Diazonaphthoquinone chemistry

Positive-Tone Photoresists based on Dissolution Inhibition by Diazonaphthoquinones. The intrinsic limitations of bis-azide—cycHzed mbber resist systems led the semiconductor industry to shift to a class of imaging materials based on diazonaphthoquinone (DNQ) photosensitizers. Both the chemistry and the imaging mechanism of these resists (Fig. 10) differ in fundamental ways from those described thus far (23). The DNQ acts as a dissolution inhibitor for the matrix resin, a low molecular weight condensation product of formaldehyde and cresol isomers known as novolac (24). The phenoHc stmcture renders the novolac polymer weakly acidic, and readily soluble in aqueous alkaline solutions. In admixture with an appropriate DNQ the polymer s dissolution rate is sharply decreased. Photolysis causes the DNQ to undergo a multistep reaction sequence, ultimately forming a base-soluble carboxyHc acid which does not inhibit film dissolution. Immersion of a pattemwise-exposed film of the resist in an aqueous solution of hydroxide ion leads to rapid dissolution of the exposed areas and only very slow dissolution of unexposed regions. In contrast with crosslinking resists, the film solubiHty is controUed by chemical and polarity differences rather than molecular size. 

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. 

The familiar positive photoresists. Hunt s HPR, Shipley s Microposit, Azoplate s AZ etc., are all two-component, resist systems, consisting of a phenolic resin matrix material and a diazonaphthoquinone sensitizer. The matrix material is essentially inert to photochemistry and was chosen for its film-forming, adhesion, chemical and thermal resistance characteristics. The chemistry of the resist action only occurs in the sensitizer molecule, the diazonaphthoquinone. A detailed description of these materials, their chemical structures and radiation chemistry will be discussed in Section 3.5.b. 

Fig. 10. Chemistry of diazonaphthoquinone—cresol novolac positive-acting resist. During pattemwise exposure, the DNQ undergoes photolysis that...

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). 

Figure 2.9. The N-alkyldiazopiperidinedione structure is typical of the 1,3-diacyl-2-diazo compounds studied at IBM. Photolysis produces a carboxylic acid analogous to the chemistry of diazonaphthoquinones. These materials absorb strongly in the DUV region, but bleach completely as indicated in the spectra of a methanolic solution bottom). Resists formulated from these materials in novolac show residual unbleachable absorbance due to the resin as shown in the spectra of thin films (top).

Chemical nature of photoresists, the chemistries involved in the photolithography, the properties of photoresists are briefly described. The discussion includes diazonaphthoquinone/novolac positive photoresists, polymer-aromatic diazide negative photoresists, photopolymerizable compositions, chalcogenide glass using systems, chemically amplified photoresists, and photoresists with an image formation in a thin layer. 

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