Photoresist polymers photosensitization

Even if a same azide is used as the sensitizer, such properties of the photoresist as photosensitivity, photocurability and adhesion to base surfaces differ depending on the property of the base polymer. That is, degree of cyclization, content of the unsaturated groups and molecular weight of the polymer affect the photoresist properties mentioned above. H.L.Hunter et al. have discussed the dependence of the sensitivity of polybutadiene photoresist on the polymer structure, and have concluded that a higher sensitivity was obtained when 1,2- and 3, -isomers were used( 7.) ... 

Nonhnear absorption is the key mechanism responsible for 3D structuring of materials, including photoresists and photosensitive resins. Optical nonhn-earities take place when intensity of the irradiating electrical approaches that of molecular couphng, which occurs at the levels of approximately 10 ° V/m or 100 GW/cm. Detailed description of optical properties of polymers can be foimd in the literature [8]. Among the optical nonhnearities, multipho-... 

Photoresist compositions consisting of pentafluoromethylvinyl carbonate derivatives, (II), were prepared by Yoon [2] and used in photosensitive polymers for exposure to light sources having a dominant wavelength of less than 157 nm. Perfluorovinyl ether, (III), monomers were prepared by DiPietro [3] and used in lithographic photoresist polymer compositions. 

Photoresist A photosensitive polymer system, which, when applied as a coating to a substrate, after interaction with ultraviolet or visible light undergoes a change in solubility. 

Dichromated Resists. The first compositions widely used as photoresists combine a photosensitive dichromate salt (usually ammonium dichromate) with a water-soluble polymer of biologic origin such as gelatin, egg albumin (proteins), or gum arabic (a starch). Later, synthetic polymers such as poly(vinyl alcohol) also were used (11,12). Irradiation with uv light (X in the range of 360—380 nm using, for example, a carbon arc lamp) leads to photoinitiated oxidation of the polymer and reduction of dichromate to Ct(III). The photoinduced chemistry renders exposed areas insoluble in aqueous developing solutions. The photochemical mechanism of dichromate sensitization of PVA (summarized in Fig. 3) has been studied in detail (13). 

Positive-Tone Photoresists based on Dissolution Inhibition by Diazonaphthoquinones. The intrinsic limitations of bis-azide—cycHzed mbber resist systems led the semiconductor industry to shift to a class of imaging materials based on diazonaphthoquinone (DNQ) photosensitizers. Both the chemistry and the imaging mechanism of these resists (Fig. 10) differ in fundamental ways from those described thus far (23). The DNQ acts as a dissolution inhibitor for the matrix resin, a low molecular weight condensation product of formaldehyde and cresol isomers known as novolac (24). The phenoHc stmcture renders the novolac polymer weakly acidic, and readily soluble in aqueous alkaline solutions. In admixture with an appropriate DNQ the polymer s dissolution rate is sharply decreased. Photolysis causes the DNQ to undergo a multistep reaction sequence, ultimately forming a base-soluble carboxyHc acid which does not inhibit film dissolution. Immersion of a pattemwise-exposed film of the resist in an aqueous solution of hydroxide ion leads to rapid dissolution of the exposed areas and only very slow dissolution of unexposed regions. In contrast with crosslinking resists, the film solubiHty is controUed by chemical and polarity differences rather than molecular size. 

Similar types of cross-linking reactions are observed for polymers to which photosensitive molecules ate chemically attached to the backbone of the polymer stmcture (Fig. 7). Radiation curing of polymers using uv and visible light energies is used widely in photoimaging and photoresist technology (Table 8) (58,59). 

These polymers need to be made photosensitive for use as photoresists and this is achieved by the incorporation of bisazide sensitisers. On exposure to light the photochemical reaction induced by the bisazide results in rapid crosslinking of the polymer rendering it insoluble in the developing solvent. 

Metal and polysilicon films are formed by a chemical-vapor deposition process using organometallic gases that react at the surface of the IC structure. Various metal silicide films may also be deposited in this manner by reaction with the surface of the silicon wafer to form metal silicides. Glass and pol3uner films are deposited or spin cast or both, as are photoresist films (those of a photosensitive material). This process is accomplished by applying a liquid polymer onto a rapidly rotating wafer. The exact method used varies from manufacturer to manufacturer and usually remains proprietary. 

Polymethacrylates containing 6-cyanouracil or 5-bromouracil units in the side chain of the polymer displayed the highest photosensitivity. Copolymers of butadiene with the methacrylate monomer with pendant 6-cyanouracil are capable of resolving 1 o features and behaved as negative photoresists. 

Direct Patterning of Photosensitive Polyimides. Photosensitive polyi-mides (PSPIs) are recently developed materials that can be directly photo-patterned like a negative photoresist (80,85,88,146-148). The most common PSPIs are polyamic acids that have been esterified with photoreactive alcohols and combined with photoinitiators to form a polymer that will crosslink under exposure to UV radiation and become insoluble. The unexposed material is selectively dissolved in a developer solution, and the patterned film is then cured to convert the cross-linked polyamic acid to a polyimide and drive off the cross-linking groups. 

Positive Photoresists. Positive resists are entirely different from negative resists. For the purposes of this discussion we restrict ourselves to visible-light-sensitive materials. Typically, these materials are mixtures of low-molecular-weight phenol-formaldehyde polymers and derivatives of naphtho-1,2-quinone diazide, the photosensitive component. The former is soluble in aqueous alkali, but the presence of the latter, a hydrophobic species, inhibits attack of this developer on the film. On irradiation the "sensitizer" is converted to a ketene, which, after reaction with water, forms a base-soluble carboxylic acid. Thus the irradiated part of the film is rendered soluble in the developer and it can be removed selectively. The important feature of this system is that the unirradiated areas are not swollen by the developer and the resolution of this material is quite high. It is possible to prepare gratings having several... 

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