Electronic Nature Transition and Magnetism Creation in Vacancy-Defected TiCO MXene under Biaxial Strain: A DFTB + U Study.

The structural, electronic, and magnetic properties of vacancy defect in TiCO MXene and the effect of strain have been investigated using the density functional tight-binding (DFTB) approach including spin-polarization with Hubbard onsite correction (DFTB + U). The band gap of pure TiCO is ∼1.3 eV, which decreases to ∼0.4 and ∼1.1 eV in the case of C- and O-vacancies, respectively, i.e., the semiconducting behavior is retained. In contrast, TiCO undergoes semiconductor-to-metal transition by the introduction of a single Ti-vacancy. This transition is the result of introduced localized states in the vicinity of the Fermi level by the vacancy. Both Ti- and O-vacancies have zero net magnetic moments. Interestingly, the nonmagnetic (NM) ground state of semiconducting TiCO turns into a magnetic semiconductor by introducing a C-vacancy with a magnetization of ∼2 μ/cell. Furthermore, we studied the effect of strain on the electronic structure and magnetic properties of Ti-, C-, and O-vacant TiCO. The nature of the band gap in the presence of single O-vacancy remains indirect in both compression and tensile strain, and the size of the band gap decreases. Compression strain on Ti-vacant TiCO changes metal into a direct semiconductor, and the metallic character remains under tensile biaxial strain. In opposition, a semiconductor-to-metal transition occurs by applying a compressive biaxial strain on C-vacant TiCO. We also find that the magnetism is preserved under tensile strain and suppressed under compression strain on V-TiCO. Moreover, we show that double C-vacancies maintain magnetism. Our findings provide important characteristics for the application of the most frequent MXene material and should motivate further investigations because experimentally achieved MXenes always contain point defects.