Intrinsic doping limit and defect-assisted luminescence in Cs4PbBr6

Young Kwang Jung, Joaquín Calbo, Ji Sang Park, Lucy D. Whalley, Sunghyun Kim, Aron Walsh

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Cs4PbBr6 is a member of the extended halide perovskite family that is built from isolated (zero-dimensional) PbBr64- octahedra with Cs+ counter ions. The material exhibits anomalous optoelectronic properties: optical absorption and weak emission in the deep ultraviolet (310-375 nm) with efficient luminescence in the green region (∼540 nm). Several hypotheses have been proposed to explain the giant Stokes shift including: (i) phase impurities; (ii) self-trapped exciton; (iii) defect emission. We explore, using first-principles theory and self-consistent Fermi level analysis, the unusual defect chemistry and physics of Cs4PbBr6. We find a heavily compensated system where the room-temperature carrier concentrations (<109 cm-3) are more than one million times lower than the defect concentrations. We show that the low-energy Br-on-Cs antisite results in the formation of a polybromide (Br3) species that can exist in a range of charge states. We further demonstrate from excited-state calculations that tribromide moieties are photoresponsive and can contribute to the observed green luminescence. Photoactivity of polyhalide molecules is expected to be present in other halide perovskite-related compounds where they can influence light absorption and emission.

Original languageEnglish
Pages (from-to)20254-20261
Number of pages8
JournalJournal of Materials Chemistry A
Volume7
Issue number35
DOIs
Publication statusPublished - 2019 Jan 1

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Luminescence
Doping (additives)
Perovskite
Light absorption
Defects
Radiation counters
Light emission
Fermi level
Excited states
Excitons
Optoelectronic devices
Carrier concentration
Physics
Impurities
Molecules
Temperature
perovskite
LDS 751

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

Cite this

Jung, Young Kwang ; Calbo, Joaquín ; Park, Ji Sang ; Whalley, Lucy D. ; Kim, Sunghyun ; Walsh, Aron. / Intrinsic doping limit and defect-assisted luminescence in Cs4PbBr6. In: Journal of Materials Chemistry A. 2019 ; Vol. 7, No. 35. pp. 20254-20261.
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Intrinsic doping limit and defect-assisted luminescence in Cs4PbBr6. / Jung, Young Kwang; Calbo, Joaquín; Park, Ji Sang; Whalley, Lucy D.; Kim, Sunghyun; Walsh, Aron.

In: Journal of Materials Chemistry A, Vol. 7, No. 35, 01.01.2019, p. 20254-20261.

Research output: Contribution to journalArticle

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