Off-Centered Pb Interstitials in PbTe

Previous calculations have demonstrated that Te vacancies are energetically the major defects in PbTe. However, the Pb interstitials are also important because experiments have shown that the volume of Pb-rich PbTe increases at a higher Pb content. In this study, density functional theory calculations were used to investigate the defect properties of low-symmetry Pb interstitials in PbTe. By breaking the higher symmetry imposed on the on-centered interstitial defects, the lowest ground state of Pb interstitial defects is off-centered along the [Formula: see text] direction. Because of the four multi-stable structures with low defect-formation energies, the defect density of Pb interstitials is expected to be approximately six times higher than previous predictions for PbTe synthesized at 900 K. In contrast to the on-centered Pb interstitials, the off-centered Pb interstitials in PbTe can exhibit long-range lattice relaxation in the [Formula: see text] direction beyond a distance of 1 nm, indicating the potential formation of weak local dipoles. This result provides an alternative explanation for the emphanitic anharmonicity of PbTe in the high-temperature regime.