Novolac resin composite photoresists

Interest in solution inhibition resist systems is not limited to photoresist technology. Systems that are sensitive to electron-beam irradiation have also been of active interest. While conventional positive photoresists may be used for e-beam applications (31,32), they exhibit poor sensitivity and alternatives are desirable. Bowden, et al, at AT T Bell Laboratories, developed a novel, novolac-poly(2-methyl-l-pentene sulfone) (PMPS) composite resist, NPR (Figure 9) (33,34). PMPS, which acts as a dissolution inhibitor for the novolac resin, undergoes spontaneous depolymerization upon irradiation (35). Subsequent vaporization facilitates aqueous base removal of the exposed regions. Resist systems based on this chemistry have also been reported by other workers (36,37). 

We wish to report first dry developable photoresists with poly(olefin sulfones) with photosensitizers like pyridine N-oxide, and then we present our study on composite resists made of poly(olefin sulfones) with novolac resins or with poly(p-hydroxystyrenes). 

Composite Photoresists Made of Poly (Olefin Sulfones) and Novolac Resins... 

Attempts have been made over time to improve the physical properties of novolacs. The use of phenol formaldehyde resins prepared in alkaline medium in photoresist compositions is mentioned in a Kalle Co. AG patent. The use of polyvinyl ethers in combination with novolacs to impart stickiness and plasticization action to the latter was patented by Christensen. Steinhoff, Isaacson, and Roelants of the Shipley Company mention the use of vinyl ethers in a patent on roller coating. Lower alkyl polyvinyl ethers, such as methyl, ethyl, butyl, and isobutyl, are added to novolac resins to improve coating flexibility and adhesion to metal surfaces as well as to improve resistance to mildly alkaline solutions. The use of styrene, methyl styrene, and styrene-maleic anhydride copolymers in combination with novolac was mentioned in several patents of both Shipley and Kalle Co. AG. When novolac is copolymerized with maleic anhydride, a resin that is readily soluble in alkaline solutions is obtained. ... 

The workhorse of the VLSI industry today is a composite novolac-diazonaphthoquinone photoresist that evolved from similar materials developed for the manufacture of photoplates used in the printing industry in the early 1900 s (23). The novolac matrix resin is a condensation polymer of a substituted phenol and formaldehyde that is rendered insoluble in aqueous base through addition of 10-20 wt% of a diazonaphthoquinone photoactive dissolution inhibitor (PAC). Upon irradiation, the PAC undergoes a Wolff rearrangement followed by hydrolysis to afford a base-soluble indene carboxylic acid. This reaction renders the exposed regions of the composite films soluble in aqueous base, and allows image formation. A schematic representation of the chemistry of this solution inhibition resist is shown in Figure 6. 

Knowledge that silyl substituents may be incorporated into standard resist chemistry to effect etching resistance has prompted several workers to evaluate silylated novolacs as matrix resins for conventional positive-photoresist formulations. Typically, these resists operate via a dissolution inhibition mechanism whereby the matrix material is rendered insoluble in aqueous base through addition of a diazonaphthoquinone. Irradiation of the composite induces a Wolff rearrangement to yield an indenecarboxylic acid (Figure 4), which allows dissolution of the exposed areas in an aqueous-base developer (35). 

---