2D-EFICACY: Control of Metastable 2D Carbide-Chalcogenide Heterolayers: Strain and Moire Engineering

The experimental isolation of graphene, a single layer of carbon atoms in a two-dimensional (2D) lattice, led to the discovery of an entirely new world of 2D materials in which the 2D nature often leads to emergent behaviors not seen in bulk systems. 2D transition metal dichalcogenides (TMDs) such as molybdenum disulfide (MoS2) exhibit physico-chemical properties that depend on the transition metal, polymorph, thickness, and presence and type of defects. Recently, a group of thin (10-100nm) transition metal carbides (TMCs), such as Mo2C, has been synthesized that exhibit a thickness-dependent superconducting critical temperature (Tc). These thin TMCs are different from MXenes, another class of 2D materials consisting of few layers of nitrides or carbides (The scientific hypothesis of the proposed synergistic computational and experimental research is that orientation and strain control within confined thin metastable TMCs, sandwiched by stable phases of TMCs and layered TMDs, will depend on kinetic and thermodynamic 'knobs' that include fast temperature changes, chalcogen diffusion through preferred crystallographic planes, reaction times, pressure, reactive atmosphere, precursors, and surfactants, which will also tailor properties such as superconductivity, magnetism, ferroelectricity, piezoelectricity, and catalytic performance.To validate the hypothesis, four tasks are proposed: The first task will synthesize ultra-thin TMCs based on Nb, W and Ti. The second task will accomplish the synthesis and basic physico-chemical characterizations of H-TMD/Cs by chalcogenization of the materials synthesized in task one, and by carbonization of TMDs. H-TMD/Cs will also be investigated for their suitability in energy conversion applications such as supercapacitors, Li and multivalent ion batteries, and electrocatalysts. These tasks will be carried out in close conjunction with density functional theory (DFT) calculations with insights into energetics, lattice parameters, stability, phase diagrams, band structures, and density of states of H-TMD/Cs. The third task will characterize and evaluate strain and moiré patterns at the interfaces of different H-TMD/Cs by high-resolution scanning transmission electron microscopy (HR-STEM), scanning tunneling microscopy (STM), and conductive tip atomic force microscopy. Nudged elastic band calculations with DFT will be performed to understand the chalcogen diffusion process, which will provide insights into the interfaces between different phases of TMCs and TMDs. The fourth task aims at quantifying the stability and dynamics of H-TMD/Cs by in-situ TEM and Raman studies under heating, strain, and electrical biasing. Phonon calculations using DFT will provide a basis for interpreting Raman spectra.This coherent framework involving synthesis, characterization, and computation will result in a broad scientific impact for energy-related applications. The ability to develop new H-TMD/Cs could enhance a range of applications that include batteries, catalysts, switches, sensors, quantum computing components and smart coatings.