Efficient and tunable photochemical charge transfer via long-lived Bloch surface wave polaritons
Source abstract
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.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Strong Light-Matter Interactions · Photochemistry and Electron Transfer Studies · Perovskite Materials and Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (60)
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1. Weisbuch, C., Nishioka, M., Ishikawa, A. & Arakawa, Y. Observation of the coupled exciton-photon mode splitting in a semiconductor quantum microcavity. Phys. Rev. Lett. 69, 3314 (1992).10.1103/PhysRevLett.69.3314 ↗
2. Hopfield, J. Theory of the contribution of excitons to the complex dielectric constant of crystals. Phys. Rev. 112, 1555 (1958).10.1103/PhysRev.112.1555 ↗
3. Ghosh, S. et al. Microcavity exciton polaritons at room temperature. Photon. Insights 1, R04 (2022).10.3788/PI.2022.R04 ↗
4. Kasprzak, J. et al. Bose–Einstein condensation of exciton polaritons. Nature 443, 409–414 (2006).10.1038/nature05131 ↗
5. Amo, A. et al. Superfluidity of polaritons in semiconductor microcavities. Nat. Phys. 5, 805–810 (2009).10.1038/nphys1364 ↗
6. Lagoudakis, K. G. et al. Quantized vortices in an exciton–polariton condensate. Nat. Phys. 4, 706–710 (2008).10.1038/nphys1051 ↗
7. Zasedatelev, A. V. et al. A room-temperature organic polariton transistor. Nat. Photon. 13, 378–383 (2019).10.1038/s41566-019-0392-8 ↗
8. Hutchison, J. A. et al. Tuning the work-function via strong coupling. Adv. Mater. 25, 2481–2485 (2013).10.1002/adma.201203682 ↗
9. Orgiu, E. et al. Conductivity in organic semiconductors hybridized with the vacuum field. Nat. Mater. 14, 1123–1129 (2015).10.1038/nmat4392 ↗
10. Rozenman, G. G., Akulov, K., Golombek, A. & Schwartz, T. Long-range transport of organic exciton-polaritons revealed by ultrafast microscopy. ACS Photon. 5, 105–110 (2018).10.1021/acsphotonics.7b01332 ↗
11. Coles, D. M. et al. Polariton-mediated energy transfer between organic dyes in a strongly coupled optical microcavity. Nat. Mater. 13, 712–719 (2014).10.1038/nmat3950 ↗
12. Du, M. et al. Theory for polariton-assisted remote energy transfer. Chem. Sci. 9, 6659–6669 (2018).10.1039/C8SC00171E ↗
13. Georgiou, K., Jayaprakash, R., Othonos, A. & Lidzey, D. G. Ultralong-range polariton-assisted energy transfer in organic microcavities. Angew. Chem. 60, 16661–16667 (2021).10.1002/anie.202105442 ↗
14. Liu, B., Huang, X., Hou, S., Fan, D. & Forrest, S. R. Photocurrent generation following long-range propagation of organic exciton–polaritons. Optica 9, 1029–1036 (2022).10.1364/OPTICA.461025 ↗
15. Nikolis, V. C. et al. Strong light-matter coupling for reduced photon energy losses in organic photovoltaics. Nat. Commun. 10, 3706 (2019).10.1038/s41467-019-11717-5 ↗
16. Bhuyan, R. et al. The rise and current status of polaritonic photochemistry and photophysics. Chem. Rev. 123, 10877–10919 (2023).10.1021/acs.chemrev.2c00895 ↗
17. Mandal, A. & Huo, P. Investigating new reactivities enabled by polariton photochemistry. J. Phys. Chem. Lett. 10, 5519–5529 (2019).10.1021/acs.jpclett.9b01599 ↗
18. Yuen-Zhou, J. & Menon, V. M. Polariton chemistry: thinking inside the (photon) box. Proc. Natl Acad. Sci. USA 116, 5214–5216 (2019).10.1073/pnas.1900795116 ↗
19. Hutchison, J. A., Schwartz, T., Genet, C., Devaux, E. & Ebbesen, T. W. Modifying chemical landscapes by coupling to vacuum fields. Angew. Chem. Int. Ed. 51, 1592–1596 (2012).10.1002/anie.201107033 ↗
20. Munkhbat, B., Wersäll, M., Baranov, D. G., Antosiewicz, T. J. & Shegai, T. Suppression of photo-oxidation of organic chromophores by strong coupling to plasmonic nanoantennas. Sci. Adv. 4, eaas9552 (2018).10.1126/sciadv.aas9552 ↗
21. Ward, A. J. et al. The impact of driving force on electron transfer rates in photovoltaic donor–acceptor blends. Adv. Mater. 27, 2496–2500 (2015).10.1002/adma.201405623 ↗
22. Unger, T. et al. The impact of driving force and temperature on the electron transfer in donor–acceptor blend systems. J. Phys. Chem. C 121, 22739–22752 (2017).10.1021/acs.jpcc.7b09213 ↗
23. Paul, B. K., Samanta, A., Kar, S. & Guchhait, N. Evidence for excited state intramolecular charge transfer reaction in donor–acceptor molecule 5-(4-dimethylamino-phenyl)-penta-2,4-dienoic acid methyl ester: experimental and quantum chemical approach. J. Lumin. 130, 1258–1267 (2010).10.1016/j.jlumin.2010.02.036 ↗
24. Delesma, C., Amador-Bedolla, C., Robles, M. & Muñiz, J. Photoisomerization and its effect in the opto-electronic properties of organic photovoltaic materials: a quantum chemistry study. J. Photochem. Photobiol. A 409, 113155 (2021).10.1016/j.jphotochem.2021.113155 ↗
25. Schäfer, C., Ruggenthaler, M., Appel, H. & Rubio, A. Modification of excitation and charge transfer in cavity quantum-electrodynamical chemistry. Proc. Natl Acad. Sci. USA 116, 4883–4892 (2019).10.1073/pnas.1814178116 ↗
26. Kim, H. S., Lee, S. H., Yoo, S. & Adachi, C. Understanding of complex spin up-conversion processes in charge-transfer-type organic molecules. Nat. Commun. 15, 2267 (2024).10.1038/s41467-024-46406-5 ↗
27. Deibel, C., Strobel, T. & Dyakonov, V. Role of the charge transfer state in organic donor–acceptor solar cells. Adv. Mater. 22, 4097–4111 (2010).10.1002/adma.201000376 ↗
28. Marcus, R. A. On the theory of oxidation-reduction reactions involving electron transfer. I. J. Chem. Phys. 24, 966–978 (1956).10.1063/1.1742723 ↗
29. Sumi, H. in Electron Transfer in Chemistry (ed. Balzani, V.) Ch. 2, 64–108 (Wiley, 2001).10.1002/9783527618248.ch2 ↗
30. Hou, B., Thoss, M., Banin, U. & Rabani, E. Incoherent nonadiabatic to coherent adiabatic transition of electron transfer in colloidal quantum dot molecules. Nat. Commun. 14, 3073 (2023).10.1038/s41467-023-38470-0 ↗
31. Groenhof, G., Climent, C., Feist, J., Morozov, D. & Toppari, J. J. Tracking polariton relaxation with multiscale molecular dynamics simulations. J. Phys. Chem. Lett. 10, 5476–5483 (2019).10.1021/acs.jpclett.9b02192 ↗
32. George, J. et al. Ultra-strong coupling of molecular materials: spectroscopy and dynamics. Faraday Discuss. 178, 281–294 (2015).10.1039/C4FD00197D ↗
33. Baranov, D. G., Wersall, M., Cuadra, J., Antosiewicz, T. J. & Shegai, T. Novel nanostructures and materials for strong light–matter interactions. ACS Photon. 5, 24–42 (2018).10.1021/acsphotonics.7b00674 ↗
34. Michail, E. et al. Addressing the dark state problem in strongly coupled organic exciton-polariton systems. Nano Lett. 24, 557–565 (2024).10.1021/acs.nanolett.3c02984 ↗
35. Climent, C., Casanova, D., Feist, J. & Garcia-Vidal, F. J. Not dark yet for strong light-matter coupling to accelerate singlet fission dynamics. Cell Rep. Phys. Sci. 3, 100841 (2022).10.1016/j.xcrp.2022.100841 ↗
36. Grafton, A. B. et al. Excited-state vibration-polariton transitions and dynamics in nitroprusside. Nat. Commun. 12, 214 (2021).10.1038/s41467-020-20535-z ↗
37. Khazanov, T. et al. Embrace the darkness: an experimental perspective on organic exciton–polaritons. Chem. Phys. Rev. 4, 041305 (2023).10.1063/5.0168948 ↗
38. Dutta, A. et al. Thermal disorder prevents the suppression of ultra-fast photochemistry in the strong light-matter coupling regime. Nat. Commun. 15, 6600 (2024).10.1038/s41467-024-50532-5 ↗
39. Liu, B., Menon, V. M. & Sfeir, M. Y. Ultrafast thermal modification of strong coupling in an organic microcavity. APL Photon. 6, 016103 (2021).10.1063/5.0031560 ↗
40. Litinskaya, M., Reineker, P. & Agranovich, V. M. Fast polariton relaxation in strongly coupled organic microcavities. J. Lumin. 110, 364–372 (2004).10.1016/j.jlumin.2004.08.033 ↗
41. Schwartz, T. et al. Polariton dynamics under strong light–molecule coupling. ChemPhysChem 14, 125–131 (2013).10.1002/cphc.201200734 ↗
42. Lodden, G. H. & Holmes, R. J. Electrical excitation of microcavity polaritons by radiative pumping from a weakly coupled organic semiconductor. Phys. Rev. B 82, 125317 (2010).10.1103/PhysRevB.82.125317 ↗
43. Liscidini, M., Gerace, D., Sanvitto, D. & Bajoni, D. Guided Bloch surface wave polaritons. Appl. Phys. Lett. 98, 121118 (2011).10.1063/1.3571285 ↗
44. Pirotta, S. et al. Strong coupling between excitons in organic semiconductors and Bloch surface waves. Appl. Phys. Lett. 104, 051111 (2014).10.1063/1.4863853 ↗
45. Barachati, F. et al. Interacting polariton fluids in a monolayer of tungsten disulfide. Nat. Nanotechnol. 13, 906–909 (2018).10.1038/s41565-018-0219-7 ↗
46. Bhaskar, S., Das, P., Srinivasan, V., Bhaktha BN, S. & Ramamurthy, S. S. Bloch surface waves and internal optical modes-driven photonic crystal-coupled emission platform for femtomolar detection of aluminum ions. J. Phys. Chem. C 124, 7341–7352 (2020).10.1021/acs.jpcc.9b11092 ↗
47. Mousavi-Kiasari, S. M. G. et al. Computational design of highly-sensitive graphene-based multilayer SPR biosensor. Photonics 9, 688 (2022).10.3390/photonics9100688 ↗
48. Lerario, G. et al. High-speed flow of interacting organic polaritons. Light Sci. Appl. 6, e16212 (2017).10.1038/lsa.2016.212 ↗
49. Ma, L. et al. Single photon triggered dianion formation in TCNQ and F4TCNQ crystals. Sci. Rep. 6, 28510 (2016).10.1038/srep28510 ↗
50. Ma, L. et al. Ultrafast spectroscopic characterization of 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its radical anion (TCNQ). Chem. Phys. Lett. 609, 11–14 (2014).10.1016/j.cplett.2014.06.029 ↗
51. Hall, S. J., Budden, P. J., Zats, A. & Sfeir, M. Y. Optimizing the sensitivity of high repetition rate broadband transient optical spectroscopy with modified shot-to-shot detection. Rev. Sci. Instrum. 94, 043005 (2023).10.1063/5.0143355 ↗
52. Renken, S. et al. Untargeted effects in organic exciton–polariton transient spectroscopy: a cautionary tale. J. Chem. Phys. 155, 154701 (2021).10.1063/5.0063173 ↗
53. Schwennicke, K. et al. When do molecular polaritons behave like optical filters? Chem. Soc. Rev. 54, 6482–6504 (2025).10.1039/D4CS01024H ↗
54. Vandewal, K. et al. Efficient charge generation by relaxed charge-transfer states at organic interfaces. Nat. Mater. 13, 63–68 (2014).10.1038/nmat3807 ↗
55. Wang, M., Hertzog, M. & Börjesson, K. Polariton-assisted excitation energy channeling in organic heterojunctions. Nat. Commun. 12, 1874 (2021).10.1038/s41467-021-22183-3 ↗
56. DelPo, C. A. et al. Polariton decay in donor–acceptor cavity systems. J. Phys. Chem. Lett. 12, 9774–9782 (2021).10.1021/acs.jpclett.1c02644 ↗
57. Hong, X. et al. Ultrafast charge transfer in atomically thin MoS2/WS2 heterostructures. Nat. Nanotechnol. 9, 682–686 (2014).10.1038/nnano.2014.167 ↗
58. Chen, X., Zhang, X., Xiao, X., Wang, Z. & Zhao, J. Recent developments on understanding charge transfer in molecular electron donor-acceptor systems. Angew. Chem. Int. Ed. 62, e202216010 (2023).10.1002/anie.202216010 ↗
59. Rodovsky, D. B. et al. Quantifying the relationship between the maximum achievable voltage and current levels in low-bandgap polymer photovoltaics. J. Phys. Chem. C 117, 25955–25960 (2013).10.1021/jp410234u ↗
60. Qian, D. et al. Design rules for minimizing voltage losses in high-efficiency organic solar cells. Nat. Mater. 17, 703–709 (2018).10.1038/s41563-018-0128-z ↗