Vacancy-Driven Stabilization of the Cubic Perovskite Polymorph of CsPbI                         3

Yun Hyok Kye; Chol Jun Yu; Un Gi Jong; Kum Chol Ri; Jin Song Kim; Song Hyok Choe; Song Nam Hong; Shuzhou Li; Jacob N. Wilson; Aron Walsh

doi:10.1021/acs.jpcc.9b01552

Vacancy-Driven Stabilization of the Cubic Perovskite Polymorph of CsPbI ₃

Yun Hyok Kye, Chol Jun Yu, Un Gi Jong, Kum Chol Ri, Jin Song Kim, Song Hyok Choe, Song Nam Hong, Shuzhou Li, Jacob N. Wilson, Aron Walsh

Department of Materials Science and Engineering

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

36 Citations (Scopus)

Abstract

The inorganic halide perovskite CsPbI ₃ has shown great promise for efficient solar cells, but the instability of its cubic phase remains a major challenge. We present a route for stabilizing the cubic α-phase of CsPbI ₃ through the control of vacancy defects. Analysis of the ionic chemical potentials is performed within an ab initio thermodynamic formalism, including the effect of solution. It is found that cation vacancies lead to weakening of the interaction between Cs and PbI ₆ octahedra in CsPbI ₃ , with a decrease in the energy difference between the α- and δ-phases. Under I-rich growth conditions, which can be realized experimentally, we predict that the formation of cation vacancies can be controlled. Other synthetic strategies for cubic-phase stabilization include the growth of nanocrystals, surface capping ligands containing reductive functional groups, and extrinsic doping. Our analysis reveals mechanisms for polymorph stabilization that open a new pathway for structural control of halide perovskites.

Original language	English
Pages (from-to)	9735-9744
Number of pages	10
Journal	Journal of Physical Chemistry C
Volume	123
Issue number	15
DOIs	https://doi.org/10.1021/acs.jpcc.9b01552
Publication status	Published - 2019 Apr 18

Bibliographical note

Funding Information:
This work is supported as part of the fundamental research project “Design of Innovative Functional Materials for Energy and Environmental Application” (no. 2016-20) funded by the State Committee of Science and Technology, DPR Korea. The work in the UK has been supported by the Royal Society and the Leverhulme Trust.

Publisher Copyright:
© 2019 American Chemical Society.

All Science Journal Classification (ASJC) codes

Electronic, Optical and Magnetic Materials
Energy(all)
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

Access to Document

10.1021/acs.jpcc.9b01552

Cite this

Kye, Y. H., Yu, C. J., Jong, U. G., Ri, K. C., Kim, J. S., Choe, S. H., Hong, S. N., Li, S., Wilson, J. N., & Walsh, A. (2019). Vacancy-Driven Stabilization of the Cubic Perovskite Polymorph of CsPbI ₃ Journal of Physical Chemistry C, 123(15), 9735-9744. https://doi.org/10.1021/acs.jpcc.9b01552

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title = " Vacancy-Driven Stabilization of the Cubic Perovskite Polymorph of CsPbI 3 ",

abstract = " The inorganic halide perovskite CsPbI 3 has shown great promise for efficient solar cells, but the instability of its cubic phase remains a major challenge. We present a route for stabilizing the cubic α-phase of CsPbI 3 through the control of vacancy defects. Analysis of the ionic chemical potentials is performed within an ab initio thermodynamic formalism, including the effect of solution. It is found that cation vacancies lead to weakening of the interaction between Cs and PbI 6 octahedra in CsPbI 3 , with a decrease in the energy difference between the α- and δ-phases. Under I-rich growth conditions, which can be realized experimentally, we predict that the formation of cation vacancies can be controlled. Other synthetic strategies for cubic-phase stabilization include the growth of nanocrystals, surface capping ligands containing reductive functional groups, and extrinsic doping. Our analysis reveals mechanisms for polymorph stabilization that open a new pathway for structural control of halide perovskites.",

author = "Kye, {Yun Hyok} and Yu, {Chol Jun} and Jong, {Un Gi} and Ri, {Kum Chol} and Kim, {Jin Song} and Choe, {Song Hyok} and Hong, {Song Nam} and Shuzhou Li and Wilson, {Jacob N.} and Aron Walsh",

note = "Funding Information: This work is supported as part of the fundamental research project “Design of Innovative Functional Materials for Energy and Environmental Application” (no. 2016-20) funded by the State Committee of Science and Technology, DPR Korea. The work in the UK has been supported by the Royal Society and the Leverhulme Trust. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

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Kye, YH, Yu, CJ, Jong, UG, Ri, KC, Kim, JS, Choe, SH, Hong, SN, Li, S, Wilson, JN & Walsh, A 2019, ' Vacancy-Driven Stabilization of the Cubic Perovskite Polymorph of CsPbI ₃ ', Journal of Physical Chemistry C, vol. 123, no. 15, pp. 9735-9744. https://doi.org/10.1021/acs.jpcc.9b01552

Vacancy-Driven Stabilization of the Cubic Perovskite Polymorph of CsPbI ₃ . / Kye, Yun Hyok; Yu, Chol Jun; Jong, Un Gi et al.

In: Journal of Physical Chemistry C, Vol. 123, No. 15, 18.04.2019, p. 9735-9744.

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

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N2 - The inorganic halide perovskite CsPbI 3 has shown great promise for efficient solar cells, but the instability of its cubic phase remains a major challenge. We present a route for stabilizing the cubic α-phase of CsPbI 3 through the control of vacancy defects. Analysis of the ionic chemical potentials is performed within an ab initio thermodynamic formalism, including the effect of solution. It is found that cation vacancies lead to weakening of the interaction between Cs and PbI 6 octahedra in CsPbI 3 , with a decrease in the energy difference between the α- and δ-phases. Under I-rich growth conditions, which can be realized experimentally, we predict that the formation of cation vacancies can be controlled. Other synthetic strategies for cubic-phase stabilization include the growth of nanocrystals, surface capping ligands containing reductive functional groups, and extrinsic doping. Our analysis reveals mechanisms for polymorph stabilization that open a new pathway for structural control of halide perovskites.

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