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Bidirectional phonon emission in two-dimensional heterostructures triggered by ultrafast charge transfer

Nature Nanotechnology volume 18, pages 29–35 (2023)Cite this article

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Abstract

Photoinduced charge transfer in van der Waals heterostructures occurs on the 100 fs timescale despite weak interlayer coupling and momentum mismatch. However, little is understood about the microscopic mechanism behind this ultrafast process and the role of the lattice in mediating it. Here, using femtosecond electron diffraction, we directly visualize lattice dynamics in photoexcited heterostructures of WSe2/WS2 monolayers. Following the selective excitation of WSe2, we measure the concurrent heating of both WSe2 and WS2 on a picosecond timescale—an observation that is not explained by phonon transport across the interface. Using first-principles calculations, we identify a fast channel involving an electronic state hybridized across the heterostructure, enabling phonon-assisted interlayer transfer of photoexcited electrons. Phonons are emitted in both layers on the femtosecond timescale via this channel, consistent with the simultaneous lattice heating observed experimentally. Taken together, our work indicates strong electron–phonon coupling via layer-hybridized electronic states—a novel route to control energy transport across atomic junctions.

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Fig. 1: UED of a 2D semiconductor heterostructure.
Fig. 2: Phonon thermal transport across a monolayer WSe2/WS2 heterojunction.
Fig. 3: Lattice dynamics in a photoexcited WSe2/WS2 heterojunction.
Fig. 4: First-principles calculations of the proposed charge transfer and phonon emission mechanism.

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Data availability

The data underlying Figs. 1–4 and Supplementary Figs. 3–17 are available via Zenodo at https://doi.org/10.5281/zenodo.7328935.

Code availability

The codes and analysis scripts that support the findings of this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

We gratefully acknowledge M. Kozina, S. Park, D. Luo and T. Mattox for experimental support, and M. Naik for insightful discussions. A.R. gratefully acknowledges support through the Early Career LDRD Program of Lawrence Berkeley National Laboratory under US Department of Energy (DOE) contract no. DE-AC02-05CH11231. Sample fabrication at the Molecular Foundry was supported by the US DOE Office of Basic Energy Sciences under contract no. DE-AC02-05CH11231. E.C.R. and F.W. also acknowledge support from the US DOE, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under contract no. DE-AC02-05CH11231 (van der Waals heterostructure program KCFW16). Research at SLAC was supported by the US DOE, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division. The UED experiments were performed at the SLAC MeV-UED which 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. The computational work was supported by the Center for Computational Study of Excited State Phenomena in Energy Materials (C2SEPEM), which is funded by the DOE, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, under contract no. DE-AC02-05CH11231, as part of the Computational Materials Sciences Program. We acknowledge the use of computational resources at the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the DOE Office of Science under the above contract, using NERSC awards BES-ERCAP-2651 for the electronic structure calculations and BES-ERCAP-m3606 for the molecular dynamics simulations. Additional computational resources were provided by the Extreme Science and Engineering Discovery Environment (XSEDE) supercomputer Stampede2 at the Texas Advanced Computing Center (TACC) through the allocation TG-DMR190070 for electron–phonon calculations. E.B. and J.D.G. acknowledgs support from the Natural Science and Engineering Research Council (NSERC) Canada through the Post-Graduate Scholarship PGS D3-502559-2017 and PGS D-568202-2022, respectively. E.C.R. acknowledges support from the Department of Defense through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program. K.W. and T.T. acknowledge support from JSPS KAKENHI (grant nos. 19H05790, 20H00354 and 21H05233).

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Author notes

  1. These authors contributed equally: Aditya Sood, Jonah B. Haber.

Authors and Affiliations

  1. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Aditya Sood, Elyse Barre, Tony F. Heinz & Aaron M. Lindenberg

  2. Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA

    Aditya Sood, Johnathan D. Georgaras, Marc E. Zajac, Aaron M. Lindenberg & Felipe H. da Jornada

  3. Department of Physics, University of California Berkeley, Berkeley, CA, USA

    Jonah B. Haber, Elizabeth A. Peterson, Emma C. Regan, Feng Wang & Jeffrey B. Neaton

  4. Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Johan Carlström, Elizabeth A. Peterson, Emma C. Regan, Jeffrey B. Neaton & Archana Raja

  5. Department of Applied Physics, Stanford University, Stanford, CA, USA

    Elyse Barre & Tony F. Heinz

  6. SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Alexander H. M. Reid, Xiaozhe Shen, Jie Yang & Xijie Wang

  7. Graduate Group in Applied Science and Technology, University of California Berkeley, Berkeley, CA, USA

    Emma C. Regan

  8. International Center for Materials Nanoarchitectonics, National Institute for Materials Science, Tsukuba, Japan

    Takashi Taniguchi

  9. Research Center for Functional Materials, National Institute for Materials Science, Tsukuba, Japan

    Kenji Watanabe

  10. Kavli Energy NanoScience Institute, University of California Berkeley, Berkeley, CA, USA

    Jeffrey B. Neaton

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Contributions

A.S., A.R. and A.M.L. conceived the experiments. A.R. supervised the project. J.C. and A.R. prepared the heterostructures with inputs from E.C.R. A.S., J.C. and A.R. performed the UED experiments with support from A.H.M.R., X.S., M.E.Z., J.Y., X.W. and A.M.L. A.S. and J.C. analysed the UED data. A.S. performed the thermal transport calculations. F.H.J. designed the theoretical approach. J.B.H. and E.A.P. carried out the first-principles calculations with supervision from F.H.J. and inputs from J.B.N. E.B. performed the absorption and PL measurements under the supervision of T.F.H. J.D.G. performed the molecular dynamics simulations of thermal transport under the supervision of F.H.J. T.T. and K.W. grew the hBN crystals. A.S. and J.B.H. prepared the initial draft with significant contributions from E.A.P., F.H.J. and A.R., and feedback from J.B.N., T.F.H. and A.M.L. All the authors commented on the manuscript and approved the final version.

Corresponding authors

Correspondence to Aditya Sood, Aaron M. Lindenberg, Felipe H. da Jornada or Archana Raja.

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Nature Nanotechnology thanks Xiangfan Xu, Jin Zhao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–18 and Sections 1–5.

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Sood, A., Haber, J.B., Carlström, J. et al. Bidirectional phonon emission in two-dimensional heterostructures triggered by ultrafast charge transfer. Nat. Nanotechnol. 18, 29–35 (2023). https://doi.org/10.1038/s41565-022-01253-7

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