Structural Evolution and Photoluminescence Quenching across the FASnI3-xBrx (x = 0-3) Perovskites

Adam Balvanz; Majid Safdari; Marios Zacharias; Daehan Kim; Claire Welton; Evan H. Oriel; Mikaël Kepenekian; Claudine Katan; Christos D. Malliakas; Jacky Even; Vladislav Klepov; G. N. Manjunatha Reddy; Richard D. Schaller; Lin X. Chen; Ram Seshadri; Mercouri G. Kanatzidis

doi:10.1021/jacs.4c03669

Structural Evolution and Photoluminescence Quenching across the FASnI_3-xBr_x (x = 0-3) Perovskites

Adam Balvanz, Majid Safdari^*, Marios Zacharias, Daehan Kim, Claire Welton, Evan H. Oriel, Mikaël Kepenekian, Claudine Katan, Christos D. Malliakas, Jacky Even, Vladislav Klepov, G. N. Manjunatha Reddy, Richard D. Schaller, Lin X. Chen, Ram Seshadri, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Chemistry

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

4 Scopus citations

Abstract

One of the primary methods for band gap tuning in metal halide perovskites has been halide (I/Br) mixing. Despite widespread usage of this type of chemical substitution in perovskite photovoltaics, there is still little understanding of the structural impacts of halide alloying, with the assumption being the formation of ideal solid solutions. The FASnI_3-xBr_x (x = 0-3) family of compounds provides the first example where the assumption breaks down, as the composition space is broken into two unique regimes (x = 0-2.9; x = 2.9-3) based on their average structure with the former having a 3D and the latter having an extended 3D (pseudo 0D) structure. Pair distribution function (PDF) analyses further suggest a dynamic 5s² lone pair expression resulting in increasing levels of off-centering of the central Sn as the Br concentration is increased. These antiferroelectric distortions indicate that even the x = 0-2.9 phase space behaves as a nonideal solid-solution on a more local scale. Solid-state NMR confirms the difference in local structure yielding greater insight into the chemical nature and local distributions of the FA⁺ cation. In contrast to the FAPbI_3-xBr_x series, a drastic photoluminescence (PL) quenching is observed with x ≥ 1.9 compounds having no observable PL. Our detailed studies attribute this quenching to structural transitions induced by the distortions of the [SnBr₆] octahedra in response to stereochemically expressed lone pairs of electrons. This is confirmed through density functional theory, having a direct impact on the electronic structure.

Original language	English (US)
Pages (from-to)	16128-16147
Number of pages	20
Journal	Journal of the American Chemical Society
Volume	146
Issue number	23
DOIs	https://doi.org/10.1021/jacs.4c03669
State	Published - Jun 12 2024

Funding

This work was supported by the US Department of Energy, Office of Science, basic Energy Sciences, under award number DE-SC-0024422 (synthesis and fundamental studies of metal halides) and under the Ultrafast Science Initiative through contract number DE-AC02-06CH11357. Use of the GSECARS Raman Lab System was supported by the NSF MRI Proposal (EAR-1531583). We thank Vitali Prakapenka, Stella Chariton and Young Jay Ryu for assistance with Raman measurements. Work performed at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The crystallographic and diffuse reflectance UV\u2013vis experiments presented in this study made use of the IMSERC Crystallographic and Physical Characterization facilities at Northwestern University, which received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) resource (NSF ECCS-2025633) and Northwestern University. The silver radiation source used to collect single crystal data on FASnIBr and PDF curves was purchased with the support of the Major Research Instrumentation Program for the National Science Foundation under award CHE-1920248. The SEM-EDS data was gathered at the EPIC facility at Northwestern University\u2019s NUANCE Center, which has received support from the SHyNE resource, the IIN, and Northwestern\u2019s MRSEC program (NSF DMR-1720139). A.B. was supported by a fellowship through the National Defense Science and Engineering Graduate Fellowship Program (NDSEG), sponsored by the Air Force Research Laboratory (ARFL), the Office of Naval Research (ONR), and the Army Research Office (ARO). M.S. acknowledges financial support from the Swedish research council for sustainable development-Formas (2017-01134) through their \u201CMobility Starting Grant\u201D program which made it possible to be a visiting scholar at Northwestern University, USA. J.E. acknowledges the Institut universitaire de France. C.W. and G.N.M.R thank the European Union\u2019s Horizon 2020 Grant no. 795091 and IR INFRANALYTICS FR2054 for financial support. M.Z. acknowledges funding from the European Union (project ULTRA-2DPK/HORIZON-MSCA-2022-PF-01/Grant Agreement No. 101106654). This work was granted access to the HPC resources of TGCC under the allocation 2022-A0110907682 made by GENCI. 0.1 2.9

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

UN SDGs

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

Access to Document

10.1021/jacs.4c03669

Cite this

Balvanz, A., Safdari, M., Zacharias, M., Kim, D., Welton, C., Oriel, E. H., Kepenekian, M., Katan, C., Malliakas, C. D., Even, J., Klepov, V., Manjunatha Reddy, G. N., Schaller, R. D., Chen, L. X., Seshadri, R., & Kanatzidis, M. G. (2024). Structural Evolution and Photoluminescence Quenching across the FASnI_3-xBr_x (x = 0-3) Perovskites. Journal of the American Chemical Society, 146(23), 16128-16147. https://doi.org/10.1021/jacs.4c03669

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title = "Structural Evolution and Photoluminescence Quenching across the FASnI3-xBrx (x = 0-3) Perovskites",

abstract = "One of the primary methods for band gap tuning in metal halide perovskites has been halide (I/Br) mixing. Despite widespread usage of this type of chemical substitution in perovskite photovoltaics, there is still little understanding of the structural impacts of halide alloying, with the assumption being the formation of ideal solid solutions. The FASnI3-xBrx (x = 0-3) family of compounds provides the first example where the assumption breaks down, as the composition space is broken into two unique regimes (x = 0-2.9; x = 2.9-3) based on their average structure with the former having a 3D and the latter having an extended 3D (pseudo 0D) structure. Pair distribution function (PDF) analyses further suggest a dynamic 5s2 lone pair expression resulting in increasing levels of off-centering of the central Sn as the Br concentration is increased. These antiferroelectric distortions indicate that even the x = 0-2.9 phase space behaves as a nonideal solid-solution on a more local scale. Solid-state NMR confirms the difference in local structure yielding greater insight into the chemical nature and local distributions of the FA+ cation. In contrast to the FAPbI3-xBrx series, a drastic photoluminescence (PL) quenching is observed with x ≥ 1.9 compounds having no observable PL. Our detailed studies attribute this quenching to structural transitions induced by the distortions of the [SnBr6] octahedra in response to stereochemically expressed lone pairs of electrons. This is confirmed through density functional theory, having a direct impact on the electronic structure.",

author = "Adam Balvanz and Majid Safdari and Marios Zacharias and Daehan Kim and Claire Welton and Oriel, {Evan H.} and Mika{\"e}l Kepenekian and Claudine Katan and Malliakas, {Christos D.} and Jacky Even and Vladislav Klepov and {Manjunatha Reddy}, {G. N.} and Schaller, {Richard D.} and Chen, {Lin X.} and Ram Seshadri and Kanatzidis, {Mercouri G.}",

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Balvanz, A, Safdari, M, Zacharias, M, Kim, D, Welton, C, Oriel, EH, Kepenekian, M, Katan, C, Malliakas, CD, Even, J, Klepov, V, Manjunatha Reddy, GN, Schaller, RD , Chen, LX, Seshadri, R & Kanatzidis, MG 2024, 'Structural Evolution and Photoluminescence Quenching across the FASnI_3-xBr_x (x = 0-3) Perovskites', Journal of the American Chemical Society, vol. 146, no. 23, pp. 16128-16147. https://doi.org/10.1021/jacs.4c03669

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T1 - Structural Evolution and Photoluminescence Quenching across the FASnI3-xBrx (x = 0-3) Perovskites

AU - Balvanz, Adam

AU - Safdari, Majid

AU - Zacharias, Marios

AU - Kim, Daehan

AU - Welton, Claire

AU - Oriel, Evan H.

AU - Kepenekian, Mikaël

AU - Katan, Claudine

AU - Malliakas, Christos D.

AU - Even, Jacky

AU - Klepov, Vladislav

AU - Manjunatha Reddy, G. N.

AU - Schaller, Richard D.

AU - Chen, Lin X.

AU - Seshadri, Ram

AU - Kanatzidis, Mercouri G.

PY - 2024/6/12

Y1 - 2024/6/12

N2 - One of the primary methods for band gap tuning in metal halide perovskites has been halide (I/Br) mixing. Despite widespread usage of this type of chemical substitution in perovskite photovoltaics, there is still little understanding of the structural impacts of halide alloying, with the assumption being the formation of ideal solid solutions. The FASnI3-xBrx (x = 0-3) family of compounds provides the first example where the assumption breaks down, as the composition space is broken into two unique regimes (x = 0-2.9; x = 2.9-3) based on their average structure with the former having a 3D and the latter having an extended 3D (pseudo 0D) structure. Pair distribution function (PDF) analyses further suggest a dynamic 5s2 lone pair expression resulting in increasing levels of off-centering of the central Sn as the Br concentration is increased. These antiferroelectric distortions indicate that even the x = 0-2.9 phase space behaves as a nonideal solid-solution on a more local scale. Solid-state NMR confirms the difference in local structure yielding greater insight into the chemical nature and local distributions of the FA+ cation. In contrast to the FAPbI3-xBrx series, a drastic photoluminescence (PL) quenching is observed with x ≥ 1.9 compounds having no observable PL. Our detailed studies attribute this quenching to structural transitions induced by the distortions of the [SnBr6] octahedra in response to stereochemically expressed lone pairs of electrons. This is confirmed through density functional theory, having a direct impact on the electronic structure.

AB - One of the primary methods for band gap tuning in metal halide perovskites has been halide (I/Br) mixing. Despite widespread usage of this type of chemical substitution in perovskite photovoltaics, there is still little understanding of the structural impacts of halide alloying, with the assumption being the formation of ideal solid solutions. The FASnI3-xBrx (x = 0-3) family of compounds provides the first example where the assumption breaks down, as the composition space is broken into two unique regimes (x = 0-2.9; x = 2.9-3) based on their average structure with the former having a 3D and the latter having an extended 3D (pseudo 0D) structure. Pair distribution function (PDF) analyses further suggest a dynamic 5s2 lone pair expression resulting in increasing levels of off-centering of the central Sn as the Br concentration is increased. These antiferroelectric distortions indicate that even the x = 0-2.9 phase space behaves as a nonideal solid-solution on a more local scale. Solid-state NMR confirms the difference in local structure yielding greater insight into the chemical nature and local distributions of the FA+ cation. In contrast to the FAPbI3-xBrx series, a drastic photoluminescence (PL) quenching is observed with x ≥ 1.9 compounds having no observable PL. Our detailed studies attribute this quenching to structural transitions induced by the distortions of the [SnBr6] octahedra in response to stereochemically expressed lone pairs of electrons. This is confirmed through density functional theory, having a direct impact on the electronic structure.

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Structural Evolution and Photoluminescence Quenching across the FASnI_3-xBr_x (x = 0-3) Perovskites

Abstract

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CCDC 2335367: Experimental Crystal Structure Determination

CCDC 2335361: Experimental Crystal Structure Determination

CCDC 2335369: Experimental Crystal Structure Determination

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Structural Evolution and Photoluminescence Quenching across the FASnI3-xBrx (x = 0-3) Perovskites

Abstract

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ASJC Scopus subject areas

UN SDGs

Access to Document

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Datasets

CCDC 2335367: Experimental Crystal Structure Determination

CCDC 2335361: Experimental Crystal Structure Determination

CCDC 2335369: Experimental Crystal Structure Determination

Cite this

Structural Evolution and Photoluminescence Quenching across the FASnI_3-xBr_x (x = 0-3) Perovskites