Resist system

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. 

To achieve the best overall resist performance, the optimum PAG for a given resist system, whether ionic or nonionic, must balance the functional properties Hsted eadier in this section. The development of new photoacid generators, and the characterization of their functional properties, ate considered key to the design of resists with increased levels of performance. 

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. 25. Cross-linking reactions in a three-component resist system. Both O-alkylation and C-alkylation are shown.

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...

Fig. 3. Lithographic process using positive- and negative-resist systems. The element (a) is (b), exposed to uv radiation (c), developed and (d), the metal is...

For solvent-based ambient cure systems polyamides are often the hardeners of choice. For heat-cured systems, anhydrides are used to provide higher heat-resistance systems but at the expense of flexibiHty. 

Fans are used in parallel to obtain increased capacity in preference to a single large installation, to increase capacity at constant pressure, and for low-resistance systems requiring large capacities. It is important to study the effect of the addition or removal of fens on the system. This is done using the system resistance and the fan characteristics. 

These coatings provide the most effective fire-resistant system available but originally were deficient in paint color properties. Since, historically, the intumescence producing chemicals were quite water-soluble, coatings based thereon did not meet the shipping can stability, ease of application, environmental resistance, or aesthetic appeal required of a good protective coating. 

Some metals can be converted to a less toxic form through enzyme detoxification. The most well-described example of this mechanism is the mercury resistance system, which occurs in S. aureus,43 Bacillus sp.,44 E. coli,45 Streptomyces lividans,46 and Thiobacillus ferrooxidans 47 The mer operon in these bacteria includes two different metal resistance mechanisms.48 MerA employs an enzyme detoxification approach as it encodes a mercury reductase, which converts the divalent mercury cation into elemental mercury 49 Elemental mercury is more stable and less toxic than the divalent cation. Other genes in the operon encode membrane proteins that are involved in the active transport of elemental mercury out of the cell.50 52... 

The lithographic applications of a double-layer resist system in which the poly[p-(dimethyldiphenyldisilanylene)phenylene] film (0.2 ym thick) was used as the top imaging layer have been examined (K. Nate, T. Inoue, H. Sugiyama and M. Ishikawa, J. Appl. Polym. 

Gaia on the other hand, it also appears possible that the Earth is a highly resistant system which can deal with changes such as those induced by catastrophes. 

Stein, and S. E. Bates. From MDR to MXR new understanding of multidrug resistance systems, their properties and clinical significance,... 

Multileaf spiral-wound modules, 15 819 Multilevel 157-nm resist systems, 15 188-189... 

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). 

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