Synthesis of statistical and block copolymers containing adamantyl and norbornyl moieties by reversible addition‐fragmentation chain transfer polymerization

Abstract

The synthesis of statistical and block copolymers, consisting of monomers often used as resist materials in photolithography, using reversible addition‐fragmentation chain transfer (RAFT) polymerization is reported. Methacrylate and acrylate monomers with norbornyl and adamantyl moieties were polymerized using both dithioester and trithiocarbonate RAFT agents. Block copolymers containing such monomers were made with poly(methyl acrylate) and polystyrene macro‐RAFT agents. In addition to have the ability to control molecular weight, polydispersity, and allow block copolymer formation, the polymers made via RAFT polymerization required end‐group removal to avoid complications during the photolithography. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 943–951, 2010

Precise synthesis of poly(1-adamantyl methacrylate) by atom transfer radical polymerization

“…Various poly(meth)acrylates bearing bulky ester groups, such as bornyl, 1 isobornyl, 1-3 adamantyl [4][5][6][7] and its derivatives, [4][5][6][8][9][10][11] have been synthesized to improve the thermal properties, such as the glass transition temperature and the thermal degradation temperature, of poly(methyl methacrylate) (PMMA). For example, the incorporation of adamantyl groups into polymer structures generally produces not only a high thermal stability but also an improvement in other physical and chemical properties, such as transparency to ultraviolet light, low dielectric constant, hydrophobicity, high oxidation resistance, low surface energy and high density.…”

Living Radical Polymerization by the RAFT Process – A Third Update

“…Azide functionality is often incorporated post RAFT polymerization. 'Active ester' monomers that have been subject to RAFT polymerization (401)(402)(403)(404)(405) are shown in Fig. 12.…”

“…C 12 H 25 S S S I* [388] 306 [389] DMAm [326,[390][391][392] (DMAm) [326] St [370] St [393] PFS [200] 4VP [200,394] 390 [395] Ip [396] 394 [396] AA [397] NIPAm [367,392,398] NVC [387] (NVP) [399] PAA/NIPAm [189] AA/ PEGA [234,400] (tBMA/DMAEMA/290) [175] HEA/PEGA [401] PA/PEGA [401] AA-b-St [393] St/406 [402] HEMA/Ip [396] HEA/Ip [396] Ip/ 394 [396] AA/PEGA-b-343 [234] AA/PEGA-bSt [400] DMAm/296 [390] DMAm/PFS [169] 306-b-St [389] HADA/MADA/NLAA [403] HADM/ MADM/NLAM [403] AA/PEGA-b-344 [362] AAb-St [397] DMAm-b-NIPAm [390] DMAm/296-b-NIPAm [390] DMAm-b-NIPAm/296 [390] DMAm/296-b-NIPAm/296 [390] NIPAm-bDMAEAm [367] PFS-b-PFPVS …”

Synthesis of Narrow Molecular Weight Distribution Norbornene-Lactone Functionalized Polymers by Nitroxide-Mediated Polymerization: Candidates for 193-nm Photoresist Materials

“…For example, polymers are often used as photoresists to imprint desired patterns onto a substrate. Two CRP techniques, such as atom transfer radical polymerization (ATRP) [36][37][38][39] and reversible addition fragmentation chain transfer (RAFT) [40][41][42], have been used in the past to synthesize well-defined statistical copolymers with narrow molecular weight distribution for photoresists. Parameters that characterize pattern resolution, such as the line edge roughness (LER) and line width roughness (LWR), are influenced by physical/chemical properties, such as molecular weight, dispersity, composition and microstructure [41,[43][44][45][46].…”

“…Two CRP techniques, such as atom transfer radical polymerization (ATRP) [36][37][38][39] and reversible addition fragmentation chain transfer (RAFT) [40][41][42], have been used in the past to synthesize well-defined statistical copolymers with narrow molecular weight distribution for photoresists. Parameters that characterize pattern resolution, such as the line edge roughness (LER) and line width roughness (LWR), are influenced by physical/chemical properties, such as molecular weight, dispersity, composition and microstructure [41,[43][44][45][46]. However, one drawback that makes ATRP and RAFT undesirable for photoresist materials is the requirement of metal catalysts and the chain transfer agents, respectively [42,45], which cause undesirable coloration, pungent odor and have to be removed through additional purification steps in order to meet the high purity standards used in the microelectronic industry.…”