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

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

doi:10.1021/acsenergylett.2c00140

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

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

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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Abstract

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(FA)-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 (α) transformation to the hexagonal (δ) phase are analyzed by X-ray diffraction, optical microscopy, photoluminescence, and solid-state (ss) NMR spectroscopy techniques. The grain and subgrain boundaries exhibit different α- → δ-FAPbI₃phase 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-FAPbI₃are obtained by ¹H, ²H, and ²⁰⁷Pb ssNMR spectroscopy.

Original language	English (US)
Pages (from-to)	1534-1543
Number of pages	10
Journal	ACS Energy Letters
Volume	7
Issue number	4
DOIs	https://doi.org/10.1021/acsenergylett.2c00140
State	Published - Apr 8 2022

Funding

At Northwestern University and UCSB, this work is mainly supported by the Department of Energy, Office of Science, Basic Energy Sciences, under Grant No. SC0012541 (synthesis, structure, and characterization of physical properties). The research reported here also made use the shared facilities of the UCSB MRSEC (National Science Foundation DMR 1720256), a member of the Materials Research Facilities Network ( www.mrfn.org ). R.M.K. gratefully acknowledges the National Defense Science and Engineering Graduate fellowship for financial support. G.N.M.R. and P.R. acknowledge the funding from University of Lille and region Hauts-de-France (HDF). G.N.M.R. acknowledges the funding from I-SITE ULNE International Mobility Grant and EU-H2020 research and innovation programme under the Marie Skłodowska-Curie Grant 795091.

ASJC Scopus subject areas

Chemistry (miscellaneous)
Renewable Energy, Sustainability and the Environment
Fuel Technology
Energy Engineering and Power Technology
Materials Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1021/acsenergylett.2c00140

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@article{dce0f65ce06c4faca428db36adea3475,

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

abstract = "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(FA)-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 (α) transformation to the hexagonal (δ) phase are analyzed by X-ray diffraction, optical microscopy, photoluminescence, and solid-state (ss) NMR spectroscopy techniques. The grain and subgrain boundaries exhibit different α- → δ-FAPbI3phase 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-FAPbI3are obtained by 1H, 2H, and 207Pb ssNMR spectroscopy.",

author = "Parth Raval and Kennard, {Rhiannon M.} and Vasileiadou, {Eugenia S.} and Dahlman, {Clayton J.} and Ioannis Spanopoulos and Chabinyc, {Michael L.} and Mercouri Kanatzidis and {Manjunatha Reddy}, {G. N.}",

note = "Funding Information: At Northwestern University and UCSB, this work is mainly supported by the Department of Energy, Office of Science, Basic Energy Sciences, under Grant No. SC0012541 (synthesis, structure, and characterization of physical properties). The research reported here also made use the shared facilities of the UCSB MRSEC (National Science Foundation DMR 1720256), a member of the Materials Research Facilities Network ( www.mrfn.org ). R.M.K. gratefully acknowledges the National Defense Science and Engineering Graduate fellowship for financial support. G.N.M.R. and P.R. acknowledge the funding from University of Lille and region Hauts-de-France (HDF). G.N.M.R. acknowledges the funding from I-SITE ULNE International Mobility Grant and EU-H2020 research and innovation programme under the Marie Sk{\l}odowska-Curie Grant 795091. Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

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day = "8",

doi = "10.1021/acsenergylett.2c00140",

language = "English (US)",

volume = "7",

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T2 - Kinetics of Transformative Reactions at Grain and Subgrain Boundaries

AU - Raval, Parth

AU - Kennard, Rhiannon M.

AU - Vasileiadou, Eugenia S.

AU - Dahlman, Clayton J.

AU - Spanopoulos, Ioannis

AU - Chabinyc, Michael L.

AU - Kanatzidis, Mercouri

AU - Manjunatha Reddy, G. N.

N1 - Funding Information: At Northwestern University and UCSB, this work is mainly supported by the Department of Energy, Office of Science, Basic Energy Sciences, under Grant No. SC0012541 (synthesis, structure, and characterization of physical properties). The research reported here also made use the shared facilities of the UCSB MRSEC (National Science Foundation DMR 1720256), a member of the Materials Research Facilities Network ( www.mrfn.org ). R.M.K. gratefully acknowledges the National Defense Science and Engineering Graduate fellowship for financial support. G.N.M.R. and P.R. acknowledge the funding from University of Lille and region Hauts-de-France (HDF). G.N.M.R. acknowledges the funding from I-SITE ULNE International Mobility Grant and EU-H2020 research and innovation programme under the Marie Skłodowska-Curie Grant 795091. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/4/8

Y1 - 2022/4/8

N2 - 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(FA)-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 (α) transformation to the hexagonal (δ) phase are analyzed by X-ray diffraction, optical microscopy, photoluminescence, and solid-state (ss) NMR spectroscopy techniques. The grain and subgrain boundaries exhibit different α- → δ-FAPbI3phase 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-FAPbI3are obtained by 1H, 2H, and 207Pb ssNMR spectroscopy.

AB - 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(FA)-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 (α) transformation to the hexagonal (δ) phase are analyzed by X-ray diffraction, optical microscopy, photoluminescence, and solid-state (ss) NMR spectroscopy techniques. The grain and subgrain boundaries exhibit different α- → δ-FAPbI3phase 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-FAPbI3are obtained by 1H, 2H, and 207Pb ssNMR spectroscopy.

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VL - 7

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JO - ACS Energy Letters

JF - ACS Energy Letters

IS - 4

ER -

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

Abstract

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UN SDGs

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