The critical role of synthesis conditions on small polaron carrier concentrations in hematite—A first-principles study

Smart, Tyler J.; Chen, Mingpeng; Grieder, Andrew C.; Urena Baltazar, Valentin; Bridges, Frank; Li, Yat; Ping, Yuan

doi:10.1063/5.0074698

Title: The critical role of synthesis conditions on small polaron carrier concentrations in hematite—A first-principles study

Journal Article · 27 December 2021 · Journal of Applied Physics

DOI: https://doi.org/10.1063/5.0074698 · OSTI ID:1889534

Smart, Tyler J. ^[1];

^[2];

^[2]; Urena Baltazar, Valentin ^[2]; Bridges, Frank ^[2]; Li, Yat ^[2];

^[2]

Univ. of California, Santa Cruz, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of California, Santa Cruz, CA (United States)

Achieving highly efficient energy conversion with transition metal oxides necessitates overcoming conductivity limitations due to the formation of small polarons. Detailed understanding of the interplay among intrinsic defects, dopants, and electron polarons can help devise strategies for achieving higher carrier concentrations, therefore improving carrier conductivity. This work employs first-principles calculations to reliably predict electron polaron concentrations in a prominent polaronic oxide, hematite (Fe₂O₃), by resolving interactions between charged defects and electron polarons and keeping charge neutrality condition among all charged species. This work addresses that both V_O and Fe_i can be primary donors in undoped hematite depending on the synthesis conditions, such as synthesis temperature and oxygen partial pressure, despite the fact that V_O owns an extremely high ionization energy compared to k_BT. Furthermore, from calculations of a plethora of n-type dopants (group IV and V elements), we find that Ti, Ge, Sb, and Nb are able to raise electron polaron concentrations in hematite significantly without considering dopant clustering. However, the magnitude of electron polaron concentration increase would be smaller if the dopant has a high tendency of clustering, such as Ti. Here we reveal the critical role of synthesis conditions on tuning electron polaron concentrations of both undoped and doped hematite. Our theoretical analysis provides important insights and general design principles for engineering more conductive polaronic oxides.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC52-07NA27344; SC0012704; AC02-05CH11231

OSTI ID:: 1889534

Report Number(s):: LLNL-JRNL-840237; 1061416

Journal Information:: Journal of Applied Physics, Journal Name: Journal of Applied Physics Journal Issue: 24 Vol. 130; ISSN 0021-8979

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
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Title: The critical role of synthesis conditions on small polaron carrier concentrations in hematite—A first-principles study

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