Low-energy pathways lead to self-healing defects in CsPbBr3

Miskin, Kumar; Cao, Yi; Marland, Madaline; Shaikh, Farhan; Moore, David T.; Marohn, John A.; Clancy, Paulette

doi:10.1039/D5CP01641J

Low-energy pathways lead to self-healing defects in CsPbBr₃

Journal Article · Wed Jun 18 00:00:00 EDT 2025 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/D5CP01641J· OSTI ID:2574739

^[1]; ^[1]; Marland, Madaline ^[1]; Shaikh, Farhan ^[1]; ^[2]; Marohn, John A. ^[3]; ^[1]

Johns Hopkins Univ., Baltimore, MD (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Cornell Univ., Ithaca, NY (United States)

Self-regulation of free charge carriers in perovskites via Schottky defect formation has been posited as the origin of the well-known defect-tolerance of metal halide perovskite materials. Understanding the mechanisms of self-regulation promises to lead to the fabrication of better performing solar cell materials with higher efficiencies. We investigate many such mechanisms here for CsPbBr₃, a popular representative of a more commercially viable all-inorganic metal halide perovskite. We investigate different atomic-level mechanisms and pathways of the diffusion and recombination of neutral and charged interstitials and vacancies (Schottky pairs) in CsPbBr₃. We use nudged elastic band calculations and ab initio-derived pseudopotentials within quantum ESPRESSO to determine energies of formation and migration and hence the activation energies for these defects. While halide vacancies are known to exhibit low formation energies, the migration of interstitials is less studied. Our calculations uncover interstitial defect pathways capable of producing an activation energy at, or below, the single experimental value of 0.53 eV observed for the slow, temperature-dependent recovery of light-induced conductivity in bulk CsPbBr₃. Our work reveals the existence of a low-energy diffusion pathway involving a concerted “domino effect” of interstitials, with the net result that interstitials can diffuse more readily over longer distances than expected. This observation suggests that defect self-healing can be promoted if the “domino effect” strategy can be engaged.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC36-08GO28308; SC0022305

OSTI ID:: 2574739

Report Number(s):: NREL/JA--4B00-96032

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 29 Vol. 27; ISSN 1463-9076; ISSN 1463-9084

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CsPbBr3
Schottky pairs
perovskites

Low-energy pathways lead to self-healing defects in CsPbBr3

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References (65)

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Low-energy pathways lead to self-healing defects in CsPbBr₃