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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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.
McIver, J. W., Hsieh, D., Steinberg, H., Jarillo-Herrero, P. & Gedik, N. Control over topological insulator photocurrents with light polarization. Nat. Nanotechnol. 7, 96–100 (2011).
Hatano, T., Ishihara, T., Tikhodeev, S. G. & Gippius, N. A. Transverse photovoltage induced by circularly polarized light. Phys. Rev. Lett. 103, 103906 (2009).
Bai, Q. Manipulating photoinduced voltage in metasurface with circularly polarized light. Opt. Express 23, 5348–5356 (2015).
Yokoyama, A., Yoshida, M., Ishii, A. & Kato, Y. K. Giant circular dichroism in individual carbon nanotubes induced by extrinsic chirality. Phys. Rev. X 4, 011005 (2014).
Ma, Q. et al. Direct optical detection of Weyl fermion chirality in a topological semimetal. Nat. Phys. 13, 842–847 (2017).
Yang, Y., da Costa, R. C., Fuchter, M. J. & Campbell, A. J. Circularly polarized light detection by a chiral organic semiconductor transistor. Nat. Photon. 7, 634–638 (2013).
Li, W. et al. Circularly polarized light detection with hot electrons in chiral plasmonic metamaterials. Nat. Commun. 6, 8379 (2015).
Wang, Y. H., Steinberg, H., Jarillo-Herrero, P. & Gedik, N. Observation of Floquet–Bloch states on the surface of a topological insulator. Science 342, 453–457 (2013).
Higuchi, T., Heide, C., Ullmann, K., Weber, H. B. & Hommelhoff, P. Light-field-driven currents in graphene. Nature 550, 224–228 (2017).
Aca, E. T., Buchsbaum, S. F., Combs, C., Fornasiero, F. & Siwy, Z. S. Biomimetic potassium-selective nanopores. Sci. Adv. 5, eaav2568 (2019).
Cheng, C., Jiang, G., Simon, G. P., Liu, J. Z. & Li, D. Low-voltage electrostatic modulation of ion diffusion through layered graphene-based nanoporous membranes. Nat. Nanotechnol. 13, 685–690 (2018).
Wang, R. et al. Temperature-sensitive artificial channels through pillararene-based host-guest interactions. Angew. Chem. Int. Ed. Engl. 56, 5294–5298 (2017).
Zhang, Z. et al. Improved osmotic energy conversion in heterogeneous membrane boosted by three-dimensional hydrogel interface. Nat. Commun. 11, 875 (2020).
Schroeder, T. B. H. et al. An electric-eel-inspired soft power source from stacked hydrogels. Nature 552, 214–218 (2017).
Sun, Y. et al. A biomimetic chiral-driven ionic gate constructed by pillararene-based host-guest systems. Nat. Commun. 9, 2617 (2018).
Sun, Y. et al. A light-regulated host-guest-based nanochannel system inspired by channelrhodopsins protein. Nat. Commun. 8, 260 (2017).
Xie, X., Crespo, G. A., Mistlberger, G. & Bakker, E. Photocurrent generation based on a light-driven proton pump in an artificial liquid membrane. Nat. Chem. 6, 202–207 (2014).
Mourot, A. et al. Rapid optical control of nociception with an ion-channel photoswitch. Nat. Methods 9, 396–402 (2012).
White, W., Sanborn, C. D., Reiter, R. S., Fabian, D. M. & Ardo, S. Observation of photovoltaic action from photoacid-modified Nafion due to light-driven ion transport. J. Am. Chem. Soc. 139, 11726–11733 (2017).
Xiao, K. et al. Artificial light-driven ion pump for photoelectric energy conversion. Nat. Commun. 10, 74 (2019).
Palmer, B. A. et al. A highly reflective biogenic photonic material from core-shell birefringent nanoparticles. Nat. Nanotechnol. 15, 138–144 (2020).
Roberts, N. W., Chiou, T. H., Marshall, N. J. & Cronin, T. W. A biological quarter-wave retarder with excellent achromaticity in the visible wavelength region. Nat. Photon. 3, 641–644 (2009).
Chiou, T. H. et al. Circular polarization vision in a stomatopod crustacean. Curr. Biol. 18, 429–434 (2008).
Tang, Z. et al. Photo-driven active ion transport through a Janus microporous membrane. Angew. Chem. Int. Ed. Engl. 59, 6244–6248 (2020).
Yang, J. et al. Photo-induced ultrafast active ion transport through graphene oxide membranes. Nat. Commun. 10, 1171 (2019).
Xiao, K. et al. Photo-driven ion transport for a photodetector based on an asymmetric carbon nitride nanotube membrane. Angew. Chem. Int. Ed. Engl. 58, 12574–12579 (2019).
Edel, J. B., Kornyshev, A. A., Kucernak, A. R. & Urbakh, M. Fundamentals and applications of self-assembled plasmonic nanoparticles at interfaces. Chem. Soc. Rev. 45, 1581–1596 (2016).
Kotov, N. A., Meldrum, F. C., Wu, C. & Fendler, J. H. Monoparticulate layer and Langmuir–Blodgett-type multiparticulate layers of size-quantized cadmium sulfide clusters: a colloid-chemical approach to superlattice construction. J. Phys. Chem. 98, 2735–2738 (1994).
Udayabhaskararao, T. et al. Tunable porous nanoallotropes prepared by post-assembly etching of binary nanoparticle superlattices. Science 358, 514–518 (2017).
Knoppe, S. & Bürgi, T. Chirality in thiolate-protected gold clusters. Acc. Chem. Res. 47, 1318–1326 (2014).
Zhang, Q. et al. Unraveling the origin of chirality from plasmonic nanoparticle–protein complexes. Science 365, 1475–1478 (2019).
Chen, W. et al. Nanoparticle superstructures made by polymerase chain reaction: collective interactions of nanoparticles and a new principle for chiral materials. Nano Lett. 9, 2153–2159 (2009).
Ma, W. et al. Chiral inorganic nanostructures. Chem. Rev. 117, 8041–8093 (2017).
Ben-Moshe, A., Maoz, B. M., Govorov, A. O. & Markovich, G. Chirality and chiroptical effects in inorganic nanocrystal systems with plasmon and exciton resonances. Chem. Soc. Rev. 42, 7028–7041 (2013).
Ebbesen, T. W., Lezec, H. J., Ghaemi, H. F., Thio, T. & Wolff, P. A. Extraordinary optical transmission through sub-wavelength hole arrays. Nature 391, 667–669 (1998).
Zhao, J., Li, B., Onda, K., Feng, M. & Petek, H. Solvated electrons on metal oxide surfaces. Chem. Rev. 106, 4402–4427 (2006).
Matricardi, C. et al. Gold nanoparticle plasmonic superlattices as surface-enhanced Raman spectroscopy substrates. ACS Nano 12, 8531–8539 (2018).
Wang, D., Guan, J., Hu, J., Bourgeois, M. R. & Odom, T. W. Manipulating light–matter interactions in plasmonic nanoparticle lattices. Acc. Chem. Res. 52, 2997–3007 (2019).
Mueller, N. S. et al. Deep strong light–matter coupling in plasmonic nanoparticle crystals. Nature 583, 780–784 (2020).
Lee, S. H. et al. Highly photoresponsive and wavelength-selective circularly-polarized-light detector based on metal-oxides hetero-chiral thin film. Sci. Rep. 6, 19580 (2016).
Chen, C. et al. Circularly polarized light detection using chiral hybrid perovskite. Nat. Commun. 10, 1927 (2019).
Do, T. D., Kincannon, W. M. & Bowers, M. T. Phenylalanine oligomers and fibrils: the mechanism of assembly and the importance of tetramers and counterions. J. Am. Chem. Soc. 137, 10080–10083 (2015).
Singh, V., Rai, R. K., Arora, A., Sinha, N. & Thakur, A. K. Therapeutic implication of l-phenylalanine aggregation mechanism and its modulation by d-phenylalanine in phenylketonuria. Sci. Rep. 4, 3875 (2014).
Amdursky, N. & Stevens, M. M. Circular dichroism of amino acids: following the structural formation of phenylalanine. ChemPhysChem 16, 2768–2774 (2015).
Xia, Y. et al. Self-assembly of self-limiting monodisperse supraparticles from polydisperse nanoparticles. Nat. Nanotechnol. 6, 580–587 (2011).
Naaman, R., Paltiel, Y. & Waldeck, D. H. Chiral molecules and the electron spin. Nat. Rev. Chem. 3, 250–260 (2019).
Senocrate, A., Kotomin, E. & Maier, J. On the way to optoionics. Helv. Chim. Acta 103, e2000073 (2020).
Brongersma, M. L., Halas, N. J. & Nordlander, P. Plasmon-induced hot carrier science and technology. Nat. Nanotechnol. 10, 25–34 (2015).
Clavero, C. Plasmon-induced hot-electron generation at nanoparticle/metal-oxide interfaces for photovoltaic and photocatalytic devices. Nat. Photon. 8, 95–103 (2014).
Nakanishi, H. et al. Photoconductance and inverse photoconductance in films of functionalized metal nanoparticles. Nature 460, 371–375 (2009).
Cortes, E. et al. Plasmonic hot electron transport drives nano-localized chemistry. Nat. Commun. 8, 14880 (2017).
Hapiot, P., Konovalov, V. V. & Saveant, J.-M. Application of laser pulse photoinjection of electrons from metal electrodes to the determination of reduction potentials of organic radicals in aprotic solvents. J. Am. Chem. Soc. 117, 1428–1434 (1995).
González-Rubio, G. et al. Micelle-directed chiral seeded growth on anisotropic gold nanocrystals. Science 368, 1472–1477 (2020).
Di Nuzzo, D. et al. Circularly polarized photoluminescence from chiral perovskite thin films at room temperature. ACS Nano 14, 7610–7616 (2020).
Zhao, X. et al. Tuning the interactions between chiral plasmonic films and living cells. Nat. Commun. 8, 2007 (2017).
Hu, L., Chen, M., Fang, X. & Wu, L. Oil–water interfacial self-assembly: a novel strategy for nanofilm and nanodevice fabrication. Chem. Soc. Rev. 41, 1350–1362 (2012).
Gao, J., Feng, Y., Guo, W. & Jiang, L. Nanofluidics in two-dimensional layered materials: inspirations from nature. Chem. Soc. Rev. 46, 5400–5424 (2017).
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.
The authors declare no competing interests.
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Supplementary Figs. 1–22 and Tables 1–3.
The contributions to electrostatic potential from the NP core and surface ligands under different wavelengths of light: the case of 12 Phe ligands.
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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