Journal
ACS APPLIED POLYMER MATERIALS
Volume 3, Issue 3, Pages 1426-1435Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsapm.0c01291
Keywords
thioxanthone-based photoinitiators; two-photon polymerization nanoprinting; direct laser writing; high-speed nanolithography; low-temperature phosphorescence spectroscopy
Funding
- National Science Foundation (NSF) through the Scalable Nano-manufacturing Program [1634832]
- NSF [1609151]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1609151] Funding Source: National Science Foundation
- Directorate For Engineering
- Div Of Civil, Mechanical, & Manufact Inn [1634832] Funding Source: National Science Foundation
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ITX is a common photoinitiator in DLW polymerization processes due to its high-efficiency photoinitiating abilities. However, improved photoinitiating materials are required for advanced high-throughput nanomanufacturing techniques. Thioxanthone-based photoinitiators with tailored optical and charge transfer properties were designed and synthesized to demonstrate enhanced two-photon polymerization DLW for superresolution properties.
Nanolithographic printing by direct laser writing (DLW) photopolymerization has attracted increased attention in recent years, as the speed of this printing has increased, while the feature sizes that have been realized have decreased well into the nanoscale regime. Specifically, isopropyl thioxanthone (ITX) has been utilized as one of the common photoinitiators in DLW polymerization processes because of its high-efficiency photoinitiating abilities and its ability to have its initiation properties inhibited through the application of a second wavelength of light. However, improved photoinitiating materials that are built from this successful archetype are required, by both academic and industrial circles, if advanced high-throughput nanomanufacturing techniques are to be implemented. Here, next-generation thioxanthone-based photoinitiators with tailored optical and charge transfer properties were computationally designed and subsequently synthesized. Particularly, branches with specifically modulated electron donor and electron acceptor qualities, relative to the ITX core, were coupled to the initial thioxanthone substrate. After having their molecular and optical properties characterized in full, it was evident that these initiators possessed a clear advancement in terms of photopolymerization initiation relative to ITX. As such, a champion photoinitiator chemistry was brought forward to demonstrate enhanced two-photon polymerization DLW such that superresolution properties were exhibited. In this way, we introduce a clear means by which to systematically design future photoinitiators for enhanced two-photon polymerization DLW nanoprinting processes.
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