We investigate Second Harmonic Generation (SHG) in monolayer WS2 both deposited on a SiO2/Si substrate or suspended using transmission electron microscopy grids. We find unusually large second order nonlinear susceptibility, with an estimated value of deff ~ 4.5 nm/V nearly three orders of magnitude larger than other common nonlinear crystals. In order to quantitatively characterize the nonlinear susceptibility of two-dimensional (2D) materials, we have developed a formalism to model SHG based on the Green's function with a 2D nonlinear sheet source. In addition, polarized SHG is demonstrated as a useful method to probe the structural symmetry and crystal orientation of 2D materials. To understand the large second order nonlinear susceptibility of monolayer WS2, density functional theory based calculation is performed. Our analysis suggests the origin of the large nonlinear susceptibility in resonance enhancement and a large joint density of states, and yields an estimate of the nonlinear susceptibility value deff = 0.77 nm/V for monolayer WS2, which shows good order-of-magnitude agreement with the experimental result.

Bound exciton is a signature of sulfur vacancies, and thus, it can be used to investigate defects in atomically thin materials.

Atomically thin two-dimensional (2D) metals may be key ingredients in next-generation quantum and optoelectronic devices. However, 2D metals must be stabilized against environmental degradation and integrated into heterostructure devices at the wafer scale. The high-energy interface between silicon carbide and epitaxial graphene provides an intriguing framework for stabilizing a diverse range of 2D metals. Here we demonstrate large-area, environmentally stable, epitaxial graphene/single-crystal 2D gallium, indium, and tin heterostructures. The 2D metals are covalently bonded to SiC below but present a non-bonded interface to graphene overlayer, i.e. they are "half van der Waals" metals with strong internal gradients in bonding character. These non-centrosymmetric 2D metals open compelling opportunities for superconducting devices, topological phenomena, and advanced optoelectronic properties. For example, the reported 2D-Ga is a superconductor that combines six strongly coupled Ga-derived electron pockets with a large nearly-freeelectron Fermi surface that closely approaches the Dirac points of the graphene overlayer.Major advances in fundamental science have followed from the exfoliation, stacking, and encapsulation of atomically thin 2D layers 1 . The next step towards technological impact of 2D layers and heterostructures is to transition sophisticated "pick and place" devices to a wafer-scale platform. However, the sensitivity of 2D systems to interfacial reactions and environmental influences -especially for two-dimensional metals or small-gap semiconductors -poses challenges for large-scale integration. Very few metals resist degradation of their top few atomic layers upon environmental exposure, and for a 2D metal, these layers constitute the entire system. A general platform for producing environmentally stable and wafer-scale 2D metals that are not prone to interfacial interactions would represent a significant advance. Inspired by the success of wide-bandgap 2D gallium nitride 2 , we turn focus onto the metal alone and demonstrate a platform dubbed confinement heteroepitaxy (CHet), where the interface between epitaxial graphene (EG) and silicon carbide (SiC) stabilizes crystalline 2D forms of Group-III (Ga, In) and group-IV (Sn) elements. Defect engineering of the graphene overlayer enables uniform, large-area intercalation at the high-energy SiC/EG interface; this interface then templates intercalant crystallization at a thermodynamically defined number of atomic layers. The unreactive nature of as-grown EG on SiC (graphene plus buffer layer) performs multiple services: (1) it only partially passivates the SiC surface underneath, thereby sustaining the high-energy interface that drives intercalation; (2) it lowers the energy of the (otherwise exposed) upper surface of the metal, thus facilitating 2D morphologies; (3) it protects the newly formed 2D metal from environmental degradation after intercalation through in situ healing of the graphene defects. Stability of these 2D metals in air over months gr...

Double-resonance Raman scattering is a sensitive probe to study the electron-phonon scattering pathways in crystals. For semiconducting two-dimensional transition-metal dichalcogenides, the double-resonance Raman process involves different valleys and phonons in the Brillouin zone, and it has not yet been fully understood. Here we present a multiple energy excitation Raman study in conjunction with density functional theory calculations that unveil the double-resonance Raman scattering process in monolayer and bulk MoS2. Results show that the frequency of some Raman features shifts when changing the excitation energy, and first-principle simulations confirm that such bands arise from distinct acoustic phonons, connecting different valley states. The double-resonance Raman process is affected by the indirect-to-direct bandgap transition, and a comparison of results in monolayer and bulk allows the assignment of each Raman feature near the M or K points of the Brillouin zone. Our work highlights the underlying physics of intervalley scattering of electrons by acoustic phonons, which is essential for valley depolarization in MoS2.

Two-dimensional layers of molybdenum disulfide, MoS, have been recognized as promising materials for nanoelectronics due to their exceptional electronic and optical properties. Here we develop a new ReaxFF reactive potential that can accurately describe the thermodynamic and structural properties of MoS sheets, guided by extensive density functional theory simulations. This potential is then applied to the formation energies of five different types of vacancies, various vacancy migration barriers, and the transition barrier between the semiconducting 2H and metallic 1T phases. The energetics of ripplocations, a recently observed defect in van der Waals layers, is examined, and the interplay between these defects and sulfur vacancies is studied. As strain engineering of MoS sheets is an effective way to manipulate the sheets' electronic and optical properties, the new ReaxFF description can provide valuable insights into morphological changes that occur under various loading conditions and defect distributions, thus allowing one to tailor the electronic properties of these 2D crystals.