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Many-Exciton Quantum Dynamics in a Ruddlesden–Popper Tin Iodide

Journal Article · · Journal of Physical Chemistry. C
We present a study on the many-body exciton interactions in a Ruddlesden–Popper tin halide, namely, (PEA)2SnI4 (PEA = phenylethylammonium), using coherent two-dimensional electronic spectroscopy. The optical dephasing times of the third-order polarization observed in these systems are determined by exciton many-body interactions and lattice fluctuations. We investigate the excitation-induced dephasing (EID) and observe a significant reduction of the dephasing time with increasing excitation density as compared to its lead counterpart (PEA)2PbI4, which we have previously reported in a separate publication [J. Chem. Phys. 2020, 153, 164706]. Surprisingly, we find that the EID interaction parameter is four orders of magnitude higher in (PEA)2SnI4 than that in (PEA)2PbI4. This increase in the EID rate may be due to exciton localization arising from a more statically disordered lattice in the tin derivative. This is supported by the observation of multiple closely spaced exciton states and the broadening of the linewidth with increasing population time (spectral diffusion), which suggests a static disordered structure relative to the highly dynamic lead-halide. Additionally, we find that the exciton nonlinear coherent lineshape shows evidence of a biexcitonic state with low binding energy (<10 meV) not observed in the lead system. We model the lineshapes based on a stochastic scattering theory that accounts for the interaction with a nonstationary population of dark background excitations. Our study provides evidence of differences in the exciton quantum dynamics between tin- and lead-based Ruddlesden–Popper metal halides (RPMHs) and links them to the exciton–exciton interaction strength and the static disorder aspect of the crystalline structure.
Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
European Union Horizon’s 2020 research and innovation program; National Science Foundation (NSF); Robert A. Welch Foundation; USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
89233218CNA000001
OSTI ID:
2469619
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 43 Vol. 127; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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