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

Nature Materials volume 16, pages 722–729 (2017)Cite this article

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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.

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Figure 1: System under investigation.
Figure 2: Transient absorption measurements of annealed dyad molecule thin films.
Figure 3: Quantitative TA analysis.
Figure 4: Calculated non-local dielectric permittivity manipulated by HMM image dipole interactions.
Figure 5: Modelling and schematics.

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Acknowledgements

This work has been carried out in the framework of CNRS International Associated Laboratory ‘Functional nanostructures: morphology, nanoelectronics and ultrafast optics’ (LIA NANOFUNC). K.J.L., Y.X., J.H.W., E.K., J.-C.R., J.W.W. and P.A. were supported by funding of the Ministry of Science, ICT & Future Planning, Korea (201000453, 2015001948, 2014M3A6B3063706). P.A. would like to thank the Canon Foundation in Europe for supporting his Fellowship. The authors also acknowledge the International Research Network (GDRI, CNRS) on ‘Functional Materials for Organic Optics, Electronics and Devices’ (FUNMOOD). The authors are also grateful to J.-Y. Bigot, M. Vomir, M. Barthelemy and O. Cregut for their contributions in setting up and optimizing the femtosecond pump–probe set-up used in this study. The authors thank Pohang Accelerator Laboratory (PAL) in South Korea for giving us the opportunity to perform the GIXS measurements in the frame of the proposal number ‘2014-1st-9A-015’. The authors are grateful to MEST and POSTECH for supporting the GIXS experiments, to T. J. Shin and H. Ahn as well as other staff members from 9A U-SAXS beamline for assistance with adjustments and help. B. Heinrich is warmly acknowledged for his contributions to the GIXS measurements and data analysis.

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  1. Jean-Charles Ribierre

    Present address: Present address: OPERA, Kyushu University, Fukuoka 819-0388, Japan.,

Authors and Affiliations

  1. Department of Physics, CNRS-Ewha International Research Center, Ewha Womans University, Seoul 03760, South Korea

    Kwang Jin Lee, Yiming Xiao, Jae Heun Woo, Eunsun Kim, Jean-Charles Ribierre, Jeong Weon Wu & Pascal André

  2. Sorbonne Universités, UPMC Univ. Paris 06, CNRS, Institut Parisien de Chimie Moléculaire, UMR 8232, Chimie des Polymères, 4 place Jussieu, 75005 Paris, France

    Yiming Xiao, David Kreher, André-Jean Attias & Fabrice Mathevet

  3. Division of Physical Metrology, Center for Length, Korea Research Institute of Standards and Science (KRISS), Daejeon 34113, South Korea

    Jae Heun Woo

  4. RIKEN, Wako, Saitama 351-0198, Japan

    Pascal André

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Contributions

K.J.L., J.-C.R., J.W.W. and P.A. designed the experiments; Y.X. synthesized the dyad molecules under the supervision of F.M., D.K. and A.-J.A.; Y.X., BH and F.M. completed the GIXS measurements. K.J.L. completed the transient measurements and analysis with some assistance from J.H.W. and E.K., and with feedback from P.A.; K.J.L., J.W.W. and P.A. developed the model used to describe the system and discussed the results. K.J.L. completed all the numerical calculations. K.J.L. and P.A. prepared the figures. P.A. wrote the manuscript and Supplementary Information, except the GIXS and dyad preparation. K.J.L., J.-C.R., J.W.W. and P.A. replied to the reviewer comments and altered the manuscript accordingly. All the authors commented on the manuscript.

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Correspondence to Jean-Charles Ribierre, Jeong Weon Wu or Pascal André.

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Lee, K., Xiao, Y., Woo, J. et al. Charge-transfer dynamics and nonlocal dielectric permittivity tuned with metamaterial structures as solvent analogues. Nature Mater 16, 722–729 (2017). https://doi.org/10.1038/nmat4907

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