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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
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LIQUID PHOTORESISTS
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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.
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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.
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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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Ketene
Indene Carboxylic Acid
-COOH
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Novolac
Low Novolac + DNQ
FIGURE 26.5 photoresists. Chemistry mechanism of positive-acting liquid
plating). The chemistry involves the conversion of a base-insoluble diazonaphthalquinone to the base-soluble indene acid. Thus, this photo-driven conversion alters the solubility of the base material in alkaline solutions, allowing for image formation (see Fig. 26.5).
ELECTROPHORETIC DEPOSITABLE PHOTORESISTS
Electrophoretic depositable (ED) photoresists12,13 were introduced in the late 1980s with expectations of broad adoption by the interconnect industry. The early materials were modifications of those used for coating automobiles and appliances. These fast-coating processes provide a defect-free film of high durability on conductive substrates and are well suited to large-volume production.Anodically and cathodically deposited materials that are both positive and negative acting have been introduced but have achieved limited market penetration in the interconnect industry. Advances in dry-film photoresists and liquid photoresists reduced the interest in implementing a new photoresist process. (A detailed discussion of electrophoretic depositable photoresists is included in Sec. 17.1.6 of the fourth edition of this handbook.)
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