Understanding Instability in Formamidinium Lead Halide Perovskites: Kinetics of Transformative Reactions at Grain and Subgrain Boundaries

Raval, Parth; Kennard, Rhiannon M.; Vasileiadou, Eugenia S.; Dahlman, Clayton J.; Spanopoulos, Ioannis; Chabinyc, Michael L.; Kanatzidis, Mercouri; Manjunatha Reddy, G. N.

doi:10.1021/acsenergylett.2c00140

Understanding Instability in Formamidinium Lead Halide Perovskites: Kinetics of Transformative Reactions at Grain and Subgrain Boundaries

Journal Article · Tue Mar 29 00:00:00 EDT 2022 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.2c00140· OSTI ID:1870315

Raval, Parth ^[1]; ^[2]; ^[3]; ^[2]; ^[3]; ^[2]; ^[3]; ^[4]

Univ. Lille (France); Northwestern University
Univ. of California, Santa Barbara, CA (United States)
Northwestern Univ., Evanston, IL (United States)
Univ. Lille (France); Northwestern Univ., Evanston, IL (United States)

Transformative and reconstructive reactions impart significant structural changes at particle boundaries of hybrid perovskites, which influence environmental stability and optoelectronic properties of these materials. Here, we investigate the moisture-induced transformative reactions in formamidinium based perovskites FAPbX₃ (X=I, Br) and show that the ambient stability of these materials can be adjusted from a few hours to several months. For FAPbI₃, roles of water vapor, particle size, and light illumination on the kinetic pathways of the cubic (a) transformation to the hexagonal (d) phase are analyzed by X-ray diffraction, optical microscopy, photoluminescence and solid-state NMR spectroscopy techniques. The grain and sub-grain boundaries exhibit different α→δ-FAPbI₃ phase transformation kinetics. Our study suggests that the dynamic transformation involves the local water-induced dissolution of the cubic phase occurring at the crystal surfaces followed by precipitation of the hexagonal phase. Insights into structures and dynamics of a kinetically trapped α-|δ-FAPbI₃ are obtained by ¹H, ²H, and ²⁰⁷Pb ssNMR spectroscopy.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Santa Barbara, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012541

OSTI ID:: 1870315

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 4 Vol. 7; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Understanding Instability in Formamidinium Lead Halide Perovskites: Kinetics of Transformative Reactions at Grain and Subgrain Boundaries

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