We report on the first and versatile cellulose-based photoresist, which can be applied in direct laser writing and allows the fabrication of structures with a resolution of less than 1 μm and a feature size of less than 500 nm via two-photon absorption. Therefore, cellulose diacetate is functionalised with methacrylic acid anhydride to introduce photo-crosslinkable side groups into the cellulose chain. The photoresist consists of the methacrylated cellulose diacetate and a photoinitiator both dissolved in acetone. The cellulose-based photoresist can be applied to generate two- and three-dimensional hierarchical structures and clears the way to the design and fabrication of biomimetic architectures solely made from biopolymers.
A photo-crosslinkable cellulose-based resist, which can be applied in direct laser writing (DLW), was synthesised. It enables the generation of two- and three-dimensional hierarchical structures with a feature size of less than 500 nm via two-photon absorption. This new photoresist paves the way towards designing and fabricating biomimetic architectures solely made from biopolymers.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
Ashori A, Babaee M, Jonoobi M, Hamzeh Y (2014) Solvent-free acetylation of cellulose nanofibers for improvingcompatibility and dispersion. Carbohydr Polym 102:369–375
Auclair N, Kaboorani A, Riedl B, Landry V (2015) Acrylated betulin as a comonomer for bio-based coatings. Part I: characterization, photo-polymerization behavior and thermal stability. Ind Crops Prod 76:530–537
Barud HS, de Araújo Júnior AM, Santos DB et al (2008) Thermal behavior of cellulose acetate produced from homogeneous acetylation of bacterial cellulose. Thermochim Acta 471:61–69
Çakmakçi E, Güngör A, Kayaman-Apohan N, Kuruca SE, Çetin MB, Dar KA (2012) Cell growth on in situ photo-cross-linked electrospun acrylated cellulose acetate butyrate. J Biomater Sci 23:887–899
Deng F, Ge X, Zhang Y, Li M-C, Cho UR (2015) Synthesis and characterization of microcrystalline cellulose-graft-poly(methyl methacrylate) copolymers and their application as rubber reinforcements. J Appl Polym Sci 132:42666
Deubel M, von Freymann G, Wegener M, Pereira S, Busch K, Soukoulis CM (2004) Direct laser writing of three-dimensional photonic-crystal templates for telecommunications. Nat. Mater 3:444–447
Fertier L, Koleilat H, Stemmelen M, Giani O, Joly-Duhamel C, Lapinte V, Robin J-J (2013) The use of renewable feedstock in UV-curable materials—a new age for polymers and green chemistry. Prog Polym Sci 38:932–962
Fischer J, Wegener M (2013) Three-dimensional optical laser lithography beyond the diffraction limit. Laser Photonics Rev 7:22–44
Hampe R, Heinze T (2014) Studies about the solvent-dependent substitution pattern of starch acetates. Macromol Mater Eng 299:1188–1196
Heinze T, Liebert T (2001) Unconventional methods in cellulose functionalization. Prog Polym Sci 26:1689–1762
Ho CMB, Mishra A, Hu K, An J, Kim Y-J, Yoon Y-J (2017) Femtosecond-laser-based 3D printing for tissue engineering and cell biology applications. ACS Biomater Sci Eng 3:2198–2214
Hohmann JK, Renner M, Waller EH, von Freymann G (2015) Three-dimensional μ-printing: an enabling technology. Adv Opt Mater 3:1488–1507
Kamath M, Kincaid J, Mandal BK (1996) Interpenetrating polymer networks of photocrosslinkable cellulose derivatives. J Appl Polym Sci 59:45–50
Klemm D, Heublein B, Fink H-P, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44:3358–3393
Li HF, Li H, Zhong X, Li X, Gibril ME, Zhang Y, Han K, Yu M (2012) Study on the chemical modification of cellulose in ionic liquid with maleic anhydride. Adv Mater Res 581:287–291
Lide DR (1994) Handbook of chemistry and physics. CRC Press, Boca Raton
Ligon SC, Liska R, Stampfl J, Gurr M, Mülhaupt R (2017) Polymers for 3D printing and customized additive manufacturing. Chem Rev 117:10212–10290
Marsano E, De Paz L, Tambuscio E, Bianchi E (1998) Cellulose methacrylate: synthesis and liquid crystalline behaviour of solutions and gels. Polym 39:4289–4294
Maruo S, Nakamura O, Kawata S (1997) Three-dimensional microfabrication with two photon-absorbed photopolymerization. Opt Lett 22:132–134
Mayer F, Richter S, Hübner P, Jabbour T, Wegener M (2017) 3D fluorescence-based security features by 3D laser lithography. Adv Mater Technol 2:1–5
Oakdale JS, Ye J, Smith WL, Biener J (2016) Post-print UV curing method for improving the mechanical properties of prototypes derived from two-photon lithography. Opt Express 24:27077–27086
Park Y-J, Lim D-H, Kim H-J, Park D-S, Sung I-K (2009) UV- and thermal-curing behaviors of dual-curable adhesives based on epoxy acrylate oligomers. Int J Adhes Adhes 29:710–717
Pereira RF, Bártolo PJ (2015) 3D bioprinting of photocrosslinkable hydrogel constructs. J Appl Polym Sci 42458:1–15
Qi A, Hoo SP, Friend J, Yeo L, Yue Z, Chan PPY (2014) Hydroxypropyl cellulose methacrylate as a photo-patternable and biodegradable hybrid paper substrate for cell culture and other bioapplications. Adv Healthc Mater 3:543–554
Reeves R, Ribeiro A, Lombardo L, Boyer R, Leach JB (2010) Synthesis and characterization of carboxymethylcellulose-methacrylate hydrogel cell scaffolds. Polymers (Basel) 2:252–264
Sun HB, Matsuo S, Misawa H (1999) Three-dimensional photonic crystal structures achieved with two-photon-absorption photopolymerization of resin. Appl Phys Lett 74:786–788
Takács E, Wojnárovits L, Földváry CS, Borsa J, Sajó I (2001) Radiation activation of cotton-cellulose prior to alkali treatment. Res Chem Intermed 27:837–845
Thiele S, Arzenbacher K, Gissibl T, Giessen H, Herkommer AM (2017) 3D-printed eagle eye: compound microlens system for foveated imaging. Sci Adv 3:1–6
Träskman B, Tammela V (1986) The preparation and properties of vinyl cellulose. J Appl Polym Sci 31:2043–2054
Trombino S, Cassano R, Bloise E, Muzzalupo R, Tavano L, Picci N (2009) Synthesis and antioxidant activity evaluation of a novel cellulose hydrogel containing trans-ferulic acid. Carbohydr Polym 75:184–188
Waller E, von Freymann G (2016) Spatio-temporal proximity characteristics in 3D μ-printing via multi-photon absorption. Polymers 8:297/1–297/13
Wang S, Lu A, Zhang L (2016) Recent advances in regenerated cellulose materials. Prog Polym Sci 53:169–206
Wondraczek H, Kotiaho A, Fardim P, Heinze T (2011) Photoactive polysaccharides. Carbohydr Polym 83:1048–1061
Woolley JT (1975) Refractive index of soybean leaf cell walls. Plant Physiol 55:172–174
Zhao D, Huang J, Zhong Y, Li K, Zhang L, Cai J (2016) High-strength and high-toughness double-cross-linked cellulose hydrogels: a new strategy using sequential chemical and physical cross-linking. Adv Funct Mater 26:6279–6287
The financial support from German Science Foundation (DFG) for funding our work within the priority program “Tailored Disorder—A science-and engineering-based approach to materials design for advanced photonic applications” (SPP-1839) is gratefully acknowledged. We thank the team from the Nano Structuring Centre (NSC) at University of Kaiserslautern for their support with scanning electron microscopy and Dr. Christina Rösch from the group of Prof. Christiane Ziegler at University of Kaiserslautern for the roughness measurements.
About this article
Cite this article
Rothammer, M., Heep, M., von Freymann, G. et al. Enabling direct laser writing of cellulose-based submicron architectures. Cellulose 25, 6031–6039 (2018). https://doi.org/10.1007/s10570-018-2002-1
- Cellulose methacrylate
- Bio-based photoresist
- Direct laser writing
- Submicron patterning