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Efficient and tunable photochemical charge transfer via long-lived Bloch surface wave polaritons

Nature Nanotechnology volume 20, pages 1618–1624 (2025)Cite this article

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Abstract

Hybrid light–matter molecular exciton–polariton states have been proposed as a strategy to directly modify the efficiency and rate of photoinduced molecular charge transfer reactions. However, the efficacy of polariton-driven photochemistry remains an open question owing to the experimental challenges to tease out this effect. Here we demonstrate conditions under which photoinduced polaritonic charge transfer can be achieved and visualized using momentum-resolved ultrafast spectroscopy. Key conditions for charge transfer are satisfied using Bloch surface wave polaritons, which exhibit favourable dispersion characteristics that permit the selective pumping of hybrid states with long lifetimes (100–400 fs) that permit vibrationally assisted charge transfer between a donor and an acceptor molecule dispersed in a polymer matrix. Using this approach, we tune the energetic driving force for charge separation, reducing it by as much as 0.5 eV compared with the bare exciton pumping with an internal quantum efficiency of 0.77. These results corroborate the notion that tunable and efficient polariton-driven molecular charge transfer is indeed possible using carefully constructed photonic systems.

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Fig. 1: CT processes in uncoupled and strongly coupled donor–acceptor systems.
Fig. 2: Highlighting CT signatures in PM605–TCNQ blend film.
Fig. 3: Lifetime of BSW polaritons for different in-plane momenta.
Fig. 4: Driving selective and efficient CT with BSW polaritons.

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Data availability

The data that support the plots and other findings in the work are available in the article and the Supplementary Information file, and are available from the corresponding author on reasonable request. Additional raw data used in our analyses are available at https://doi.org/10.6084/m9.figshare.29459198.

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Acknowledgements

This work was supported by the Gordon and Betty Moore Foundation (grant number 12235). V.M.M. was supported by the US Air Force Office of Scientific Research-MURI Grant FA9550-22-1-0317.

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Authors and Affiliations

  1. Photonics Initiative, Advanced Science Research Center, City University of New York, New York, NY, USA

    Kamyar Rashidi, Evripidis Michail, Bernardo Salcido-Santacruz, Yamuna Paudel & Matthew Y. Sfeir

  2. Department of Physics, Graduate Center, City University of New York, New York, NY, USA

    Kamyar Rashidi, Evripidis Michail, Yamuna Paudel, Vinod M. Menon & Matthew Y. Sfeir

  3. Department of Chemistry, Graduate Center, City University of New York, New York, NY, USA

    Bernardo Salcido-Santacruz

  4. Department of Physics, City College of New York, New York, NY, USA

    Vinod M. Menon

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Contributions

M.Y.S. conceived the experimental idea and supervised the project. The pump–probe measurements and analysis of the corresponding data were performed by K.R. with help from E.M. and M.Y.S. K.R. fabricated and modelled the dielectric photonic devices. E.M., K.R. and Y.P. fabricated and modelled the metal photonic devices. B.S.-S. performed the spectroelectrochemistry measurements. K.R., E.M., V.M.M. and M.Y.S. interpreted the results together with all of the authors. The paper was written by K.R. and M.Y.S. with input from all co-authors.

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Correspondence to Matthew Y. Sfeir.

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Supplementary Figs. 1–24, Discussion and Tables 1–4.

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Rashidi, K., Michail, E., Salcido-Santacruz, B. et al. Efficient and tunable photochemical charge transfer via long-lived Bloch surface wave polaritons. Nat. Nanotechnol. 20, 1618–1624 (2025). https://doi.org/10.1038/s41565-025-01995-0

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