Deep-UV resist materials

The seminal work on deep-UV resist materials which incorporate chemical amplification was started at IBM San Jose s Research Laboratory in 1979 when FrSchet and Willson first prepared poly(4-t-butyloxycarbonyloxy styrene) and end-capped copolymers of o-phthalaldehyde and 3-nitro-l,2-phthalic dicarboxaldehyde. 

TURNER ET AL. Thermally Stable, Deep-UV Resist Materials... 

We became interested in poly(l-trimethylsilyl-l-propyne) [poly(TMSP)] after the initial report of its synthesis (9). Poly(TMSP) possesses many of the qualities needed in a practical deep-UV resist material a high silicon content (—25%) thermal stability excellent film-forming properties and a chromo-phore, the conjugated backbone, that absorbs strongly in the deep-UV region. Our initial work with poly(TMSP) showed that it had one serious drawback its sensitivity toward degradation by deep-UV radiation was poor, and doses of >1 J/cm are required for the definition of a positive-tone pattern. 

For other thermally stable dissolution inhibitors based on diazo Meldnim s acid, see, for example, S.R. Turner, K.D. McKean, and L.A. Pedersen, Thermally stable, deep UV resist materials, ACS Symposium Series 346, p. 200, American Chemical Society, Washington, DC (1987). 

Deep-UV resists comprised of matrix polymers and a 2,6-dinitrobenzyl tosylate photoactive acid generator have been described and compared to previously reported onium salt systems. Although these resists exhibited lower sensitivity than onium salt-based materials, the contrast and processibility are superior. The use of a matrix polymer capable of radiation-induced chain scission improves the sensitivity and allows the 2,6-dinitrobenzyl tosylate acid generator to more nearly... 

Various materials have been examined for use as deep UV resists poly(methyl methacrylate) (PMMA) (1), poly(methyl isopropenyl ketone) (PMIPK) fS.7L and the novolak-Meldrum s acid solution inhibition system (S). Each however has a problem related to sensitivity and/or resolution. While PMMA is insensitive to light of X > 230 nm because of its weak absorption, its high resolution properties make it an attractive starting point for the design of a resist that will perform well in the 230-280 region. The photochemical properties of PMMA could be modified by the incorporation of a small percentage of photolabile groups so as to have both the desired sensitivity and base polymer properties. 

Deep-UV resists have also been prepared by changing both sensitizer and matrix resin. For example, materials combining o-nitrobenzyl ester derivatives of cholic acid with a P(MMA-MAA) matrix resin (Scheme V) have been reported (59-61). Upon photolysis, the nitrobenzyl ester dissolution... 

Silylated methacrylates are also useful in positive, chain scission, bilevel deep-UV resists (30, 31). However, the silyl substituent must be carefully selected to avoid an excessive decrease in Tg. For example, pentamethyl-disiloxypropyl methacrylate has limited utility in resist applications, because it decreases the Tg (30). Copolymerization with other monomers may yield glassy, oxygen-resistant materials, but syntheses requiring controlled polymerization of three or more constituents may be unduly complicated. 

A negative deep UV resist can be produced from a composition of 3-octylPT with the cross-linker ethylene [l,2-bis(4-azido-2,3,5,6-tetrafluorobenzoate)] [150]. Grid patterns can be reproduced without distortion on an electrically conductive electron beam resist material containing substituted PT like 3-dodecyloxyPT [151,152]. 

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). 

Recently, nonionic acid precursors based on nitrobenzyl ester photochemistry have been developed for chemically amplified resist processes (78-80). These ester based materials (Figure 8) exhibit a number of advantages over the onium salt systems. Specifically, the esters are easily synthesized, are soluble in a variety organic solvents, are nonionic in character, and contain no potential device contaminants such as arsenic or antimony. In addition, their absorption characteristics are well suited for deep-UV exposure. 

The development of new classes of cationic photoinitiators has played a critical role in the production of highly sensitive, acid-catalyzed deep-uv photoresists. Sulfonium salts have been widely used in this respect (4). These materials are relatively easy to prepare and structural modifications can be used to produce desired wavelength sensitivity. Triphenylsulfonium salts are particularly well suited for deep-uv application and in addition can be photosensitized for longer wavelength. These salts are quite stable thermally and certain ones such as the hexafluoroantimonate salt are soluble in casting solvents and thus easily incorporated within resist materials. 

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