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Helical polymers for dissymmetric circularly polarized light imaging

Nature volume 617, pages 92–99 (2023)Cite this article

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Abstract

Control of the spin angular momentum (SAM) carried in a photon provides a technologically attractive element for next-generation quantum networks and spintronics1,2,3,4,5. However, the weak optical activity and inhomogeneity of thin films from chiral molecular crystals result in high noise and uncertainty in SAM detection. Brittleness of thin molecular crystals represents a further problem for device integration and practical realization of chiroptical quantum devices6,7,8,9,10. Despite considerable successes with highly dissymmetric optical materials based on chiral nanostructures11,12,13, the problem of integration of nanochiral materials with optical device platforms remains acute14,15,16. Here we report a simple yet powerful method to fabricate chiroptical flexible layers via supramolecular helical ordering of conjugated polymer chains. Their multiscale chirality and optical activity can be varied across the broad spectral range by chiral templating with volatile enantiomers. After template removal, chromophores remain stacked in one-dimensional helical nanofibrils producing a homogeneous chiroptical layer with drastically enhanced polarization-dependent absorbance, leading to well-resolved detection and visualization of SAM. This study provides a direct path to scalable realization of on-chip detection of the spin degree of freedom of photons necessary for encoded quantum information processing and high-resolution polarization imaging.

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Fig. 1: Fabrication of a highly dissymmetric homochiral active layer and its application in a photon spin sensor.
Fig. 2: Chiroptical properties and molecular packing information of polymeric films after chiral doping and templating.
Fig. 3: Device performances of CP photodetectors based on chiral doped polymeric films.
Fig. 4: Optical activities of chiral doped polymeric films.
Fig. 5: SAM sensing and spin helicity trajectory visualization.

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Source data are provided with this paper. All other data are available from the corresponding authors on request. 

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Acknowledgements

This work was supported by the Samsung Research Funding Center of Samsung Electronics under project no. SRFC-MA1602-51. This work was also supported by the National Research Foundation of Korea (grant nos. 2020R1A2B5B03094499, 2021R1A4A1032515 and 2023R1A2C3007715), and Nano Material Technology Development Program (grant nos. 2017M3A7B8063825 and 2021M3D1A2049323) funded through the National Research Foundation of Korea by the Ministry of Science and ICT. The Institute of Engineering Research at Seoul National University provided research facilities for this work. N.A.K. thanks Vannevar Bush Fellowship ‘Ceramic Chiral Nanostructures’, administered by the Office of Naval Research. J.M. is grateful for the unrestricted support from Richard and Judith Wien Professorship.

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Author notes

  1. These authors contributed equally: Inho Song, Jaeyong Ahn

Authors and Affiliations

  1. School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Seoul, Republic of Korea

    Inho Song, Jaeyong Ahn, Sang Hyuk Lee & Joon Hak Oh

  2. Department of Chemistry, Purdue University, West Lafayette, IN, USA

    Inho Song & Jianguo Mei

  3. Pohang Accelerator Laboratory, Pohang University of Science and Technology, Pohang, Republic of Korea

    Hyungju Ahn

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

    Nicholas A. Kotov

  5. Department of Chemical Engineering, Biointerface Institute, University of Michigan, Ann Arbor, MI, USA

    Nicholas A. Kotov

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Contributions

I.S. and J.A. contributed equally to this work. J.H.O. and N.A.K. conceived the project and planned experiments. I.S. and J.A. performed instrumental analyses and device characterization. H.A. carried out GIWAXD interpretation. S.H.L. assisted with device fabrication and electrical characterizations. I.S., J.A., H.A., J.M., N.A.K. and J.H.O. wrote the manuscript, with discussion of results and feedback on the manuscript provided by all authors.

Corresponding authors

Correspondence to Nicholas A. Kotov or Joon Hak Oh.

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Extended data figures and tables

Extended Data Fig. 1 UV-vis absorption and CD spectra of assorted conjugated polymer/chiral additive blends.

Various conjugated polymers and chiral additives were used to fabricate the homochiral active layer. Among them, only fluorene-based and CPDT-based polymers exhibited strong CD signals. In addition, PCPDTTBTT, well-known in photon-absorbing devices, displayed broader UV-vis absorption and CD spectra compared with F8T2.

Extended Data Fig. 2 gabs spectra of CPDT-based neat and doped polymer films after thermal annealing.

Optimized films were formed using 30 mg mL−1 PCPDTTBTT in toluene. Doped films included 50 wt% of R5011 or S5011 in total solute.

Extended Data Fig. 3 Chiroptical properties of CPDT-based polymer films.

a, CD intensity maxima of CPDT-based doped thin film as a function of chiral additive content. b, gabs maxima of CPDT-based doped thin films as a function of film thickness.

Extended Data Fig. 4 XPS and ToF-SIMS characterization of CPDT-based polymer films.

a, Narrow-scan XPS results for elemental oxygen in CPDT-based polymer films before and after thermal annealing and doping. b, ToF-SIMS relative ion intensity graph comparing CPDT-based neat and doped polymer films before and after annealing. S-containing ions are C3H5S− (black), C2HS− (red), and C4HS− (blue). O-containing ions are O− (black), OH− (red), and C2OH− (blue).

Extended Data Fig. 5 Specific detectivity and gPh values of CP photodetectors.

a,b, Specific detectivity and gPh values of CP photodetectors as a function of chiral dopant concentration (a) and chiral film thickness (b).

Extended Data Fig. 6 gPh and specific detectivity of CP photodetectors with various device configurations.

Device configuration was as follows: green, ITO/active layer/MoO3/Au; red, ITO/ZnO/active layer/MoO3/Au; blue, ITO/ZnO/active layer (with 1 wt% PC70BM)/MoO3/Au.

Extended Data Fig. 7 CD spectra in various circularly polarized beam exposure conditions.

a,b, S5011-doped (a) and R5011-doped (b) PCPDTTBTT films considering the azimuthal sample rotation, sample flipping, and incidence angle modulation (θR: rotation angle of the sample; θI: incidence angle of the beam).

Extended Data Fig. 8 Ternary notation application of CP photodetectors.

Current was recorded in the CP photodetectors under three incident light conditions (dark, left-handed circularly polarized [LCP], and right-handed circularly polarized [RCP]) for ternary notation-based information transfer (bottom); it was recorded using conventional binary notation as a comparison (top). Binary and ternary notations are described in the table on the right.

Extended Data Fig. 9 30 × 30 matrix CP photodetectors irradiated with the opposite handedness of the CP beam and corresponding photocurrent mapping.

a, 2D photocurrent map recorded in conventional photodetection mode with oblique irradiation incident angle of 10°. b, Schematic illustration of 30 × 30 photodiode arrays with normal angle of incident light shaped “ε” or “3”. c,d, Corresponding comparison 2D histograms in conventional photodetection mode exhibiting simple “clover” shape (c) and in CP detection mode representing distinguishable “ε” and “3” (d).

Extended Data Table 1 Atomic concentrations of neat PCPDTTBTT and chiral doped polymeric active layers before and after thermal annealing based on XPS measurements
Full size table

Supplementary information

Supplementary Information

This file contains: Supplementary Notes 1–13, Figs. 1–55, Tables 1 and 2 and references.

Supplementary Video 1

Recordings of dynamic degree of circular polarization measurement. Time-dependent photocurrents of CP photodetectors measured by rotating the QWP in 15° increments from 0 to 360° for polarized beam generation.

Supplementary Video 2

Recordings of real-time spatiotemporal spin helicity detection and imaging. An 8 × 8 matrix array customized with a software-controlled multichannel data acquisition system represented three different digital signals depending on the CP state of the light.

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Song, I., Ahn, J., Ahn, H. et al. Helical polymers for dissymmetric circularly polarized light imaging. Nature 617, 92–99 (2023). https://doi.org/10.1038/s41586-023-05877-0

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