Bond Valences and Anharmonicity in Vacancy-Ordered Double Perovskite Halides

Maughan, Annalise E.; Paecklar, Arnold A.; Neilson, James Richmond

doi:10.1039/C8TC03527J

Title: Bond Valences and Anharmonicity in Vacancy-Ordered Double Perovskite Halides

Journal Article · 19 October 2018 · Journal of Materials Chemistry C

DOI: https://doi.org/10.1039/C8TC03527J · OSTI ID:1478240

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Colorado State Univ., Fort Collins, CO (United States). Department of Chemistry

We report that anharmonic lattice dynamics are intimately linked with optical and electronic properties in perovskite halides semiconductors. Vacancy-ordered double perovskites are a subset of the perovskite halide family containing isolated octahedral units. The absence of polyhedral connectivity engenders the vacancy-ordered double perovskites with additional degrees of dynamic freedom, which presents an ideal structural framework to study dynamic-property relationships in perovskite halide semiconductors. In the present study, we examine the structure and bonding origins of anharmonicity in the vacancy-ordered double perovskites Cs₂Sn_1-xTe_xI₆. While X-ray diffraction indicates that all members adopt the cubic vacancy-ordered double perovskite structure, the local coordination environment probed by X-ray pair distribution function (XPDF) analysis reveals asymmetry of the Cs–I/I–I pair correlation that smoothly decreases with increasing tellurium content. Temperature-dependent neutron total scattering suggests that this asymmetry in the PDF occurs due to anharmonic lattice dynamics arising from octahedral tilting and Cs⁺ displacements, as supported by Reverse Monte Carlo simulations of the Cs₂SnI₆ and Cs₂TeI₆ end members. We further correlate the trends in asymmetry and anharmonicity with the bond valence sum of the Cs⁺ ion, and find that the anharmonicity vanishes when the bonding preferences of the Cs⁺ are satisfied by the size of the cuboctahedral void. Lastly, this study presents a simple and effective approach for understanding the origin of anharmonicity in vacancy-ordered double perovskite materials.

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Research Organization:: Colorado State Univ., Fort Collins, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0016083; AC02-06CH11357

OSTI ID:: 1478240

Alternate ID(s):: OSTI ID: 1479127

Journal Information:: Journal of Materials Chemistry C, Vol. 6, Issue 44; ISSN 2050-7526

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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