Structure and Stability of the Iodide Elpasolite, Cs2AgBiI6

Kluherz, Kyle T.; Mergelsberg, Sebastian T.; De Yoreo, James J.; Gamelin, Daniel R.

doi:10.1021/acs.chemmater.3c01511

Title: Structure and Stability of the Iodide Elpasolite, Cs₂AgBiI₆

Journal Article · Wed Jul 12 00:00:00 EDT 2023 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.3c01511· OSTI ID:2222691

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University of Washington, Seattle, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Iodide elpasolites (or double perovskites, A₂B'B"I₆, B' = M⁺, B" = M³⁺) are predicted to be promising alternatives to lead-based perovskite semiconductors for photovoltaic and optoelectronic applications, but no iodide elpasolite has ever been definitively prepared or structurally characterized. Iodide elpasolites are widely predicted to be unstable due to favorable decomposition to the competing A₃B₂I₉ (B = M³⁺) phase. Here, we report the results of synchrotron XRD and X-ray total scattering measurements on putative Cs₂AgBiI₆ nanocrystals made via anion exchange from parent Cs₂AgBiBr₆ nanocrystals. Rietveld refinement of XRD and PDF data shows that these nanocrystals indeed exhibit a tetragonal ($$I$$$\overline{4}$$$$m$) elpasolite structure, making them the first example of a structurally characterized iodide elpasolite. In conclusion, a series of experiments probing structural relaxation and the effects of surface ligation or grain size all point to the critical role of surface free energy in stabilizing the iodide elpasolite phase in these nanocrystals.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: AC05-76RL01830; AC02-06CH11357; FWP 56674; DMR-1719797; NNCI-2025489; NNCI-1542101

OSTI ID:: 2222691

Report Number(s):: PNNL-SA-182221

Journal Information:: Chemistry of Materials, Vol. 35, Issue 14; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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