Cross-linking plasma polymers

The effect of the cross-linking of resist polymer films is to make the film stable to heat such that it cannot be made to flow or melt. A fully cross-linked resist polymer film is practically insoluble in most solvents, although it can be stripped with oxygen plasma etching. Its plasma etch resistance is superior to a similar film that is not cross-linked. 

Chemical processes in thin polymer surface layers are stimulated by all major plasma components, especially by electrons, ions, excited particles, atoms, radicals, and UV radiation. The major primaiy products of plasma polymer treatment are free radicals, non-saturated organic compounds, cross-links between polymer macromolecules, products of destruction of the polymer chains, and gas-phase products (mostly molecular lydrogen). Processes for the formation of radicals on the polymer surface under plasma treatment, which are due to electron impact and UV radiation, are related to breaking of R-H and C-C bonds in polymer macromolecules ... 

Fig. 37. Resist images obtained with a cross-linking monocomponent TSI resist (PHOST polymer), cross-linked by photo-oxidation using light at 193-nm wavelength. After exposure, the film was treated with a vapor of dimethyl silyl dimethyl amine and then plasma developed using O2—RIE (122).

When -xylene is used as the monomer feed in a plasma polymer process, PX may play an important role in the formation of the plasma polymer. The plasma polymer from -xylene closely resembles the Gorham process polymer in the infrared, although its spectmm contains evidence for minor amounts of nonlinear, branched, and cross-linked chains as well. Furthermore, its solubiUty and low softening temperature suggest a material of very low molecular weight (15). 

The major use of vinylpyrrohdinone is as a monomer in manufacture of poly(vinylpyrrohdinone) (PVP) homopolymer and in various copolymers, where it frequendy imparts hydrophilic properties. When PVP was first produced, its principal use was as a blood plasma substitute and extender, a use no longer sanctioned. These polymers are used in pharmaceutical and cosmetic appHcations, soft contact lenses, and viscosity index improvers. The monomer serves as a component in radiation-cured polymer compositions, serving as a reactive diluent that reduces viscosity and increases cross-linking rates (see... 

Poljraer surfaces can be easily modified with microwave or radio-frequency-energized glow discharge techniques. The polymer surface cross-links or oxidizes, depending on the nature of the plasma atmosphere. Oxidizing (oxygen) and nonoxidizing (helium) plasmas can have a wide variety of effects on polymer surface wettability characteristics (92). 

The most important reaction in blood clotting is the conversion, catalyzed by thrombin, of the soluble plasma protein fibrinogen (factor 1) into polymeric fibrin, which is deposited as a fibrous network in the primary thrombus. Thrombin (factor 11a) is a serine proteinase (see p. 176) that cleaves small peptides from fibrinogen. This exposes binding sites that spontaneously allow the fibrin molecules to aggregate into polymers. Subsequent covalent cross-linking of fibrin by a transglutaminase (factor Xlll) further stabilizes the thrombus. 

Plasma films are usually highly cross-linked, resistant to higher temperatures, resistant to abrasion and chemical attack, and are highly adherent to the surface. Adhesion to the surface is generally high both because the growing polymer complex can fit the surface contour and thus lock-itself in (physical adhesion), and because in many instances, the species are active enough to chemically react with the surface molecules to chemically bond to the surface. The surface can be prepared so that the chemical reaction is enhanced. 

Quantitative characterization of plasma-polymer films, especially of ultrathin fluorinated carbon plasma polymer films, has been performed by ToF-SIMS to study changes in the surface composition and molecular distribution. CFX films on silicon and polyethylene terephthalate (PET) substrates were exposed to a pulsed Ar/CHF3 plasma by varying the deposition time from 10-90 s.111-113 The results show differences in film growth and CFX cross linking for the silicon and PET substrates.111... 

Cross-Linking of Linear Polymers Occurs Outside the Plasma Membrane... 

---