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3 and strip at pH 13 Often these alkaline-stable materials are developed at high temperatures In the past, several photoresists were formulated for exposure at a visible wavelength, 450 nm, using specialized exposure equipment either visible lasers or magnified projection printing More recently, laser direct imaging (LDI) based on the Ar+ laser output clustered around 360 nm has been commercialized Conventional photoresists can be exposed on LDI equipment, but higher photospeed has been key to the productivity and economics of LDI Photoresists requiring only 10 mJ/cm2 are now commercially available for the major applications In general, these high-speed photoresist processes are similar to conventional ones, but improvements include photospeed, sensitivity to yellow safelights, and postlamination hold4 Novel aqueous-developable photoresists have been formulated to process in dilute acidic media.

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A dry film based on electrophoretic depositable (ED) materials was shown to have excellent stability in strong alkaline solutions, potentially useful for etching polyimides or for full-build electroless copper plating5.

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Semiaqueous- and Solvent-Developable Dry Films Semiaqueous-developable photoresists are used when increased resistance to chemical attack is required, such as the highly alkaline solutions used in polyimide etching or gold and precious metal plating applications. Their composition is similar to the aqueous-developable photoresists, but the polymer backbone is less alkaline-soluble.This increased chemical stability provides accurate image transfer by maintaining the integrity of the surface and sidewalls and minimizing underplating. Semiaqueous-developer chemistry is slightly alkaline (sodium

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tetraborate) and contains an organic assist, typically butyl cellusolve. Process control for this mixture is more complicated than that used for aqueous development. Solvent-developable dry-film photoresists were the first to be commercially produced. Since they are the only materials that can withstand the harsh conditions in some chemical processing sequences, they still have some interest. They are based on methyl methacrylate polymers and a Michler s ketone initiation system similar to that used for aqueous-developable photoresists. Although they can have very high contrast, they are prone to scumming, leaving residue in the spaces between exposed photoresist features after development. Slight etching of the underlying substrate is often required to have a clean image-transfer step, especially for pattern-plating applications. Traditionally these materials were developed in trichloroethane and stripped in methylene chloride. However, as the hazards associated with chlorinated hydrocarbons were recognized, use of these solvents has been practically eliminated. This has forced the use of alternative develop and strip chemistries for solvent development.6

Liquid photoresists come in a variety of chemistries.7 Many are simply coatable forms of the dry-film materials. They have been used primarily for patterning innerlayers and are applied to the substrate by roller, spray, curtain, or electrostatic coating techniques.These methods are discussed later in the chapter (with equipment). Applied thickness is typically 6 to 15 mm, giving superior resolution compared to dry-film resists that are generally thicker. Since resolution is approximated by the thickness, they have the ability to resolve features less than 25 mm. Conformation of liquid photoresist to the copper substrate is generally very good, and it is possible to achieve high yield at 50 mm features and less.8 However, cleanliness of the substrate and the coating and drying operation is critical. Liquid photoresists are dried to allow for hard contact with the phototool during exposure, maximizing resolution. If soft or off contact is used, resolution and yield decrease, especially for features 100 mm or less. For the majority of liquid photoresists, the developing and stripping conditions are similar to those for aqueous-developable dry films: mild alkaline sodium carbonate and strong alkaline sodium hydroxide. Exceptions are positive-acting novolac-based photoresists, thermal photoresists,9 and negative-acting acid-developable photoresists.

Negative-Acting Liquid Photoresists The chemistry of the typical materials is similar to that of the aqueous-developable dry films. They depend on a radical chain reaction to promote cross-linking in the acrylic polymer.Their sensitivities differ depending on the initiator system chosen. Materials are available with minimal solvent content, and a few are diluted with water.10,11 This reduces the emissions from coating and drying that must be contained and treated. Acid-developable photoresists mentioned in the dry-film aqueous section can also be formulated as electrophoretic-depositable liquids. These materials have high contrast, good resolution, and chemical stability in strongly alkaline solutions since they are developed in aqueous acid solutions.

Positive-Acting Liquid Photoresists The other alternative is a positive tone novolac resin-based system that finds its application most usually in the semiconductor industry for imaging integrated circuits. It has excellent resolution and chemical stability in acid and a large number of basic solutions (precious metal

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