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Polarization-sensitive optoionic membranes from chiral plasmonic nanoparticles

Nature Nanotechnology volume 17, pages 408–416 (2022)Cite this article

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Abstract

Optoelectronic effects differentiating absorption of right and left circularly polarized photons in thin films of chiral materials are typically prohibitively small for their direct photocurrent observation. Chiral metasurfaces increase the electronic sensitivity to circular polarization, but their out-of-plane architecture entails manufacturing and performance trade-offs. Here, we show that nanoporous thin films of chiral nanoparticles enable high sensitivity to circular polarization due to light-induced polarization-dependent ion accumulation at nanoparticle interfaces. Self-assembled multilayers of gold nanoparticles modified with l-phenylalanine generate a photocurrent under right-handed circularly polarized light as high as 2.41 times higher than under left-handed circularly polarized light. The strong plasmonic coupling between the multiple nanoparticles producing planar chiroplasmonic modes facilitates the ejection of electrons, whose entrapment at the membrane–electrolyte interface is promoted by a thick layer of enantiopure phenylalanine. Demonstrated detection of light ellipticity with equal sensitivity at all incident angles mimics phenomenological aspects of polarization vision in marine animals. The simplicity of self-assembly and sensitivity of polarization detection found in optoionic membranes opens the door to a family of miniaturized fluidic devices for chiral photonics.

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Fig. 1: Polarization-sensitive optoionic effects in nanofilms from chiral plasmonic NPs.
Fig. 2: Photocurrent generation across nanofilms from l-Phe-NPs.
Fig. 3: Uniqueness of Phe-NPs for generating CPL-dependent photocurrent.
Fig. 4: Photocurrent generation via plasmon-driven ejection of electrons to the particle–medium interface.
Fig. 5: CPL detection using multilayer nanofilms.

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Source data are provided with this paper. All data that support the findings of this study have been included in the main text and Supplementary Information. Any additional materials and data are available from the corresponding authors on reasonable request.

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Acknowledgements

C.X. acknowledges support from the National Key Research and Development Program of China (grant no. 2017YFA0206902), W.Z. acknowledges support from the National Key Research and Development Program of China (grant no. 2017YFA0303400), H.K., L.X. and M.S. acknowledge support from the National Natural Science Foundation of China (grant nos. 21925402, 32071400 and 21977038), H.K. acknowledges support from the Natural Science Foundation of Jiangsu Province (grant no. BK20212014), W.Z. acknowledges support from the National Natural Science Foundation of China (grant nos. 11774036 and 12174032) and from the National Natural Science Foundation of China/Research Grants Council (grant no. 11861161002). N.A.K. is grateful for support from the National Science Foundation via projects NSF 1463474 “Energy- and Cost-Efficient Manufacturing Employing Nanoparticles” and NSF 1566460 “Nanospiked Particles for Photocatalysis”. R.K. acknowledges support from the Minerva Foundation with funding from the Federal German Ministry for Education and Research. F.M.C., W.R.G., M.C.S., E.B.C.-N., E.C.P. and A.F.M. are grateful to the Brazilian funding agencies CAPES (finance code 001), CNPq-INCT (573742/2008-1) and FAPESP (2012/15147-4, 2013/07296-2, 2014/50249-8, 2015/12851-0 and 2017/11986-5) for financial support and the HPC resources provided by the SDumont supercomputer at the National Laboratory for Scientific Computing (LNCC/MCTI, Brazil; http://sdumont.lncc.br) and by the Cloud@UFSCar (https://www.sin.ufscar.br). A.F.M. is grateful to MEC/PET for a fellowship and to CNPq for a research fellowship.

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Author notes

  1. These authors contributed equally: Jiarong Cai, Wei Zhang, Liguang Xu.

Authors and Affiliations

  1. State Key Laboratory of Food Science and Technology, Jiangnan University, Wuxi, China

    Jiarong Cai, Liguang Xu, Changlong Hao, Wei Ma, Maozhong Sun, Xiaoling Wu, Chuanlai Xu & Hua Kuang

  2. International Joint Research Laboratory for Biointerface and Biodetection, School of Food Science and Technology, Jiangnan University, Wuxi, China

    Jiarong Cai, Liguang Xu, Changlong Hao, Wei Ma, Maozhong Sun, Xiaoling Wu, Chuanlai Xu & Hua Kuang

  3. Institute of Applied Physics and Computational Mathematics, Beijing, China

    Wei Zhang

  4. Beijing Computational Science Research Centre, Beijing, China

    Wei Zhang

  5. The Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, China

    Liguang Xu, Chuanlai Xu & Hua Kuang

  6. Department of Chemistry, National University of Singapore, Singapore, Singapore

    Xian Qin, Jiahui Xu & Xiaogang Liu

  7. Brazilian Biorenewables National Laboratory, Brazilian Center for Research in Energy and Materials, Campinas, Brazil

    Felippe Mariano Colombari

  8. Department of Chemistry, Federal University of São Carlos, São Carlos, Brazil

    André Farias de Moura, Mariana Cristina Silva, Evaldo Batista Carneiro-Neto, Weverson Rodrigues Gomes & Ernesto Chaves Pereira

  9. CNRS, University of Bordeaux, Pessac, France

    Renaud A. L. Vallée

  10. Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot, Israel

    Rafal Klajn

  11. Department of Chemical Engineering, University of Michigan, Ann Arbor, MI, USA

    Nicholas A. Kotov

  12. Biointerfaces Institute, University of Michigan, Ann Arbor, MI, USA

    Nicholas A. Kotov

  13. Michigan Institute for Translational Nanotechnology, Ypsilanti, MI, USA

    Nicholas A. Kotov

  14. Science Center for Future Foods, Jiangnan University, Wuxi, China

    Hua Kuang

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Contributions

H.K., R.K., N.A.K. and C.X. conceived the project and designed the experiments. J.C. was responsible for electrochemical, CD and CPL measurements. W.Z. was responsible for the calculations of optical response (absorption and circular dichroism) and photocurrent calculations based on the Poisson–Nernst–Planck equation. L.X. and C.H. performed the HRTEM, TEM, SEM and AFM experiments. L.X. and W.M. carried out the preparation of gold nanofilms. M.S. and X.W. were responsible for the synthesis and modification of gold NPs with different particle sizes. F.M.C., W.R.G., M.C.S., E.B.C.-N., E.C.P. and A.F.de.M. designed, executed and analysed the simulations of DFT calculations, electrodynamics calculations and finite element calculations and wrote the corresponding text. R.A.L.V., X.L., X.Q. and J.X. carried out calculations related to the interaction between Phe and gold. H.K. and N.A.K. conceptualized the work. C.X. supervised the study. H.K., R.K., N.A.K. and C.X. analysed and discussed the results and wrote the manuscript.

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Correspondence to Chuanlai Xu, Rafal Klajn, Nicholas A. Kotov or Hua Kuang.

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Supplementary Figs. 1–22 and Tables 1–3.

Supplementary Video 1

The contributions to electrostatic potential from the NP core and surface ligands under different wavelengths of light: the case of 12 Phe ligands.

Supplementary Video 2

The contributions to electrostatic potential from the NP core and surface ligands under different wavelengths of light: the case of 4 Cit ligands + 8 Phe ligands.

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Cai, J., Zhang, W., Xu, L. et al. Polarization-sensitive optoionic membranes from chiral plasmonic nanoparticles. Nat. Nanotechnol. 17, 408–416 (2022). https://doi.org/10.1038/s41565-022-01079-3

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