Torsional deformation modulation of the electronic structure and optical properties of molybdenum ditelluride systems doped with halogen atoms X (X = F, Cl, Br, I): a first-principles study.

Context: Using a first-principles plane-wave pseudopotential technique within the context of density-functional theory, the electronic structure and optical properties of the molybdenum ditelluride system doped with halogen atoms X (X = F, Cl, Br, I) were investigated. The electronic structure, density of states, charge transfer, and optical properties of halogen atom X doped on MoTe monolayer are systematically calculated and analyzed. It shows that the Fermi energy level is shifted upward after doping with halogen atoms. With F-MoTe doping, the geometrical distortion is the most pronounced, the charge transfer number is the highest, and the semiconductor shifts from a direct band gap to an indirect band gap. When the torsional deformation is between 1° and 5°, the F-doped MoTe system stays an indirect band gap semiconductor and transitions to quasi-metal at 6°. It is shown that the torsional deformation can modulate the electronic properties of the doped structure and realize the semiconductor-metal transition.

Optical Properties: The F-doped system has a strong absorption peak reflection peak after torsion, and with the increase of torsion angle, the absorption peak is red-shifted, and the reflection peak is blue-shifted. Moreover, the absorption and reflection peaks start to decrease with the rise of the torsion angle.

Methods: We apply the generalized gradient approximation plane-wave pseudopotential technique based on Perdew-Burke-Ernzerhof (PBE) generalized functions, under the first principles of the density-functional theory framework. The overall optimization of the intrinsic molybdenum ditelluride structure and the halogen atom X-doped molybdenum ditelluride structure was carried out. Then, the F-doped molybdenum ditelluride system was selected for torsional deformation with torsion angles from 1° to 6° for computational analysis.

Specific Method: To make the presentation more accessible, the atoms in the F-doped molybdenum ditelluride system were colored differently. The pink chain edge atoms were first reversed by θ°. Then, the blue chain edge atoms were reversed by θ° in the other direction. The middle row of atoms was adjusted accordingly to the different twisting angles of the two sides by doing the corresponding torsion with the torsion angle θ°/2 and fixing the individual atoms. The calculation employs the Monkhorst-Pack particular K-point sampling method. The 3 × 3 × 1 inverted-space K-point grid is utilized for material structure optimization calculations in each model, and the 9 × 9 × 1 K-point grid is used for material electronic structure calculations. A 15 Å vacuum layer is put on the crystal surface of vertical monolayer molybdenum ditelluride supercells to avoid interactions with adjoining cells.