Strong Electron–Phonon Coupling and Self-Trapped Excitons in the Defect Halide Perovskites A3M2I9 (A = Cs, Rb; M = Bi, Sb)

McCall, Kyle M.; Stoumpos, Constantinos C.; Kostina, Svetlana S.; Kanatzidis, Mercouri G.; Wessels, Bruce W.

doi:10.1021/acs.chemmater.7b01184

Title: Strong Electron–Phonon Coupling and Self-Trapped Excitons in the Defect Halide Perovskites A₃M₂I₉ (A = Cs, Rb; M = Bi, Sb)

Journal Article · Thu Apr 20 00:00:00 EDT 2017 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.7b01184· OSTI ID:1494819

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Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering
Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering

The optical and electronic properties of Bridgman grown single crystals of the wide-bandgap semiconducting defect halide perovskites A₃M₂I₉ (A = Cs, Rb; M = Bi, Sb) have been investigated. Intense Raman scattering was observed at room temperature for each compound, indicating high polarizability and strong electron–phonon coupling. Both low-temperature and room-temperature photoluminescence (PL) were measured for each compound. Cs₃Sb₂I₉ and Rb₃Sb₂I₉ have broad PL emission bands between 1.75 and 2.05 eV with peaks at 1.96 and 1.92 eV, respectively. The Cs₃Bi₂I₉ PL spectra showed broad emission consisting of several overlapping bands in the 1.65–2.2 eV range. Evidence of strong electron–phonon coupling comparable to that of the alkali halides was observed in phonon broadening of the PL emission. Effective phonon energies obtained from temperature-dependent PL measurements were in agreement with the Raman peak energies. A model is proposed whereby electron–phonon interactions in Cs₃Sb₂I₉, Rb₃Sb₂I₉, and Cs₃Bi₂I₉ induce small polarons, resulting in trapping of excitons by the lattice. The recombination of these self-trapped excitons is responsible for the broad PL emission. Finally, Rb₃Bi₂I₉, Rb₃Sb₂I₉, and Cs₃Bi₂I₉ exhibit high resistivity and photoconductivity response under laser photoexcitation, indicating that these compounds possess potential as semiconductor hard radiation detector materials.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0002522; AC02-06CH11357

OSTI ID:: 1494819

Journal Information:: Chemistry of Materials, Vol. 29, Issue 9; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 451 works

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Pressure-induced emission of cesium lead halide perovskite nanocrystals. Ma, Zhiwei; Liu, Zhun; Lu, Siyu Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.33885	text	January 2018
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Title: Strong Electron–Phonon Coupling and Self-Trapped Excitons in the Defect Halide Perovskites A₃M₂I₉ (A = Cs, Rb; M = Bi, Sb)