Polymer photosensitized crosslinking

The before mentioned physically incorporated porphyrins or phthalocyanines in crosslinked polymers photosensitize efficiently the reduction of Fast Red A (FRA) (in the presence of L-ascorbic acid, AA, in DMF or water, Fig. 2) . Mainly the photosensitized reaction in water is interesting in the future water splitting. The reaction in water (Fig. 2) is explained by oxidative quenching (Eq. 2). 

Photosensitized crosslinking of polymers has been the subject of numerous publications [l - 30], concerned mainly with poly(ethylene), poly(vinyl alcohol), various vinyl copolymers, copolymers of maleic anhydride and/or phtalic anhydride with styrene and some polymers derivated from cinnamic acid. The following compounds were used as sensitizers benzophenone, 4-chloro- and 4,4-dimethylbenzophenone [l, 3-6, 8, 9l, oC -and -derivatives of anthraquinone [3, 23] acetophenone, hydroquinone, triphenylmethane and pyridine li.] chlorobenzene and no less than trichlorinated n-paraffins [6], a complex of zink chloride with o-dia-nizidine fill potassium bichromate [l2j, anthracene fl3, 14] 2,5-methoxy-4-amino-trans-stilbene [l5], benzyl ideneacetophenone fl6-l8] -thiophenylacetophenone,... 

On this substructure a thin dense layer (in the range of 0.5 to 10 pm thick) is coated that has a very high separation capability. Different coating techniques are in use, most commonly a solution of the respective polymer in an appropriate solvent is spread onto the porous substructure. The solvent is evaporated, followed by further treatment to effect crosslinking of the polymer. Photosensitive, solvent-free prepolymers may be used for coatings that are later crosslinked by irradiation, e.g. with UV-light or electrons. 

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. 

If (P ) is terminated by a chain transfer to a solvent or a monomer, a graft copolymer is formed, or, if the termination is from a combination, a crosslinked network polymer is formed. If the pre-existing polymer (B) contains an end group that itself is photosensitive (or can produce a radical by interacting with photoinitiator) and in the presence of a vinyl monomer (A), block copolymer of type AB can be produced if the photosensitive group is on one end of the polymeric chain. Type ABA block copolymer can be produced if the polymer chain (B) contains a photosensitive group on both ends. 

Modified PS by use of BF3-OEt2 catalyst had better properties comparised with virgin PS and other modified polymers. High thermostability and photosensitivity of modified PS compared with virgin PS are explained by the crosslinked structure of macromolecules formed during the processes of thermo- and phototreatment. 

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. 

Reactions with Isocyanates. The reaction of alcohols with isocyanates to form carbamates is well known and similar reactions with poly(vinyl alcohol) would be expected. Until recently, the only available reaction conditions were to use a heterogeneous reaction mixture or to run the reaction in a poor solvent for poly(vinyl alcohol). The best poly(vinyl alcohol) solvents, water and formaide derivatives, react rapidly with isocyanates. Nevertheless, several such reactions have been run in the past and we will cite only a few of them. A potentially photosensitive polymer was made by the reaction of allyl isocyanate with poly(vinyl alcohol) (57) and several workers have crosslinked poly(vinyl alcohol) with hexamethylene diisocyanate (58.59). 

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. 

Some new electronic applications of polyimide-siloxane adhesives have been already partially reviewed. In addition, the development of photo-crosslinkable copolymers has been of great interest for the development of components of electronic devices [126]. The general field of photosensitive polymers was reviewed by Horie and Hamishita in 1995 [127]. A number of papers have investi-... 

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