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Reconfigurable chiroptical nanocomposites with chirality transfer from the macro- to the nanoscale

Nature Materials volume 15, pages 461–468 (2016)Cite this article

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Abstract

Nanostructures with chiral geometries exhibit strong polarization rotation. However, achieving reversible modulation of chirality and polarization rotation in device-friendly solid-state films is difficult for rigid materials. Here, we describe nanocomposites, made by conformally coating twisted elastic substrates with films assembled layer-by-layer from plasmonic nanocolloids, whose nanoscale geometry and rotatory optical activity can be reversibly reconfigured and cyclically modulated by macroscale stretching, with up to tenfold concomitant increases in ellipticity. We show that the chiroptical activity at 660 nm of gold nanoparticle composites is associated with circular extinction from linear effects. The polarization rotation at 550 nm originates from the chirality of nanoparticle chains with an S-like shape that exhibit a non-planar buckled geometry, with the handedness of the substrate’s macroscale twist determining the handedness of the S-like chains. Chiroptical effects at the nexus of mechanics, excitonics and plasmonics open new operational principles for optical and optoelectronic devices from nanoparticles, carbon nanotubes and other nanoscale components.

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Figure 1: Strain-modulated rotatory optical activity in AuNP multilayers.
Figure 2: Stresses in twisted PDMS substrates with LBL composite films.
Figure 3: Strain-induced chiroptically active NP assemblies on buckled sides.
Figure 4: Simulated chiroptical properties of S-like AuNP chains.
Figure 5: Strain-modulated chiroptical multilayers from semiconducting nanotubes.

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Acknowledgements

Y.K. thanks the Rackham Graduate School for a predoctoral fellowship. O.A. thanks the European Commission for Marie Curie IIF Fellowship PIIF-GA-2012-330513, Nanochirality. This material is based on work partially supported by the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0000957. We acknowledge support from NSF under grant ECS-0601345; CBET 0933384; CBET 0932823; and CBET 1036672. The work is also partially supported by the US Department of Defense under Grant Award No. MURI W911NF-12-1-0407. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (Ministry of Education) (No. NRF-2015R1D1A1A01058029). We thank the University of Michigan’s Electron Microscopy and Analysis Laboratory (EMAL) for its assistance with electron microscopy, and for NSF grants (numbers DMR-0320740 and DMR-9871177), for funding the FEI Nova Nanolab Dualbeam Focused Ion Beam Workstation and Scanning Electron Microscope and the JEOL 2010F analytical electron microscope used in this work. We also thank EMAL and the College of Engineering for assistance with the Bruker NanoStar Small-Angle X-ray Scattering System. We wish to acknowledge use of the Microscopy & Image-analysis Laboratory (MIL) at the University of Michigan for preparation of STED samples and obtaining images.

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Author notes

  1. Yoonseob Kim and Bongjun Yeom: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109-2136, USA

    Yoonseob Kim, Bongjun Yeom & Nicholas A. Kotov

  2. Biointerfaces Institute, University of Michigan, Ann Arbor, Michigan 48109-2136, USA

    Yoonseob Kim, Bongjun Yeom & Nicholas A. Kotov

  3. Department of Chemical Engineering, Myongji University, Yongin, Gyeonggi-do 449-728, South Korea

    Bongjun Yeom

  4. Departamento Física Aplicada i Òptica, Universitat de Barcelona, Barcelona 08028, Spain

    Oriol Arteaga

  5. Nano-Bio Electron Microscopy Research Group, Korea Basic Science Institute (KBSI), 169-148 Gwahak-ro, Yuseong-gu, Daejeon 34133, Republic of Korea

    Seung Jo Yoo, Sang-Gil Lee & Jin-Gyu Kim

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Contributions

N.A.K., Y.K. and B.Y. conceived the project and designed the experiments. Y.K. and B.Y. carried out the design and fabrication of the chiroptical LBL films, performed basic optical experiments and carried out the calculations. O.A. provided fundamentals of the Mueller matrix. Y.K. obtained all Mueller matrix data, and Y.K. and O.A. analysed the data. Y.K. obtained STED microscopy data. S.J.Y., S.-G.L. and J.-G.K. obtained 3D TEM tomography data.

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Correspondence to Nicholas A. Kotov.

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Kim, Y., Yeom, B., Arteaga, O. et al. Reconfigurable chiroptical nanocomposites with chirality transfer from the macro- to the nanoscale. Nature Mater 15, 461–468 (2016). https://doi.org/10.1038/nmat4525

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