Quasi-Van der Waals Epitaxial Growth of γ'-GaSe Nanometer-Thick Films on GaAs(111)B Substrates.

GaSe is an important member of the post-transition-metal chalcogenide family and is an emerging two-dimensional (2D) semiconductor material. Because it is a van der Waals material, it can be fabricated into atomic-scale ultrathin films, making it suitable for the preparation of compact, heterostructure devices. In addition, GaSe possesses unusual optical and electronic properties, such as a shift from an indirect-bandgap single-layer film to a direct-bandgap bulk material, rare intrinsic p-type conduction, and nonlinear optical behaviors. These properties make GaSe an appealing candidate for the fabrication of field-effect transistors, photodetectors, and photovoltaics. However, the wafer-scale production of pure GaSe single-crystal thin films remains challenging. This study develops an approach for the direct growth of nanometer-thick GaSe films on GaAs substrates by using molecular beam epitaxy. It yields smooth thin GaSe films with a rare γ'-polymorph. We analyze the formation mechanism of γ'-GaSe using density-functional theory and speculate that it is stabilized by Ga vacancies since the formation enthalpy of γ'-GaSe tends to become lower than that of other polymorphs when the Ga vacancy concentration increases. Finally, we investigate the growth conditions of GaSe, providing valuable insights for exploring 2D/three-dimensional (3D) quasi-van der Waals epitaxial growth.

Wafer-Scale Synthesis of Highly Oriented 2D Topological Semimetal PtTe2 via Tellurization.

Platinum ditelluride (1T-PtTe2) is a two-dimensional (2D) topological semimetal with a distinctive band structure and flexibility of van der Waals integration as a promising candidate for future electronics and spintronics. Although the synthesis of large-scale, uniform, and highly crystalline films of 2D semimetals system is a prerequisite for device application, the synthetic methods meeting these criteria are still lacking. Here, we introduce an approach to synthesize highly oriented 2D topological semimetal PtTe2 using a thermally assisted conversion called tellurization, which is a cost-efficient method compared to the other epitaxial deposition methods. We demonstrate that achieving highly crystalline 1T-PtTe2 using tellurization is not dependent on epitaxy but rather relies on two critical factors: (i) the crystallinity of the predeposited platinum (Pt) film and (ii) the surface coverage ratio of the Pt film considering lateral lattice expansion during transformation. By optimizing the surface coverage ratio of the epitaxial Pt film, we successfully obtained 2 in. wafer-scale uniformity without in-plane misalignment between antiparallelly oriented domains. The electronic band structure of 2D topological PtTe2 is clearly resolved in momentum space, and we observed an interesting 6-fold gapped Dirac cone at the Fermi surface. Furthermore, ultrahigh electrical conductivity down to ∼3.8 nm, which is consistent with that of single crystal PtTe2, was observed, proving its ultralow defect density.

Wafer-Scale Production of Two-Dimensional Tin Monoselenide: Expandable Synthetic Platform for van der Waals Semiconductor-Based Broadband Photodetectors.

A synthetic platform for industrially applicable two-dimensional (2D) semiconductors that addresses the paramount issues associated with large-scale production, wide-range photosensitive materials, and oxidative stability has not yet been developed. In this study, we attained the 6 in. scale production of 2D SnSe semiconductors with spatial homogeneity using a rational synthetic platform based on the thermal decomposition of solution-processed single-source precursors. The long-range structural and chemical homogeneities of the 2D SnSe layers are manifested using comprehensive spectroscopic analyses. Furthermore, the capability of the SnSe-based photodetectors for broadband photodetection is distinctly verified. The photoresponsivity and detectivity of the SnSe-based photodetectors are 5.89 A W-1 and 1.8 × 1011 Jones at 532 nm, 1.2 A W-1 and 3.7 × 1010 Jones at 1064 nm, and 0.14 A W-1 and 4.3 × 109 Jones at 1550 nm, respectively. The minimum rise times for the 532 and 1064 nm lasers are 62 and 374 µs, respectively. The photoelectrical analysis of the 5 × 5 SnSe-based photodetector array reveals 100% active devices with 95.06% photocurrent uniformity. We unequivocally validated that the air and thermal stabilities of the photocurrent yielded from the SnSe-based photodetector are determined to be >30 d in air and 160 °C, respectively, which are suitable for optoelectronic applications.

A Wafer-Scale Nanoporous 2D Active Pixel Image Sensor Matrix with High Uniformity, High Sensitivity, and Rapid Switching.

2D transition-metal dichalcogenides (TMDs) have been successfully developed as novel ubiquitous optoelectronics owing to their excellent electrical and optical characteristics. However, active-matrix image sensors based on TMDs have limitations owing to the difficulty of fabricating large-area integrated circuitry and achieving high optical sensitivity. Herein, a large-area uniform, highly sensitive, and robust image sensor matrix with active pixels consisting of nanoporous molybdenum disulfide (MoS2 ) phototransistors and indium-gallium-zinc oxide (IGZO) switching transistors is reported. Large-area uniform 4-inch wafer-scale bilayer MoS2 films are synthesized by radio-frequency (RF) magnetron sputtering and sulfurization processes and patterned to be a nanoporous structure consisting of an array of periodic nanopores on the MoS2 surface via block copolymer lithography. Edge exposure on the nanoporous bilayer MoS2 induces the formation of subgap states, which promotes a photogating effect to obtain an exceptionally high photoresponsivity of 5.2 × 104 A W-1 . A 4-inch-wafer-scale image mapping is successively achieved using this active-matrix image sensor by controlling the device sensing and switching states. The high-performance active-matrix image sensor is state-of-the-art in 2D material-based integrated circuitry and pixel image sensor applications.

Defect-Induced in Situ Atomic Doping in Transition Metal Dichalcogenides via Liquid-Phase Synthesis toward Efficient Electrochemical Activity.

Transition metal dichalcogenides (TMDs), due to their fascinating properties, have emerged as potential next-generation semiconducting nanomaterials across diverse fields of applications. When combined with other material systems, precise control of the intrinsic properties of the TMDs plays a vital role in maximizing their performance. Defect-induced atomic doping through introduction of a chalcogen vacancy into the TMDs lattices is known to be a promising strategy for modulating their characteristic properties. As a result, there is a need to develop tunable and scalable synthesis routes to achieve vacancy-modulated TMDs. Herein, we propose a facile liquid-phase ligand exchange approach for scalable, uniform, and vacancy-tunable synthesis of TMDs films. Varying the relative molar ratio of the chalcogen to transition metal precursors enabled the in situ modulation of the chalcogen vacancy concentrations without necessitating additional post-treatments. When employed as the electrocatalyst in the hydrogen evolution reaction (HER), the vacancy-modulated TMDs, exhibiting a synergetic effect on the energy level matching to the reduction potential of water and optimized free energy differences in the HER pathways, showed a significant enhancement in the hydrogen production via the improved charge transfer kinetics and increased active sites. The proposed approach for synthesizing tunable vacancy-modulated TMDs with wafer-scale synthesis capability is, therefore, promising for better practical applications of TMDs.

Atomic Layer MoS2xTe2(1-x) Ternary Alloys: Two-Dimensional van der Waals Growth, Band gap Engineering, and Electrical Transport.

Ternary alloys in two-dimensional (2D) transition-metal dichalcogenides allow band gap tuning and phase engineering and change the electrical transport type. A process of 2D van der Waals epitaxial growth of molybdenum sulfide telluride alloys (MoS2xTe2(1-x), 0 ≤ x ≤ 1) is presented for synthesizing few-atomic-layer films on SiO2 substrates using metal-organic chemical vapor deposition. Raman spectra, X-ray photoelectron spectra, photoluminescence (PL), and electrical transport properties of few-atomic-layer MoS2xTe2(1-x) (0 ≤ x ≤ 1) films are systematically investigated. The strong PL peaks at 80 K from MoS2xTe2(1-x) (0.45 ≤ x ≤ 0.93) reveal a composition-controllable optical band gap (Eg = 1.55-1.91 eV at 80 K). Electrical transport properties of MoS2xTe2(1-x) alloys, where 0 ≤ x ≤ 0.8 and 0.93 ≤ x ≤ 1, exhibit p-type and n-type semiconducting behaviors, respectively. Remarkably, an increase in the Te composition of a few-atomic-layer MoS2xTe2(1-x) (0 ≤ x ≤ 1) film left-shifts the threshold voltage of a MoS2xTe2(1-x) (0 ≤ x ≤ 1) field-effect transistor. The narrower band gap energies of MoS2xTe2(1-x) films with higher Te content cause a decrease in the on/off current ratios.

Wafer-Scale Synthesis of High-Quality Semiconducting Two-Dimensional Layered InSe with Broadband Photoresponse.

Large-scale synthesis of two-dimensional (2D) materials is one of the significant issues for fabricating layered materials into practical devices. As one of the typical III-VI semiconductors, InSe has attracted much attention due to its outstanding electrical transport property, attractive quantum physics characteristics, and dramatic photoresponse when it is reduced to atomic scale. However, scalable synthesis of single phase 2D InSe has not yet been achieved so far, greatly hindering further fundamental studies and device applications. Here, we demonstrate the direct growth of wafer-scale layered InSe nanosheets by pulsed laser deposition (PLD). The obtained InSe layers exhibit good uniformity, high crystallinity with macro texture feature, and stoichiometric growth by in situ precise control. The characterization of optical properties indicates that PLD grown InSe nanosheets have a wide range tunable band gap (1.26-2.20 eV) among the large-scale 2D crystals. The device demonstration of field-effect transistor shows the n-type channel feature with high mobility of 10 cm2 V-1 s-1. Upon illumination, InSe-based phototransistors show a broad photoresponse to the wavelengths from ultraviolet to near-infrared. The maximum photoresponsivity attains 27 A/W, plus a response time of 0.5 s for the rise and 1.7 s for the decay, demonstrating the strong and fast photodetection ability. Our findings suggest that the PLD grown InSe would be a promising choice for future device applications in the 2D limit.