Charge-transfer dynamics and nonlocal dielectric permittivity tuned with metamaterial structures as solvent analogues

Kwang Jin Lee, Yiming Xiao, Jae Heun Woo, Eunsun Kim, David Kreher, André Jean Attias, Fabrice Mathevet, Jean Charles Ribierre, Jeong Weon Wu, Pascal André

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14 Citations (Scopus)

Abstract

Charge transfer (CT) is a fundamental and ubiquitous mechanism in biology, physics and chemistry. Here, we evidence that CT dynamics can be altered by multi-layered hyperbolic metamaterial (HMM) substrates. Taking triphenylene:perylene diimide dyad supramolecular self-assemblies as a model system, we reveal longer-lived CT states in the presence of HMM structures, with both charge separation and recombination characteristic times increased by factors of 2.4 and 1.7 - that is, relative variations of 140 and 73%, respectively. To rationalize these experimental results in terms of driving force, we successfully introduce image dipole interactions in Marcus theory. The non-local effect herein demonstrated is directly linked to the number of metal-dielectric pairs, can be formalized in the dielectric permittivity, and is presented as a solid analogue to local solvent polarity effects. This model and extra PH3T:PC60BM results show the generality of this non-local phenomenon and that a wide range of kinetic tailoring opportunities can arise from substrate engineering. This work paves the way toward the design of artificial substrates to control CT dynamics of interest for applications in optoelectronics and chemistry.

Original languageEnglish
Pages (from-to)722-729
Number of pages8
JournalNature Materials
Volume16
Issue number7
DOIs
Publication statusPublished - Jul 1 2017

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanics of Materials
  • Mechanical Engineering

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    Lee, K. J., Xiao, Y., Woo, J. H., Kim, E., Kreher, D., Attias, A. J., Mathevet, F., Ribierre, J. C., Wu, J. W., & André, P. (2017). Charge-transfer dynamics and nonlocal dielectric permittivity tuned with metamaterial structures as solvent analogues. Nature Materials, 16(7), 722-729. https://doi.org/10.1038/nmat4907