Sublimation-based wafer-scale monolayer WS2 formation via self-limited thinning of few-layer WS2.

Atomically-thin monolayer WS2 is a promising channel material for next-generation Moore's nanoelectronics owing to its high theoretical room temperature electron mobility and immunity to short channel effect. The high photoluminescence (PL) quantum yield of the monolayer WS2 also makes it highly promising for future high-performance optoelectronics. However, the difficulty in strictly growing monolayer WS2, due to its non-self-limiting growth mechanism, may hinder its industrial development because of the uncontrollable growth kinetics in attaining the high uniformity in thickness and property on the wafer-scale. In this study, we report a scalable process to achieve a 4 inch wafer-scale fully-covered strictly monolayer WS2 by applying the in situ self-limited thinning of multilayer WS2 formed by sulfurization of WOx films. Through a pulsed supply of sulfur precursor vapor under a continuous H2 flow, the self-limited thinning process can effectively trim down the overgrown multilayer WS2 to the monolayer limit without damaging the remaining bottom WS2 monolayer. Density functional theory (DFT) calculations reveal that the self-limited thinning arises from the thermodynamic instability of the WS2 top layers as opposed to a stable bottom monolayer WS2 on sapphire above a vacuum sublimation temperature of WS2. The self-limited thinning approach overcomes the intrinsic limitation of conventional vapor-based growth methods in preventing the 2nd layer WS2 domain nucleation/growth. It also offers additional advantages, such as scalability, simplicity, and possibility for batch processing, thus opening up a new avenue to develop a manufacturing-viable growth technology for the preparation of a strictly-monolayer WS2 on the wafer-scale.

Liquid-Metal-Printed Ultrathin Oxides for Atomically Smooth 2D Material Heterostructures.

Two-dimensional (2D) semiconductors are promising channel materials for continued downscaling of complementary metal-oxide-semiconductor (CMOS) logic circuits. However, their full potential continues to be limited by a lack of scalable high-k dielectrics that can achieve atomically smooth interfaces, small equivalent oxide thicknesses (EOTs), excellent gate control, and low leakage currents. Here, large-area liquid-metal-printed ultrathin Ga2O3 dielectrics for 2D electronics and optoelectronics are reported. The atomically smooth Ga2O3/WS2 interfaces enabled by the conformal nature of liquid metal printing are directly visualized. Atomic layer deposition compatibility with high-k Ga2O3/HfO2 top-gate dielectric stacks on a chemical-vapor-deposition-grown monolayer WS2 is demonstrated, achieving EOTs of ∼1 nm and subthreshold swings down to 84.9 mV/dec. Gate leakage currents are well within requirements for ultrascaled low-power logic circuits. These results show that liquid-metal-printed oxides can bridge a crucial gap in dielectric integration of 2D materials for next-generation nanoelectronics.

Gate-Defined Quantum Confinement in CVD 2D WS2.

Temperature-dependent transport measurements are performed on the same set of chemical vapor deposition (CVD)-grown WS2 single- and bilayer devices before and after atomic layer deposition (ALD) of HfO2 . This isolates the influence of HfO2 deposition on low-temperature carrier transport and shows that carrier mobility is not charge impurity limited as commonly thought, but due to another important but commonly overlooked factor: interface roughness. This finding is corroborated by circular dichroic photoluminescence spectroscopy, X-ray photoemission spectroscopy, cross-sectional scanning transmission electron microscopy, carrier-transport modeling, and density functional modeling. Finally, electrostatic gate-defined quantum confinement is demonstrated using a scalable approach of large-area CVD-grown bilayer WS2 and ALD-grown HfO2 . The high dielectric constant and low leakage current enabled by HfO2 allows an estimated quantum dot size as small as 58 nm. The ability to lithographically define increasingly smaller devices is especially important for transition metal dichalcogenides due to their large effective masses, and should pave the way toward their use in quantum information processing applications.

Quantum Transport in Two-Dimensional WS2 with High-Efficiency Carrier Injection through Indium Alloy Contacts.

Two-dimensional transition metal dichalcogenides (TMDCs) have properties attractive for optoelectronic and quantum applications. A crucial element for devices is the metal-semiconductor interface. However, high contact resistances have hindered progress. Quantum transport studies are scant as low-quality contacts are intractable at cryogenic temperatures. Here, temperature-dependent transfer length measurements are performed on chemical vapor deposition grown single-layer and bilayer WS2 devices with indium alloy contacts. The devices exhibit low contact resistances and Schottky barrier heights (∼10 kΩ µm at 3 K and 1.7 meV). Efficient carrier injection enables high carrier mobilities (∼190 cm2 V-1 s-1) and observation of resonant tunnelling. Density functional theory calculations provide insights into quantum transport and properties of the WS2-indium interface. Our results reveal significant advances toward high-performance WS2 devices using indium alloy contacts.

Anisotropic Collective Charge Excitations in Quasimetallic 2D Transition-Metal Dichalcogenides.

The quasimetallic 1T' phase 2D transition-metal dichalcogenides (TMDs) consist of 1D zigzag metal chains stacked periodically along a single axis. This gives rise to its prominent physical properties which promises the onset of novel physical phenomena and applications. Here, the in-plane electronic correlations are explored, and new mid-infrared plasmon excitations in 1T' phase monolayer WSe2 and MoS2 are observed using optical spectroscopies. Based on an extensive first-principles study which analyzes the charge dynamics across multiple axes of the atomic-layered systems, the collective charge excitations are found to disperse only along the direction perpendicular to the chains. Further analysis reveals that the interchain long-range coupling is responsible for the coherent 1D charge dynamics and the spin-orbit coupling affects the plasmon frequency. Detailed investigation of these charge collective modes in 2D-chained systems offers opportunities for novel device applications and has implications for the underlying mechanism that governs superconductivity in 2D TMD systems.

Employing a Bifunctional Molybdate Precursor To Grow the Highly Crystalline MoS2 for High-Performance Field-Effect Transistors.

Growth of the large-sized and high-quality MoS2 single crystals for high-performance low-power electronic applications is an important step to pursue. Despite the significant improvement made in minimizing extrinsic MoS2 contact resistance based on interfacial engineering of the devices, the electron mobility of field-effect transistors (FETs) made of a synthetic monolayer MoS2 is yet far below the expected theoretical values, implying that the MoS2 crystal quality needs to be further improved. Here, we demonstrate the high-performance two-terminal MoS2 FETs with room-temperature electron mobility up to ∼90 cm2 V-1 s-1 based on the sulfurization growth of the bifunctional precursor, sodium molybdate dihydrate. This unique transition-metal precursor, serving as both the crystalline Mo source and seed promotor (sodium), could facilitate the lateral growth of the highly crystalline monolayer MoS2 crystals (edge length up to ∼260 µm). Substrate surface treatment with oxygen plasma prior to the deposition of the Mo precursor is fundamental to increase the wettability between the Mo source and the substrate, promoting the thinning and coalescence of the source clusters during the growth of large-sized MoS2 single crystals. The control of growth temperature is also an essential step to grow a strictly monolayer MoS2 crystal. A proof-of-concept for thermoelectric device integration utilizing monolayer MoS2 sheds light on its potential in low-voltage and self-powered electronics.

Modification of Vapor Phase Concentrations in MoS2 Growth Using a NiO Foam Barrier.

Single-layer molybdenum disulfide (MoS2) has attracted significant attention due to its electronic and physical properties, with much effort invested toward obtaining large-area high-quality monolayer MoS2 films. In this work, we demonstrate a reactive-barrier-based approach to achieve growth of highly homogeneous single-layer MoS2 on sapphire by the use of a nickel oxide foam barrier during chemical vapor deposition. Due to the reactivity of the NiO barrier with MoO3, the concentration of precursors reaching the substrate and thus nucleation density is effectively reduced, allowing grain sizes of up to 170 µm and continuous monolayers on the centimeter length scale being obtained. The quality of the monolayer is further revealed by angle-resolved photoemission spectroscopy measurement by observation of a very well resolved electronic band structure and spin-orbit splitting of the bands at room temperature with only two major domain orientations, indicating the successful growth of a highly crystalline and well-oriented MoS2 monolayer.

Thermally Stable Mesoporous Perovskite Solar Cells Incorporating Low-Temperature Processed Graphene/Polymer Electron Transporting Layer.

In the short time since its discovery, perovskite solar cells (PSCs) have attained high power conversion efficiency but their lack of thermal stability remains a barrier to commercialization. Among the experimentally accessible parameter spaces for optimizing performance, identifying an electron transport layer (ETL) that forms a thermally stable interface with perovskite and which is solution-processable at low-temperature will certainly be advantageous. Herein, we developed a mesoporous graphene/polymer composite with these advantages when used as ETL in CH3NH3PbI3 PSCs, and a high efficiency of 13.8% under AM 1.5G solar illumination could be obtained. Due to the high heat transmission coefficient and low isoelectric point of mesoporous graphene-based ETL, the PSC device enjoys good chemical and thermal stability. Our work demonstrates that the mesoporous graphene-based scaffold is a promising ETL candidate for high performance and thermally stable PSCs.

Graphene and Graphene-like Molecules: Prospects in Solar Cells.

Graphene is constantly hyped as a game-changer for flexible transparent displays. However, to date, no solar cell fabricated on graphene electrodes has out-performed indium tin oxide in power conversion efficiency (PCE). This Perspective covers the enabling roles that graphene can play in solar cells because of its unique properties. Compared to transparent and conducting metal oxides, graphene may not have competitive advantages in terms of its electrical conductivity. The unique strength of graphene lies in its ability to perform various enabling roles in solar cell architectures, leading to overall improvement in PCE. Graphene can serve as an ultrathin and transparent diffusion barrier in solar cell contacts, as an intermediate layer in tandem solar cells, as an electron acceptor, etc. Inspired by the properties of graphene, chemists are also designing graphene-like molecules in which the topology of π-electron array, donor-acceptor structures, and conformation can be tuned to offer a new class of light-harvesting materials.

Chemically doped radial junction characteristics in silicon nanowires.

We evaluate the boron (B) and phosphorus (P) core-surface codoped radial p-n junction characteristics in silicon nanowires (SiNWs) using density functional theory calculations. We find that the formation of radial p-n junction is energetically favorable. The stability depends on the diameter of SiNWs and the dopant concentration. Generally, a higher concentration of B-P pair dopants results in a more stable nanowire. More importantly, we predict that the radial p-n junction can evolve into a Schottky-like junction in relatively highly doped SiNWs when the diameter increases, attributing to the change of the core p-doping characteristic, that is, the core p-junction becomes metallic, while the n-junction near the surface remains semiconducting. The interfacial contact between the junctions is found to be the key for such change. Our calculated results support an experimental observation in SiNW solar cells.

First-principles study of silicon nanowire approaching the bulk limit.

First-principles density functional theory calculations on hydrogenated silicon nanowires (SiNWs) with diameters up to 7.3 nm are carried out for comparing to experimentally relevant SiNWs and evaluating its radial doping profiles. We show that the direct band gap nature of both the small diameter (110) and (100) SiNWs fades when the diameter reaches beyond about 4 nm, where the difference of direct and indirect band gaps are close, within the experimental measurement uncertainty of ±0.1 eV, suggesting the diameter size where the gap nature transition starts. In addition, we reveal that core-surface boron (B) codoped SiNW forms more preferably at large diameter than that of the surface-surface codoped one, attributing to the lower energy configuration raised by the core B dopant at large diameter SiNW. More importantly, the diameter for such a preferential transition increases as the doping concentration decreases. Our results rationalize photoluminescent measurements and radial doping distributions of SiNWs.