Polystyrene-based negative resists

It was indicated earlier that swelling limits resolution in solvent-developed negative resists. It was also intimated that swelling effects could be minimized if there were a sufficient polarity change between the exposed and non-exposed areas of the type mentioned in the previous discussion of the PBOCST system. A similar principle was utilized by Hofer et al., (145-146) at IBM, based on ion pair formation. The resist consists of a polystyrene polymer to which tetrathiofulvalene (TTF) units have been attached. When spun down with an acceptor such as CBr4, a complex is formed which, on irradiation, undergoes an electron transfer reaction to form an ion pair ... 

Table 3.5. Polystyrene-Based Cross-Linking Negative DUV Resists...

Another example is thermally depolymerizable polycarbonates that are sensitized with onium salt cationic photoinitiators (139). As discussed previously (Section 3.2.3), one of the positive-negative resists based on polystyrene with pendant tertiary butyl carbonate protecting groups undergoes acid-catalyzed thermolysis to generate poly( p-vinylphenol), carbon dioxide, and isobutene. Therefore, if the tertiary butyl carbonate moiety is incorporated in the polymer backbone as a repeating unit, such polymers will... 

Many negative electron resists recently developed for dry-etching processes are based on the polystyrene (PSt) structure because of the relatively high stability against dry-etching reactions and high Tg of PSt. Another advantage of PSt is the availability of nearly mono-dispersed polymer. 

When some or all of the phenyl rings are substituted with halogen (Scheme 6.11), the radiation sensitivity and the cross-linking efficiency of polystyrene can be enhanced significantly. Negative electron-beam resist formulated from iodi-nated and chlorinated polystyrene and based on this approach have been reported. Sensitivity of about 2 p.C/cm and resolution of about 1-p.m features have been demonstrated with these materials. ... 

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