Asynchronous Photoexcited Electronic and Structural Relaxation in Lead-Free Perovskites

Cunming Liu, Yingqi Wang, Huifang Geng, Taishan Zhu, Elif Ertekin, David Gosztola, Sizhuo Yang, Jier Huang, Bin Yang, Keli Han, Sophie E. Canton, Qingyu Kong, Kaibo Zheng, Xiaoyi Zhang

Research output: Contribution to journalArticle

Abstract

Vacancy-ordered lead-free perovskites with more-stable crystalline structures have been intensively explored as the alternatives for resolving the toxic and long-term stability issues of lead halide perovskites (LHPs). The dispersive energy bands produced by the closely packed halide octahedral sublattice in these perovskites are meanwhile anticipated to facility the mobility of charge carriers. However, these perovskites suffer from unexpectedly poor charge carrier transport. To tackle this issue, we have employed the ultrafast, elemental-specific X-ray transient absorption (XTA) spectroscopy to directly probe the photoexcited electronic and structural dynamics of a prototypical vacancy-ordered lead-free perovskite (Cs3Bi2Br9). We have discovered that the photogenerated holes quickly self-trapped at Br centers, simultaneously distorting the local lattice structure, likely forming small polarons in the configuration of Vk center (Br2 - dimer). More significantly, we have found a surprisingly long-lived, structural distorted state with a lifetime of ∼59 μs, which is ∼3 orders of magnitude slower than that of the charge carrier recombination. Such long-lived structural distortion may produce a transient "background" under continuous light illumination, influencing the charge carrier transport along the lattice framework.

Original languageEnglish (US)
Pages (from-to)13074-13080
Number of pages7
JournalJournal of the American Chemical Society
Volume141
Issue number33
DOIs
StatePublished - Aug 21 2019

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Structural relaxation
Charge carriers
halide
Lead
Carrier transport
X-Ray Absorption Spectroscopy
Crystal lattices
Vacancies
Poisons
perovskite
atomic absorption spectroscopy
Lighting
Polarons
Genetic Recombination
recombination
Structural dynamics
Absorption spectroscopy
probe
Dimers
Band structure

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Asynchronous Photoexcited Electronic and Structural Relaxation in Lead-Free Perovskites. / Liu, Cunming; Wang, Yingqi; Geng, Huifang; Zhu, Taishan; Ertekin, Elif; Gosztola, David; Yang, Sizhuo; Huang, Jier; Yang, Bin; Han, Keli; Canton, Sophie E.; Kong, Qingyu; Zheng, Kaibo; Zhang, Xiaoyi.

In: Journal of the American Chemical Society, Vol. 141, No. 33, 21.08.2019, p. 13074-13080.

Research output: Contribution to journalArticle

Liu, C, Wang, Y, Geng, H, Zhu, T, Ertekin, E, Gosztola, D, Yang, S, Huang, J, Yang, B, Han, K, Canton, SE, Kong, Q, Zheng, K & Zhang, X 2019, 'Asynchronous Photoexcited Electronic and Structural Relaxation in Lead-Free Perovskites', Journal of the American Chemical Society, vol. 141, no. 33, pp. 13074-13080. https://doi.org/10.1021/jacs.9b04557
Liu, Cunming ; Wang, Yingqi ; Geng, Huifang ; Zhu, Taishan ; Ertekin, Elif ; Gosztola, David ; Yang, Sizhuo ; Huang, Jier ; Yang, Bin ; Han, Keli ; Canton, Sophie E. ; Kong, Qingyu ; Zheng, Kaibo ; Zhang, Xiaoyi. / Asynchronous Photoexcited Electronic and Structural Relaxation in Lead-Free Perovskites. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 33. pp. 13074-13080.
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