Abstract
Direct visualization of ultrafast coupling between charge carriers and lattice degrees of freedom in photoexcited semiconductors has remained a long-standing challenge and is critical for understanding the light-induced physical behaviour of materials under extreme non-equilibrium conditions. Here we obtain a direct visualization of the structural dynamics in monocrystalline 2D perovskites. We achieve this by monitoring the evolution of wavevector-resolved ultrafast electron diffraction intensity following above-bandgap high-density photoexcitation. Our analysis reveals a light-induced ultrafast reduction in antiferro-distortion resulting from a strong interaction between the electron–hole plasma and perovskite lattice, which induces an in-plane octahedra rotation towards a more symmetric phase. Correlated ultrafast spectroscopy performed at the same carrier density as ultrafast electron diffraction reveals that the creation of a dense electron–hole plasma triggers the relaxation of lattice distortion at shorter timescales by modulating the crystal cohesive energy. Finally, we show that the interaction between carrier gas and lattice can be altered by tailoring the rigidity of the 2D perovskite by choosing an appropriate organic spacer layer.
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Data availability
All of the data supporting the findings of this study are available in the Article and Supplementary Information. Any additional data are available from the corresponding authors upon reasonable request. Source data are provided with this paper.
Code availability
The analysis code for this study is available from the corresponding authors upon reasonable request.
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Acknowledgements
The work at Rice University was supported by the DOE-EERE 0008843 program. W.L. acknowledges the National Science Foundation Graduate Research Fellowship Program. This material is based on work supported by the National Science Foundation Graduate Research Fellowship Program under grant no. NSF 20-587. Any opinions, findings and conclusions or recommendations expressed in this material are those of the author and do not necessarily reflect the views of the National Science Foundation. J.H. acknowledges financial support from the China Scholarships Council (no. 202107990007). J. Even acknowledges financial support from the Institut Universitaire de France. Work at Northwestern University was supported by the Office of Naval Research (ONR) under grant N00014-20-1-2725. Part of the work at ISCR and Institut FOTON was funded by the European Union’s Horizon 2020 research and innovation program under grant agreement no.861985 (PeroCUBE) and by the Agence Nationale pour la Recherche (MORELESS project). For DFT calculations, this work was granted access to the HPCresources of TGCC under the allocation 2020-A0090907682 made by GENCI. MeV-UED is operated as part of the Linac Coherent Light Source at the SLAC National Accelerator Laboratory, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. S.L. thanks the Robert A. Welch Foundation for support through the Charles W. Duncan, Jr.-Welch Chair in Chemistry (C-0002), and acknowledges financial support from the US Department of Energy, Office of Science, Basic Energy Sciences, CPIMS program, under award no. DE-339SC0016534 (W.-Y.C).
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Contributions
A.D.M. and J.-C.B. conceived and designed the experiment. J.H. and S.S. synthesized the perovskite single crystals, and W.L. prepared the samples with help from J.H. and H.Z. H.Z. performed the optical absorbance characterizations. W.L., H.Z., S.S. and A.F. performed the UED experiments with help from A.A., M.-F.L., A.B., X.Z., X.W. and U.B. H.Z. performed the data analysis with assistance from J. Essman and I.M., with guidance from J.-C.B., J. Even and M.G.K. Phonon modelling was carried out by C.Q. with guidance from J. Even and C.K. W.Y. performed the TA measurements with guidance from S.L. J.-C.B. and A.D.M. wrote the manuscript with inputs from all the authors. All the authors read the manuscript and agreed to its contents, and all the data are reported in the main text and Supplementary Information.
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Supplementary Discussions 1–11, Figs. 1–26, Tables 1 and 2 and references.
Source data
Source Data Fig. 1
Statistically averaged and normalized electron diffraction maps at negative time delay for DJ n = 2 crystal (Fig. 1c).
Source Data Fig. 2
Angular-integrated diffraction plots at 2 ps, compared with the simulated intensity response (Fig. 2d).
Source Data Fig. 3
Bragg peak intensity plots versus time (Fig. 3a). Evolution of carrier temperatures versus time (Fig. 3d). Calculated saturation densities versus carrier temperature (Fig. 3e).
Source Data Fig. 4
Angular-integrated diffraction plot (20–40 ps) for DJ n = 2, DJ n = 3, RP n = 2 and RP n = 4 crystals (Fig. 4c). Histogram of rise-time constants (Fig. 4d).
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Zhang, H., Li, W., Essman, J. et al. Ultrafast relaxation of lattice distortion in two-dimensional perovskites. Nat. Phys. 19, 545–550 (2023). https://doi.org/10.1038/s41567-022-01903-6
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DOI: https://doi.org/10.1038/s41567-022-01903-6
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