Critical Role of Surface Termination of Sapphire Substrates in Crystallographic Epitaxial Growth of MoS2 Using Inorganic Molecular Precursors.

A highly reproducible route for the epitaxial growth of single-crystalline monolayer MoS2 on a C-plane sapphire substrate was developed using vapor-pressure-controllable inorganic molecular precursors MoOCl4 and H2S. Microscopic, crystallographic, and spectroscopic analyses indicated that the epitaxial MoS2 film possessed outstanding electrical and optical properties, excellent homogeneity, and orientation selectivity. The systematic investigation of the effect of growth temperature on the crystallographic orientations of MoS2 revealed that the surface termination of the sapphire substrate with respect to the growth temperature determines the crystallographic orientation selectivity of MoS2. Our results suggest that controlling the surface to form a half-Al-terminated surface is a prerequisite for the epitaxial growth of MoS2 on a C-plane sapphire substrate. The insights on the growth mechanism, especially the significance of substrate surface termination, obtained through this study will aid in designing efficient epitaxial growth routes for developing single-crystalline monolayer transition metal dichalcogenides.

Growth of Monolayer and Multilayer MoS2 Films by Selection of Growth Mode: Two Pathways via Chemisorption and Physisorption of an Inorganic Molecular Precursor.

We report facile growth methods for high-quality monolayer and multilayer MoS2 films using MoOCl4 as the vapor-phase molecular Mo precursor. Compared to the conventional covalent solid-type Mo precursors, the growth pressure of MoOCl4 can be precisely controlled. This enables the selection of growth mode by adjusting growth pressure, which facilitates the control of the growth behavior as the growth termination at a monolayer or as the continuous growth to a multilayer. In addition, the use of carbon-free precursors eliminates concerns about carbon contamination in the produced MoS2 films. Systematic studies for unveiling the growth mechanism proved two growth modes, which are predominantly the physisorption and chemisorption of MoOCl4. Consequently, the thickness of MoS2 can be controlled by our method as the application demands.

Tunable Optical Transition in 2H-MoS2 via Direct Electrochemical Engineering of Vacancy Defects and Surface S-C Bonds.

Although surface engineering has been regarded to be a great approach to modulate the optical and electrical properties of nanomaterials, the spontaneous covalent functionalization on semiconducting 2H-MoS2 is a notoriously difficult process, while several reactions have been performed on metallic 1T-MoS2. This limitation in functionalization is attributed to the difficulty of electron transfer from 2H-TMD to the reacting molecules due to its semiconducting property and neutral charge state. Unfortunately, this is an all too important prerequisite step toward creating chemically reactive radical species for surface functionalization reactions. Herein, an electrochemical approach was developed for facilitating direct surface functionalization of 2H-MoS2 with 4-bromobenzene diazonium tetraborate (4-BBDT). Successful functionalization was characterized using various microscopic and spectroscopic analyses. During the course of investigating the change of optical transition seen for modified 2H-MoS2 using photoluminescence measurement combined with theoretical calculations, our study uncovered that the controlling S-C bond and sulfur vacancy generation could tune the electronic structure of functionalized 2H-MoS2.