Halide Perovskites Breathe Too: The Iodide–Iodine Equilibrium and Self-Doping in Cs2SnI6

Vigil, Julian A.; Wolf, Nathan R.; Slavney, Adam H.; Matheu, Roc; Saldivar Valdes, Abraham; Breidenbach, Aaron; Lee, Young S.; Karunadasa, Hemamala I.

doi:10.1021/acscentsci.4c00056

Title: Halide Perovskites Breathe Too: The Iodide–Iodine Equilibrium and Self-Doping in Cs₂SnI₆

Journal Article · 01 April 2024 · ACS Central Science

DOI: https://doi.org/10.1021/acscentsci.4c00056 · OSTI ID:2446776

^[1]; Wolf, Nathan R. ^[2]; Slavney, Adam H. ^[2]; Matheu, Roc ^[2]; Saldivar Valdes, Abraham ^[2]; Breidenbach, Aaron ^[3]; Lee, Young S. ^[3];

^[3]

Stanford Univ., CA (United States); SLAC
Stanford Univ., CA (United States)
Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

The response of an oxide crystal to the atmosphere can be personified as breathing-a dynamic equilibrium between O₂ gas and O^2– anions in the solid. We characterize the analogous defect reaction in an iodide double-perovskite semiconductor, Cs₂SnI₆. Here, I₂ gas is released from the crystal at room temperature, forming iodine vacancies. The iodine vacancy defect is a shallow electron donor and is therefore ionized at room temperature; thus, the loss of I2 is accompanied by spontaneous n-type self-doping. Conversely, at high I₂ pressures, I₂ gas is resorbed by the perovskite, consuming excess electrons as I₂ is converted to 2I^–. Halide mobility and irreversible halide loss or exchange reactions have been studied extensively in halide perovskites. However, the reversible exchange equilibrium between iodide and iodine [2I^–_(s) ↔ I_2(g) + 2e^–] described here has often been overlooked in prior studies, though it is likely general to halide perovskites and operative near room temperature, even in the dark. An analysis of the 2I^–_(s)/I_2(g) equilibrium thermodynamics and related transport kinetics in single crystals of Cs₂SnI₆ therefore provides insight toward achieving stable composition and electronic properties in the large family of iodide perovskite semiconductors.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357; AC02-76SF00515

OSTI ID:: 2446776

Journal Information:: ACS Central Science, Journal Name: ACS Central Science Journal Issue: 4 Vol. 10; ISSN 2374-7943

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Crystals
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Defects in solids
Electrical conductivity
Perovskites

Title: Halide Perovskites Breathe Too: The Iodide–Iodine Equilibrium and Self-Doping in Cs2SnI6

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Title: Halide Perovskites Breathe Too: The Iodide–Iodine Equilibrium and Self-Doping in Cs₂SnI₆