Lateral WSe2 Homojunction through Metal Contact Doping: Excellent Self-powered Photovoltaic Photodetector

Here an IR-heating chemical vapor deposition (CVD) approach enabling fast 2D-growth of WSe₂ thin films is reported, and the great potential of metal contact doping in building CVD-grown WSe₂-based lateral homojunction is demonstrated by contacting with TiN/Ni metals in favor of holes/electrons injection. Shortening nanosheet channel to ≈2 µm leads to pronounced enhancement in the performance of diode. The fabricated WSe₂-based diode exhibits high rectification ratios without the need of gate modulation and can work efficiently as photovoltaic cell, with maximum open circuit voltage reaching up to 620 mV and a high power conversion efficiency over 15%, empowering it as superb self-powered photodetector for visible to near-infrared lights, with photoresponsivity over 0.5 A W⁻¹ and a fast photoresponse speed of 10 µs under 520 nm illumination. It is of practical significance to achieve well-performed photovoltaic devices with CVD-grown WSe₂ using fab-friendly metals and simple processing, which will help pave the way toward future mass production of optoelectronic chips.     

van der Waals Epitaxial Growth of Atomically Thin 2D Metals on Dangling‐Bond‐Free WSe2 and WS2

2D metals have attracted considerable recent attention for their special physical properties, such as charge density waves, magnetism, and superconductivity. However, despite some recent efforts, the synthesis of ultrathin 2D metals nanosheets down to monolayer thickness remains a significant challenge. Herein, by using atomically flat 2D WSe₂ or WS₂ as the growth substrate, the synthesis of atomically thin 2D metallic MTe₂ (M = V, Nb, Ta) single crystals with the thickness down to the monolayer regime and the creation of atomically thin MTe₂/WSe₂ (WS₂) vertical heterojunctions is reported. Comparison with the growth on the SiO₂/Si substrate under the same conditions reveals that the utilization of the dangling‐bond‐free WSe₂ or WS₂ as the van der Waals epitaxy substrates is crucial for the successful realization of atomically thin MTe₂ (M = V, Nb, Ta) nanosheets. It is further shown that the epitaxial grown 2D metals can function as van der Waals contacts for 2D semiconductors with little interface damage and improved electronic performance. This study defines a robust van der Waals epitaxy pathway to ultrathin 2D metals, which is essential for fundamental studies and potential technological applications of this new class of materials at the 2D limit.     

Large-Scale,Controllable Synthesis of Ultrathin Platinum Diselenide Ribbons for Efficient Electrocatalytic Hydrogen Evolution

2D platinum diselenide (PtSe₂) exhibits exceptional layer-dependent electrical properties and high catalytic activity for hydrogen evolution reactions, making it an ideal system for studying structure–activity correlations. However, the synthesis of high-quality atomically thin PtSe₂ materials has proven challenging. This study presents a simple chemical vapor deposition method for synthesizing high-quality ultrathin 1T-PtSe₂ ribbons on Au foils, making it easily applicable. Theoretical and experimental results confirm that these atomically thin 1T-PtSe₂ ribbons possess abundant catalytic sites and can serve as ideal electrocatalysts. This study advances the large-scale synthesis and potential application of ultrathin transition metal disulfides and presents a novel method for designing and synthesizing highly active ultrathin catalysts.     

Epitaxial Growth and Characterization of p-Type ZnO

N-doped p-type ZnO thin films were grown on c-sapphire substrates, semi-insulating GaN templates, and n-type ZnO substrates by metal organic chemical vapor deposition (MOCVD). Diethylzinc and oxygen were used as precursors for Zn and O, respectively, while ammonia (NH₃) and nitrous oxide (N₂O) were employed as the nitrogen dopant sources. X-ray diffraction (XRD) studies depicted highly oriented N-doped ZnO thin films. Photoluminescence (PL) measurements showed a main emission line around 380 nm, corresponding to an energy gap of 3.26 eV. Nitrogen concentration in the grown films was analyzed by secondary ion mass spectrometry (SIMS) and was found to be on the order of 10¹⁸ cm⁻³. Electrical properties of N-doped ZnO epilayers grown on semi-insulating GaN:Mg templates were measured by the Hall effect and the results indicated p-type with carrier concentration on the order of 10¹⁷ cm⁻³.     

Role of Molecular Sieves in the CVD Synthesis of Large‐Area 2D MoTe2

The synthesis of high‐quality 2D MoTe₂ with a desired phase on SiO₂/Si substrate is crucial to its diverse applications. A side reaction of Te with the substrate Si leading to SiTe and Si₂Te₃ tends to happen during growth, resulting in the failure to obtain MoTe₂. It has been found that molecular sieves can adsorb the silicon telluride byproducts and eliminate the influence of the side reaction during the chemical vapor deposition synthesis of MoTe₂. With the help of molecular sieves, few‐layer 1T′ MoTe₂ can be grown from the MoO_x precursor. Pure 1T′ MoTe₂ and 2H MoTe₂ regions in centimeter‐sized areas synthesized on the same piece of SiO₂/Si substrate can be obtained by using an overlapped geometry. The strategy provides a new method to controllably synthesize MoTe₂ with desired phases and can be generalizable to the synthesis of other tellurium‐based layered materials.     

Sub‐Millimeter‐Scale Monolayer p‐Type H‐Phase VS2

2D H‐phase vanadium disulfide (VS₂) is expected to exhibit tunable semiconductor properties as compared with its metallic T‐phase structure, and thus is of promise for future electronic applications. However, to date such 2D H‐phase VS₂ nanostructures have not been realized in experiment likely due to the polymorphs of vanadium sulfides and thermodynamic instability of H‐phase VS₂. Preparation of H‐phase VS₂ monolayer with lateral size up to 250 µm, as a new member in the 2D transition metal dichalcogenides (TMDs) family, is reported. A unique growth environment is built by introducing the molten salt‐mediated precursor system as well as the epitaxial mica growth platform, which successfully overcomes the aforementioned growth challenges and enables the evolution of 2D H‐phase structure of VS₂. The honeycomb‐like structure of H‐phase VS₂ with broken inversion symmetry is confirmed by spherical aberration‐corrected scanning transmission electron microscopy and second harmonic generation characterization. The phase structure is found to be ultra‐stable up to 500 K. The field‐effect device study further demonstrates the p‐type semiconducting nature of the 2D H‐phase VS₂. The study introduces a new phase‐stable 2D TMDs materials with potential features for future electronic devices.     

Carrier Type Control of WSe2 Field‐Effect Transistors by Thickness Modulation and MoO3 Layer Doping

Control of the carrier type in 2D materials is critical for realizing complementary logic computation. Carrier type control in WSe₂ field‐effect transistors (FETs) is presented via thickness engineering and solid‐state oxide doping, which are compatible with state‐of‐the‐art integrated circuit (IC) processing. It is found that the carrier type of WSe₂ FETs evolves with its thickness, namely, p‐type (<4 nm), ambipolar (≈6 nm), and n‐type (>15 nm). This layer‐dependent carrier type can be understood as a result of drastic change of the band edge of WSe₂ as a function of the thickness and their band offsets to the metal contacts. The strong carrier type tuning by solid‐state oxide doping is also demonstrated, in which ambipolar characteristics of WSe₂ FETs are converted into pure p‐type, and the field‐effect hole mobility is enhanced by two orders of magnitude. The studies not only provide IC‐compatible processing method to control the carrier type in 2D semiconductor, but also enable to build functional devices, such as, a tunable diode formed with an asymmetrical‐thick WSe₂ flake for fast photodetectors.     

Controlled Layer Thinning and p‐Type Doping of WSe2 by Vapor XeF2

This report presents a simple and efficient method of layer thinning and p‐type doping of WSe₂ with vapor XeF₂. With this approach, the surface roughness of thinned WSe₂ can be controlled to below 0.7 nm at an etched depth of 100 nm. By selecting appropriate vapor XeF₂ exposure times, 23‐layer and 109‐layer WSe₂ can be thinned down to monolayer and bilayer, respectively. In addition, the etching rate of WSe₂ exhibits a significant dependence on vapor XeF₂ exposure pressure and thus can be tuned easily for thinning or patterning applications. From Raman, photoluminescence, X‐ray photoelectron spectroscopy (XPS), and electrical characterization, a p‐doping effect of WSe₂ induced by vapor XeF₂ treatment is evident. Based on the surface composition analysis with XPS, the causes of the p‐doping effect can be attributed to the presence of substoichiometric WO_x (x < 3) overlayer, trapped reaction product of WF₆, and nonstoichiometric WSe_x (x > 2). Furthermore, the p‐doping level can be controlled by varying XeF₂ exposure time. The thinning and p‐doping of WSe₂ with vapor XeF₂ have the advantages of easy scale‐up, high etching selectivity, excellent controllability, and compatibility with conventional complementary metal‐oxide‐semiconductor fabrication processes, which is promising for applications of building WSe₂ devices with versatile functionalities.     

Switchable and Reversible p+/n+ Doping in 2D Semiconductors by Ionic 2D Minerals

2D semiconductors are promising for fabricating miniaturized and flexible electronic devices. The manipulation of polarities in 2D semiconductors is key to fabricate functional devices and circuits. However, the switchable and reversible control of polarity in 2D semiconductors is challenging due to their ultrathin body. Herein, a reversible and non-destructive method is developed to dope 2D semiconductors by using ionic 2D minerals as the electrostatic gating. The 2D semiconductor channel can be reversibly transformed between n⁺ and p⁺ types with carrier concentrations of 1.59 × 10¹³ and 6.82 × 10¹² cm⁻², respectively. With the ability to in situ control carrier type and concentration in 2D semiconductors by ionic gating, a reversible PN/NP junction and programmable logic gate are demonstrated in such devices. This 2D mineral materials-based ionic doping approach provides an alternative method for achieving multi-functional and complex circuits in an all-2D material flatform.     

Redox Photochemistry on Van Der Waals Surfaces for Reversible Doping in 2D Materials

Despite the van der Waals (vdW) surfaces are usually chemically inert, un-destructive, scalable, and reversible redox reactions are introduced on the vdW surfaces of 2D anisotropic semiconductors ReX₂ (X = S or Se) facilitated by simple photochemistry. Ultraviolet (UV) light (with humid) and laser exposure can reversibly oxidize and reduce rhenium disulfide (ReS₂) and rhenium diselenide (ReSe₂), respectively, yielding a pronounced doping effect with good control. Evidenced by Raman spectroscopy, dynamic force microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy, the grafting and removal of covalently functionalized oxygen groups on the perfect vdW surfaces are confirmed. The optical and electrical properties can be thereby reversibly tunable in wide ranges. Such optical direct-writing and rewritable capability via solvent/contaminant-free approach for chemical doping are compelling in the coming era of 2D materials.     

High Crystal Quality 2D Manganese Phosphorus Trichalcogenide Nanosheets and their Photocatalytic Activity

Transition metal phosphorus trichalcogenides (MPX₃, X = S, Se) are layered materials possessing high chemical diversity and wide range of applications in a broad wave length spectrum. Theoretical studies reveal that auspicious activity of photocatalytic water splitting can be realized from them. However, experimental efforts have so far been challenged with the synthesis bottleneck. Described herein is the general chemical vapor deposition (CVD) growth method and photocatalytic activity of these materials. A novel route to systematically grow MnPX₃ nanosheets on flexible carbon fiber substrate is reported. The temperature profile of the CVD process is carefully optimized that confer a facile and successful conversion of oxide precursor to phospho‐trichalcogenide with high crystallinity. Moreover, the obtained manganese‐based phosphorus trichalcogenide nanosheets demonstrate promising activity in sacrificial agent‐free photocatalytic water splitting under simulated solar light (AM 1.5G). This study provides a significant stepping stone in exploring the fascinating world of functional 2D materials and pursuing performance enhancement.     

Elastic Properties of 2D Ultrathin Tungsten Nitride Crystals Grown by Chemical Vapor Deposition

3D transition metal nitrides are well recognized for their good electrical conductivity, superior mechanical properties, and high chemical stability. Recently, 2D transition metal nitrides have been successfully prepared in the form of nanosheets and show potential application in energy storage. However, the synthesis of highly crystalline and well‐shaped 2D nitrides layers is still in demand for the investigation of their intrinsic physical properties. The present paper reports the growth of ultrathin tungsten nitride crystals on SiO₂/Si substrates by a salt‐assisted chemical vapor deposition method. High‐resolution transmission microscopy confirms the as‐grown samples are highly crystalline WN. The stiffness of ultrathin WN is investigated by atomic force microscopy–based nanoindentation with the film suspended on circular holes. The 3D Young's modulus of few‐layer (4.5 nm thick or more) WN is determined to be 3.9 × 10² ± 1.6 × 10² GPa, which is comparable with the best experimental reported values in the 2D family except graphene and hexagonal boron nitride. The synthesis approach presented in this paper offers the possibilities of producing and utilizing other highly crystalline 2D transition‐metal nitride crystals.     

Tuning the Electronic and Photonic Properties of Monolayer MoS2 via In Situ Rhenium Substitutional Doping

Doping is a fundamental requirement for tuning and improving the properties of conventional semiconductors. Recent doping studies including niobium (Nb) doping of molybdenum disulfide (MoS₂) and tungsten (W) doping of molybdenum diselenide (MoSe₂) have suggested that substitutional doping may provide an efficient route to tune the doping type and suppress deep trap levels of 2D materials. To date, the impact of the doping on the structural, electronic, and photonic properties of in situ‐doped monolayers remains unanswered due to challenges including strong film substrate charge transfer, and difficulty achieving doping concentrations greater than 0.3 at%. Here, in situ rhenium (Re) doping of synthetic monolayer MoS₂ with ≈1 at% Re is demonstrated. To limit substrate film charge transfer, r‐plane sapphire is used. Electronic measurements demonstrate that 1 at% Re doping achieves nearly degenerate n‐type doping, which agrees with density functional theory calculations. Moreover, low‐temperature photoluminescence indicates a significant quench of the defect‐bound emission when Re is introduced, which is attributed to the Mo O bond and sulfur vacancies passivation and reduction in gap states due to the presence of Re. The work presented here demonstrates that Re doping of MoS₂ is a promising route toward electronic and photonic engineering of 2D materials.     

Physical vapor deposited 2D bismuth for CMOS technology

Two-dimensional (2D) bismuth, bismuthene, is an emerging pnictogen family member that has received increasing research attention in the past few years, which could yield exotic electrical, thermal, and optical properties due to unique band structure. This review provides a holistic view of recent research advances on 2D bismuth material synthesis and device applications in complementary metal oxide semiconductor (CMOS) technology. Firstly, the atomic and band structure of bismuthene is reviewed as the fundamental understanding of its physical properties. Then, it highlights material synthesis of 2D bismuth atomic sheets with emphasis on physical vapor deposition method with accurate layer controllability and process compatibility with CMOS technology. Moreover, it will survey latest applications of 2D bismuth in terms of electronic, optic, thermoelectric, spintronic and magnetic nanodevices. 2D bismuth derivatives (Bi–X, X = Sb, Te, Se) will also be mentioned as a promising strategy to further improve device performance. At last, it concludes with a brief summary on the current challenges and future prospects in 2D bismuth and its derivatives for innovative electronics, sensors and other devices compatible with CMOS techniques.     

Large‐Area Chemical Vapor Deposited MoS2 with Transparent Conducting Oxide Contacts toward Fully Transparent 2D Electronics

2D semiconductors are poised to revolutionize the future of electronics and photonics, much like transparent oxide conductors and semiconductors have revolutionized the display industry. Herein, these two types of materials are combined to realize fully transparent 2D electronic devices and circuits. Specifically, a large‐area chemical vapor deposition process is developed to grow monolayer MoS₂ continuous films, which are, for the first time, combined with transparent conducting oxide (TCO) contacts. Transparent conducting aluminum doped zinc oxide contacts are deposited by atomic layer deposition, with composition tuning to achieve optimal conductivity and band‐offsets with MoS₂. The optimized process gives fully transparent TCO/MoS₂ 2D electronics with average visible‐range transmittance of 85%. The transistors show high mobility (4.2 cm² V^?1 s^?1), fast switching speed (0.114 V dec^?1), very low threshold voltage (0.69 V), and large switching ratio (4 × 10⁸). To our knowledge, these are the lowest threshold voltage and subthreshold swing values reported for monolayer chemical vapor deposition MoS₂ transistors. The transparent inverters show fast switching properties with a gain of 155 at a supply voltage of 10 V. The results demonstrate that transparent conducting oxides can be used as contact materials for 2D semiconductors, which opens new possibilities in 2D electronic and photonic applications.     

Collective Dipole‐Dominated Doping of Monolayer MoS2: Orientation and Magnitude Control via the Supramolecular Approach

Molecular doping is a powerful, tuneable, and versatile method to modify the electronic properties of 2D transition metal dichalcogenides (TMDCs). While electron transfer is an isotropic process, dipole‐induced doping is a collective phenomenon in which the orientation of the molecular dipoles interfaced to the 2D material is key to modulate and boost this electronic effect, despite it is not yet demonstrated. A novel method toward the molecular functionalization of monolayer MoS₂ relying on the molecular self‐assembly of metal phthalocyanine and the orientation‐controlled coordination chemistry of axial ligands is reported here. It is demonstrated that the subtle variation of position and type of functional groups exposed on the pyridinic ligand, yields a molecular dipole with programed magnitude and orientation which is capable to strongly influence the opto‐electronic properties of monolayer MoS₂. In particular, experimental results revealed that both p‐ and n‐type doping can be achieved by modulating the charge carrier density up to 4.8 10¹² cm^?2. Density functional theory calculations showed that the doping mechanism is primarily resulting from the effect of dipole‐induced doping rather than charge transfer. The strategy to dope TMDCs is a highly modulable and robust, and it enables to enrich the functionality of 2D materials‐based devices for high‐performance applications in optoelectronics.     

Large‐Area Bilayer ReS2 Film/Multilayer ReS2 Flakes Synthesized by Chemical Vapor Deposition for High Performance Photodetectors

Rhenium disulfide (ReS₂) is attracting more and more attention for its thickness‐depended direct band gap. As a new appearing 2D transition metal dichalcogenide, the studies on synthesis method via chemical vapor deposition (CVD) is still rare. Here a systematically study on the CVD growth of continuous bilayer ReS₂ film and single crystalline hexagonal ReS₂ flake, as well as their corresponding optoelectronic properties is reported. Moreover, the growth mechanism has been proposed, accompanied with simulation study. High‐performance photodetector based on ReS₂ flake shows a high responsivity of 604 A·W^?1, high external quantum efficiency of 1.50 × 10⁵ %, and fast response time of 2 ms. ReS₂ film‐based photodetector exhibits weaker performance than the flake one; however, it still demonstrates a much faster response time (≈10³ ms) than other reported CVD‐grown ReS₂‐based photodetector (≈10⁴–10⁵ ms). Such good properties of ReS₂ render it a promising future in 2D optoelectronics.     

Ga掺杂ZnO薄膜的MOCVD生长及其特性

利用低压MOCVD技术在(0002)蓝宝石上外延获得高质量的ZnO∶Ga单晶薄膜,并研究了Ga的不同掺杂浓度对材料电学和光学特性的影响．当Ga/Zn气相摩尔比为3.2 at%时,ZnO(0002)峰半高宽仅为0.26°,载流子浓度高达2.47e19cm－3,透射率高于90%;当载流子浓度升高时,吸收边出现明显的Burstein-Moss蓝移效应．同时室温光致发光谱显示,紫外峰位随载流子浓度的增加而发生红移,峰形展宽,这和Ga高掺杂所引起的能带重整化效应有关．当Ga/Zn比达到6.3 at%时,由于高掺杂浓度下Ga的自补偿效应导致载流子浓度下降．     

2D Bi2O2Te Semiconductor with Single-Crystal Native Oxide Layer

Following logic in the silicon semiconductor industry, the existence of native oxide and suitable fabrication technology is essential for 2D semiconductors in planar integronics, which are surface-sensitive to typical coating technologies. To date, very few types of integronics are found to possess this feature. Herein, the 2D Bi₂O₂Te developed recently is reported to possess large-area synthesis and controllable thermal oxidation behavior toward single-crystal native oxides. This shows that surface-adsorbed oxygen atoms are inclined to penetrate across [Bi₂O₂]_n²ⁿ⁺ layers and bond with the underlying [Te]_n²ⁿ⁻ at elevated temperatures, transforming directly into [TeO₄]_n²ⁿ⁻ with the basic architecture remaining stable. The oxide can be adjusted to form in an accurate layer-by-layer manner with a low-stress sharp interface. The native oxide Bi₂TeO₆ layer (bandgap of ≈2.9 eV) exhibits visible-light transparency and is compatible with wet-chemical selective etching technology. These advances demonstrate the potential of Bi₂O₂Te in planar-integrated functional nanoelectronics such as tunnel junction devices, field-effect transistors, and memristors.