Defect Properties, Anion Ordering, and Photochromic Mechanism in Yttrium Oxyhydride

Rowberg, Andrew J. E.; Van de Walle, Chris G.

doi:10.1021/acs.jpcc.4c04988

Title: Defect Properties, Anion Ordering, and Photochromic Mechanism in Yttrium Oxyhydride

Journal Article · 16 November 2024 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.4c04988 · OSTI ID:2481167

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University of California, Santa Barbara, CA (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
University of California, Santa Barbara, CA (United States)

Yttrium oxyhydride (YHO) undergoes a reversible photochromic transition when exposed to ultraviolet light. However, the mechanism for this transformation is not fully understood, and the structure and precise chemical composition of YHO remain under debate. Here, we use first-principles density functional theory calculations with a hybrid functional to study the structure, chemical stability, and point defect properties of YHO. As experiments have shown, we find that YHO prefers a cubic structure, with H and O anions present in equal concentrations and located on tetrahedral sites. Stoichiometric and ordered YHO is chemically stable, but it has a wide band gap of 5.01 eV, considerably larger than that measured in experiments (2.4–3.8 eV). On the other hand, Y4H10O has a smaller band gap of 2.97 eV and also has a region of chemical stability; thus, the actual material may include some fraction of this H-rich structure. The defect chemistry of YHO is dominated by anionic antisite species (H_O and O_H), with hydrogen interstitials (H_i) and vacancies (V_H) also present in reasonably high concentrations. We show that antisite disorder lowers the band gap relative to the perfectly ordered structure, bringing the magnitude of the gap into closer agreement with experiment. Based on our calculations of defect migration and the positions of defect states relative to the band edges, we link the onset of photochromic behavior to the reaction H_O^– → V_O⁰ + H_i^–, which follows photoexcitation of a H_O⁺ defect. H_i^– can subsequently migrate away and be trapped by additional H_O⁺ defects, contributing to the persistence of the reaction, while the resultant oxygen vacancy, V_O⁰, introduces an occupied defect state that leads to optical absorption at visible wavelengths. Our results can explain reported discrepancies between experimental and computational results for YHO, and they allow us to propose specific atomic-scale processes that can lead to photochromism. In conclusion, understanding these mechanisms is key for unlocking YHO’s application in devices ranging from smart windows and optoelectronics to electrochemical synapses for neural networks.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 2481167

Report Number(s):: LLNL--JRNL-866506; 1101283

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 47 Vol. 128; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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