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Exciton polaron formation and hot-carrier relaxation in rigid Dion–Jacobson-type two-dimensional perovskites

Nature Materials (2024)Cite this article

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Abstract

The efficiency of two-dimensional Dion–Jacobson-type materials relies on the complex interplay between electronic and lattice dynamics; however, questions remain about the functional role of exciton–phonon interactions. Here we establish the robust polaronic nature of the excitons in these materials at room temperature by combining ultrafast spectroscopy and electronic structure calculations. We show that polaronic distortion is associated with low-frequency (30–60 cm−1) lead iodide octahedral lattice motions. More importantly, we discover how targeted ligand modification of this two-dimensional perovskite structure manipulates exciton–phonon coupling, exciton polaron population and carrier cooling. At high excitation density, stronger exciton–phonon coupling increases the hot-carrier lifetime, forming a hot-phonon bottleneck. Our study provides detailed insight into the exciton–phonon coupling and its role in carrier cooling in two-dimensional perovskites relevant for developing emerging hybrid semiconductor materials with tailored properties.

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Fig. 1: Structure, steady-state and time-resolved data of 2D DJ-type perovskites.
Fig. 2: Frequency, phase, amplitude analysis of wavepacket, and impulsive generation of coherent phonons.
Fig. 3: Participating phonon modes, comparison of reorganization energies and exciton polaron formation.
Fig. 4: Manipulation of carrier relaxation via ligand engineering.

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Data availability

The authors declare that all data supporting the findings of this study are available within the paper and Supplementary Information files. Additional images are available from the corresponding authors upon request. Source data are provided with this paper.

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Acknowledgements

Financial support was provided by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences, of the US Department of Energy through grant no. DE-SC0015429. Additionally, this work was supported by the US Department of Energy, Office of Basic Energy Sciences under contract DE-SC0020437. D.F.C. acknowledges support from the National Science Foundation under grant CHE-1955407. F.A. acknowledges support from the Department of Energy, Office of Basic Energy Sciences under contract DE-SC0018080. S.S. acknowledges support from the Department of Energy, Office of Basic Energy Sciences under contract DE-SC0023402. R.Z. and D.S.S. acknowledge support from the NSERC of Canada and the E.W.R. Steacie Memorial Fellowship. M.Z. acknowledges funding by the European Union (project ULTRA-2DPK/HORIZON-MSCA-2022-PF-01/grant agreement no. 101106654).

Author information

Author notes

  1. These authors contributed equally: Somnath Biswas, Ruyan Zhao, Fatimah Alowa.

Authors and Affiliations

  1. Department of Chemistry, Princeton Uiversity, Princeton, NJ, USA

    Somnath Biswas & Gregory D. Scholes

  2. Department of Chemistry, University of Toronto, Toronto, Ontario, Canada

    Ruyan Zhao & Dwight S. Seferos

  3. Division of Materials Science and Engineering, Boston University, Boston, MA, USA

    Fatimah Alowa

  4. Université de Rennes, INSA Rennes, CNRS, Institut FOTON - UMR 6082, F-35000, Rennes, France

    Marios Zacharias

  5. Department of Electrical and Computer Engineering, Boston University, Boston, MA, USA

    Sahar Sharifzadeh

  6. Department of Chemistry, Boston University, Boston, MA, USA

    David F. Coker

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Contributions

S.B., G.D.S., D.S.S. and R.Z initiated the project. S.B. designed and conceptualized the study, performed ultrafast experiments and validated and analysed the experimental data. S.B. wrote the original draft and led the revision and editing. F.A., M.Z., S.S. and D.F.C. designed the computational study, F.A. ran calculations and S.B., F.A., M.Z., S.S. and D.F.C. analysed the theoretical results. R.Z. and D.S.S. designed and fabricated the materials. S.B., G.D.S. and D.F.C. extensively discussed the data. All authors contributed to writing the manuscript.

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Correspondence to Dwight S. Seferos or Gregory D. Scholes.

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Biswas, S., Zhao, R., Alowa, F. et al. Exciton polaron formation and hot-carrier relaxation in rigid Dion–Jacobson-type two-dimensional perovskites. Nat. Mater. (2024). https://doi.org/10.1038/s41563-024-01895-z

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