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

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

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

Abstract

The logic in the design of a halide-mixed APb(I1−xBrx)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.

Keywords

density functional theory; inorganic perovskite solar cells; mixed perovskite solar cells; photovoltaics; redox chemistry; nanoinclusions, Article, photovoltaics, Chemistry, redox chemistry, mixed perovskite solar cells, nanoinclusions, QD1-999, density functional theory, inorganic perovskite solar cells

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citations
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
4
Top 10%
Average
Average
Green
gold
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