New Polyoxometalates Containing Hybrid Polymers and Their Potential for Nano-Patterning

Two new polyoxometalate (POM)‐based hybrid monomers (Bu4N)5(H)[P2V3W15O59{(OCH2)3CNHCO(CH3)CCH2}] (2) and (S(CH3)2C6H4OCOC(CH3)=CH2)6[PV  2Mo10O40] (5) were developed by grafting polymerizable organic units covalently or electrostatically onto Wells–Dawson and Keggin‐type clusters and were characte...

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Bibliographic Details
Published in:Chemistry : a European journal 2015-01, Vol.21 (5), p.2250-2258
Main Authors: Kalyani, Vishwanath, Satyanarayana, V. S. V., Singh, Vikram, Pradeep, Chullikkattil P., Ghosh, Subrata, Sharma, Satinder K., Gonsalves, Kenneth E.
Format: Article
Language:English
Subjects:
Acetal resins
Chemistry
cluster compounds
Clusters
Electron beams
NMR spectroscopy
Offset printing
organic-inorganic hybrid composites
Photoresists
Polymerization
Polymers
polyoxometalates
Polyoxometallates
Ultraviolet
X-rays
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Summary:Two new polyoxometalate (POM)‐based hybrid monomers (Bu4N)5(H)[P2V3W15O59{(OCH2)3CNHCO(CH3)CCH2}] (2) and (S(CH3)2C6H4OCOC(CH3)=CH2)6[PV  2Mo10O40] (5) were developed by grafting polymerizable organic units covalently or electrostatically onto Wells–Dawson and Keggin‐type clusters and were characterized by analytical and spectroscopic techniques including ESI‐MS and/or single‐crystal X‐ray diffraction analyses. Radical initiated polymerization of 2 and 5 with organic monomers (methacryloyloxy)phenyldimethylsulfonium triflate (MAPDST) and/or methylmethacrylate (MMA) yielded a new series of POM/polymer hybrids that were characterized by 1H, 31P NMR and IR spectroscopic techniques, gel‐permeation chromatography as well as thermal analyses. Preliminary tests were conducted on these POM/polymer hybrids to evaluate their properties as photoresists using electron beam (E‐beam)/extreme ultraviolet (EUV) lithographic techniques. It was observed that the POM/polymer hybrid of 2 with MAPDST exhibited improved sensitivity under EUV lithographic conditions in comparison to the MAPDST homopolymer resist possibly due to the efficient photon harvesting by the POM clusters from the EUV source. All POM‐ed up: Polyoxometalate (POM) pendent polymers have been synthesized and tested for their photoresist applications under electron beam (E‐beam) and extreme ultraviolet (EUV) lithographic techniques, which revealed the sensitizing role of the [P2V3W15O62]9− cluster derivative in EUV photoresists (see figure).
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201405369