Two–Photon Printing of Shape–Memory Microstructures and Metasurfaces via Radical–Mediated Thiol–Vinyl Hydrothiolation
Abstract
Abstract Shape‐memory resists capable of high‐resolution curing into arbitrarily designed structures are increasingly demanded for soft robotics, optical sensors, microscale manufacturing, and biomedicine. Amorphous, shape‐memory thiol‐vinyl networks are printed using two‐photon polymerization (2PP) curing of a simple resin formulated with commercially available reagents. The ability to print high‐resolution feature sizes down to 200 nm is attributed to the use of radical‐mediated, thiol‐vinyl step‐growth polymerization that quickly cross‐links the resin, limiting diffusive transport. The thermomechanical behavior of the 2PP‐cured material analyzed in compression, tension, and three‐point bending is similar to the behavior of the UV‐polymerized samples. To demonstrate the ability to design, field, and test 4D responsive microstructures, an array of nine springs with coil diameters of 330 µm is printed. Following compressive shape‐fixing, printed arrays can release 11 µJ of stored elastic strain energy when reheated. Further, a new concept of dichroic‐memory of a metamaterial device is demonstrated by printing a twisted woodpile structure with circular dichroism as characterized by Mueller Matrix ellipsometry. The results of this study demonstrate how combining high‐resolution 2PP curing with stimuli‐responsive molecular architectures can further the engineering of responsive microstructures and metamaterials.
- Publication Date:
- Research Org.:
- Univ. of Rochester, NY (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)
- OSTI Identifier:
- 1875682
- Alternate Identifier(s):
- OSTI ID: 1860424
- Report Number(s):
- 2022-85; 1727; 2688
Journal ID: ISSN 2365-709X; ECCS‐1530540; TRN: US2307241
- Grant/Contract Number:
- NA0003856; CBET-1827904
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Materials Technologies
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 9; Journal ID: ISSN 2365-709X
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; two-photon polymerization; shape-memory; metamaterials; stimuli-responsive polymers; glassy networks; actuators
Citation Formats
Jeske, Madelyn P., Zhang, Wenshi, and Anthamatten, Mitchell. Two–Photon Printing of Shape–Memory Microstructures and Metasurfaces via Radical–Mediated Thiol–Vinyl Hydrothiolation. United States: N. p., 2022.
Web. doi:10.1002/admt.202101725.
Jeske, Madelyn P., Zhang, Wenshi, & Anthamatten, Mitchell. Two–Photon Printing of Shape–Memory Microstructures and Metasurfaces via Radical–Mediated Thiol–Vinyl Hydrothiolation. United States. https://doi.org/10.1002/admt.202101725
Jeske, Madelyn P., Zhang, Wenshi, and Anthamatten, Mitchell. Wed .
"Two–Photon Printing of Shape–Memory Microstructures and Metasurfaces via Radical–Mediated Thiol–Vinyl Hydrothiolation". United States. https://doi.org/10.1002/admt.202101725. https://www.osti.gov/servlets/purl/1875682.
@article{osti_1875682,
title = {Two–Photon Printing of Shape–Memory Microstructures and Metasurfaces via Radical–Mediated Thiol–Vinyl Hydrothiolation},
author = {Jeske, Madelyn P. and Zhang, Wenshi and Anthamatten, Mitchell},
abstractNote = {Abstract Shape‐memory resists capable of high‐resolution curing into arbitrarily designed structures are increasingly demanded for soft robotics, optical sensors, microscale manufacturing, and biomedicine. Amorphous, shape‐memory thiol‐vinyl networks are printed using two‐photon polymerization (2PP) curing of a simple resin formulated with commercially available reagents. The ability to print high‐resolution feature sizes down to 200 nm is attributed to the use of radical‐mediated, thiol‐vinyl step‐growth polymerization that quickly cross‐links the resin, limiting diffusive transport. The thermomechanical behavior of the 2PP‐cured material analyzed in compression, tension, and three‐point bending is similar to the behavior of the UV‐polymerized samples. To demonstrate the ability to design, field, and test 4D responsive microstructures, an array of nine springs with coil diameters of 330 µm is printed. Following compressive shape‐fixing, printed arrays can release 11 µJ of stored elastic strain energy when reheated. Further, a new concept of dichroic‐memory of a metamaterial device is demonstrated by printing a twisted woodpile structure with circular dichroism as characterized by Mueller Matrix ellipsometry. The results of this study demonstrate how combining high‐resolution 2PP curing with stimuli‐responsive molecular architectures can further the engineering of responsive microstructures and metamaterials.},
doi = {10.1002/admt.202101725},
journal = {Advanced Materials Technologies},
number = 9,
volume = 7,
place = {United States},
year = {Wed Mar 30 00:00:00 EDT 2022},
month = {Wed Mar 30 00:00:00 EDT 2022}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Optical gecko toe: Optically controlled attractive near-field forces between plasmonic metamaterials and dielectric or metal surfaces
journal, May 2012
- Zhang, J.; MacDonald, K. F.; Zheludev, N. I.
- Physical Review B, Vol. 85, Issue 20
Stimuli Responsive Shape Memory Microarchitectures
journal, December 2020
- Elliott, Luizetta V.; Salzman, Erika E.; Greer, Julia R.
- Advanced Functional Materials, Vol. 31, Issue 9
Natural optical activity vs circular Bragg reflection studied by Mueller matrix ellipsometry
journal, October 2016
- Arteaga, Oriol
- Thin Solid Films, Vol. 617
3D metamaterials
journal, January 2019
- Kadic, Muamer; Milton, Graeme W.; van Hecke, Martin
- Nature Reviews Physics, Vol. 1, Issue 3
Shaping reverberating sound fields with an actively tunable metasurface
journal, June 2018
- Ma, Guancong; Fan, Xiying; Sheng, Ping
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 26
Natural optical activity as the origin of the large chiroptical properties in π-conjugated polymer thin films
journal, December 2020
- Wade, Jessica; Hilfiker, James N.; Brandt, Jochen R.
- Nature Communications, Vol. 11, Issue 1
Symmetry-Breaking Actuation Mechanism for Soft Robotics and Active Metamaterials
journal, October 2019
- Wu, Shuai; Ze, Qiji; Zhang, Rundong
- ACS Applied Materials & Interfaces, Vol. 11, Issue 44
Thiol-Ene Click Chemistry
journal, February 2010
- Hoyle, Charles E.; Bowman, Christopher N.
- Angewandte Chemie International Edition, Vol. 49, Issue 9, p. 1540-1573
Polymer architecture as key to unprecedented high-resolution 3D-printing performance: The case of biodegradable hexa-functional telechelic urethane-based poly-ε-caprolactone
journal, April 2021
- Arslan, Aysu; Steiger, Wolfgang; Roose, Patrice
- Materials Today, Vol. 44
Soft optical metamaterials
journal, May 2020
- Chen, Yixin; Ai, Bin; Wong, Zi Jing
- Nano Convergence, Vol. 7, Issue 1
A brief review of dynamic mechanical metamaterials for mechanical energy manipulation
journal, April 2021
- Wu, Lingling; Wang, Yong; Chuang, Kuochih
- Materials Today, Vol. 44
Thiol-ene “click” reactions and recent applications in polymer and materials synthesis
journal, January 2010
- Lowe, Andrew B.
- Polym. Chem., Vol. 1, Issue 1
A bar and hinge model formulation for structural analysis of curved-crease origami
journal, November 2020
- Woodruff, Steven R.; Filipov, Evgueni T.
- International Journal of Solids and Structures, Vol. 204-205
Photopolymerized thiol-ene systems as shape memory polymers
journal, September 2010
- Nair, Devatha P.; Cramer, Neil B.; Scott, Timothy F.
- Polymer, Vol. 51, Issue 19
A review of additive manufacturing of metamaterials and developing trends
journal, November 2021
- Fan, Junxiang; Zhang, Lei; Wei, Shuaishuai
- Materials Today, Vol. 50
Large‐Scale Synthesis of a New Polymeric Carbon Nitride—C 3 N 3 with Good Photoelectrochemical Performance
journal, April 2020
- Feng, Jiaxin; Li, Ming
- Advanced Functional Materials, Vol. 30, Issue 23
Magnetic Macroporous Hydrogels as a Novel Approach for Perfused Stem Cell Culture in 3D Scaffolds via Contactless Motion Control
journal, January 2018
- Rödling, Lisa; Volz, Esther Magano; Raic, Annamarija
- Advanced Healthcare Materials, Vol. 7, Issue 9
Design Formulae for Elliptical Cross-Section Helical Springs
journal, December 1992
- Nagaya, Kosuke; Hirata, Yasuo; Tsurumi, Toyoaki
- Journal of Mechanical Design, Vol. 114, Issue 4
Controlling propagation and coupling of waveguide modes using phase-gradient metasurfaces
journal, April 2017
- Li, Zhaoyi; Kim, Myoung-Hwan; Wang, Cheng
- Nature Nanotechnology, Vol. 12, Issue 7
Three-dimensional micropatterning of bioactive hydrogels via two-photon laser scanning photolithography for guided 3D cell migration
journal, July 2008
- Lee, Soo-Hong; Moon, James J.; West, Jennifer L.
- Biomaterials, Vol. 29, Issue 20
Giant Circular Dichroism at Visible Frequencies Enabled by Plasmonic Ramp-Shaped Nanostructures
journal, February 2019
- Rajaei, Mohsen; Zeng, Jinwei; Albooyeh, Mohammad
- ACS Photonics, Vol. 6, Issue 4
Functional Materials for Two‐Photon Polymerization in Microfabrication
journal, August 2019
- Carlotti, Marco; Mattoli, Virgilio
- Small, Vol. 15, Issue 40
Femtosecond laser-induced two-photon polymerization of inorganic–organic hybrid materials for applications in photonics
journal, January 2003
- Serbin, J.; Egbert, A.; Ostendorf, A.
- Optics Letters, Vol. 28, Issue 5
Triple Shape Memory Materials Incorporating Two Distinct Polymer Networks Formed by Selective Thiol–Michael Addition Reactions
journal, July 2014
- Chatani, Shunsuke; Wang, Chen; Podgórski, Maciej
- Macromolecules, Vol. 47, Issue 15
Precise 3D printing of micro/nanostructures using highly conductive carbon nanotube-thiol-acrylate composites
conference, April 2016
- Liu, Y.; Xiong, W.; Jiang, L. J.
- SPIE LASE, SPIE Proceedings
4D Printing at the Microscale
journal, December 2019
- Spiegel, Christoph A.; Hippler, Marc; Münchinger, Alexander
- Advanced Functional Materials, Vol. 30, Issue 26
Voxelated Molecular Patterning in Three-Dimensional Freeforms
journal, July 2019
- Tabrizi, Mohsen; Ware, Taylor H.; Shankar, M. Ravi
- ACS Applied Materials & Interfaces, Vol. 11, Issue 31
Three-Dimensional Microstructured Azobenzene-Containing Gelatin as a Photoactuable Cell Confining System
journal, December 2017
- Pennacchio, Fabrizio A.; Fedele, Chiara; De Martino, Selene
- ACS Applied Materials & Interfaces, Vol. 10, Issue 1
Magnetically driven active topography for long-term biofilm control
journal, May 2020
- Gu, Huan; Lee, Sang Won; Carnicelli, Joseph
- Nature Communications, Vol. 11, Issue 1
Light-driven micron-scale 3D hydrogel actuator produced by two-photon polymerization microfabrication
journal, February 2020
- Zheng, Chenglin; Jin, Feng; Zhao, Yuanyuan
- Sensors and Actuators B: Chemical, Vol. 304
Layered liquid crystal elastomer actuators
journal, June 2018
- Guin, Tyler; Settle, Michael J.; Kowalski, Benjamin A.
- Nature Communications, Vol. 9, Issue 1