Dislocations in SrTiO3: Easy To Reduce but Not so Fast for Oxygen Transport

D Marrocchelli and LX Sun and B Yildiz, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 137, 4735-4748 (2015).

DOI: 10.1021/ja513176u

The effect of dislocations on the chemical, electrical and transport properties in oxide materials is important for electrochemical devices, such as fuel cells and resistive switches, but these effects have remained largely unexplored at the atomic level. In this work, by using large-scale atomistic simulations, we uncover how a < 100 >011 edge dislocation in SrTiO3, a prototypical perovskite oxide, impacts the local defect chemistry and oxide ion transport. We find that, in the dilute limit, oxygen vacancy formation energy in SrTiO3 is lower at sites close to the dislocation core, by as much as 2 eV compared to that in the bulk. We show that the formation of a space-charge zone based on the redistribution of charged oxygen vacancies can be captured quantitatively at atomistic level by mapping the vacancy formation energies around the dislocation. Oxide-ion diffusion was studied for a low vacancy concentration regime (ppm level) and a high vacancy concentration regime (up to 2.5%). In both cases, no evidence of pipe- diffusion, i.e., significantly enhanced mobility of oxide ions, was found as determined from the calculated migration barriers, contrary to the case in metals. However, in the low vacancy concentration regime, the vacancy accumulation at the dislocation core gives rise to a higher diffusion coefficient, even though the oxide-ion mobility itself is lower than that in the bulk. Our findings have important implications for applications of perovskite oxides for information and energy technologies. The observed lower oxygen vacancy formation energy at the dislocation core provides a quantitative and direct explanation for the electronic conductivity of dislocations in SrTiO3 and related oxides studied for red-ox based resistive switching. Reducibility and electronic transport at dislocations can also be quantitatively engineered into active materials for fuel cells, catalysis, and electronics.

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