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Among their numerous technological applications, semi-coherent oxide heterostructures have emerged as promising candidates for applications in intermediate temperature solid oxide fuel cell electrolytes, wherein interfaces influence ionic transport.Since misfit dislocations impact ionic transport in these materials, oxygen vacancy formation and migration at misfit dislocations in oxide heterostructures are central to their performance as an ionic conductor. Herein, we report high-throughput atomistic simulations to predict thousands of activation energy barriers for oxygen vacancy migration at misfit dislocations in SrTiO3/BaZrO3 heterostructures. Dopants display a noticeable effect as higher activation energies are uncovered in their vicinity. Interface layer chemistry has a fundamental influence on the magnitude of activation energy barriers since they are dissimilar at misfit dislocations as compared to coherent terraces. Lower activation energies are uncovered when oxygen vacancies migrate toward misfit dislocations, but higher energies when they hop away, revealing that oxygen vacancies would get trapped at misfit dislocations and impact ionic transport. The results herein offer atomic scale insights into ionic transport at misfit dislocations and fundamental factors governing the ionic conductivity of thin film oxide electrolytes.
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Interface layer chemistry dependent oxygen defect formation in BaZrO 3 (110)/SrTiO 3 (100) heterostructures
Mismatched complex oxide thin films and heterostructures based on perovskites have key applications in technologies such as solid oxide fuel cells, batteries, and solar cells because of emerging properties at the interface. Although lattice mismatch and resulting misfit dislocations are one of the fundamental reasons for the emergence of new properties at the interface, their precise role is not well understood. In light of this, we have used first principles calculations to study BaZrO3(110)/SrTiO3(100) heterostructures for thin film electrolyte applications and predict the interfacial stability as a function of termination layer chemistry. Atomic scale structure and electronic structure of oxygen vacancies at doped interfaces was further studied to comprehend their stability and location preference at the interface. Strong dependence of oxygen vacancy formation on termination layer chemistry is observed. Among the four possible interfaces, oxygen vacancies exhibit a thermodynamic preference to form at the TiO2–ZrO2 interface. Results herein shed light on the fundamental aspects of mismatched perovskite oxide interfaces and their influence on thermodynamic stability of oxygen vacancy defects, which influences ionic transport and is imperative to design next-generation thin film oxide electrolytes.
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- Award ID(s):
- 2042311
- PAR ID:
- 10660615
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Energy Advances
- Volume:
- 5
- Issue:
- 1
- ISSN:
- 2753-1457
- Page Range / eLocation ID:
- 43 to 55
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Mismatched complex oxide thin films and heterostructures have gained significant traction for use as electrolytes in intermediate temperature solid oxide fuel cells, wherein interfaces exhibit variation in ionic conductivity as compared to the bulk. Although misfit dislocations present at interfaces in these structures impact ionic conductivity, the fundamental mechanisms responsible for this effect are not well understood. To this end, a kinetic lattice Monte Carlo (KLMC) model was developed to trace oxygen vacancy diffusion at misfit dislocations in SrTiO3/BaZrO3 heterostructures and elucidate the atomistic mechanisms governing ionic diffusion at oxide interfaces. The KLMC model utilized oxygen vacancy migration energy barriers computed using molecular statics. While some interfaces promote oxygen vacancy diffusion, others impede their transport. Fundamental factors such as interface layer chemistry, misfit dislocation structure, and starting and ending sites of migrating ions play a crucial role in oxygen diffusivity. Molecular dynamics (MD) simulations were further performed to support qualitative trends for oxygen vacancy diffusion. Overall, the agreement between KLMC and MD is quite good, though MD tends to predict slightly higher conductivities, perhaps a reflection of nuanced structural relaxations that are not captured by KLMC. The current framework comprising KLMC modeling integrated with molecular statics offers a powerful tool to perform mechanistic studies focused on ionic transport in thin film oxide electrolytes and facilitate their rational design.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1039/D5YA00220F
