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Structure and Stability of the Iodide Elpasolite, Cs2AgBiI6

Cite this: Chem. Mater. 2023, 35, 14, 5699–5708
Publication Date (Web):July 12, 2023
https://doi.org/10.1021/acs.chemmater.3c01511
Copyright © 2023 American Chemical Society

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    Abstract

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    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 X-ray diffraction (XRD) and X-ray total scattering measurements on putative Cs2AgBiI6 nanocrystals made via anion exchange from parent Cs2AgBiBr6 nanocrystals. Rietveld refinement of XRD and pair distribution functions (PDF) data shows that these nanocrystals indeed exhibit a tetragonal (Im) elpasolite structure, making them the first example of a structurally characterized iodide elpasolite. 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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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.3c01511.

    • Absorbance of Cs2AgBiBr6 nanocrystals (blue) and anion-exchanged Cs2AgBiI6 nanocrystals (orange) used for X-ray total scattering measurements (Figure S1); X-ray scattering data collected for Cs2AgBiI6 nanocrystals (Figure S2); comparison of Rietveld refinement results using synchrotron X-ray scattering data for Cs2AgBiI6 nanocrystals (Figure S3); example radial distribution function of the residuals from the Rietveld refinements (Figure S4); residuals after last Rietveld refinement for each structure considered here (Table S1); Rietveld refinement results using synchrotron X-ray scattering data (Figures S5 and S6); synchrotron XRD patterns for each sample in a series from Cs2AgBiBr6 to Cs2AgBiI6 plotted in Q-space (Figure S7); real-space fit to the Cs2AgBiI6 PDF data using cubic (Fm3̅m) and tetragonal (Im) structural models, run using pdfgui (Figures S8 and S9); absorption spectra and XRD patterns (Figure S10); TEM images of Cs2AgBiX6 (X = Br, I) nanocrystals exposed to various organic compounds (Figure S11); absorption and XRD data for Cs2AgBiI6 nanocrystals (Figure S12); TEM images of the Cs2AgBiX6 (X = Br, I) nanocrystals from Figure S12 (Figure S13); absorption and XRD data for Cs2AgBiBr6 nanocrystals exposed to various small molecules (Figure S14); TEM images of Cs2AgBiBr6 nanocrystals exposed to select small-molecule additives (Figure S15); water contents of select additives and solvents measured using Karl–Fischer titration (Table S2); gradual anion exchange of a thermally evaporated thin film of Cs2AgBiBr6 using TMSI vapor (Figure S16); SEM EDX mapping of finalpolycrystalline thin film from slow anion-exchange reaction series (Figure S17); XRD patterns of Cs2AgBiI6 nanocrystal film samples heated to various temperatures under nitrogen atmosphere for 30 min (ex situ) (Figure S18); SEM images of Cs2AgBiI6 nanocrystal thin films before and after heating (ex situ) (Figure S19); in situ XRD data for a film of Cs2AgBiI6 nanocrystals heated in air (Figure S20); TEM images of in situ heating experiments on Cs2AgBiI6 nanocrystals (Figure S21); additional TEM images of in situ heating experiments on Cs2AgBiI6 nanocrystals with deliberately broad size distribution, including large branched nanorods (Figure S22); absorption spectra of Cs2AgBiI6 nanocrystals heated in hexanes solution (Figure S23); and TEM EDX data for a representative Cs2AgBiX6 (X = Br, I) elpasolite NC sample prepared from Cs2AgBiBr6 NCs by partial anion exchange using TMSI (Figure S24) (PDF)

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    Cited By

    This article is cited by 2 publications.

    1. Jianning Feng, Qinxuan Cao, Jie Xue, Haipeng Lu. Synthesis of Metastable Silver-Lanthanide Double Perovskite Nanocrystals with White-Light Emission. Inorganic Chemistry 2024, 63 (4) , 2241-2246. https://doi.org/10.1021/acs.inorgchem.3c04203
    2. Greggory T. Kent, Jiale Zhuang, Kaitlin R. Albanese, Arava Zohar, Emily Morgan, Anna Kallistova, Linus Kautzsch, Alexander A. Mikhailovsky, Pratap Vishnoi, Ram Seshadri, Anthony K. Cheetham. Hybrid Iodide Perovskites of Divalent Alkaline Earth and Lanthanide Elements. Journal of the American Chemical Society 2023, 145 (50) , 27850-27856. https://doi.org/10.1021/jacs.3c11494