Resist materials sensitivity

Titanium siUcides are used in the preparation of abrasion- and heat-resistant refractories. Compositions based on mixtures of Ti Si, TiC, and diamond have been claimed to make wear-resistant cutting-tool tips (157). Titanium siUcide can be used as an electric—resistant material, in electrically conducting ceramics (158), and in pressure-sensitive elastic resistors, the electric resistance of which varies with pressure (159). 

Certain conditions, ultimately dictated by economics, make the substitution of more resistant materials a wise choice. Stainless steels (not sensitized) of any grade or composition do not form tubercles in oxygenated water neither do brasses, cupronickels, titanium, or aluminum. However, each of these alloys may suffer other problems that would preclude their use in a specific environment. 

Because silver, gold and copper electrodes are easily activated for SERS by roughening by use of reduction-oxidation cycles, SERS has been widely applied in electrochemistry to monitor the adsorption, orientation, and reactions of molecules at those electrodes in-situ. Special cells for SERS spectroelectrochemistry have been manufactured from chemically resistant materials and with a working electrode accessible to the laser radiation. The versatility of such a cell has been demonstrated in electrochemical reactions of corrosive, moisture-sensitive materials such as oxyhalide electrolytes [4.299]. 

To date, we have exercised these materials in basically three types of multilayer lithographic applications (1) as short wavelength contrast enhancing layers, (2) as imagable 02-RIE resistant materials in bilayer processes and (3) as radiation sensitive materials for multilayer, e-beam processes. 

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. 

A number of new resist materials which provide very high sensitivities have been developed in recent years [1-3]. In general, these systems owe their high sensitivity to the achievement of chemical amplification, a process which ensures that each photoevent is used in a multiplicative fashion to generate a cascade of successive reactions. Examples of such systems include the electron-beam induced [4] ringopening polymerization of oxacyclobutanes, the acid-catalyzed thermolysis of polymer side-chains [5-6] or the acid-catalyzed thermolytic fragmentation of polymer main-chains [7], Other important examples of the chemical amplification process are found in resist systems based on the free-radical photocrosslinking of acrylated polyols [8]. 

We have also performed preliminary imaging experiments usin E-beam exposure, these experiments indicate that the 80 20 copolymer is a sensitive E-beam resist material which requires an exposure dose of < ljiC/cm. Further experiments involving both E-beam and X-ray exposure are in progress. 

The most familiar negative photoresists are examples of two-component, resist materials. These include Kodak s KTFR, Merck s Selectilux N, Hunt s HNR, etc., all of which consist of a cyclized synthetic rubber matrix resin which is radiation insensitive but forms excellent films. This resin is combined with a bis-arylazide sensitizer. 

The positive resist materials evolved from discoveries made by the Kalle Corporation in Germany who developed the first positive-acting photoresist based on the use of a novolac matrix resin and a diazoquinone photoactive compound or sensitizer. The original materials were designed to produce photoplates used in the printing industry. These same materials have been adopted by semi-conductor fabrication engineers and continue to function effectively in that more demanding application. 

C The Epoxy Resists. The first negative tone electron beam resist materials with useful sensitivity were based on utilizing the radiation chemistry of the oxirane or epoxy moiety. The most widely used of these materials, COP (Figure 32) is a copolymer of glycidyl methacrylate and ethyl acrylate and was developed at Bell Laboratories (43,44). COP has found wide applicability in the manufacturing of photomasks. The active element... 

An example of the wavelength matching technique is apparent in the work of Taylor et. al. (58,59). Taylor and coworkers at Bell Laboratories have demonstrated very high sensitivity in 2,3-dichloropropyl acrylate-based resist systems for exposure to the palladium emission line. The sensitivity of these materials is in part the result of the high absorption cross section of chlorine for the palladium radiation. With the exception of apparent sensitivity perterbations that can be explained on the basis of unique absorption characteristics, there seem not to be new principles involved in the design of resist materials for ion beam or x-ray exposure. 

The latest addition to this list of dry developing resist materials is a contribution from IBM s San Jose Research Laboratory (66-67) that evolved from efforts to design positive-tone resist materials that incorporate chemical amplification. These efforts were stimulated by the fact that the quantum yield of typical diazoquinones of the sort used in the formulation of positive photoresists is 0.2 to 0.3 thus, three or four photons are required to transform a single molecule of sensitizer. This places a fundamental limit on the photo-sensitivity of such systems. 

In order to circumvent this sensitivity limitation, the San Jose researchers sought to design resist materials that incorporate chemical amplification of the sort that characterizes the silver halide photographic emulsion system. In these systems a single photo event initiates a cascade of subsequent chemical reactions that ultimately result in the intended function. 

Two interesting attempts to redesign these resist materials have been reported. The first consisted of altering the structure of the sensitizer such that it bleaches in the DUV (70). The resulting resist provided adequate sensitivity but suffered from sensitizer volatility and solubility problems and profile degradation was experienced in films over 0.5 jiim micron thickness due to the unbleachable absorbance of the matrix resin from which the resist was formulated. 

Wilkins and coworkers have redesigned both the sensitizer and the matrix resin (78-79). They have tested a variety of o-nitrobenzyl esters of cholic acid as sensitizers. These substances, like the diazoquinones, are insoluble in aqueous base but undergo a photo-reaction that yields base soluble products. The matrix resin chosen for the new sensitizer materials is a copolymer of methyl methacrylate and methacrylic acid that is far more transparent than novolac resins in the DUV. The new resist materials are reported to have useful sensitivity (ca. 00mJ/cm ) and extremely high contrast. The resist formulation is essentially aliphatic in nature and would be expected to be less stable to dry etching environments than the aromatic-based novolac resin materials (24). 

Attempts to improve the DUV sensitivity of PMMA have spawned a variety of new DUV resist materials. Notable among these are copolymers of methyl methacrylate and indenone (80) which are reported to provide positive-tone resist function at 20 to 60 mJicnP in the DUV and copolymers of methyl methacrylate and 3-oximino-2-butanone (81). The latter materials provide a substantial increase in sensitivity over PMMA and are capable of 1 micron resolution. 

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