Thermal stability of nonmagnetic Cd and In impurities in Fe3O4

Abstract

Magnetite (Fe3O4) was doped with radioactive 111mCd and 111In ions as impurities, and their residence sites and thermal stability were investigated by means of time-differential perturbed angular correlation (TDPAC) spectroscopy. Well-defined TDPAC spectra unequivocally show their sites: Cd ions are stably located only in the tetrahedral A site in all the temperature range of the present observation (77 K–873 K); In ions also specifically occupy the A site at low temperature, but at high temperature part of them select the B site in a reversible fashion. The energy difference between the A and B sites for the accommodation of In was experimentally determined to be 0.119 (9) eV by assuming a Boltzmann distribution for the populations of the 111In probe in the respective sites. The element-dependent thermal stabilities observed for Cd and In were well corroborated by density functional theory calculations. The successful observation of thermally activated site-to-site displacement of impurity In ions in Fe3O4 is reported.