Electron-beam resist methacrylate

C The Epoxy Resists. The first negative tone electron beam resist materials with useful sensitivity were based on utilizing the radiation chemistry of the oxirane or epoxy moiety. The most widely used of these materials, COP (Figure 32) is a copolymer of glycidyl methacrylate and ethyl acrylate and was developed at Bell Laboratories (43,44). COP has found wide applicability in the manufacturing of photomasks. The active element... 

Polymers of -Substituted Benzyl Methacrylates and Aliphatic Aldehydes as New Types of Electron-Beam Resists... 

In this article we will describe two different types of positive electron-beam resists, which were briefly reported in our previous communications (2,3). One is the homopolymer or copolymer with methyl methacrylate and a-substituted benzyl methacrylate, which forms methacrylic acid units in the polymer chain on exposure to an electron-beam and can be developed by using an alkaline solution developer. In this case, the structural change in the side group of the polymer effectively alters the solubility properties of the exposed polymer, and excellent contrast between the exposed and unexposed areas is obtained. The other is a self developing polyaldehyde resist, which is depolymerized into a volatile monomer upon electron-beam exposure. The sensitivity was extremely high without using any sensitizer. 

Positive Electron-beam Resist of Poly (a-substituted Benzyl Methacrylate). The electron-beam resist behaviors of poly(a-substituted benzyl methacrylate)s are given in Table III. When the exposed resist films were developed with a mixture of MIBK and IPA, the sensitivities of these polymers were on the order of 10-4 C/cm2. When a dilute solution of sodium methoxide in methanol was used as a developer, the sensitivity was enhanced as compared with the former case, and increased with an increase in the bulkiness of the ester group of the polymer except for poly(a,a-diphenylethyl methacrylate). 

The radiation degradation of poly(2-octyne) occurs only in the presence of oxygen. Its degradation products contain carbonyl and hydroxyl groups, and so dissolve in polar solvents (e.g., acetone). Such solubility change is essential to resist materials. The Gs value (number of main-chain scission per 100 eV of absorbed dose) of poly(2-octyne) is ca. 12. It is noteworthy that this value is higher than that of poly-(methyl methacrylate) (Gs ca. 2)118) which is being used as electron-beam resists. 

Poly(glycidyl methacrylate) (PGMA), a well-known negative electron beam resist first reported by Hirai et al. (55), actually functions as a positive-tone resist upon DUV exposure (Table 3.1) (56). The epoxide functionality responsible for cross-linking under electron beam exposure does not absorb in the DUV region, and the response of PGMA to DUV radiation is determined by the absorption due to the n — tt transition of the carbonyl chromo-... 

Lin et al. (J77) replaced PMMA with IBM terpolymer resist (a terpol-ymer of MM A, methacrylic acid, and methacrylic anhydride developed as an electron beam resist), which has a higher thermal stability and a higher DUV sensitivity. 

Typical resists include cyclized polyisoprene with a photosensitive crosslinking agent (ex bisazide) used in many negative photoresists, novolac resins with diazoquinone sensitizers and imidazole catalysts for positive photoresists, poly(oxystyrenes) with photosensitizers for UV resists, polysilanes for UV and X-ray resists, and polymethacrylates and methacrylate-styrenes for electron-beam resists (Clegg and Collyer, 1991). Also note the more recent use of novolac/diazonaphthoquinone photoresists for mid-UV resists for DRAM memory chips and chemically amplified photoacid-catalysed hydroxystyrene and acrylic resists for deep-UV lithography (Choudhury, 1997). 

Poly(methyl methacrylate), PMMA, has remained the standard by which to judge positive-working electron-beam resists for over a dozen years (1>.2 .3 4) Hundreds of rival polymers have been disclosed. Most of them exceed PMMA in sensitivity. However, the combination of properties which include stability, sensitivity, contrast, adhesion, and solubility have kept PMMA in the limelight. 

As indicated above, the introduction of electron-withdrawing groups is one of the strategies for improving the sensitivity of PMMA-type resists. This is best exemplified by fluorination in the ester moiety of PMMA, which has produced many useful electron-beam resists, such as poly(perfluorobutyl methacrylate) (XXII),... 

Gipstein, W. Moreau, and O. Need, Poly(methyl methacrylate isobutylene) copolymers as highly sensitive electron beam resists, J. Electrochem. Soc. 123, 1105 (1976). 

Ito, Chemical amplification resists for microlithography, Adv. Polym. Sci. 173, 112 113 (2005) K. Hatada, T. Kitayama, S. Danjo, Y. Tsuhokura, H. Yuki, K. Morikawa, H. Aritome, and S. Namha, Pol3miers of alpha substituted henzyl methacrylates as a new t)fpe of electron beam resist, Polym. Bull. 10, 45 (1983). 

Figure 41. A plot of sensitivity to Mo (5.4k) x-ray radiation and 20 kV electron beam radiation for several resists. EPB is epoxidized polybutadiene, P(GMA-EA) is a copolymer of glycidyl methacrylate and ethyl acrylate (COP), PGMA is poly (glycidyl methacrylate), PBS is poly (butene-1 -sulfone), FBM-1 is poly (2,2,3,3-tetrafluoropropyl methacrylate), P(MMA-MA) is a copolymer of methyl methacrylate and methacrylic acid, PMMA is poly (methyl methacrylate). (Reproduced with permission from Ref. 56J...

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