Combining Organic Cations of Different Sizes Grants Improved Control over Perovskitoid Dimensionality and Bandgap

Isaiah W. Gilley; Hyoung Woo Kwon; Cheng Liu; Yi Yang; Chuying Huang; Haoyue Wan; Abdulaziz S.R. Bati; Evan H. Oriel; Mikaël Kepenekian; Badri Vishal; Stefan Zeiske; Khasim Saheb Bayikadi; Taylor E. Wiggins; Eugenia S. Vasileiadou; Bin Chen; Richard D. Schaller; Jacky Even; Stefaan De Wolf; Edward H. Sargent; Mercouri G. Kanatzidis

doi:10.1021/jacs.4c17654

Combining Organic Cations of Different Sizes Grants Improved Control over Perovskitoid Dimensionality and Bandgap

Isaiah W. Gilley, Hyoung Woo Kwon, Cheng Liu, Yi Yang, Chuying Huang, Haoyue Wan, Abdulaziz S.R. Bati, Evan H. Oriel, Mikaël Kepenekian, Badri Vishal, Stefan Zeiske, Khasim Saheb Bayikadi, Taylor E. Wiggins, Eugenia S. Vasileiadou, Bin Chen, Richard D. Schaller, Jacky Even, Stefaan De Wolf, Edward H. Sargent^*, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Chemistry

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

Abstract

Because mixed-halide wide-bandgap (1.6-2.0 eV) perovskite solar cells suffer from operating instability related to light-induced halide segregation, it is of interest to study alternative means of bandgap widening. Perovskitoids combine wide bandgaps and structural stability resulting from face- or edge-sharing octahedral connections in their crystal structures. Unfortunately, there existed no prior reports of three-dimensional (3D) perovskitoids having direct bandgaps with optical absorption edges less than 2.2 eV. As the most significant predictor of perovskitoid bandgaps is the fraction of corner-sharing in their crystal structures, we hypothesized that increasing the amount of corner-sharing would access lower bandgaps than previously reported. We accomplished this by mixing a spacer cation within the size range for 3D perovskitoid formation with a smaller perovskite-forming cation. We explored three spacer cations of different sizes: ethylammonium (EA), cyclopropylammonium (c-C3A), and cyclobutylammonium (c-C4A), combining these with methylammonium (MA), and found that the middle cation, c-C3A, pairs with MA to form a 3D perovskitoid with the formula (c-C3A)₃(MA)₃Pb₅I₁₆ and a direct bandgap with an optical absorption edge at 2.0 eV. Solution-processed films of this perovskitoid showed improved light stability over mixed-halide perovskites, and solar cells based on these films exhibit increased maximum power point operating stability compared to reference mixed-halide devices.

Original language	English (US)
Pages (from-to)	7777-7787
Number of pages	11
Journal	Journal of the American Chemical Society
Volume	147
Issue number	9
DOIs	https://doi.org/10.1021/jacs.4c17654
State	Published - Mar 5 2025

Funding

This work was supported in part by the US Department of Energy, Office of Science, Basic Energy Sciences, under award number DE-SC0024422 (MGK: synthesis and fundamental studies of metal halides). We also acknowledge the support provided by the National Science Foundation under Grant No. DGE-2234667 and CHE-2404059. A.S.R.B. acknowledges support from the King Abdullah University of Science and Technology (KAUST) through the Ibn Rushd Postdoctoral Fellowship award. This work was provided with HPC resources by GENCI at TGCC and CINES thanks to the grant 2024-A0170907682 on the supercomputers Joliot Curie/Irene Rome and Adastra Genoa. 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. This work made use of the IMSERC, EPIC, and GIANTFab facilities at Northwestern University. IMSERC has received support from the Soft and Hybrid Nanotechnology Experimental (ShyNE) Resource (NSF ECCS-2025633), the State of Illinois, the International Institute for Nanotechnology (IIN), and Northwestern University. EPIC has received support from the ShyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern\u2019s MRSEC program (NSF DMR-2308961). GIANTFab is supported by the Paula M. Trienens Institute for Sustainability and Energy and the Office of the Vice President for Research at Northwestern.

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)

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Gilley, I. W., Kwon, H. W., Liu, C., Yang, Y., Huang, C., Wan, H., Bati, A. S. R., Oriel, E. H., Kepenekian, M., Vishal, B., Zeiske, S., Bayikadi, K. S., Wiggins, T. E., Vasileiadou, E. S., Chen, B., Schaller, R. D., Even, J., De Wolf, S., Sargent, E. H., & Kanatzidis, M. G. (2025). Combining Organic Cations of Different Sizes Grants Improved Control over Perovskitoid Dimensionality and Bandgap. Journal of the American Chemical Society, 147(9), 7777-7787. https://doi.org/10.1021/jacs.4c17654

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title = "Combining Organic Cations of Different Sizes Grants Improved Control over Perovskitoid Dimensionality and Bandgap",

abstract = "Because mixed-halide wide-bandgap (1.6-2.0 eV) perovskite solar cells suffer from operating instability related to light-induced halide segregation, it is of interest to study alternative means of bandgap widening. Perovskitoids combine wide bandgaps and structural stability resulting from face- or edge-sharing octahedral connections in their crystal structures. Unfortunately, there existed no prior reports of three-dimensional (3D) perovskitoids having direct bandgaps with optical absorption edges less than 2.2 eV. As the most significant predictor of perovskitoid bandgaps is the fraction of corner-sharing in their crystal structures, we hypothesized that increasing the amount of corner-sharing would access lower bandgaps than previously reported. We accomplished this by mixing a spacer cation within the size range for 3D perovskitoid formation with a smaller perovskite-forming cation. We explored three spacer cations of different sizes: ethylammonium (EA), cyclopropylammonium (c-C3A), and cyclobutylammonium (c-C4A), combining these with methylammonium (MA), and found that the middle cation, c-C3A, pairs with MA to form a 3D perovskitoid with the formula (c-C3A)3(MA)3Pb5I16 and a direct bandgap with an optical absorption edge at 2.0 eV. Solution-processed films of this perovskitoid showed improved light stability over mixed-halide perovskites, and solar cells based on these films exhibit increased maximum power point operating stability compared to reference mixed-halide devices.",

author = "Gilley, {Isaiah W.} and Kwon, {Hyoung Woo} and Cheng Liu and Yi Yang and Chuying Huang and Haoyue Wan and Bati, {Abdulaziz S.R.} and Oriel, {Evan H.} and Mika{\"e}l Kepenekian and Badri Vishal and Stefan Zeiske and Bayikadi, {Khasim Saheb} and Wiggins, {Taylor E.} and Vasileiadou, {Eugenia S.} and Bin Chen and Schaller, {Richard D.} and Jacky Even and {De Wolf}, Stefaan and Sargent, {Edward H.} and Kanatzidis, {Mercouri G.}",

note = "Publisher Copyright: {\textcopyright} 2025 American Chemical Society.",

year = "2025",

month = mar,

day = "5",

doi = "10.1021/jacs.4c17654",

language = "English (US)",

volume = "147",

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Gilley, IW, Kwon, HW, Liu, C, Yang, Y, Huang, C, Wan, H, Bati, ASR, Oriel, EH, Kepenekian, M, Vishal, B, Zeiske, S, Bayikadi, KS, Wiggins, TE, Vasileiadou, ES, Chen, B , Schaller, RD, Even, J, De Wolf, S, Sargent, EH & Kanatzidis, MG 2025, 'Combining Organic Cations of Different Sizes Grants Improved Control over Perovskitoid Dimensionality and Bandgap', Journal of the American Chemical Society, vol. 147, no. 9, pp. 7777-7787. https://doi.org/10.1021/jacs.4c17654

TY - JOUR

T1 - Combining Organic Cations of Different Sizes Grants Improved Control over Perovskitoid Dimensionality and Bandgap

AU - Gilley, Isaiah W.

AU - Kwon, Hyoung Woo

AU - Liu, Cheng

AU - Yang, Yi

AU - Huang, Chuying

AU - Wan, Haoyue

AU - Bati, Abdulaziz S.R.

AU - Oriel, Evan H.

AU - Kepenekian, Mikaël

AU - Vishal, Badri

AU - Zeiske, Stefan

AU - Bayikadi, Khasim Saheb

AU - Wiggins, Taylor E.

AU - Vasileiadou, Eugenia S.

AU - Chen, Bin

AU - Schaller, Richard D.

AU - Even, Jacky

AU - De Wolf, Stefaan

AU - Sargent, Edward H.

AU - Kanatzidis, Mercouri G.

PY - 2025/3/5

Y1 - 2025/3/5

N2 - Because mixed-halide wide-bandgap (1.6-2.0 eV) perovskite solar cells suffer from operating instability related to light-induced halide segregation, it is of interest to study alternative means of bandgap widening. Perovskitoids combine wide bandgaps and structural stability resulting from face- or edge-sharing octahedral connections in their crystal structures. Unfortunately, there existed no prior reports of three-dimensional (3D) perovskitoids having direct bandgaps with optical absorption edges less than 2.2 eV. As the most significant predictor of perovskitoid bandgaps is the fraction of corner-sharing in their crystal structures, we hypothesized that increasing the amount of corner-sharing would access lower bandgaps than previously reported. We accomplished this by mixing a spacer cation within the size range for 3D perovskitoid formation with a smaller perovskite-forming cation. We explored three spacer cations of different sizes: ethylammonium (EA), cyclopropylammonium (c-C3A), and cyclobutylammonium (c-C4A), combining these with methylammonium (MA), and found that the middle cation, c-C3A, pairs with MA to form a 3D perovskitoid with the formula (c-C3A)3(MA)3Pb5I16 and a direct bandgap with an optical absorption edge at 2.0 eV. Solution-processed films of this perovskitoid showed improved light stability over mixed-halide perovskites, and solar cells based on these films exhibit increased maximum power point operating stability compared to reference mixed-halide devices.

AB - Because mixed-halide wide-bandgap (1.6-2.0 eV) perovskite solar cells suffer from operating instability related to light-induced halide segregation, it is of interest to study alternative means of bandgap widening. Perovskitoids combine wide bandgaps and structural stability resulting from face- or edge-sharing octahedral connections in their crystal structures. Unfortunately, there existed no prior reports of three-dimensional (3D) perovskitoids having direct bandgaps with optical absorption edges less than 2.2 eV. As the most significant predictor of perovskitoid bandgaps is the fraction of corner-sharing in their crystal structures, we hypothesized that increasing the amount of corner-sharing would access lower bandgaps than previously reported. We accomplished this by mixing a spacer cation within the size range for 3D perovskitoid formation with a smaller perovskite-forming cation. We explored three spacer cations of different sizes: ethylammonium (EA), cyclopropylammonium (c-C3A), and cyclobutylammonium (c-C4A), combining these with methylammonium (MA), and found that the middle cation, c-C3A, pairs with MA to form a 3D perovskitoid with the formula (c-C3A)3(MA)3Pb5I16 and a direct bandgap with an optical absorption edge at 2.0 eV. Solution-processed films of this perovskitoid showed improved light stability over mixed-halide perovskites, and solar cells based on these films exhibit increased maximum power point operating stability compared to reference mixed-halide devices.

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Combining Organic Cations of Different Sizes Grants Improved Control over Perovskitoid Dimensionality and Bandgap

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