Thermodynamic Stabilization of Mixed-Halide Perovskites against Phase Segregation

Eline M. Hutter; Loreta A. Muscarella; Francesca Wittmann; Jan Versluis; Lucie McGovern; Huib J. Bakker; Young-Won Woo; Young-Kwang Jung; Aron Walsh; Bruno Ehrler

doi:10.1016/j.xcrp.2020.100120

Thermodynamic Stabilization of Mixed-Halide Perovskites against Phase Segregation

Eline M. Hutter, Loreta A. Muscarella, Francesca Wittmann, Jan Versluis, Lucie McGovern, Huib J. Bakker, Young-Won Woo, Young-Kwang Jung, Aron Walsh, Bruno Ehrler

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

Mixing iodide and bromide in halide perovskite semiconductors is an effective strategy to tune their band gap; therefore, mixed-halide perovskites hold great promise for color-tunable LEDs and tandem solar cells. However, the band gap of mixed-halide perovskites is unstable under (sun-)light, since the halides segregate into domains of different band gaps. Using pressure-dependent ultrafast transient absorption spectroscopy, we find that high external pressure increases the range of stable halide mixing ratios. Chemical compression, by inserting a smaller cation, has the same effect, which means that any iodide:bromide ratio can be stabilized by tuning the crystal volume and compressibility. We interpret these findings as an increased thermodynamic stabilization through alteration of the Gibbs free energy via the largely overlooked PΔV term. Mixed-halide perovskites could be the next-generation solar cell and LED material, but their composition and hence color of absorption and emission are unstable. Hutter et al. find that the range of thermodynamically stable compositions is substantially enlarged upon compression, guiding a more rational design toward color-tunable perovskites with stable emission.

Original language	English
Article number	100120
Journal	Cell Reports Physical Science
Volume	1
Issue number	8
DOIs	https://doi.org/10.1016/j.xcrp.2020.100120
Publication status	Published - 26 Aug 2020
Externally published	Yes

Funding

The work of E.M.H., L.A.M., F.W., J.V., L.M., H.J.B., and B.E. is part of the Dutch Research Council (NWO) and was performed at the research institute AMOLF. This research was also supported by the Creative Materials Discovery Program through the National Research Foundation of Korea (NRF), funded by the Ministry of Science and ICT ( 2018M3D1A1058536 ). We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC ( EP/P020194/1 ). The authors thank Henk-Jan Boluijt for the design of Figure 1 A. The work of E.M.H. L.A.M. F.W. J.V. L.M. H.J.B. and B.E. is part of the Dutch Research Council (NWO) and was performed at the research institute AMOLF. This research was also supported by the Creative Materials Discovery Program through the National Research Foundation of Korea (NRF), funded by the Ministry of Science and ICT (2018M3D1A1058536). We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1). The authors thank Henk-Jan Boluijt for the design of Figure 1A. E.M.H. conceived the idea and performed the pressure-dependent TA experiments and data analysis together with L.A.M. under the supervision of B.E. F.W. performed the XRD and pressure-dependent UV-VIS measurements and assisted in the sample preparation together with L.M. J.V. assisted in the TA experiments under the supervision of H.J.B. Thermodynamic calculations were performed by A.W. Y.-W.W. and Y.-K.J. The manuscript was written by E.M.H. and A.W. with input from all of the other authors. The authors declare no competing interests.

Funders	Funder number
Ministry of Science and ICT	2018M3D1A1058536
Engineering and Physical Sciences Research Council	EP/P020194/1
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
National Research Foundation of Korea

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title = "Thermodynamic Stabilization of Mixed-Halide Perovskites against Phase Segregation",

abstract = "Mixing iodide and bromide in halide perovskite semiconductors is an effective strategy to tune their band gap; therefore, mixed-halide perovskites hold great promise for color-tunable LEDs and tandem solar cells. However, the band gap of mixed-halide perovskites is unstable under (sun-)light, since the halides segregate into domains of different band gaps. Using pressure-dependent ultrafast transient absorption spectroscopy, we find that high external pressure increases the range of stable halide mixing ratios. Chemical compression, by inserting a smaller cation, has the same effect, which means that any iodide:bromide ratio can be stabilized by tuning the crystal volume and compressibility. We interpret these findings as an increased thermodynamic stabilization through alteration of the Gibbs free energy via the largely overlooked PΔV term. Mixed-halide perovskites could be the next-generation solar cell and LED material, but their composition and hence color of absorption and emission are unstable. Hutter et al. find that the range of thermodynamically stable compositions is substantially enlarged upon compression, guiding a more rational design toward color-tunable perovskites with stable emission.",

author = "Hutter, {Eline M.} and Muscarella, {Loreta A.} and Francesca Wittmann and Jan Versluis and Lucie McGovern and Bakker, {Huib J.} and Young-Won Woo and Young-Kwang Jung and Aron Walsh and Bruno Ehrler",

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AU - Hutter, Eline M.

AU - Muscarella, Loreta A.

AU - Wittmann, Francesca

AU - Versluis, Jan

AU - McGovern, Lucie

AU - Bakker, Huib J.

AU - Woo, Young-Won

AU - Jung, Young-Kwang

AU - Walsh, Aron

AU - Ehrler, Bruno

PY - 2020/8/26

Y1 - 2020/8/26

N2 - Mixing iodide and bromide in halide perovskite semiconductors is an effective strategy to tune their band gap; therefore, mixed-halide perovskites hold great promise for color-tunable LEDs and tandem solar cells. However, the band gap of mixed-halide perovskites is unstable under (sun-)light, since the halides segregate into domains of different band gaps. Using pressure-dependent ultrafast transient absorption spectroscopy, we find that high external pressure increases the range of stable halide mixing ratios. Chemical compression, by inserting a smaller cation, has the same effect, which means that any iodide:bromide ratio can be stabilized by tuning the crystal volume and compressibility. We interpret these findings as an increased thermodynamic stabilization through alteration of the Gibbs free energy via the largely overlooked PΔV term. Mixed-halide perovskites could be the next-generation solar cell and LED material, but their composition and hence color of absorption and emission are unstable. Hutter et al. find that the range of thermodynamically stable compositions is substantially enlarged upon compression, guiding a more rational design toward color-tunable perovskites with stable emission.

AB - Mixing iodide and bromide in halide perovskite semiconductors is an effective strategy to tune their band gap; therefore, mixed-halide perovskites hold great promise for color-tunable LEDs and tandem solar cells. However, the band gap of mixed-halide perovskites is unstable under (sun-)light, since the halides segregate into domains of different band gaps. Using pressure-dependent ultrafast transient absorption spectroscopy, we find that high external pressure increases the range of stable halide mixing ratios. Chemical compression, by inserting a smaller cation, has the same effect, which means that any iodide:bromide ratio can be stabilized by tuning the crystal volume and compressibility. We interpret these findings as an increased thermodynamic stabilization through alteration of the Gibbs free energy via the largely overlooked PΔV term. Mixed-halide perovskites could be the next-generation solar cell and LED material, but their composition and hence color of absorption and emission are unstable. Hutter et al. find that the range of thermodynamically stable compositions is substantially enlarged upon compression, guiding a more rational design toward color-tunable perovskites with stable emission.

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Thermodynamic Stabilization of Mixed-Halide Perovskites against Phase Segregation

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