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Mechano-tunable chiral metasurfaces via colloidal assembly

Nature Materials volume 20, pages 1024–1028 (2021)Cite this article

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Abstract

Dynamic control of circular polarization in chiral metasurfaces is being used in many photonic applications. However, simple fabrication routes to create chiral materials with considerable and fully tunable chiroptical responses at visible and near-infrared wavelengths are scarce. Here, we describe a scalable bottom-up approach to construct cross-stacked nanoparticle chain arrays that have a circular dichroism of up to 11°. Due to their layered design, the strong superchiral fields of the inter-layer region are accessible to chiral analytes, resulting in a tenfold enhanced sensitivity in a chiral sensing proof-of-concept experiment. In situ restacking and local mechanical compression enables full control over the entire set of circular dichroism characteristics, namely sign, magnitude and spectral position. Strain-induced reconfiguration opens up an intriguing route towards actively controlled pixel arrays using local deformation, which fosters continuous polarization engineering and multi-channel detection.

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Fig. 1: Chiral assemblies by macroscopic stacking of achiral chain substrates.
Fig. 2: CD tuned by inter-layer rotation.
Fig. 3: Enhanced detection of chiral molecules by exploiting the inter-layer region.
Fig. 4: Strain-induced spectral tuning of CD response.

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Data availability

We declare that all data supporting the findings of this study are included within the paper and its Supplementary Information files. Source data are available from the corresponding authors upon reasonable request.

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Acknowledgements

This project was financially supported by the Volkswagen Foundation through a Freigeist Fellowship to T.A.F.K. A.F. and A.M.S. acknowledge financial support from the German Research Foundation (DFG) through the project no. 407193529 ‘Immobilization of ordered plasmonic nanostructures at surfaces of polymeric melts’. The elite study programme Macromolecular Science organized by Elitenetzwerk Bayern and University of Bayreuth is acknowledged for support to P.T.P. Z.Z. thanks the Alexander von Humboldt foundation for support. G.K.A. acknowledges financial support by the DFG through project no. 265191195 ‘Interaction between Transport and Wetting Processes’ (CRC 1194, A06). We thank A. Spickenheuer for advice in mechanical simulations as well as M. Müller and B. Urban for attenuated total reflection Fourier-transform infrared spectroscopy measurements. M. Schubert, C. Ng and Y. Yu are acknowledged for helpful discussions in preparation of this work.

Author information

Author notes

  1. Vaibhav Gupta

    Present address: Institute of Particle Technology, Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, Germany

  2. These authors contributed equally: Patrick T. Probst, Martin Mayer.

Authors and Affiliations

  1. Institute of Physical Chemistry and Polymer Physics, Leibniz-Institut für Polymerforschung Dresden e.V., Dresden, Germany

    Patrick T. Probst, Martin Mayer, Vaibhav Gupta, Anja Maria Steiner, Ziwei Zhou, Günter K. Auernhammer, Tobias A. F. König & Andreas Fery

  2. Center for Advancing Electronics Dresden (cfaed), Technische Universität Dresden, Dresden, Germany

    Patrick T. Probst, Martin Mayer, Anja Maria Steiner, Tobias A. F. König & Andreas Fery

  3. Department of Physics at Interfaces, Max-Planck-Institut für Polymerforschung, Mainz, Germany

    Günter K. Auernhammer

  4. Department of Physical Chemistry of Polymeric Materials, Technische Universität Dresden, Dresden, Germany

    Andreas Fery

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Contributions

P.T.P., M.M., G.K.A., T.A.F.K. and A.F. contributed to the design, data analysis and preparation of the manuscript. T.A.F.K. and A.F. made a considerable contribution to the conception and design of the work. V.G. and P.T.P. designed and prepared the templates used for colloidal assembly. A.M.S. synthesized the nanoparticles. P.T.P. carried out the assembly experiments and characterized the samples using scanning electron microscopy, atomic force microscopy and vis-NIR spectroscopy. M.M. acquired and evaluated the spectroscopic ellipsometry data. Z.Z. carried out the initial measurements using conventional CD spectroscopy. M.M. and P.T.P. performed electromagnetic and mechanical simulations, respectively. All authors provided critical feedback and helped shape the research, analysis and manuscript.

Corresponding authors

Correspondence to Tobias A. F. König or Andreas Fery.

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Peer review information Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Comparison of active chiral plasmonic systems.

This plot is based on the values summarized in Supplementary Table 1. The modulation depth of CD magnitude is represented by the diameter of the bubbles (determined at the wavelength of the original CD peak). Examples that show active spectral tuning are shown as crosses. The empty circle indicates a system switching between two discrete enantiomorphs without intermediate configurations. The colour code describes whether the system is able to switch the sign of CD response at a specific wavelength (green) or not (black). The values found for the system presented in this work are depicted in blue (modes CD1 through CD5 as indicated in Fig. 2a).

Extended Data Fig. 2 Gold nanoparticle lines assembled inside nanochannels over macroscopic areas.

a, Representative scanning electron overview micrograph. b, Polarized photographs of a particle chain substrate illuminated with linear polarization perpendicular/parallel to the particle chains. The excitation of transversal/longitudinal plasmon mode allows only the complementary colour (magenta/green) to be transmitted (cf. Supplementary Fig. 4). c, Scanning electron micrographs measured at the spots indicated in b. The filling rates were calculated from zoomed in micrographs where single particles could be resolved (see Supplementary Fig. 3 for calculation). Only far away from the initial particle front (left edge) the filling rate decreased (S3). The scanning electron micrographs show material contrast (ESB detector) to capture particles as bright pixels. Scale bar in a and c, 2 µm. Scale bar in b, 2 mm.

Extended Data Fig. 3 Details on CD derived from spectroscopic ellipsometry data.

a,b, Measured circularly polarized and unpolarized extinction spectra of samples stacked at ±10° (a) and ±45° (b). c,d, g-factor \(g = 2\left( {Ext_{{\mathrm{LCP}}} - Ext_{{\mathrm{RCP}}}} \right)/\left( {Ext_{{\mathrm{LCP}}} + Ext_{{\mathrm{RCP}}}} \right)\) (c) and CD (d) calculated from extinction spectra of aforementioned samples. ‘a.u.’, arbitrary units.

Extended Data Fig. 4 Simulated field distribution for mode CD1 for a −45° stack excited by LCP/RCP light.

a,b, Contour plots and selected cross sections (insets) of electric (a) and magnetic fields (b). As visualized in a, this mode has a clear longitudinal character, with a predominant electric field orientation along the particle chains.

Extended Data Fig. 5 Simulated field distribution for mode CD4 for a −45° stack excited by LCP/RCP light.

a,b,c, Contour plots and selected cross sections (insets) of electric (a), magnetic (b) and superchiral fields (c). As visualized in a, this mode has a clear transversal character, with a predominant electric field orientation perpendicular to the particle chains.

Supplementary information

Supplementary Information

Supplementary Notes 1–4, Figs. 1–12 and Table 1.

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Probst, P.T., Mayer, M., Gupta, V. et al. Mechano-tunable chiral metasurfaces via colloidal assembly. Nat. Mater. 20, 1024–1028 (2021). https://doi.org/10.1038/s41563-021-00991-8

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