Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

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

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

Subjects

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).

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

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.

Similar content being viewed by others

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.

References

  1. Naumov, P., Chizhik, S., Panda, M. K., Nath, N. K. & Boldyreva, E. Mechanically responsive molecular crystals. Chem. Rev. 115, 12440–12490 (2015).

    CAS  Google Scholar 

  2. Sotome, H. et al. Cycloreversion reaction of a diarylethene derivative at higher excited states attained by two-color, two-photon femtosecond pulsed excitation. J. Am. Chem. Soc. 139, 17159–17167 (2017).

    CAS  Google Scholar 

  3. Sotome, H. et al. Geometrical evolution and formation of the photoproduct in the cycloreversion reaction of a diarylethene derivative probed by vibrational spectroscopy. ChemPhysChem 21, 1524–1530 (2020).

    CAS  Google Scholar 

  4. Morimoto, M. & Irie, M. A diarylethene cocrystal that converts light into mechanical work. J. Am. Chem. Soc. 132, 14172–14178 (2010).

    CAS  Google Scholar 

  5. Halabi, J. M., Ahmed, E., Sofela, S. & Naumov, P. Performance of molecular crystals in conversion of light to mechanical work. Proc. Natl Acad. Sci. USA 118, e2020604118 (2021).

    CAS  Google Scholar 

  6. White, T. J. & Broer, D. J. Programmable and adaptive mechanics with liquid crystal polymer networks and elastomers. Nat. Mater. 14, 1087–1098 (2015).

    CAS  Google Scholar 

  7. Kuenstler, A. S., Clark, K. D., Read de Alaniz, J. & Hayward, R. C. Reversible actuation via photoisomerization-induced melting of a semicrystalline poly (azobenzene). ACS Macro Lett. 9, 902–909 (2020).

    CAS  Google Scholar 

  8. Eisenbach, C. D. Isomerization of aromatic azo chromophores in poly(ethyl acrylate) networks and photomechanical effect. Polymer 21, 1175–1179 (1980).

    CAS  Google Scholar 

  9. Iwaso, K., Takashima, Y. & Harada, A. Fast response dry-type artificial molecular muscles with [c2]daisy chains. Nat. Chem. 8, 625–632 (2016).

    CAS  Google Scholar 

  10. Shibata, K., Muto, K., Kobatake, S. & Irie, M. Photocyclization/cycloreversion quantum yields of diarylethenes in single crystals. J. Phys. Chem. A 106, 209–214 (2002).

    CAS  Google Scholar 

  11. Turowska-Tyrk, I. & Trzop, E. Monitoring structural transformations in crystals. 6. The [4 + 4] photodimerization of 9-methylanthracene. Acta Crystallogr. B. Struct. Sci. Cryst. Eng. Mater. 59, 779–786 (2003).

    Google Scholar 

  12. Terao, F., Morimoto, M. & Irie, M. Light‐driven molecular‐crystal actuators: rapid and reversible bending of rodlike mixed crystals of diarylethene derivatives. Angew. Chem. Int. Ed. 51, 901–904 (2012).

    CAS  Google Scholar 

  13. Kitagawa, D. & Kobatake, S. Crystal thickness dependence of photoinduced crystal bending of 1,2-bis(2-methyl-5-(4-(1-naphthoyloxymethyl)phenyl)-3-thienyl)perfluorocyclopentene. J. Phys. Chem. C 117, 20887–20892 (2013).

    CAS  Google Scholar 

  14. Kobatake, S., Hasegawa, H. & Miyamura, K. High-convertible photochromism of a diarylethene single crystal accompanying the crystal shape deformation. Cryst. Growth Des. 11, 1223–1229 (2011).

    CAS  Google Scholar 

  15. Tong, F. et al. Photomechanically induced magnetic feld response by controlling molecular orientation in 9-methylanthracene microcrystals. Angew. Chem. Int. Ed. 57, 7080–7084 (2018).

    CAS  Google Scholar 

  16. Kobatake, S., Takami, S., Muto, H., Ishikawa, T. & Irie, M. Rapid and reversible shape changes of molecular crystals on photoirradiation. Nature 446, 778–781 (2007).

    CAS  Google Scholar 

  17. Dong, X. et al. Hybrid organic–inorganic photon-powered actuators based on aligned diarylethene nanocrystals. Chem. Mater. 31, 1016–1022 (2019).

    CAS  Google Scholar 

  18. Lan, T. & Chen, W. Hybrid nanoscale organic molecular crystals assembly as a photon-controlled actuator. Angew. Chem. Int. Ed. 52, 6496–6500 (2013).

    CAS  Google Scholar 

  19. Berman, A. et al. Biological control of crystal texture: a widespread strategy for adapting crystal properties to function. Science 259, 776–779 (1993).

    CAS  Google Scholar 

  20. Hooks, D. E., Fritz, T. & Ward, M. D. Epitaxy and molecular organization on solid substrates. Adv. Mater. 13, 227–241 (2001).

    CAS  Google Scholar 

  21. Varghese, S. et al. Epitaxial growth of light-responsive azobenzene molecular crystal actuators on oriented polyethylene films. J. Mater. Chem. C 8, 694–699 (2020).

    CAS  Google Scholar 

  22. Jean-Ruel, H. et al. Femtosecond dynamics of the ring closing process of diarylethene: a case study of electrocyclic reactions in photochromic single crystals. J. Phys. Chem. A 115, 13158–13168 (2011).

    CAS  Google Scholar 

  23. Ward, M. D. Bulk crystals to surfaces: combining X-ray diffraction and atomic force microscopy to probe the structure and formation of crystal interfaces. Chem. Rev. 101, 1697–1726 (2001).

    CAS  Google Scholar 

  24. Damman, P., Coppée, S., Geskin, V. M. & Lazzaroni, R. What is the mechanism of oriented crystal growth on rubbed polymer substrates? Topography vs epitaxy. J. Am. Chem. Soc. 124, 15166–15167 (2002).

    CAS  Google Scholar 

  25. Lansakara, T. I., Tong, F., Bardeen, C. J. & Tivanski, A. V. Mechanical properties and photomechanical fatigue of macro- and nanodimensional diarylethene molecular crystals. Nano Lett. 20, 6744–6749 (2020).

    CAS  Google Scholar 

  26. Dong, X. et al. Effects of template and molecular nanostructure on the performance of organic–inorganic photomechanical actuator membranes. Adv. Funct. Mater. 30, 1902396 (2019).

    Google Scholar 

  27. Guo, T., Zheng, X. & Palffy-Muhoray, P. Impedance matching in an elastic actuator. Soft Matter 17, 4191–4194 (2021).

    CAS  Google Scholar 

  28. Irie, M., Kobatake, S. & Horichi, M. Reversible surface morphology changes of a photochromic diarylethene single crystal by photoirradiation. Science 291, 1769–1772 (2001).

    CAS  Google Scholar 

  29. Ufimtsev, I. S. & Martinez, T. J. Quantum chemistry on graphical processing units. 1. Strategies for two-electron integral evaluation. J. Chem. Theory Comput. 4, 222–231 (2008).

    CAS  Google Scholar 

  30. Ufimtsev, I. S. & Martinez, T. J. Quantum chemistry on graphical processing units. 2. Direct self-consistent-field implementation. J. Chem. Theory Comput. 5, 1004–1015 (2009).

    CAS  Google Scholar 

  31. Ufimtsev, I. S. & Martinez, T. J. Quantum chemistry on graphical processing units. 3. Analytical energy gradients, geometry optimization, and first principles molecular dynamics. J. Chem. Theory Comput. 5, 2619–2628 (2009).

    CAS  Google Scholar 

  32. Timoshenko, S. Analysis of bi-metal thermostats. J. Opt. Soc. Am. 11, 233–255 (1925).

    CAS  Google Scholar 

  33. Nath, N. K. et al. Surface and bulk effects in photochemical reactions and photomechanical effects in dynamic molecular crystals. J. Am. Chem. Soc. 137, 13866–13875 (2015).

    CAS  Google Scholar 

  34. Koshima, H., Matsuo, R., Matsudomi, M., Uemura, Y. & Shiro, M. Light-driven bending crystals of salicylidenephenylethylamines in enantiomeric and racemate forms. Cryst. Growth Des. 13, 4330–4337 (2013).

    CAS  Google Scholar 

  35. Samanta, R. et al. Mechanical actuation and patterning of rewritable crystalline monomer–polymer heterostructures via topochemical polymerization in a dual-responsive photochromic organic material. ACS Appl. Mater. Interfaces 12, 16856–16863 (2020).

    CAS  Google Scholar 

  36. Li, C., Moon, J., Yun, J.-H., Kim, H. & Cho, M. Influence of external loads on structure and photoactuation in densely crosslinked azo-incorporated liquid crystalline polymers. Polymer 129, 252–260 (2017).

    CAS  Google Scholar 

  37. Li, M. H., Keller, P., Li, B., Wang, X. & Brunet, M. Light‐driven side‐on nematic elastomer actuators. Adv. Mater. 15, 569–572 (2003).

    CAS  Google Scholar 

  38. Ube, T., Takado, K. & Ikeda, T. Photomobile materials with interpenetrating polymer networks composed of liquid-crystalline and amorphous polymers. J. Mater. Chem. C 3, 8006–8009 (2015).

    CAS  Google Scholar 

  39. Lee, K. M. et al. Enhancement of photogenerated mechanical force in azobenzene‐functionalized polyimides. Angew. Chem. Int. Ed. 124, 4193–4197 (2012).

    Google Scholar 

  40. Wang, D. H., Wie, J. J., Lee, K. M., White, T. J. & Tan, L.-S. Impact of backbone rigidity on the photomechanical response of glassy, azobenzene-functionalized polyimides. Macromolecules 47, 659–667 (2014).

    CAS  Google Scholar 

  41. Zhou, H., Kuenstler, A. S., Xu, W., Hu, M. & Hayward, R. C. A semicrystalline poly (azobenzene) exhibiting room temperature light-induced melting, crystallization, and alignment. Macromolecules 55, 10330–10340 (2022).

    CAS  Google Scholar 

  42. Osaki, M. et al. Photoresponsive polymeric actuator cross-linked by an 8-armed polyhedral oligomeric silsesquioxane. Eur. Polym. J. 134, 109806 (2020).

    CAS  Google Scholar 

  43. Svanidze, A., Guo, T., Zheng, X. & Palffy-Muhoray, P. Light-induced stress and work in photomechanical materials. Phys. Rev. E 103, L051002 (2021).

    CAS  Google Scholar 

  44. Kitagawa, D. & Kobatake, S. Crystal thickness dependence of photoinduced crystal bending of 1,2-bis(2-methyl-5-(4-(1-naphthoyloxymethyl)phenyl)-3-thienyl) perfluorocyclopentene. J. Phys. Chem. C 117, 20887–20892 (2013).

    CAS  Google Scholar 

  45. Hirano, A., Hashimoto, T., Kitagawa, D., Kono, K. & Kobatake, S. Dependence of photoinduced bending behavior of diarylethene crystals on ultraviolet irradiation power. Cryst. Growth Des. 17, 4819–4825 (2017).

    CAS  Google Scholar 

  46. Irie, M., Fukaminato, T., Matsuda, K. & Kobatake, S. Photochromism of diarylethene molecules and crystals: memories, switches, and actuators. Chem. Rev. 114, 12174–12277 (2014).

    CAS  Google Scholar 

Download references

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

Authors
  1. Wenwen Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. David M. Sanchez
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Umberto Raucci
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hantao Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xinning Dong
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Mingqiu Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Christopher J. Bardeen
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Todd J. Martinez
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Ryan C. Hayward
    View author publications

    You can also search for this author in PubMed Google Scholar

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.

Ethics declarations

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.

Peer review

Peer review information

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

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

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.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-023-01610-4

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing