Two cations A and B in A2BO4 spinels appear in precise 2:1 Daltonian ratio ("line compounds") only at very low temperature. More typically, at finite temperature, they tend to become either A rich or B rich. Here we survey the experimentally observed stoichiometry asymmetries and describe the first-principles framework for calculating these. Defect calculations based on first principles are used to calculate the enthalpies of substitution of A atom ΔH(ATd) and B atom ΔH(BOh) and determine their site occupancies leading to (non)-stoichiometry. In Co2ZnO4, the result of the calculation for site occupancy compares well with that measured via anomalous x-ray diffraction. Further, the calculated phase boundary also compares well with that measured via Rietveld refinement of x-ray diffraction data on bulk ceramic sintered samples of Co2ZnO4 and Rh 2ZnO4. These results show that Co2ZnO 4 is heavily Co nonstoichiometric above 500C, whereas Rh 2ZnO4 is slightly Zn nonstoichiometric. We found that, in general, the calculated ΔH(ATd) is smaller than ΔH(BOh), if the A-rich competing phase is isostructural with the A2BO4 host, for example, A2AO4, whereas B-rich competing phase is not, for example, BO. This observation is used to qualitatively explain nonstoichiometry and solid solutions observed in other spinels.
|ジャーナル||Physical Review B - Condensed Matter and Materials Physics|
|出版ステータス||出版済み - 8月 22 2011|
!!!All Science Journal Classification (ASJC) codes