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Photo-actuators via epitaxial growth of microcrystal arrays in polymer membranes

Nature Materials volume 22, pages 1152–1159 (2023)Cite this article

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Abstract

Photomechanical crystals composed of three-dimensionally ordered and densely packed photochromes hold promise for high-performance photochemical actuators. However, bulk crystals with high structural ordering are severely limited in their flexibility, resulting in poor processibility and a tendency to fragment upon light exposure, while previous nano- or microcrystalline composites have lacked global alignment. Here we demonstrate a photon-fuelled macroscopic actuator consisting of diarylethene microcrystals in a polyethylene terephthalate host matrix. These microcrystals survive large deformations and show a high degree of three-dimensional ordering dictated by the anisotropic polyethylene terephthalate, which critically also has a similar stiffness. Overall, these ordered and compliant composites exhibit rapid response times, sustain a performance of over at least hundreds of cycles and generate work densities exceeding those of single crystals. Our composites represent the state-of-the-art for photochemical actuators and enable properties unattainable by single crystals, such as controllable, reversible and abrupt jumping (photosalient behaviour).

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Fig. 1: DAE in biaxially aligned microcrystal composites.
Fig. 2: Growth of DMPT-PFCP crystals in PETE templates.
Fig. 3: Characterization of biaxially aligned DMPT-PFCP crystals.
Fig. 4: Photomechanical properties of composites.
Fig. 5: Photomechanical performance enabled by composites.

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Data availability

The data that support the plots within this paper and other findings of this study are available at https://doi.org/10.25810/vm46-e710. Additional data related to this paper may be requested from the corresponding author.

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Acknowledgements

This work was under the support of the Office of Naval Research through the MURI programme on Photomechanical Materials (ONR N00014-18-1-2624). Lawrence Livermore National Laboratory is operated by Lawrence Livermore National Security for the US Department of Energy, National Nuclear Security Administration under contract DE-AC52-07NA27344. M.H. was supported by the Air Force Office of Scientific Research through grant 21RT0488. We thank H. Zhao, Y. Hu and F. Tong for assistance with crystal analysis and helpful discussions.

Author information

Author notes

  1. Wenwen Xu

    Present address: Sichuan University-Pittsburgh Institute, Sichuan University, Chengdu, China

  2. David M. Sanchez

    Present address: Design Physics Division, Lawrence Livermore National Laboratory, Livermore, CA, USA

  3. Umberto Raucci

    Present address: Italian Institute of Technology, Genoa, Italy

Authors and Affiliations

  1. Department of Chemical and Biological Engineering, University of Colorado Boulder, Boulder, CO, USA

    Wenwen Xu, Hantao Zhou & Ryan C. Hayward

  2. Department of Chemistry, Stanford University, Stanford, CA, USA

    David M. Sanchez, Umberto Raucci & Todd J. Martinez

  3. Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    David M. Sanchez, Umberto Raucci & Todd J. Martinez

  4. Department of Polymer Science and Engineering, University of Massachusetts Amherst, Amherst, MA, USA

    Hantao Zhou & Mingqiu Hu

  5. Department of Chemistry, University of California, Riverside, Riverside, CA, USA

    Xinning Dong & Christopher J. Bardeen

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Contributions

This project was under the supervision of R.C.H.; R.C.H. and C.J.B. proposed the conceptual idea; W.X. designed and conducted the major experiments; D.M.S., U.R. and T.J.M. conducted the theoretical calculations; H.Z., X.D. and M.H. were involved in X-ray characterization; all authors contributed to the analysis and interpretation of the results; and W.X. drafted the initial paper, which was revised by all authors.

Corresponding author

Correspondence to Ryan C. Hayward.

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Competing interests

The University of Colorado Boulder has filed a US Patent Application (18/318,926, inventors: Wenwen Xu, Ryan C. Hayward) on the preparation of hybrid polymer/crystal photomechanical materials. The other authors declare no competing interests.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–23, Tables 1–8, Notes 1–3, captions for Videos 1–4 and References.

Supplementary Video 1

A nylon ball is glued at the tip of an 11-μm-thick actuator. The actuator performs lifting and unlifting under alternating UV and green light.

Supplementary Video 2

The actuation of an 11-μm-thick actuator under 5 ms pulsed UV light. The video was recorded at 5,000 f.p.s. The playback speed is 30 f.p.s.

Supplementary Video 3

During the latent period of the photosalient 11 μm composite, the hind leg of the composite first slides and gets pinned on the ratchet surface to accumulate elastic strain energy. Quickly releasing the stored elastic energy results in fast jumping behaviour. Both the recording and playback speeds for this video are 60 f.p.s.

Supplementary Video 4

Right after the latent period, the composite quickly leaps towards the vertical wall. The composite can be reset by green light and can repeat the jumping behaviour. The video was taken at 4,000 f.p.s., and the playback speed is 30 f.p.s.

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Xu, W., Sanchez, D.M., Raucci, U. et al. Photo-actuators via epitaxial growth of microcrystal arrays in polymer membranes. Nat. Mater. 22, 1152–1159 (2023). https://doi.org/10.1038/s41563-023-01610-4

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