Dissolution inhibition for novolac-based

The Influence of Structure on Dissolution Inhibition for Novolac-Based Photoresists Adaption of the Probabilistic Approach... 

The second type of chemically amplified depolymerization resist mechanism depends upon the incorportation of C-O bonds into the polymer backbone which can be cleaved by either hydrolysis or addolysis. This concept was first advanced by Crivello, who proposed that polymers such as polycarbonates and polyesters could undergo photo-induced add catalyzed hydrolysis reaction in polymeric film (9, 76). Although polymers could be designed to undergo catalytic chain cleavage in the presence of add, such an approach depends upon the inclusion of stoichiometic amounts of water in the polymer film. Uttle further work was reported on this concept until recently, when a new system for dissolution inhibition was described based upon the hydrolysis of polysilyl ethers in a novolac resin (24). 

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. 

While "conventional positive photoresists" are sensitive, high-resolution materials, they are essentially opaque to radiation below 300 nm. This has led researchers to examine alternate chemistry for deep-UV applications. Examples of deep-UV sensitive dissolution inhibitors include aliphatic diazoketones (61-64) and nitrobenzyl esters (65). Certain onium salts have also recently been shown to be effective inhibitors for phenolic resins (66). A novel e-beam sensitive dissolution inhibition resist was designed by Bowden, et al a (67) based on the use of a novolac resin with a poly(olefin sulfone) dissolution inhibitor. The aqueous, base-soluble novolac is rendered less soluble via addition of -10 wt % poly(2-methyl pentene-1 sulfone)(PMPS). Irradiation causes main chain scission of PMPS followed by depolymerization to volatile monomers (68). The dissolution inhibitor is thus effectively "vaporized", restoring solubility in aqueous base to the irradiated portions of the resist. Alternate resist systems based on this chemistry have also been reported (69,70). 

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). 

The addition of specialized small molecules to a polymer coating is the functional basis for most photoresists. Conventional positive-working photoresists function owing to the difference in solubility caused by the imagewise exposure of a small molecule naphthalene diazoquinone sulfonate ester (NDS). The presence of this small molecule dramatically inhibits the dissolution of the novolac binder while its photodecomposition accelerates the binder dissolution in aqueous base. 

However, the photochemistry itself does not make a relief image. Rather it is used to modify the solubility of the polymeric binder. The diazoquinone compounds used in resists are referred to as dissolution inhibitors or photoactive components (PAC s). The addition of a diazoquinone molecule dramatically inhibits the dissolution rate of a thin film of a novolac resin. Upon exposure, the dissolution rate of the novolac based resist is considerably faster than the rate for the novolac alone. The accelerated dissolution rate may be caused by formation of acid eind its subsequent ionization during development or by enhauiced diffusion of the developer into the coating because of changes caused by the formation and fate of the nitrogen (2). 

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). 

For a positive resist based on dissolution inhibition chemistry such as the DNQ/novolac resist system, the rate of the reaction tr between the developer with the resist (comprised of resin R, a photoactive compound that acts as a dissolution inhibitor M, but which is converted to product P on exposure to UV light, which in turn enhances the dissolution rate of the resin) is given by... 

Several limitations of this model show that it is not the main mechanism for dissolution inhibition in DNQ/novolac systems. First, the reaction does not occur with all inhibitors. Diazodiones such as Meldrum s Diazo do not undergo base-catalyzed azo-coupling, but they are effective inhibitors (77). Also, Murata et al (72) showed that efficient dissolution inhibition can be observed with inhibitors that do not have diazo functionality. For example, phenyl naphthyl sulfonate is a better dissolution inhibitor than the corresponding phenyl DNQ sulfonate indicating that the dissolution inhibition ability can be attributed to the sulfonate ester of the DNQ, not the DNQ chromophore itself (Figure 2). Despite the shortcomings of the Stonewall Model, it was an important contribution to the understanding of dissolution inhibition, because it was the first microscopic, molecular-interaction model for inhibition. 

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 resist system which supported the i-line technology for many years in an exclusive manner was so-called diazonaphthoquinone (DNQ)/novolac resists (Fig. 5). This type of resists originally invented for printing by Suss [2] is a two-component system consisting of a novolac resin and a photoactive compound (PAC), diazonaphthoquinone. The novolac resin is soluble in aqueous base in virtue of the acidic phenolic OH functionality. However, the lipophilic diazonaphthoquinone dispersed in the phenolic matrix inhibits the dissolution of the resin film in an aqueous base developer. UV irradiation of the photoactive compound results in formation of a highly reactive carbene, accompanied... 

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