Rapid thiol-yne-mediated fabrication and dual postfunctionalization of micro-resolved 3D mesostructures

Quick, A. S., De Los Santos Pereira, A., Bruns, M., Bückmann, T., Rodriguez-Emmenegger, C., Wegener, M., & Barner-Kowollik, C. (2015) Rapid thiol-yne-mediated fabrication and dual postfunctionalization of micro-resolved 3D mesostructures. Advanced Functional Materials, 25(24).

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Abstract

3D mesostructures with a height of up to 1 mm and micrometer feature size are fabricated employing a writing speed of 1 cm s-1 via direct laser writing utilizing a novel functional photoresist based on the radical coupling reaction of thiols and alkynes. The refractive index of the resist - consisting of a tetrafunctional thiol, a tetrafunctional alkyne and a photoinitiator - is tailored to be compatible with the employed high numerical aperture (NA) objective lens, thus enabling a Dip-in configuration. Mesostructures are characterized by scanning electron microscopy, optical photography, and nondestructive 3D time-of-flight secondary ion mass spectrometry. Woodpile photonic crystals are fabricated as benchmark structures in order to investigate the axial resolution. Verification of the chemical fabrication mechanism is achieved via transmission Fourier transform infrared (FTIR) spectroscopy of fabricated cuboid structures by monitoring the decrease of corresponding thiol and alkyne absorption peaks. Postmodification reactions, namely the thiol-Michael addition and the copper-catalyzed azide alkyne cycloaddition, are conducted employing residual thiols and alkynes throughout the cuboid structures. Successful dual and orthogonal modification throughout the structure and on the surface is achieved and verified utilizing transmission FTIR spectroscopy and time-of-flight secondary ion mass spectrometry. Reactive 3D mesostructures with micrometer feature size are fabricated via dip-in direct laser writing employing the radical thiol-yne coupling reaction. Axial resolution and the polymerization process of the photoresist are investigated. Residual thiols and alkynes are exploited for postmodification reactions, namely thiol-Michael addition and copper-catalyzed azide alkyne cycloaddition, demonstrating successful dual functionalization throughout the structure and on the surface. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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ID Code: 99443
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :3
Export Date: 5 September 2016
CODEN: AFMDC
Correspondence Address: Rodriguez-Emmenegger, C.; Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic V.v.i., Heyrovsky sq. 2, Czech Republic
Funding Details: DAAD, German Academic Exchange Service
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Keywords: click chemistry, direct laser writing, dual functionalization, microstructures, photochemistry, Addition reactions, Catalysis, Chemical bonds, Chemical reactions, Copper, Cycloaddition, Fabrication, Fourier transform infrared spectroscopy, Hydrocarbons, Mass spectrometry, Micrometers, Microstructure, Photochemical reactions, Photoresists, Refractive index, Scanning electron microscopy, Secondary emission, Spectrometry, Azide-alkyne cycloaddition, Functionalizations, High numerical apertures, Polymerization process, Radical coupling reactions, Time of flight secondary ion mass spectrometry, Secondary ion mass spectrometry
DOI: 10.1002/adfm.201500683
ISSN: 1616301X
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 26 Sep 2016 04:35

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