Polymeric materials have been used to realize optical systems that, through periodic variations of their structural or optical properties, interact with light-generating holographic signals. Complex holographic systems can also be dynamically controlled through exposure to external stimuli, yet they usually contain only a single type of holographic mode. Here, we report a conjugated organogel that reversibly displays three modes of holograms in a single architecture. Using dithering mask lithography, we realized two-dimensional patterns with varying cross-linking densities on a conjugated polydiacetylene. In protic solvents, the organogel contracts anisotropically to develop optical and structural heterogeneities along the third dimension, displaying holograms in the form of three-dimensional full parallax signals, both in fluorescence and bright-field microscopy imaging. In aprotic solvents, these heterogeneities diminish as organogels expand, recovering the two-dimensional periodicity to display a third hologram mode based on iridescent structural colours. Our study presents a next-generation hologram manufacturing method for multilevel encryption technologies.
Subscribe to Journal
Get full journal access for 1 year
only $17.42 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
All data supporting this study are available within the paper and/or are available from the authors upon reasonable request.
Kang, Y., Walish, J. J., Gorishnyy, T. & Thomas, E. L. Broad-wavelength-range chemically tunable block-copolymer photonic gels. Nat. Mater. 6, 957–960 (2007).
Matsubara, K., Watanabe, M. & Takeoka, Y. A thermally adjustable multicolor photochromic hydrogel. Angew. Chem. Int. Ed. 46, 1688–1692 (2007).
Kim, H. et al. Structural colour printing using a magnetically tunable and lithographically fixable photonic crystal. Nat. Photonics 3, 534–540 (2009).
Honda, M., Seki, T. & Takeoka, Y. Dual tuning of the photonic band-gap structure in soft photonic crystals. Adv. Mater. 21, 1801–1804 (2009).
Holtz, J. H. & Asher, S. A. Polymerized colloidal crystal hydrogel films as intelligent chemical sensing materials. Nature 389, 829–832 (1997).
Sagara, Y. & Kato, T. Mechanically induced luminescence changes in molecular assemblies. Nat. Chem. 1, 605–610 (2009).
Chiappelli, M. C. & Hayward, R. C. Photonic multilayer sensors from photo-crosslinkable polymer films. Adv. Mater. 24, 6100–6104 (2012).
Wang, Q. M., Gossweiler, G. R., Craig, S. L. & Zhao, X. H. Cephalopod-inspired design of electro-mechano-chemically responsive elastomers for on-demand fluorescent patterning. Nat. Commun. 5, 4899 (2014).
Luo, W. et al. Steric-repulsion-based magnetically responsive photonic crystals. Adv. Mater. 26, 1058–1064 (2014).
Xiao, F. B. et al. Smart photonic crystal hydrogel material for uranyl ion monitoring and removal in water. Adv. Funct. Mater. 27, 1702147 (2017).
Couturier, J. P., Sutterlin, M., Laschewsky, A., Hettrich, C. & Wischerhoff, E. Responsive inverse opal hydrogels for the sensing of macromolecules. Angew. Chem. Int. Ed. 54, 6641–6644 (2015).
Asher, S. A., Holtz, J., Liu, L. & Wu, Z. J. Self-assembly motif for creating submicron periodic materials. Polymerized crystalline colloidal arrays. J. Am. Chem. Soc. 116, 4997–4998 (1994).
Weissman, J. M., Sunkara, H. B., Tse, A. S. & Asher, S. A. Thermally switchable periodicities and diffraction from mesoscopically ordered materials. Science 274, 959–960 (1996).
Campbell, M., Sharp, D. N., Harrison, M. T., Denning, R. G. & Turberfield, A. J. Fabrication of photonic crystals for the visible spectrum by holographic lithography. Nature 404, 53–56 (2000).
Tondiglia, V. P., Natarajan, L. V., Sutherland, R. L., Tomlin, D. & Bunning, T. J. Holographic formation of electro-optical polymer-liquid crystal photonic crystals. Adv. Mater. 14, 187–191 (2002).
Orosco, M. M., Pacholski, C., Miskelly, G. M. & Sailor, M. J. Protein-coated porous-silicon photonic crystals for amplified optical detection of protease activity. Adv. Mater. 18, 1393–1396 (2006).
Yoon, J., Lee, W. & Thomas, E. L. Thermochromic block copolymer photonic gel. Macromolecules 41, 4582–4584 (2008).
Tay, S. et al. An updatable holographic three-dimensional display. Nature 451, 694–698 (2008).
Zhou, Y., Hauser, A. W., Bende, N. P., Kuzyk, M. G. & Hayward, R. C. Waveguiding microactuators based on a photothermally responsive nanocomposite hydrogel. Adv. Funct. Mater. 26, 5447–5452 (2016).
Lim, H. S., Lee, J. H., Walish, J. J. & Thomas, E. L. Dynamic swelling of tunable full-color block copolymer photonic gels via counterion exchange. ACS Nano 6, 8933–8939 (2012).
Kim, S. et al. Silk inverse opals. Nat. Photonics 6, 817–822 (2012).
Burgess, I. B., Lončar, M. & Aizenberg, J. Structural colour in colourimetric sensors and indicators. J. Mater. Chem. C 1, 6075–6086 (2013).
Lee, G. H. et al. Chameleon-inspired mechanochromic photonic films composed of non-close-packed colloidal arrays. ACS Nano 11, 11350–11357 (2017).
Jiang, N. et al. Laser interference lithography for the nanofabrication of stimuli-responsive Bragg stacks. Adv. Funct. Mater. 28, 1702715 (2018).
Zhao, Q. L., Wang, Y. L., Cui, H. Q. & Du, X. M. Bio-inspired sensing and actuating materials. J. Mater. Chem. C 7, 6493–6511 (2019).
Liao, J. L. et al. Multiresponsive elastic colloidal crystals for reversible structural color patterns. Adv. Funct. Mater. 29, 1902954 (2019).
Watanabe, T. et al. Photoresponsive hydrogel microstructure fabricated by two-photon initiated polymerization. Adv. Funct. Mater. 12, 611–614 (2002).
Li, J., Liang, G. Q., Zhu, X. L. & Yang, S. Exploiting nanoroughness on holographically patterned three-dimensional photonic crystals. Adv. Funct. Mater. 22, 2980–2986 (2012).
Beristain, M. F., Estrada, M. R., Ortega, A., Claverie, A. L. & Ogawa, T. Radical stabilization of aromatic diacetylenes (dinaphthylbutadiynes) in the free radical polymerization of methyl methacrylate. Polym. J. 48, 963–967 (2016).
Beristain, M. F., Munoz, E. & Ogawa, T. Polymerization of diphenylbutadiyne derivatives in solution by free radical initiator. J. Macromol. Sci. A 44, 605–611 (2007).
Beristain, M. F., Bucio, E., Burillo, G., Munoz, E. & Ogawa, T. Study on the interaction of diarylbutadiynes with free radicals: Interaction with propagating radicals of some vinyl monomers. Polym. Bull. 43, 357–364 (1999).
Kim, J. M. et al. A polydiacetylene-based fluorescent sensor chip. J. Am. Chem. Soc. 127, 17580–17581 (2005).
Lee, J., Kim, H. J. & Kim, J. Polydiacetylene liposome arrays for selective potassium detection. J. Am. Chem. Soc. 130, 5010–5011 (2008).
Lee, J., Jun, H. & Kim, J. Polydiacetylene-liposome microarrays for selective and sensitive mercury(II) detection. Adv. Mater. 21, 3674–3677 (2009).
Lauher, J. W., Fowler, F. W. & Goroff, N. S. Single-crystal-to-single-crystal topochemical polymerizations by design. Acc. Chem. Res. 41, 1215–1229 (2008).
Day, D. & Lando, J. B. Structure determination of a poly(diacetylene) monolayer. Macromolecules 13, 1483–1487 (1980).
Menzel, H., Mowery, M. D., Cai, M. & Evans, C. E. Vertical positioning of internal molecular scaffolding within a single molecular layer. J. Phys. Chem. B 102, 9550–9556 (1998).
Batchelder, D. N. et al. Self-assembled monolayers containing polydiacetylenes. J. Am. Chem. Soc. 116, 1050–1053 (1994).
Carpick, R. W., Sasaki, D. Y., Marcus, M. S., Eriksson, M. A. & Burns, A. R. Polydiacetylene films: a review of recent investigations into chromogenic transitions and nanomechanical properties. J. Phys. Condens. Matter 16, R679–R697 (2004).
Filhol, J. S. et al. Polymorphs and colors of polydiacetylenes: a first principles study. J. Am. Chem. Soc. 131, 6976–6988 (2009).
Goodman, J. W. Introduction to Fourier Optics (Roberts and Company Publishers, 2005).
Vyas, U. & Christensen, D. Ultrasound beam simulations in inhomogeneous tissue geometries using the hybrid angular spectrum method. IEEE Trans. Ultrason. Ferroelectr. Freq. Control 59, 1093–1100 (2012).
Yang, J. M., Li, J. W., He, S. L. & Wang, L. H. V. Angular-spectrum modeling of focusing light inside scattering media by optical phase conjugation. Optica 6, 250–256 (2019).
Duan, X. Y., Kamin, S. & Liu, N. Dynamic plasmonic colour display. Nat. Commun. 8, 14606 (2017).
Wen, D. D., Cadusch, J. J., Meng, J. & Crozier, K. B. Multifunctional dielectric metasurfaces consisting of color holograms encoded into color printed images. Adv. Funct. Mater. 30, 1906415 (2020).
Lee, J. et al. Universal process-inert encoding architecture for polymer microparticles. Nat. Mater. 13, 524–529 (2014).
Liu, Y. et al. Inkjet-printed unclonable quantum dot fluorescent anti-counterfeiting labels with artificial intelligence authentication. Nat. Commun. 10, 2409 (2019).
Kamat, N. P. et al. Sensing membrane stress with near IR-emissive porphyrins. Proc. Natl Acad. Sci. USA 108, 13984–13989 (2011).
This study was supported by the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (NRF-2017M3D9A1073922, NRF-2014R1A5A1009799), the Civil Military Technology Development Project of the Institute of Civil Military Technology Cooperation Center (ICMTC) funded by the Ministry of Trade, Industry and Energy, the Defense Acquisition Program Administration of Korea (18-CM-SS-13) and the Korea Environment Industry & Technology Institute (KEITI) through its Ecological Imitation-based Environmental Pollution Management Technology Development Project and funded by the Korea Ministry of Environment (MOE) (2019002790007).
The authors declare no competing interests.
Peer review information Nature Materials thanks Chenfeng Ke, Yukikazu Takeoka and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Methods, Notes 1–11, Figs. 1–62, Tables 1 and 2 and captions for Supplementary Videos 1–13.
Reversible volume change of conjugated PDA organogel microstructures upon exposure to ACN and methanol (bright-field).
Reversible volume change of conjugated PDA organogel microstructures upon exposure to ACN and methanol (fluorescence).
A shift of 3D-focused light of the organogel patterned with a square dithering mask as the direction of incident light changes slightly. When the direction of incident light changed slightly, the 3D-focused light shifted accordingly with the physical structure remaining stationary.
Temporal evolution of 3D parallax signal above the physical structure of the organogel patterned with a hexagon dithering mask during the solvent exchange to water.
Reversible 3D full parallax signals generation of the conjugated PDA organogel microstructures patterned by various dithering masks upon exposure to ACN and methanol (bright-field).
Reversible 3D full parallax signals generation of the conjugated PDA organogel microstructures patterned by various dithering masks upon exposure to ACN and methanol (fluorescence).
Reversible cryptographic patterns of dithering mask-patterned conjugated PDA organogel microstructures (bright-field).
Reversible cryptographic patterns of dithering mask-patterned conjugated PDA organogel microstructures (fluorescence).
The structural colour change of dithering mask (horizontal and vertical) patterned PDA microstructures array according to the incident light angle.
Dithering mask-patterned PDA organogel microstructure array exhibiting ‘T’ and ‘S’ upon rotation of incident light angle by 90°.
Hidden code decryption of the 4 × 4 and 5 × 5 encoded PDA organogels by rotating the samples by 90°.
Multicolour masterpiece holograms of PDA organogels by changing the focal plane.
Selective structural colour change of PDA organogels patterned with horizontal and vertical line masks by rotating the portable imaging device.
About this article
Cite this article
Oh, J., Baek, D., Lee, T.K. et al. Dynamic multimodal holograms of conjugated organogels via dithering mask lithography. Nat. Mater. (2021). https://doi.org/10.1038/s41563-020-00866-4