Decoding ultrafast polarization responses in lead halide perovskites by the two-dimensional optical Kerr effect
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- Department of Chemistry, Columbia University, New York, NY 10027,
- Harvard John A. Paulson School of Engineering &, Applied Sciences, Harvard University, Cambridge, Massachusetts 02138,, Department of Materials Science, ETH Zurich, CH-8092 Zürich, Switzerland,
- Computational Laboratory for Hybrid/Organic Photovoltaics, Istituto CNR di Scienze e Tecnologie Chimiche “Giulio Natta,” 06123 Perugia, Italy,
- Computational Laboratory for Hybrid/Organic Photovoltaics, Istituto CNR di Scienze e Tecnologie Chimiche “Giulio Natta,” 06123 Perugia, Italy,, Department of Chemistry, Biology and Biotechnology, University of Perugia, 06123 Perugia, Italy,, CompuNet, Istituto Italiano di Tecnologia, 16163 Genova, Italy
The ultrafast polarization response to incident light and ensuing exciton/carrier generation are essential to outstanding optoelectronic properties of lead halide perovskites (LHPs). A large number of mechanistic studies in the LHP field to date have focused on contributions to polarizability from organic cations and the highly polarizable inorganic lattice. For a comprehensive understanding of the ultrafast polarization response, we must additionally account for the nearly instantaneous hyperpolarizability response to the propagating light field itself. While light propagation is pivotal to optoelectronics and photonics, little is known about this in LHPs in the vicinity of the bandgap where stimulated emission, polariton condensation, superfluorescence, and photon recycling may take place. Here we develop two-dimensional optical Kerr effect (2D-OKE) spectroscopy to energetically dissect broadband light propagation and dispersive nonlinear polarization responses in LHPs. In contrast to earlier interpretations, the below-bandgap OKE responses in both hybrid CH3NH3PbBr3 and all-inorganic CsPbBr3 perovskites are found to originate from strong hyperpolarizability and highly anisotropic dispersions. In both materials, the nonlinear mixing of anisotropically propagating light fields results in convoluted oscillatory polarization dynamics. Based on a four-wave mixing model, we quantitatively derive dispersion anisotropies, reproduce 2D-OKE frequency correlations, and establish polarization-dressed light propagation in single-crystal LHPs. Moreover, our findings highlight the importance of distinguishing the often-neglected anisotropic light propagation from underlying coherent quasiparticle responses in various forms of ultrafast spectroscopy.
- Research Organization:
- Columbia Univ., New York, NY (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC); US Air Force Office of Scientific Research (AFOSR); US Office of Naval Research (ONR)
- Grant/Contract Number:
- SC0010692; FA9550-18-1-002; N00014-18-1-2080
- OSTI ID:
- 1765015
- Alternate ID(s):
- OSTI ID: 1851423
- Journal Information:
- Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 118 Journal Issue: 7; ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of SciencesCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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