Here, the GGA+U method with PAW potentials implemented in VASP was utilized for all the structural energy calculations. First, the Hubbard-U parameter was calibrated to describe Fe from 2+ to 4+ (U = 3 was selected, as done previously).4 The charge state of Fe in different LSF phases was then determined by interpreting the DFT-predicted Fe magnetic moment. The oxygen vacancy formation energy as a function of oxygen non-stoichiometry (δ) was then calculated at 0K in vacuum by varying the size of the supercell, with oxygen vacancy interactions being enabled by the periodic boundary conditions. The oxygen vacancy concentration (c) at elevated temperatures at an oxygen partial pressure of 0.21 atm was then determined using a previously developed thermodynamic model.4 Next, the oxygen migration barriers between all the possible oxygen vacancy sites in each material were calculated and compared at 0K. The oxygen vacancy diffusivity (D) at elevated temperature and an oxygen partial pressure of 0.21 atm was then determined by assuming Arrhenius behavior of the diffusion coefficient and a temperature and oxygen partial pressure independent migration energy. Lastly, the ionic conductivity was determined from the oxygen vacancy concentration and the diffusivity by applying Einstein’s relation and the definition of the ionic conductivity.
For all modeled LSF compositions (i.e. cubic SrFeO3, rhombohedral La0.5Sr0.5FeO3, cubic La0.5Sr0.5FeO3, and orthorhombic LaFeO3), the oxygen vacancies remained dilute (i.e. they did not interact) when the oxygen nonstoichiometry (δ) was < 0.1. When δ > 0.1, the oxygen vacancy formation energy was observed to increase for SrFeO3 and La0.5Sr0.5FeO3-δ with increasing δ. However, the oxygen vacancy formation energy in LaFeO3 remained constant for δ = 0 to 0.25.
The calculated oxygen migration barriers for cubic SrFeO3 were 0.58 and 0.62 eV at δ = 0.04 and 0.13, respectively. Due to the presence of multiple oxygen vacancy migration paths in tetragonal and orthorhombic strontium ferrite, the minimum energy path was considered (the migration paths in Figure 1 are designated by different Wyckoff positions traversed by the oxygen atoms). For tetragonal and orthorhombic strontium ferrites the migration barriers were 0.77 and 1.17 eV, respectively. In LaFeO3, the calculated oxygen vacancy migration barrier was 0.88 eV which is comparable to the 0.77 eV observed in oxygen tracer diffusion experiments.5
Additional work aimed at calculating the oxygen vacancy formation energies, migration barriers, and ionic conductivities of other LSF compositions are in progress.
References
1. Hombo et al., J. Solid State Chem., 84, 138 (1990).
2. Maiya et al., Solid State Ion., 99, 1 (1997).
3. Yang et al., Solid State Ion., 249, 123 (2013).
4. Das et al., J Mater Chem A , In Press, http://dx.doi.org/10.1039/C6TA10357J (2017).