Deep-UV applications

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). 

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. 

The chemically amplified resists reported here for deep-UV applications require a post-exposure thermal treatment process step to effect the deprotection reaction. This step has proven to be critical, and in order to understand the processing considerations it is instructive to discuss, qualitatively, the various primary and secondary reactions that occur with these systems during both exposure and PEB, ie ... 

Negative Resists for Deep UV. There has been considerable effort recently devoted to the design of negative resists for deep-UV application. Iwayanagi and co-workers (37) have reported on the properties of resists composed of cyclized polyisoprene and several bisazides whose absorption maxima lie within the deep-UV region. Since the sensitizers do not absorb in the visible region they are referred to as "white resists" and are claimed to be 60-450 times more sensitive than PMMA. One of these resist is available commercially as... 

Norbornene photoresist monomers, (VII), effective for deep UV applications were prepared by Rahman [7]. 

Application to Dry-Developed Single-Layer Deep-UV Resists... 

As for negative deep UV resist, O Toole et al. have exhibited half-micron pattern resolution in 0.5 micron film thickness using the new resist and PIE process (10). The pattern profiles, however, were re-entrant, due to the large photo absorption and the applications to single-layer-resist system have not been presented (11). 

Azide-phenolic resin photoresists have been reported by workers at Hitachi. They are used for i-line (12) or for deep UV light (13), and the applications to KrF excimer laser lithography have not been demonstrated. 

This paper describes the successful synthesis and examination of polyfr-(amino /9-thiosulfate) ether] (PATE), a water soluble photolabile polymer. Evidence has been presented that the PATE polymer is zwitterionic and forms weak associations in aqueous solutions. Heat treatment of PATE films result in extensive crosslinking, presumably through a disulfide bond. This work presents strong evidence that PATE is activated by deep UV radiation, and that a disulfide crosslink is formed. Sensitization experiments demonstrate that the crosslinking reaction can be induced by a triplet sensitizer. Finally, preliminary results point out the potential for application of PATE films as active photoimaging systems. 

The object of this study is to develop new photoresists for deep-UV lithography, by using the reversible photoreaction of pyrimidine bases (17-19). Applicability of pyrimidine containing polymers to both negative and positive type photoresists is due to this photoreversible reaction in which cyclobutane dimers are either formed or cleaved depending on the exposure wavelength (Scheme 2). 

A mixture of three isomeric cresols is used in a commercially available cresol-formaldehyde Novolak resin. This mixed Novolak resin, Varcum resin (12), provides adequate properties as a host resin for near-UV- and mid-UV-photoresist applications. Gipstein and his co-workers prepared pure cresol-formaldehyde Novolak resin from each isomeric cresol and compared their spectroscopic and resist characteristics (13). Their data on the UV-absorption spectra of each cresol-formaldehyde Novolak resin together with the commercially available Varcum resin are as follows the absorbances of 0.2 jim thick Novolak films at 250 nm are 0.165(Varcum), 0.096(o-cresol), 0.092(m-cresol), and 0.055(p-cresol). The so-called "window" in the UV absorption at around 250 nm is a maximum with the p-cresol-formaldehyde Novolak resin, while the other isomeric cresol and formaldehyde Novolak resins yielded similar UV absorptions at this wavelength. The smallest UV absorption at 254 nm is an advantage for the p-cresol-formaldehyde Novolak when the resin is used for a deep UV photoresist with a suitable photoactive compound (14). 

DNQ from regions of high concentration to regions of low concentration at the edges of the exposed areas (5). The application of a deep-UV flood exposure during a postbake step can increase contrast, again by the formation of a less base-soluble surface skin (35). 

Fiber-optic UV-vis spectrophotometers are well suited to a clean-in-place application. For analytes with signals in the deep UV, best results will be obtained with a deuterium source and short fiber runs. Further out in the UV and visible regions, a xenon flash lamp... 

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