AbstractComputer simulation techniques have been used to investigate defect formation and the diffusion of Ca and Mg in diopside. It was found that isolated, non-interacting CaO and MgO Schottky defects had the lowest formation energies (3.66 and 3.97 eV respectively); oxygen Frenkel defects are the most favourable oxygen defects (formation energies 3.93 eV). Magnesium and calcium self-diffusion in the c-direction of diopside is easiest by a vacancy mechanism involving either direct jumps along the c-direction, or double jumps in the b-c plane. In the extrinsic regime, diffusion activation energies for Mg are predicted to be 9.82 eV (direct route) and 1.97 eV (double jump route); for Ca diffusion, activation energies are predicted to be 6.62 eV (direct route) and 5.63 eV (double jump route). If additional vacancies (oxygen or magnesium) are present in the vicinity of the diffusion path, Ca migration energies fall to 1.97–2.59 eV. At elevated temperatures in the intrinsic regime, diffusion activation energies of ⩾ 5.95 eV are predicted for Mg self-diffusion and 9.29–10.28 eV for Ca self-diffusion. The values for Ca diffusion are comparable with published experimental data. It is inferred that a divacancy mechanism may operate in diopside crystals.
Chemical instability leads to unusual chemical-potential-independent defect formation and diffusion in perovskite solar cell material CH3NH3PbI3
