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

Research output: Contribution to journalArticle

7 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 languageEnglish
Pages (from-to)9735-9744
Number of pages10
JournalJournal of Physical Chemistry C
Volume123
Issue number15
DOIs
Publication statusPublished - 2019 Apr 18

Fingerprint

Polymorphism
Perovskite
Vacancies
Stabilization
stabilization
halides
Cations
Positive ions
cations
Chemical potential
perovskites
Nanocrystals
Functional groups
Solar cells
nanocrystals
solar cells
Ligands
routes
Doping (additives)
Thermodynamics

All Science Journal Classification (ASJC) codes

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

Cite this

Kye, Yun Hyok ; Yu, Chol Jun ; Jong, Un Gi ; Ri, Kum Chol ; Kim, Jin Song ; Choe, Song Hyok ; Hong, Song Nam ; Li, Shuzhou ; Wilson, Jacob N. ; Walsh, Aron. / Vacancy-Driven Stabilization of the Cubic Perovskite Polymorph of CsPbI 3 In: Journal of Physical Chemistry C. 2019 ; Vol. 123, No. 15. pp. 9735-9744.
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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; Ri, Kum Chol; Kim, Jin Song; Choe, Song Hyok; Hong, Song Nam; Li, Shuzhou; Wilson, Jacob N.; Walsh, Aron.

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

Research output: Contribution to journalArticle

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AU - Kye, Yun Hyok

AU - Yu, Chol Jun

AU - Jong, Un Gi

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AU - Kim, Jin Song

AU - Choe, Song Hyok

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AU - Li, Shuzhou

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AU - Walsh, Aron

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AB - 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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