phototransistor employed a tunable Schottky barrier that is only controlled by light and gate bias. It maintains a low dark current and an increased photocurrent. As a result, our graphene/MoS2 heterojunction phototransistor showed ultrahigh responsivity and detectivity of 2.2 × 105 A/W and 3.5 × 1013 Jones, respectively. This is a considerable improvement compared to previous pristine MoS2 phototransistors. We confirmed an effective method to develop phototransistors based on 2D materials and obtained ultrahigh performance of our phototransistor, which is promising for high-performance optoelectronic applications.

CVD-Grown Carbon Nanotube Branches on Black Silicon Stems for Ultrahigh Absorbance in Wide Wavelength Range.

We report a black silicon-carbon nanotube (bSi-CNT) hybrid structure for ultrahigh absorbance at wide spectral range of wavelength (300-1200 nm). CNTs are densely grown on entire bSi stems by chemical vapor deposition (CVD) through uniformly coating Fe catalyst. The bSi-CNT not only increases the surface roughness for enhancing the light suppression, but also allows the absorption of light in a wide wavelength range over the Si band gap (>1000 nm owing to 1.1 eV) due to the small band gap of CNT (0.6 eV). At short wavelength below Si band gap (<1000 nm), the absorbance of bSi-CNT shows average of 98.1%, while bSi shows 89.4%, which is because of high surface roughness of bSi-CNT that enhancing the light trapping. At long wavelength over Si band gap, the absorbance of bSi-CNT was maintained to 96.3% because of the absorption in CNT, while absorbance of bSi abruptly reduces with increase wavelength. Especially, the absorbance of bSi-CNT was showed 93.5% at 1200 nm, which is about 30~90% higher than previously reported bSi. Simple growth of CNTs on bSi can dramatically enhances the absorbance without using any antireflection coating layer. Thus, this study can be employed for realizing high efficiency photovoltaic, photocatalytic applications.

Unveiling the Hot Carrier Distribution in Vertical Graphene/h-BN/Au van der Waals Heterostructures for High-Performance Photodetector.

Graphene is one of the most promising materials for photodetectors due to its ability to convert photons into hot carriers within approximately 50 fs and generate long-lived thermalized states with lifetimes longer than 1 ps. In this study, we demonstrate a wide range of vertical photodetectors having a graphene/h-BN/Au heterostructure in which an hexagonal boron nitride (h-BN) insulating layer is inserted between an Au electrode and graphene photoabsorber. The photocarriers effectively tunnel through the small hole barrier (1.93 eV) at the Au/h-BN junction while the dark carriers are highly suppressed by a large electron barrier (2.27 eV) at the graphene/h-BN junction. Thus, an extremely low dark current of ∼10-13 A is achieved, which is 8 orders of magnitude lower than that of graphene lateral photodetector devices (∼10-5 A). Also, our device displays an asymmetric photoresponse behavior due to photothermionic emission at the graphene/h-BN and Au/h-BN junctions. The asymmetric behavior generates additional thermal carriers (hot carriers) to enable our device to generate photocurrents that can overcome the Schottky barrier. Furthermore, our device shows the highest value of the Iph/Idark ratio of ∼225 at 7 nm thick h-BN insulating layer, which is 3 orders of magnitude larger than that of the previously reported graphene lateral photodetectors without any active materials. In addition, we achieve a fast response speed of 12 µs of rise time and 5 µs of fall time, which are about 100 times faster than those of other graphene integrated photodetectors.

Tailoring Quantum Tunneling in a Vanadium-Doped WSe2/SnSe2 Heterostructure.

2D van der Waals layered heterostructures allow for a variety of energy band offsets, which help in developing valuable multifunctional devices. However, p-n diodes, which are typical and versatile, are still limited by the material choice due to the fixed band structures. Here, the vanadium dopant concentration is modulated in monolayer WSe2 via chemical vapor deposition to demonstrate tunable multifunctional quantum tunneling diodes by vertically stacking SnSe2 layers at room temperature. This is implemented by substituting tungsten atoms with vanadium atoms in WSe2 to provoke the p-type doping effect in order to efficiently modulate the Fermi level. The precise control of the vanadium doping concentration is the key to achieving the desired quantum tunneling diode behaviors by tuning the proper band alignment for charge transfer across the heterostructure. By constructing a p-n diode for p-type V-doped WSe2 and heavily degenerate n-type SnSe2, the type-II band alignment at low V-doping concentration is clearly shown, which evolves into the type-III broken-gap alignment at heavy V-doping concentration to reveal a variety of diode behaviors such as forward diode, backward diode, negative differential resistance, and ohmic resistance.

Schottky Barrier Variable Graphene/Multilayer-MoS2 Heterojunction Transistor Used to Overcome Short Channel Effects.

A single-layer MoS2 achieves excellent gate controllability within the nanoscale channel length of a field-effect transistor (FET) owing to an ultra-short screening length. However, multilayer MoS2 (ML-MoS2) is more vulnerable to short channel effects (SCEs) owing to its thickness and long screening length. We eliminated the SCEs in an ML-MoS2 FET (thickness of 4-13 nm) at a channel length of sub-30 nm using a Schottky barrier (SB) variable graphene/ML-MoS2 heterojunction. Although the band modulation in the ML-MoS2 channel worsens with a decrease in the channel length, which is similar to the SCEs occurring in conventional FETs, the variable Fermi level (EF) of a graphene electrode along the gate voltage allows control of the SB at the graphene/MoS2 junction and backs up the current modulation through a variable SB. Electrical measurements and a theoretical band simulation demonstrate the efficient SB modulation of our graphene nanogap (GrNG) ML-MoS2 FET with three distinct carrier transports along Vgs: a thermionic emission at a low SB, Fowler-Nordheim tunneling at a moderate SB, and direct tunneling at a high SB. Our GrNG FET shows an extremely high on-off current ratio of ∼108, which is approximately three-orders of magnitude better than a previously reported metal nanogap (MeNG) FET and a self-aligned metal/graphene nanogap FET with a similar MoS2 thickness. Our GrNG FET also exhibits a 100,000-times higher on-off ratio, 100-times lower subthreshold swing, and 10-times lower drain induced barrier.

Self-selective van der Waals heterostructures for large scale memory array.

The large-scale crossbar array is a promising architecture for hardware-amenable energy efficient three-dimensional memory and neuromorphic computing systems. While accessing a memory cell with negligible sneak currents remains a fundamental issue in the crossbar array architecture, up-to-date memory cells for large-scale crossbar arrays suffer from process and device integration (one selector one resistor) or destructive read operation (complementary resistive switching). Here, we introduce a self-selective memory cell based on hexagonal boron nitride and graphene in a vertical heterostructure. Combining non-volatile and volatile memory operations in the two hexagonal boron nitride layers, we demonstrate a self-selectivity of 1010 with an on/off resistance ratio larger than 103. The graphene layer efficiently blocks the diffusion of volatile silver filaments to integrate the volatile and non-volatile kinetics in a novel way. Our self-selective memory minimizes sneak currents on large-scale memory operation, thereby achieving a practical readout margin for terabit-scale and energy-efficient memory integration.

Tunable Negative Differential Resistance in van der Waals Heterostructures at Room Temperature by Tailoring the Interface.

Vertically stacked two-dimensional van der Waals (vdW) heterostructures, used to obtain homogeneity and band steepness at interfaces, exhibit promising performance for band-to-band tunneling (BTBT) devices. Esaki tunnel diodes based on vdW heterostructures, however, yield poor current density and peak-to-valley ratio, inferior to those of three-dimensional materials. Here, we report the negative differential resistance (NDR) behavior in a WSe2/SnSe2 heterostructure system at room temperature and demonstrate that heterointerface control is one of the keys to achieving high device performance by constructing WSe2/SnSe2 heterostructures in inert gas environments. While devices fabricated in ambient conditions show poor device performance due to the observed oxidation layer at the interface, devices fabricated in inert gas exhibit extremely high peak current density up to 1460 mA/mm2, 3-4 orders of magnitude higher than reported vdW heterostructure-based tunnel diodes, with a peak-to-valley ratio of more than 4 at room temperature. Besides, Pd/WSe2 contact in our device possesses a much higher Schottky barrier than previously reported Cr/WSe2 contact in the WSe2/SnSe2 device, which suppresses the thermionic emission current to less than the BTBT current level, enabling the observation of NDR at room temperature. Diode behavior can be further modulated by controlling the electrostatic doping and the tunneling barrier as well.

Efficient Gate Modulation in a Screening-Engineered MoS2/Single-Walled Carbon Nanotube Network Heterojunction Vertical Field-Effect Transistor.

In this report, a screening-engineered carbon nanotube (CNT) network/MoS2/metal heterojunction vertical field effect transistor (CNT-VFET) is fabricated for an efficient gate modulation independent of the drain voltage. The gate field in the CNT-VFET transports through the empty space of the CNT network without any screening layer and directly modulates the MoS2 semiconductor energy band, while the gate field from the Si back gate is mostly screened by the graphene layer. Consequently, the on/off ratio of CNT-VFET maintained 103 in overall drain voltages, which is 10 times and 1000 times higher than that of the graphene (Gr) VFET at Vsd = 0.1 (ratio = 81.9) and 1 V (ratio = 3), respectively. An energy band diagram simulation shows that the Schottky barrier modulation of CNT/MoS2 contact along the sweeping gate bias is independent of the drain voltage. On the other hand, the gate modulation of Gr/MoS2 is considerably reduced with increased drain voltage because more electrons are drawn into the graphene electrode and screens the gate field by applying a higher drain voltage to the graphene/MoS2/metal capacitor.

Intrinsic Optoelectronic Characteristics of MoS2 Phototransistors via a Fully Transparent van der Waals Heterostructure.

In the past decade, intensive studies on monolayer MoS2-based phototransistors have been carried out to achieve further enhanced optoelectronic characteristics. However, the intrinsic optoelectronic characteristics of monolayer MoS2 have still not been explored until now because of unintended interferences, such as multiple reflections of incident light originating from commonly used opaque substrates. This leads to overestimated photoresponsive characteristics inevitably due to the enhanced photogating and photoconductive effects. Here, we reveal the intrinsic photoresponsive characteristics of monolayer MoS2, including its internal responsivity and quantum efficiency, in fully transparent monolayer MoS2 phototransistors employing a van der Waals heterostructure. Interestingly, as opposed to the previous reports, the internal photoresponsive characteristics do not significantly depend on the wavelength of the incident light as long as the electron-hole pairs are generated in the same k-space. This study provides a deeper understanding of the photoresponsive characteristics of MoS2 and lays the foundation for two-dimensional materials-based transparent phototransistors.

Ultrahigh Gauge Factor in Graphene/MoS2 Heterojunction Field Effect Transistor with Variable Schottky Barrier.

Piezoelectricity of transition metal dichalcogenides (TMDs) under mechanical strain has been theoretically and experimentally studied. Powerful strain sensors using Schottky barrier variation in TMD/metal junctions as a result of the strain-induced lattice distortion and associated ion-charge polarization were demonstrated. However, the nearly fixed work function of metal electrodes limits the variation range of a Schottky barrier. We demonstrate a highly sensitive strain sensor using a variable Schottky barrier in a MoS2/graphene heterostructure field effect transistor (FET). The low density of states near the Dirac point in graphene allows large modulation of the graphene Fermi level and corresponding Schottky barrier in a MoS2/graphene junction by strain-induced polarized charges of MoS2. Our theoretical simulations and temperature-dependent electrical measurements show that the Schottky barrier change is maximized by placing the Fermi level of the graphene at the charge neutral (Dirac) point by applying gate voltage. As a result, the maximum Schottky barrier change (ΔΦSB) and corresponding current change ratio under 0.17% strain reach 118 meV and 978, respectively, resulting in an ultrahigh gauge factor of 575 294, which is approximately 500 times higher than that of metal/TMD junction strain sensors (1160) and 140 times higher than the conventional strain sensors (4036). The ultrahigh sensitivity of graphene/MoS2 heterostructure FETs can be developed for next-generation electronic and mechanical-electronic devices.

High-Performance Photoinduced Memory with Ultrafast Charge Transfer Based on MoS2 /SWCNTs Network Van Der Waals Heterostructure.

Photoinduced memory devices with fast program/erase operations are crucial for modern communication technology, especially for high-throughput data storage and transfer. Although some photoinduced memories based on 2D materials have already demonstrated desirable performance, the program/erase speed is still limited to hundreds of micro-seconds. A high-speed photoinduced memory based on MoS2 /single-walled carbon nanotubes (SWCNTs) network mixed-dimensional van der Waals heterostructure is demonstrated here. An intrinsic ultrafast charge transfer occurs at the heterostructure interface between MoS2 and SWCNTs (below 50 fs), therefore enabling a record program/erase speed of ≈32/0.4 ms, which is faster than that of the previous reports. Furthermore, benefiting from the unique device structure and material properties, while achieving high-speed program/erase operation, the device can simultaneously obtain high program/erase ratio (≈106 ), appropriate storage time (≈103  s), record-breaking detectivity (≈1016  Jones) and multibit storage capacity with a simple program/erase operation. It even has a potential application as a flexible optoelectronic device. Therefore, the designed concept here opens an avenue for high-throughput fast data communications.

Direct growth of doping controlled monolayer WSe2 by selenium-phosphorus substitution.

Although many studies have been carried out on the doping of transition metal dichalcogenides (TMDCs), introducing controllable amounts of dopants into a TMD lattice is still insufficient. Here we demonstrate doping controlled TMDC growth by the replacement of selenium with phosphorus during the synthesis of the monolayer WSe2. The phosphorus doping density was precisely controlled by fine adjustment of the amount of P2O5 dopant powder along the pre-annealing time. Raman spectroscopy, photoluminescence (PL), X-ray photoelectron spectroscopy (XPS), and high-angle annular bright field scanning tunneling electron microscopy (HAADF STEM) provide evidence that P doping occurs within the WSe2 crystal with P occupying the substitutional Se sites. With regard to its electrical characteristics, the hole majority current of P-doped WSe2 is 100-times higher than that of the intrinsic WSe2. The measured doping concentration ranged from ∼8.16 × 1010 to ∼1.20 × 1012 depending on the amount of P2O5 dopant powder by pre-annealing.