Zhili Hu

Strain-Induced Electronic Structure Changes in Stacked van der Waals Heterostructures.

Vertically stacked van der Waals heterostructures composed of compositionally different two-dimensional atomic layers give rise to interesting properties due to substantial interactions between the layers. However, these interactions can be easily obscured by the twisting of atomic layers or cross-contamination introduced by transfer processes, rendering their experimental demonstration challenging. Here, we explore the electronic structure and its strain dependence of stacked MoSe2/WSe2 heterostructures directly synthesized by chemical vapor deposition, which unambiguously reveal strong electronic coupling between the atomic layers. The direct and indirect band gaps (1.48 and 1.28 eV) of the heterostructures are measured to be lower than the band gaps of individual MoSe2 (1.50 eV) and WSe2 (1.60 eV) layers. Photoluminescence measurements further show that both the direct and indirect band gaps undergo redshifts with applied tensile strain to the heterostructures, with the change of the indirect gap being particularly more sensitive to strain. This demonstration of strain engineering in van der Waals heterostructures opens a new route toward fabricating flexible electronics.

Interface-induced warping in hybrid two-dimensional materials

Two-dimensional hybrid materials consisting of heterogeneous domains have been of great interest. Using empirical molecular dynamical simulation, we show that the morphology of such hybrid 2D materials can extend into the third dimension via strong warping intrinsic to the interfaces between the domains. The interface warping stems from the compressive stress in the domain with a larger lattice constant and even penetrates into the stretched domain. Based on classic plate theory, we analytically quantify the amplitude, wave length and penetration depth of the interface warping as functions of the lattice mismatch, achieving good agreement with the simulations. Moreover, we propose that periodically placing pentagon-heptagon dislocations along the interface can eliminate the warping in the 2D material and such defective interface can be more favorable than the warped one over a critical domain size, which is consistent with recent experimental observations. Our results suggest that the interface warping in 2D hybrid materials should be considered in further exploring their promising properties.

Solid–Vapor Reaction Growth of Transition‐Metal Dichalcogenide Monolayers

Two-dimensional (2D) layered semiconducting transition-metal dichalcogenides (TMDCs) are promising candidates for next-generation ultrathin, flexible, and transparent electronics. Chemical vapor deposition (CVD) is a promising method for their controllable, scalable synthesis but the growth mechanism is poorly understood. Herein, we present systematic studies to understand the CVD growth mechanism of monolayer MoSe2 , showing reaction pathways for growth from solid and vapor precursors. Examination of metastable nanoparticles deposited on the substrate during growth shows intermediate growth stages and conversion of non-stoichiometric nanoparticles into stoichiometric 2D MoSe2 monolayers. The growth steps involve the evaporation and reduction of MoO3 solid precursors to sub-oxides and stepwise reactions with Se vapor to finally form MoSe2 . The experimental results and proposed model were corroborated by ab initio Car-Parrinello molecular dynamics studies.

Phase crossover in transition metal dichalcogenide nanoclusters

We perform comprehensive first-principles analyses on the stability of MX2 nanoclusters. The MX2 (M = Mo, W; X = S) clusters thermodynamically show a high level of phase variability, i.e. varying from the H phase, which is the ground state of two-dimensional MX2, to the T phase with the decreasing cluster size or chemical potential of X. In addition, the lower chemical potential of X endows the clusters with a stronger propensity of shaping in hexagons, instead of commonly observed triangles, consistent with recent experiments. Based on numerical analyses, we further express the energy of different types of clusters in terms of chemical potential and cluster size, and map out a structural phase diagram. These findings call for a revisit of the lattice structures of MX2 clusters and may also rationalize the frequent observation of meta-stable T domains embedded in otherwise perfect H-MX2 monolayers.

Chemically Derived Kirigami of WSe2

Layered metal dichalcogenides have shown intriguing physical phenomena depending on their complex layer stackings and unique architectures. Here, we report novel microscale kirigami structures of multilayered WSe2 formed by a simple chemical vapor deposition and etching method. Scanning electron microscopy and atomic force microscopy reveal the unusual structure features of curved concave edges, panhandles, and sawtooth corners of these intricate multilayer architectures that result from etching. The structure-symmetry relationship and layer stackings of these WSe2 kirigami were elucidated by second-harmonic generation imaging and micro-Raman spectroscopy. We propose an etching model in which the etching behaviors of WSe2 multilayers are governed by the layer stacking of the bottom trilayer, which can successfully explain the formation process of WSe2 kirigami. This chemical etching approach could be applied to other metal dichalcogenide materials and open up new possibilities for creating novel and complex platforms for studying the rich physical properties in two-dimensional materials.