Photoinduced Phase Segregation in Mixed Halide Perovskites: Thermodynamic and Kinetic Aspects of Cl–Br Segregation

Cho, Junsang; Kamat, Prashant V.

doi:10.1002/adom.202001440

Title: Photoinduced Phase Segregation in Mixed Halide Perovskites: Thermodynamic and Kinetic Aspects of Cl–Br Segregation

Journal Article · Tue Oct 13 00:00:00 EDT 2020 · Advanced Optical Materials

DOI:https://doi.org/10.1002/adom.202001440· OSTI ID:1785810

Cho, Junsang ^[1];

^[2]

Radiation Laboratory University of Notre Dame Notre Dame IN 46556 USA
Radiation Laboratory University of Notre Dame Notre Dame IN 46556 USA, Department of Chemistry and Biochemistry University of Notre Dame Notre Dame IN 46556 USA, Department of Chemical and Biomolecular Engineering University of Notre Dame Notre Dame IN 46556 USA

Abstract Suppression of halide ion mobility remains a key issue in defining the device performances and stability of perovskite solar cells. The halide ion migration is facilitated by the lattice‐distortion‐mediated halide vacancy and hence dictated by the polarizability (or rigidity) of the halide sublattice and framework. Photoinduced halide ion segregation and dark recovery of MAPb(Cl _0.5 Br _0.5 ) ₃ films are now probed. The temperature dependence of the rate constants of segregation and dark remixing allow to determine the activation energy barriers ( E _a ) for photosegregation (38 kJ mol ⁻¹ ) and dark recovery (42 kJ mol ⁻¹ ). A comparison of the segregation activation energy ( E _a ) and excitation intensity threshold between MAPb(Cl _0.5 Br _0.5 ) ₃ and MAPb(Br _0.5 I _0.5 ) ₃ films reflects that the presence of Cl stabilizes mixed halide composition. The thermodynamic stabilization is attributed to the formation of more rigid [PbX ₆ ] ⁴⁻ frameworks with an increased barrier for halide ion migration. The thermodynamic rationale behind the intriguing halide ion mobility offers a fundamental insight into the role of Cl and design principle of perovskite solar cells with improved efficiency and long‐term stability.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: DE‐FC02‐04ER15533

OSTI ID:: 1785810

Journal Information:: Advanced Optical Materials, Journal Name: Advanced Optical Materials Vol. 9 Journal Issue: 18; ISSN 2195-1071

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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