Redox Chemistry of the Subphases of α-CsPbI2Br and β-CsPbI2Br: Theory Reveals New Potential for Photostability

Gutsev, Lavrenty Gennady; Nations, Sean; Ramachandran, Bala Ramu; Gutsev, Gennady Lavrenty; Wang, Shengnian; Aldoshin, Sergei; Duan, Yuhua

doi:10.3390/nano13020276

Title: Redox Chemistry of the Subphases of α-CsPbI2Br and β-CsPbI2Br: Theory Reveals New Potential for Photostability

Journal Article · Mon Jan 09 00:00:00 EST 2023 · Nanomaterials

DOI:https://doi.org/10.3390/nano13020276· OSTI ID:1922670

Gutsev, Lavrenty Gennady ^[1];

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Louisiana Tech Univ., Ruston, LA (United States); Russian Academy of Sciences (RAS), Moscow (Russian Federation). Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry
Louisiana Tech Univ., Ruston, LA (United States)
Florida A & M University, Tallahassee, FL (United States)
Russian Academy of Sciences (RAS), Moscow (Russian Federation). Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry
National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)

The logic in the design of a halide-mixed APb(I_1-xBr_x)₃ perovskite is quite straightforward: to combine the superior photovoltaic qualities of iodine-based perovskites with the increased stability of bromine-based perovskites. However, even small amounts of Br doped into the iodine-based materials leads to some instability. In the present report, using first-principles computations, we analyzed a wide variety of α-CsPbI₂Br and β-CsPbI₂Br phases, compared their mixing enthalpies, explored their oxidative properties, and calculated their hole-coupled and hole-free charged Frenkel defect (CFD) formations by considering all possible channels of oxidation. Nanoinclusions of bromine-rich phases in α-CsPbI₂Br were shown to destabilize the material by inducing lattice strain, making it more susceptible to oxidation. The uniformly mixed phase of α-CsPbI₂Br was shown to be highly susceptible towards a phase transformation into β-CsPbI₂Br when halide interstitial or halide vacancy defects were introduced into the lattice. The rotation of PbI₄Br₂ octahedra in α-CsPbI2Br allows it either to transform into a highly unstable apical β-CsPbI₂Br, which may phase-segregate and is susceptible to CFD, or to phase-transform into equatorial β-CsPbI₂Br, which is resilient against the deleterious effects of hole oxidation (energies of oxidation >0 eV) and demixing (energy of mixing <0 eV). Thus, the selective preparation of equatorial β-CsPbI₂Br offers an opportunity to obtain a mixed perovskite material with enhanced photostability and an intermediate bandgap between its constituent perovskites.

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Research Organization:: National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy (FE); Louisiana Board of Regents (LBR)

Grant/Contract Number:: 21-73-00080

OSTI ID:: 1922670

Journal Information:: Nanomaterials, Vol. 13, Issue 2; ISSN 2079-4991

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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