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

Abstract

Two new polyoxometalate (POM)-based hybrid monomers (Bu4 N)5 (H)[P2 V3 W15 O59 {(OCH2 )3 CNHCO(CH3 )CCH2 }] (2) and (S(CH3 )2 C6 H4 OCOC(CH3 )=CH2 )6 [PV 2Mo10 O40 ] (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 (1) H, (31) P 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.

EUV photofragmentation study of hybrid nonchemically amplified resists containing antimony as an absorption enhancer

“…[2][3][4] The concepts to be considered, among others, include essentially non-chemically amplied resists (n-CARs) and hybrids. [4][5][6][7][8][9][10][11][12][13][14][15] The design paradigm has to incorporate the basic principles of conventional resists superimposed with the specic requirements of EUVL for attaining the lower nodes. 12,15,16 The interaction of the resist thin lms with high energy EUV photons (13.5 nm) is a very complex process triggered by EUV radiation that breaks the chemical bonds and simultaneously produces ablation and a high yield of secondary electrons.…”

A Reversible Redox Reaction in a Keggin Polyoxometalate Crystal Driven by Visible Light: A Programmable Solid‐State Photochromic Switch

“…Recently, Pradeep and co-workers have generalized sulfonium based photochromic approach as well as exploredt heir catalytical properties. [11] Notably,t he ion pair (intermolecular) interactions have been the basis for photochromism in both the cationic systems,d escribed above. However,t he photoactivityo fs uch ionic systems (OAC-POM as well as OSC-POM)h as been inducedm ostly on irradiationbyU Vlight.…”

Cobalt based functional inorganic materials: Electrocatalytic water oxidation

“…Different polyoxometalate based compound are well-established as efficient catalysts towards organic reactions, photocatalytic and electrocatalytic water oxidation, proton reduction and oxygen reduction reactions. [60][61][62][63][64] Such wide field of application, notable stability and many other properties have contributed to our fascination with choosing a Keggin polyoxometalate based guest species in this case. [CoW 12 O 40 ] 6− has a Co II at the center which is tetrahedrally surrounded by four {W 3 O 10 } interconnected subunits (Scheme 5).…”