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Abstract Entropy‐stabilized oxide (ESO) research has primarily focused on discovering unprecedented structures, chemistries, and properties in the single‐phase state. However, few studies discuss the impacts of entropy stabilization and secondary phases on functionality and in particular, electrical conductivity. To address this gap, electrical transport mechanisms in the canonical ESO rocksalt (Co,Cu,Mg,Ni,Zn)O are assessed as a function of secondary phase content. When single‐phase, the oxide conducts electrons via Cu+/Cu2+small polarons. After 2 h of heat treatment, Cu‐rich tenorite secondary phases form at some grain boundaries (GBs), enhancing grain interior electronic conductivity by tuning defect chemistry toward higher Cu+carrier concentrations. 24 h of heat treatment yields Cu‐rich tenorite at all GBs, followed by the formation of anisotropic Cu‐rich tenorite and equiaxed Co‐rich spinel secondary phases in grains, further enhancing grain interior electronic conductivity but slowing electronic transport across the tenorite‐rich GBs. Across all samples, the total electrical conductivity increases (and decreases reversibly) by four orders of magnitude with heat‐treatment‐induced phase transformation by tuning the grains’ defect chemistry toward higher carrier concentration and lower migration activation energy. This work demonstrates the potential to selectively grow secondary phases in ESO grains and at GBs, thereby tuning the electrical properties using microstructure design, nanoscale engineering, and heat treatment, paving the way to develop many novel materials.
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Nucleation and growth behavior of multicomponent secondary phases in entropy-stabilized oxides
Abstract The rocksalt structured (Co,Cu,Mg,Ni,Zn)O entropy-stabilized oxide (ESO) exhibits a reversible phase transformation that leads to the formation of Cu-rich tenorite and Co-rich spinel secondary phases. Using atom probe tomography, kinetic analysis, and thermodynamic modeling, we uncover the nucleation and growth mechanisms governing the formation of these two secondary phases. We find that these phases do not nucleate directly, but rather they first form Cu-rich and Co-rich precursor phases, which nucleate in regions rich in Cu and cation vacancies, respectively. These precursor phases then grow through cation diffusion and exhibit a rocksalt-like crystal structure. The Cu-rich precursor phase subsequently transforms into the Cu-rich tenorite phase through a structural distortion-based transformation, while the Co-rich precursor phase transforms into the Co-rich spinel phase through a defect-mediated transformation. Further growth of the secondary phases is controlled by cation diffusion within the primary rocksalt phase, whose diffusion behavior resembles other common rocksalt oxides. Graphical abstract
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- Award ID(s):
- 2011967
- PAR ID:
- 10377036
- Publisher / Repository:
- Cambridge University Press (CUP)
- Date Published:
- Journal Name:
- Journal of Materials Research
- Volume:
- 38
- Issue:
- 1
- ISSN:
- 0884-2914
- Page Range / eLocation ID:
- p. 198-214
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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