Novolak polymers

As insulation between the coil and the magnetic core, a hard-cured (to 200°C) photoresist insulator is patterned. It is a novolak polymer or polyimide about 5 fim thick, which is popular for its high insulator and photolithographic properties. This provides electrical insulation as well as a planar surface for subsequent deposition of copper cods. 

The polymers evaluated are shown in Fig. 1. These twelve polymers cover typical types of organosilicon polymers, such as polysiloxane, ladder type polysiloxane, polysilane, polymethacrylate, polysilyl-styrene, and novolak. Polymers and were supplied by Shin-etsu Chemical Co., Ltd. Actually, polymer" 2 evaluated contains very small amount of vinylsiloxane for crosslinking by deep UV irradiation after coating, because the pure polysiloxane is a fluid at room temperature and is impossible to measure the etching depth. These polymers have Si-0 bonds in the main chain structure. Polymer was purchased from Shin Nisso Kako Co., Ltd. and was purified in house. Polymers 4 to 12 were synthesized in house. Polymers 1J and 12 have Si-0 bonds in side chain structure. Thermal Si02 1J was evaluated as a reference. ... 

Novolaks are phenol-formaldehyde type polymers. Novalaks are synthesised via a polycondensation reaction which is halted before the polymer becomes fully cross-linked. As Novalak polymers contain phenol units, they have reasonable solubility in aqueous base solutions. To act as a positive tone resist, the solubility of the Novolak polymer in basic solutions must be greatly enhanced. This can be achieved by using photochemically reactive additives. The additive used is a diazoanthraquinone, which undergoes a photochemically driven Wolf rearrangement reaction to produce a carboxylic acid (Scheme 13.4). 

The carboxyhc acid produced is highly soluble in the base developing solution and the dissolution of this carboxylic acid enables the Novolak polymer to be dissolved much more readily in the base developer. In fact, the solubility of the Novolak polymer is increased by several orders of magnitude in comparison to the polymer in the absence of the carboxylic acid. 

Poly(4-hydroxystyrene) [P4HS] has been suggested as a replacement candidate due to its similar phenolic functionalities to novolak polymers. P4HS... 

In addition, it is obvious that at a simflar pH value P(4HS/S) dissolves faster in NaOH solution than it does in KOH solution. The decrease in dissolution rate with the increase in the cation size of aqueous base developers is not an uneiqiected phenomena. It has been demonstrated by other authors in the dissolution study of novolak polymers with metal hydroxides as developers (8,11, 12). 

Hgh nitrile polymers Hgh oleic canola Hgh oleic sunflower Hgh ortho novolaks... 

In the case of phenoHcs, it is possible to make linear thermoplastic polymers called novolaks, but this is done by reaction of less than one mole of formaldehyde with one mole of phenol the resulting resin has a large excess of free phenol. Usually in appHcation hexamethylene tetramine (HEXA) is added to the novolak. When heated, the HEXA breaks down into ammonia and formaldehyde and enters the reaction to form a light degree of cross-links in the final product. 

Aqueous dispersions are alternatives to solutions of Hquid and soHd resins. They are usuaUy offered in 50% soHds and may contain thickeners and cosolvents as stabilizers and to promote coalescence. Both heat-reactive (resole) and nonheat-reactive (novolak) systems exist that contain unsubstituted or substituted phenols or mixtures. A related technology produces large, stable particles that can be isolated as discrete particles (44). In aqueous dispersion, the resin stmcture is designed to produce a hydrophobic polymer, which is stabilized in water by an interfacial agent. 

In the 1960s, CIBA Products Co. marketed and manufactured glycidylated o-cresol novolak resins, which had been developed by Koppers Co. as high temperature-resistant polymers. Dow offered glycidylated phenol novolak resins, SheU introduced polyglycidyl ethers of tetrafunctional phenols, and Union Carbide developed a triglycidyl p- am in oph en o1 resin. 

Positive photoresists, by contrast, are based on water-soluble novolak resins with naphthalene diazoquinone sulfonate (NDS) as the photosensi-tiser. On photolysis the NDS causes a rearrangement in the polymer to yield nitrogen gas plus an indene carboxylic acid. This latter functional group considerably increases the solubility of the polymer, hence solubilising those areas of the polymer that had been exposed to light. 

Phenol-formaldehyde resins using prepolymers such as novolaks and resols are widely used in industrial fields. These resins show excellent toughness and thermal-resistant properties, but the general concern over the toxicity of formaldehyde has resulted in limitations on their preparation and use. Therefore, an alternative process for the synthesis of phenolic polymers avoiding the use of formaldehyde is strongly desired. 

The polymer used in this study was a m,p-cresol novolak ( 1 =14000, Mn =1300). Melamine resins were obtained from American Cyanamid Co. Polymer/crosslinker formulations were prepared using 23 wt % novolak in cellosolve acetate and 15 parts per hundred crosslinker based on novolak solids. p-Toluenesulfonic acid was... 

Onium salts have been widely used as an acid generator for photo-, EB, and x-ray resist. In addition, aromatic polymers such as novolak and polyhydroxystyrene have been often used as a base polymer for EB and x-ray resist. The reaction mechanisms in a typical resist system have been investigated by pulse radiolysis [43,52,77-88], SR exposure [79,80,83-85], and product analysis [88]. Figure 6 shows the acid-generation mechanisms induced by ionizing radiation in triphenylsulfonium triflate solution in acetonitrile. The yields of products from electron beam and KrF excimer laser irradiation of 10 mM triphenylsulfonium triflate solution in acetonitrile are shown in Fig. 7 to clarify the... 

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. 

Phenolic, (I), and naphtholic, (II), condensation polymers containing cyclopentane were previously prepared by Sue et al. (1). These materials were subsequently epoxidized with epichlorohydrin and used in electronic devices as ICs and Lumen solubility indexes (LSIs). In a subsequent investigation by Abe et al. (2) novolak resins functionalized with thiophene, (III), were prepared and used as adhesives. 

When two polymeric systems are mixed together in a solvent and are spin-coated onto a substrate, phase separation sometimes occurs, as described for the application of poly (2-methyl-1-pentene sulfone) as a dissolution inhibitor for a Novolak resin (4). There are two ways to improve the compatibility of polymer mixtures in addition to using a proper solvent modification of one or both components. The miscibility of poly(olefin sulfones) with Novolak resins is reported to be marginal. To improve miscibility, Fahrenholtz and Kwei prepared several alkyl-substituted phenol-formaldehyde Novolak resins (including 2-n-propylphenol, 2-r-butylphenol, 2-sec-butylphenol, and 2-phenylphenol). They discussed the compatibility in terms of increased specific interactions such as formation of hydrogen bonds between unlike polymers and decreased specific interactions by a bulky substituent, and also in terms of "polarity matches" (18). In these studies, 2-ethoxyethyl acetate was used as a solvent (4,18). Formation of charge transfer complexes between the Novolak resins and the poly (olefin sulfones) is also reported (6). 

Novolak resins with epichlorohydrin are thermally cross-linked, and the resultant polymer layers show excellent mechanical and dielectric properties... 

Another type of negative tone Novolak resin was obtained by direct incorporation of the photoactive chromophore into the polymer chains as shown... 

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