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Compositionally complex oxides (CCOs) are an emerging class of materials encompassing high entropy and entropy stabilized oxides. These promising advanced materials leverage tunable chemical bond structure, lattice distortion, and chemical disorder for unprecedented properties. Grain boundary (GB) and point defect segregation to GBs are relatively understudied in CCOs even though they can govern macroscopic material properties. For example, GB segregation can govern local chemical (dis)order and point defect distribution, playing a critical role in electrochemical reaction kinetics, and charge and mass transport in solid electrolytes. However, compared with conventional oxides, GBs in multi-cation CCO systems are expected to exhibit more complex segregation phenomena and, thus, prove more difficult to tune through GB design strategies. Here, GB segregation was studied in a model perovskite CCO LaFe0.7Ni0.1Co0.1Cu0.05Pd0.05O3−x textured thin film by (sub-)atomic-resolution scanning transmission electron microscopy imaging and spectroscopy. It is found that GB segregation is correlated with cation reducibility—predicted by an Ellingham diagram—as Pd and Cu segregate to GBs rich in oxygen vacancies (VO··). Furthermore, Pd and Cu segregation is highly sensitive to the concentration and spatial distribution of VO·· along the GB plane, as well as fluctuations in atomic structure and elastic strain induced by GB local disorder, such as dislocations. This work offers a perspective of controlling segregation concentration of CCO cations to GBs by tuning reducibility of CCO cations and oxygen deficiency, which is expected to guide GB design in CCOs.
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The hidden structure dependence of the chemical life of dislocations
Dislocations are one-dimensional defects in crystals, enabling their deformation, mechanical response, and transport properties. Less well known is their influence on material chemistry. The severe lattice distortion at these defects drives solute segregation to them, resulting in strong, localized spatial variations in chemistry that determine microstructure and material behavior. Recent advances in atomic-scale characterization methods have made it possible to quantitatively resolve defect types and segregation chemistry. As shown here for a Pt-Au model alloy, we observe a wide range of defect-specific solute (Au) decoration patterns of much greater variety and complexity than expected from the Cottrell cloud picture. The solute decoration of the dislocations can be up to half an order of magnitude higher than expected from classical theory, and the differences are determined by their structure, mutual alignment, and distortion field. This opens up pathways to use dislocations for the compositional and structural nanoscale design of advanced materials.
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- Award ID(s):
- 1709803
- PAR ID:
- 10276436
- Date Published:
- Journal Name:
- Science Advances
- Volume:
- 7
- Issue:
- 16
- ISSN:
- 2375-2548
- Page Range / eLocation ID:
- eabf0563
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1126/sciadv.abf0563
