Direct Spectroscopic Observation of the Hole Polaron in Lead Halide Perovskites

Liu, Cunming; Tsai, Hsinhan; Nie, Wanyi; Gosztola, David J.; Zhang, Xiaoyi

doi:10.1021/acs.jpclett.0c01708

Title: Direct Spectroscopic Observation of the Hole Polaron in Lead Halide Perovskites

Journal Article · Mon Jul 13 00:00:00 EDT 2020 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.0c01708· OSTI ID:1726211

Liu, Cunming ^[1];

^[2];

^[3];

^[1]

Argonne National Lab. (ANL), Argonne, IL (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Center for Integrated Nanotechnologies (CINT)
Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials

Intrinsic photophysical origin of lead halide perovskites (LHPs) succeeding in optolectronic applications still remains hotly debated. In this study, by using the ultrafast X-ray transient absorption spectroscopy, we successfully tracked the fate of photogenerated charge carriers at room temperature within the thin films of two classic LHPs, namely MAPbBr₃ (MA: CH₃NH₃) and FAPbBr₃ (FA: CH(NH₂)₂). We clearly observed in both thin films that the hole polaron is formed by localizing the photogenerated hole at Br 4p orbital and concurrently distorting the local structure surrounding Br atom after the photoexcitation. Furthermore, the bigger cation FA in the cavity of [PbBr₆]^4- octahedral framework induces larger hole polaron effect due to its p orbital hybridization into valence and conduction bands, correlating with the slower charge carrier recombination dynamics. Our direct experimental observation of the localized hole polaron in perovskites should advance the fundamental comprehension of charge carrier behavior within LHPs and their related devices.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

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

Grant/Contract Number:: AC02-06CH11357; 89233218CNA000001

OSTI ID:: 1726211

Alternate ID(s):: OSTI ID: 1674972

Report Number(s):: LA-UR-20-24148

Journal Information:: Journal of Physical Chemistry Letters, Vol. 11, Issue 15; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
polarons
thin films
carrier dynamics
electrical conductivity
perovskites

Title: Direct Spectroscopic Observation of the Hole Polaron in Lead Halide Perovskites

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