Negative tone

Acid-C t lyzed Chemistry. Acid-catalyzed reactions form the basis for essentially all chemically amplified resist systems for microlithography appHcations (61). These reactions can be generally classified as either cross-linking (photopolymerization) or deprotection reactions. The latter are used to unmask acidic functionality such as phenohc or pendent carboxyhc acid groups, and thus lend themselves to positive tone resist apphcations. Acid-catalyzed polymer cross-linking and photopolymerization reactions, on the other hand, find appHcation in negative tone resist systems. Representative examples of each type of chemistry are Hsted below. 

Fig. 24. Representative cross-linking systems employed in negative tone CA resists, (a) Epoxy polymers requiring organic solvent development, (b) PHOST-based cross-linking systems requiring aqueous development, (c) Monomeric cross-linking agents used in PHOST matrix polymers.

Fig. 36. Representative bilayer resist systems. Both CA and non-CA approaches are illustrated (116—119). (a) Cross-linking E-beam resist, 193-nm thin-film imaging resist (b) acid-cataly2ed negative-tone cross-linking system (c) positive-tone CA resist designed for 193-nm appHcations and (d) positive-tone...

The use of phenolic polymers in photocrosslinkable systems usually involves multicomponent systems which incorporate polyfunctional low molecular weight crosslinkers. For example, Feely et al. [9] have used hydroxymethyl melamine in combination with a photoactive diazonaphthoquinone which produces an indene carboxylic acid upon irradiation to crosslink a novolac resin. Similarly, Iwayanagi et al. [10] have used photoactive bisazides in combination with poly(p-hydroxy-sty-rene) to afford a negative-tone resist material which does not swell upon development in aqueous base. 

From these observations, a photooxidative scheme has been developed in which a hydrophobic resist becomes hydrophilic upon oxidation induced by deep UV (248 and 193 nm) radiation. Subsequent treatment with TiCLi followed by oxygen reactive ion etching then affords high-resolution, negative-tone patterns. Studies are currently underway to minimize the line edge roughness and background residue present in such patterns. 

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... 

In 1979, Smith and co-workers described the development of a system they called PDF (which presumably stands for Plasma Developable Photoresist) that is based on the use of a material, the structure of which has not yet been divulged 61). In this process the resist is coated in the usual fashion and exposed optically. The exposed film is then subjected to a baking cycle that produces a relief image of negative-tone that is, depressions are generated in unexposed areas (Figure 45). This relief structure is... 

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