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Nano-achiral complex composites for extreme polarization optics

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Abstract

Composites from 2D nanomaterials show uniquely high electrical, thermal and mechanical properties1,2. Pairing their robustness with polarization rotation is needed for hyperspectral optics in extreme conditions3,4. However, the rigid nanoplatelets have randomized achiral shapes, which scramble the circular polarization of photons with comparable wavelengths. Here we show that multilayer nanocomposites from 2D nanomaterials with complex textured surfaces strongly and controllably rotate light polarization, despite being nano-achiral and partially disordered. The intense circular dichroism (CD) in nanocomposite films originates from the diagonal patterns of wrinkles, grooves or ridges, leading to an angular offset between axes of linear birefringence (LB) and linear dichroism (LD). Stratification of the layer-by-layer (LBL) assembled nanocomposites affords precise engineering of the polarization-active materials from imprecise nanoplatelets with an optical asymmetry g-factor of 1.0, exceeding those of typical nanomaterials by about 500 times. High thermal resilience of the composite optics enables operating temperature as high as 250 °C and imaging of hot emitters in the near-infrared (NIR) part of the spectrum. Combining LBL engineered nanocomposites with achiral dyes results in anisotropic factors for circularly polarized emission approaching the theoretical limit. The generality of the observed phenomena is demonstrated by nanocomposite polarizers from molybdenum sulfide (MoS2), MXene and graphene oxide (GO) and by two manufacturing methods. A large family of LBL optical nanocomponents can be computationally designed and additively engineered for ruggedized optics.

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Fig. 1: Nanocomposites from 2D nanomaterials prepared by M1; uniform, tunable LH and RH polarization rotation.
Fig. 2: Nanocomposites from 2D nanomaterials prepared by M2; real-time-reconfigurable polarization rotation.
Fig. 3: Generation and modulation of strong CPCE.
Fig. 4: Polarization imaging in the NIR range using thermally resilient composites.

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Data availability

The authors declare that the data supporting the findings of this study are available in the article and its supplementary information files. Source data are provided with this paper.

Code availability

The codes used for chirality index calculations are available from https://github.com/aslozada/kanon and https://github.com/colombarifm/OPD_chirality_index.

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Acknowledgements

This work was primarily supported by the Vannevar Bush DoD Fellowship to N.A.K. titled ‘Engineered Chiral Ceramics’ ONR N000141812876. This work was also supported by the ‘Center of Complex Particle Systems (COMPASS)’ (Grant No. NSF 2243104) and in part by the Office of Naval Research (MURI N00014-20-1-2479), ONR COVID-19 Newton Award ‘Pathways to Complexity with ‘Imperfect’ Nanoparticles’ HQ00342010033, AFOSR FA9550-20-1-0265, Graph Theory Description of Network Material. A.F.d.M. is indebted to CNPq and FAPESP (grant 2013/07296-2) for their financial support. We are grateful for the HPC resources provided by the SDumont supercomputer at the National Laboratory for Scientific Computing (LNCC/MCTI, Brazil, http://sdumont.lncc.br). A.J., B.S., R.V. and D.N. are grateful for support from the Materials and Manufacturing Directorate and Air Force Office of Scientific Research of the Air Force Research Laboratory. Michigan Center for Materials Characterization (MC)2 is acknowledged for instrument support. Early discovery of amino acid decoration on MoS2 by M. Zhou is gratefully acknowledged.

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Authors and Affiliations

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

    Jun Lu, Wenbing Wu, Kody Whisnant, **aoyang Zhong, Won** Choi, Joerg Lahann & Nicholas A. Kotov

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

    Jun Lu, Wenbing Wu, Kody Whisnant, **aoyang Zhong, Won** Choi, Joerg Lahann & Nicholas A. Kotov

  3. Center for Complex Particle Systems (COMPASS), University of Michigan, Ann Arbor, MI, USA

    Jun Lu, Wenbing Wu, Kody Whisnant, Joerg Lahann & Nicholas A. Kotov

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

    Felippe Mariano Colombari

  5. Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson AFB, Dayton, OH, USA

    Ali Jawaid, Richard A. Vaia & Dhriti Nepal

  6. UES, Inc., Dayton, OH, USA

    Ali Jawaid

  7. ARCTOS Technology Solutions, Beavercreek, OH, USA

    Bryan Seymour

  8. Department of Materials Science and Engineering, Cornell University, Ithaca, NY, USA

    Nikolaos Chalmpes

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

    André Farias de Moura

  10. Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI, USA

    Nicholas A. Kotov

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  1. Jun Lu
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Contributions

J. Lu and N.A.K. designed the experiments and analysed the data. J. Lu fabricated the composites. W.W. prepared the Ag film, ran the mechanical testing and contributed to property discussions. J. Lu, K.W. and W.W. ran the AFM imaging and studied the structure of composites. A.J., N.C. and R.V. prepared the MoS2 nanoplatelets. B.S. and D.N. synthesized pristine Ti3C2Tx nanoplatelets. F.C. and A.F.d.M. performed the density functional theory and molecular dynamics simulations and chirality index calculations. X.Z. and J. Lahann performed the measurement and data analysis for the refractive index of Ti3C2Tx composites, which was used by J. Lu on finite-difference time-domain simulations. W.C. assisted J. Lu with MMP measurement and contributed to property discussions. J. Lu, W.W., F.C., A.F.d.M., D.N., R.V. and N.A.K. contributed to the writing of the paper, with feedback from all authors. N.A.K. conceived and supervised the project.

Corresponding authors

Correspondence to Richard A. Vaia, André Farias de Moura, Dhriti Nepal or Nicholas A. Kotov.

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Supplementary Video 1

Distribution of electrostatic potentials of L-Cys-capped MoS2 nanoplatelets under different excitation wavelengths.

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Lu, J., Wu, W., Colombari, F.M. et al. Nano-achiral complex composites for extreme polarization optics. Nature 630, 860–865 (2024). https://doi.org/10.1038/s41586-024-07455-4

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