Molybdenum disulphide is a layered transition metal dichalcogenide that has recently raised considerable interest due to its unique semiconducting and opto-electronic properties. Although several theoretical studies have suggested an electronic phase transition in molybdenum disulphide, there has been a lack of experimental evidence. Here we report comprehensive studies on the pressure-dependent electronic, vibrational, optical and structural properties of multilayered molybdenum disulphide up to 35 GPa. Our experimental results reveal a structural lattice distortion followed by an electronic transition from a semiconducting to metallic state at B19 GPa, which is confirmed by ab initio calculations. The metallization arises from the overlap of the valance and conduction bands owing to sulphur-sulphur interactions as the interlayer spacing reduces. The electronic transition affords modulation of the opto-electronic gain in molybdenum disulphide. This pressuretuned behaviour can enable the development of novel devices with multiple phenomena involving the strong coupling of the mechanical, electrical and optical properties of layered nanomaterials.

Controlling the band gap by tuning the lattice structure through pressure engineering is a relatively new route for tailoring the optoelectronic properties of two-dimensional (2D) materials. Here, we investigate the electronic structure and lattice vibrational dynamics of the distorted monolayer 1T-MoS2 (1T') and the monolayer 2H-MoS2 via a diamond anvil cell (DAC) and density functional theory (DFT) calculations. The direct optical band gap of the monolayer 2H-MoS2 increases by 11.7% from 1.85 to 2.08 eV, which is the highest reported for a 2D transition metal dichalcogenide (TMD) material. DFT calculations reveal a subsequent decrease in the band gap with eventual metallization of the monolayer 2H-MoS2, an overall complex structure-property relation due to the rich band structure of MoS2. Remarkably, the metastable 1T'-MoS2 metallic state remains invariant with pressure, with the J2, A1g, and E2g modes becoming dominant at high pressures. This substantial reversible tunability of the electronic and vibrational properties of the MoS2 family can be extended to other 2D TMDs. These results present an important advance toward controlling the band structure and optoelectronic properties of monolayer MoS2 via pressure, which has vital implications for enhanced device applications.

Tungsten disulfide (WS2) is a layered transition metal dichalcogenide (TMD) that differs from other two-dimensional (2D) compounds such as graphene due to its unique semiconducting, tunable-band-gap nature. Multilayered WS2 exhibits an indirect band gap Eg of ∼1.3 eV, along with a higher load-bearing ability that is promising for strain-tuning device applications, but the electronic properties of multilayered WS2 at higher strain conditions (i.e., static strain >12%) remain an open question. Here we have studied the structural, electronic, electrical, and vibrational properties of multilayered WS2 at hydrostatic pressures up to ∼35 GPa experimentally in a diamond anvil cell and theoretically using first-principles ab initio calculations. Our results show that WS2 undergoes an isostructural semiconductor-to-metallic (S-M) transition at approximately 22 GPa at 280 K, which arises from the overlap of the highest valence and lowest conduction bands. The S-M transition is caused by increased sulfur-sulfur interactions as the interlayer spacing decreases with applied hydrostatic pressure. The metalization in WS2 can be alternatively interpreted as a 2D to 3D (three-dimensional) phase transition that is associated with a substantial modulation of the charge carrier characteristics including a 6-order decrease in resistivity, a 2-order decrease in mobility, and a 4-order increase in carrier concentration. These distinct pressure-tunable characteristics of the dimensionalized WS2 differentiate it from other TMD compounds such as MoS2 and promise future developments in strain-modulated advanced devices.

Due to the drastically different intralayer versus interlayer bonding strengths, the mechanical, thermal, and electrical properties of two-dimensional (2D) materials are highly anisotropic between the in-plane and out-of-plane directions. The structural anisotropy may also play a role in chemical reactions, such as oxidation, reduction, and etching. Here, the composition, structure, and electrical properties of mechanically exfoliated WSe 2 nanosheets on SiO 2 /Si substrates were studied as a function of the extent of thermal oxidation. A major component of the oxidation, as indicated from optical and Raman data, starts from the nano-sheet edges and propagates laterally towards the center. Partial oxidation also occurs in certain areas at the surface of the flakes, which are shown to be highly conductive by microwave impedance microscopy. Using secondary ion mass spectroscopy, we also observed extensive oxidation at the WSe 2 −SiO 2 interface. The combination of multiple microcopy methods can thus provide vital information on the spatial evolution of chemical reactions on 2D materials and the nanoscale electrical properties of the reaction products.Keywords: Tungsten diselenide, 2D materials, thermal oxidation, microwave impedance microscopy, secondary ion mass spectroscopy 2 Layered van der Waals (vdW) materials, in which the electronic properties are inherently anisotropic, have been studied for a relatively long time [1], and have also attracted renewed interest in recent years [1,2]. This family of materials include elemental atomic sheets (e.g.,, and phosphorene [6,7]) and transition metal dichalcogenides [8] (TMDCs, e.g., MoS 2 and WSe 2 ), among others, presenting a wide array of candidates for research and applications. Given the extensive knowledge obtained on the solidstate chemistry of conventional Group IV elemental semiconductors and III-V compounds, and the potential use of vdW materials in nanoelectronics, it is anticipated that much effort will be devoted to investigate the spatial and temporal evolution of various chemical reactions [9], such as solution or vapor-based synthesis, reduction and oxidation, wet and dry etching, in 2D materials. Specifically, the understanding of these processes from atomic to mesoscopic length scales will provide important insight on their performance at the device level.The oxidation process of TMDCs is of particular interest due to its strong influence on the characteristics of devices that are not hermetically sealed and could potentially be oxidized in ambient environments. In addition, the fully oxidized products, e.g., WO 3 , are semiconducting metal oxides with a band gap in the range of 2.5 -3.7 eV, which may find applications in many areas [10][11][12]. To date, the oxidation of TMDCs has been studied at elevated temperatures [13], under intense laser illumination [14], and upon exposure to oxygen plasma [15] or ozone [16]. In contrast to conventional semiconductors such as silicon, the TMDCs show larger oxidative reactivity at the edges and surfac...

Abstract-One-dimensional semiconductor nanostructures (nanowires (NWs), nanotubes, nanopillars, nanorods, etc.) based photodetectors (PDs) have been gaining traction in the research community due to their ease of synthesis and unique optical, mechanical, electrical, and thermal properties. Specifically, the physics and technology of NW PDs offer numerous insights and opportunities for nanoscale optoelectronics, photovoltaics, plasmonics, and emerging negative index metamaterials devices. The successful integration of these NW PDs on CMOS-compatible substrates and various low-cost substrates via direct growth and transfer-printing techniques would further enhance and facilitate the adaptation of this technology module in the semiconductor foundries. In this paper, we review the unique advantages of NW-based PDs, current device integration schemes and practical strategies, recent device demonstrations in lateral and vertical process integration with methods to incorporate NWs in PDs via direct growth (nanoepitaxy) methods and transfer-printing methods, and discuss the numerous technical design challenges. In particular, we present an ultrafast surface-illuminated PD with 11.4-ps full-width at half-maximum (FWHM), edge-illuminated novel waveguide PDs, and some novel concepts of light trapping to provide a full-length discussion on the topics of: 1) low-resistance contact and interfaces for NW integration; 2) high-speed design and impedance matching; and 3) CMOS-compatible massmanufacturable device fabrication. Finally, we offer a brief outlook into the future opportunities of NW PDs for consumer and military application.