Article | Published:

Hydroxypropyl cellulose photonic architectures by soft nanoimprinting lithography

Nature Photonicsvolume 12pages343348 (2018) | Download Citation

Abstract

As contamination and environmental degradation increase, there is a huge demand for new eco-friendly materials. Despite its use for thousands of years, cellulose and its derivatives have gained renewed interest as favourable alternatives to conventional plastics, due to their abundance and lower environmental impact. Here, we report the fabrication of photonic and plasmonic structures by moulding hydroxypropyl cellulose into submicrometric periodic lattices, using soft lithography. This is an alternative way to achieve structural colour in this material, which is usually obtained by exploiting its chiral nematic phase. Cellulose-based photonic crystals are biocompatible and can be dissolved in water or not depending on the derivative employed. Patterned cellulose membranes exhibit tunable colours and may be used to boost the photoluminescence of a host organic dye. Furthermore, we show how metal coating these cellulose photonic architectures leads to plasmonic crystals with excellent optical properties acting as disposable surface-enhanced Raman spectroscopy substrates.

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References

  1. 1.

    Plastics—the Facts 2016 https://www.plasticseurope.org/application/files/4315/1310/4805/plastic-the-fact-2016.pdf (PlasticsEurope, 2016).

  2. 2.

    Hoeng, F., Denneulin, A. & Bras, J. Use of nanocellulose in printed electronics: a review. Nanoscale 8, 13131–13154 (2016).

  3. 3.

    Lagerwall, J. et al. Cellulose nanocrystal-based materials: from liquid crystal self-assembly and glass formation to multifunctional thin films. NPG Asia Mater. 6, e80 (2014).

  4. 4.

    Zhu, H. et al. Wood-derived materials for green electronics, biological devices, and energy applications. Chem. Rev. 116, 9305–9374 (2016).

  5. 5.

    Dumanli, A. et al. Controlled, bio-inspired self-assembly of cellulose-based chiral reflectors. Adv. Opt. Mater. 2, 646–650 (2014).

  6. 6.

    Fernandes, S. et al. Mind the microgap in iridescent cellulose nanocrystal films. Adv. Mater. 29, 1603560 (2017).

  7. 7.

    Águas, H. et al. Thin film silicon photovoltaic cells on paper for flexible indoor applications. Adv. Funct. Mater. 25, 3592–3598 (2015).

  8. 8.

    Ha, D., Fang, Z., Hu, L. & Munday, J. Paper-based anti-reflection coatings for photovoltaics. Adv. Energy Mater. 4, 1301804 (2014).

  9. 9.

    Espinha, A. et al. Shape memory cellulose-based photonic reflectors. ACS Appl. Mater. Inter. 8, 31935–31940 (2016).

  10. 10.

    Wu, T. et al. A bio-inspired cellulose nanocrystal-based nanocomposite photonic film with hyper-reflection and humidity-responsive actuator properties. J. Mater. Chem. C. 4, 9687–9696 (2016).

  11. 11.

    Polavarapu, L. & Liz-Marzán, L. Towards low-cost flexible substrates for nanoplasmonic sensing. Phys. Chem. Chem. Phys. 15, 5288–5300 (2013).

  12. 12.

    Tian, L. et al. Bacterial nanocellulose-based flexible surface enhanced Raman scattering substrate. Adv. Mater. Interfaces 3, 1600214 (2016).

  13. 13.

    Gilbert, R. & Patton, P. Liquid crystal formation in cellulose and cellulose derivatives. Prog. Polym. Sci. 9, 115–131 (1983).

  14. 14.

    Werbowyj, R. & Gray, D. Liquid crystalline structure in aqueous hydroxypropyl cellulose solutions. Mol. Cryst. Liq. Cryst. 34, 97–103 (1976).

  15. 15.

    Kamita, G. et al. Biocompatible and sustainable optical strain sensors for large-area applications. Adv. Opt. Mater. 4, 1950–1954 (2016).

  16. 16.

    Xia, Y. & Whitesides, G. Soft lithography. Angew. Chem. Int. Ed. 37, 550–575 (1998).

  17. 17.

    Espinha, A., Serrano, M., Blanco, A. & López, C. Thermoresponsive shape-memory photonic nanostructures. Adv. Opt. Mater. 2, 516–521 (2014).

  18. 18.

    Worgull, M. et al. Hot embossing and thermoforming of biodegradable three-dimensional wood structures. RSC Adv. 3, 20060–20064 (2013).

  19. 19.

    Mäkelä, T., Kainlauri, M., Willberg-Keyriläinen, P., Tammelin, T. & Forsström, U. Fabrication of micropillars on nanocellulose films using a roll-to-roll nanoimprinting method. Microelectron. Eng. 163, 1–6 (2016).

  20. 20.

    Mäkelä, T., Haatainen, T. & Ahopelto, J. Roll-to-roll printed gratings in cellulose acetate web using novel nanoimprinting device. Microelectron. Eng. 88, 2045–2047 (2011).

  21. 21.

    Werbowyj, R. & Gray, D. Optical properties of hydroxypropyl cellulose liquid crystals. I. Cholesteric pitch and polymer concentration. Macromolecules 17, 1512–1520 (1984).

  22. 22.

    Odom, T., Love, J., Wolfe, D., Paul, K. & Whitesides, G. Improved pattern transfer in soft lithography using composite stamps. Langmuir 18, 5314–5320 (2002).

  23. 23.

    Kabra, B., Gehrke, S. & Spontak, R. Microporous, responsive hydroxypropyl cellulose gels. 1. Synthesis and microstructure. Macromolecules 31, 2166–2173 (1998).

  24. 24.

    Yang, A. et al. Unidirectional lasing from template-stripped two-dimensional plasmonic crystals. ACS Nano 9, 11582–11588 (2015).

  25. 25.

    de Arquer, F., Mihi, A. & Konstantatos, G. Large-area plasmonic-crystal-hot-electron-based photodetectors. ACS Photon. 2, 950–957 (2015).

  26. 26.

    James, T., Mulvaney, P. & Roberts, A. The plasmonic pixel: large area, wide gamut color reproduction using aluminum nanostructures. Nano Lett. 16, 3817–3823 (2016).

  27. 27.

    Cheng, F., Gao, J., Luk, T. & Yang, X. Structural color printing based on plasmonic metasurfaces of perfect light absorption. Sci. Rep. 5, 11045 (2015).

  28. 28.

    Fudouzi, H. & Xia, Y. Photonic papers and inks: color writing with colorless materials. Adv. Mater. 15, 892–896 (2003).

  29. 29.

    Min, K., Kim, S., Kim, C. & Kim, S. Colored and fluorescent nanofibrous silk as a physically transient chemosensor and vitamin deliverer. Sci. Rep. 7, 5448 (2017).

  30. 30.

    Espinha, A., Serrano, M., Blanco, A. & López, C. Random lasing in novel dye-doped white paints with shape memory. Adv. Opt. Mater. 3, 1080–1087 (2015).

  31. 31.

    Macias, G., Alba, M., Marsal, L. & Mihi, A. Surface roughness boosts the SERS performance of imprinted plasmonic architectures. J. Mater. Chem. C. 4, 3970–3975 (2016).

  32. 32.

    Bae, H. et al. Physically transient memory on a rapidly dissoluble paper for security application. Sci. Rep. 6, 38324 (2016).

  33. 33.

    Hwang, S. et al. A physically transient form of silicon electronics. Science 337, 1640–1644 (2012).

  34. 34.

    Tao, H. et al. Silk-based conformal, adhesive, edible food sensors. Adv. Mater. 24, 1067–1072 (2012).

  35. 35.

    Luchs, J., Nelinson, D. & Macy, J. Efficacy of hydroxypropyl cellulose ophthalmic inserts (LACRISERT) in subsets of patients with dry eye syndrome: findings from a patient registry. Cornea 29, 1417–1427 (2010).

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Acknowledgements

The authors acknowledge M. Simón and A. Gómez for AFM measurements. The Spanish Ministerio de Economía, Industria y Competitividad (MINECO) is gratefully acknowledged for its support through grant no. SEV-2015-0496 in the framework of the Spanish Severo Ochoa Centre of Excellence programme and also for its support through grant MAT2016-79053-P. A.M. was funded by a Ramón y Cajal fellowship (RYC-2014-16444). This project has received funding from the European Research Council under the European Union’s Horizon 2020 research and innovation programme (grant agreement no. 637116, ENLIGHTMENT).

Author information

Affiliations

  1. Institut de Ciència de Materials de Barcelona, Consejo Superior de Investigaciones Científicas, Barcelona, Spain

    • André Espinha
    • , Camilla Dore
    • , Cristiano Matricardi
    • , Maria Isabel Alonso
    • , Alejandro R. Goñi
    •  & Agustín Mihi
  2. Institució Catalana de Recerca i Estudis Avançats, Barcelona, Spain

    • Alejandro R. Goñi

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Contributions

A.E. and C.D. developed the concept, fabricated and characterized the samples. C.M. provided patterned PDMS moulds. A.R.G. and M.I.A. carried out photoluminescence and Raman measurements. A.E and A.M. wrote the manuscript. All authors contributed to fruitful discussions and corrected the manuscript. A.M. supervised the research.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Agustín Mihi.

Supplementary information

  1. Supplementary Information

    Additional information including a comparison of replica moulding and hot embossing fabrication methods, scanning electron microscopy images, micro-Raman experiments and electric field simulations.

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DOI

https://doi.org/10.1038/s41566-018-0152-1