Transformation of electronic properties and structural phase transition from HfN to Hf3N4

We report investigation of the structural phase transition and electronic properties of Hf1−x N (0 ⩽ x ⩽ 0.25) using first principles calculations. The defective NaCl-type structure with Hf vacancies (VHf) is found to be stable over a large phase region. Hf3N4 with the Zr3N4-type structure is only stable in relative small region and readily destabilized when the stoichiometric ratio of N to Hf deviates from 4/3. The electronic and optic properties of Hf1−x N are controlled by the concentration of VHf. The full depletion of excess free electrons from Hf atoms results in the structural phase transition of Hf3N4.

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