ADHESION PROMOTION

The most commonly used insulator in semiconductor devices is silicon dioxide (Si02), which is typically formed on the surface of the silicon wafer by thermal oxidation of the surface with oxygen or water vapor at a temperature between 1000 and 1200°C. It is also possible to deposit the oxide layer onto a substrate that is not 

A fresh surface of thermally grown silicon dioxide, it must be pointed out, is hydrophobic. However, it quickly reacts with water vapor in the atmosphere to form silanol (Si—OH) and gradually becomes hydrophilic. In fact, the chemical vapor deposition of silicon dioxide forms only a silanolated surface. Being fairly hydrophobic, resists do not adhere well to hydrophilic surfaces such as Si02-These surfaces contain hydroxyl groups as illustrated in Reaction [11.1]. The adhesion failure of resist films on such surfaces is often observed in the course of development or wet etching. As a result, a surface treatment to promote adhesion is necessary before the resist film is deposited on such surfaces.  

A method for enhancing adhesion of resist materials onto surfaces of silicon dioxide and other semiconducting substrates was invented by Collins and Deverse, and involves subjecting the surface to an atmosphere containing the 

Deverse, Process for improving photoresist adhesion, U.S. Patent 

Hydroxylated silicon HMDS (adhesion promoter) wafer surface (hydrophilic) 

---

Hybrid Circuits. The use of parylenes as a hybrid circuit coating is based on much the same rationale as its use in circuit boards. A significant distinction Hes in obtaining adhesion to the ceramic substrate material, the success of which determines the eventual performance of the coated part. Adhesion to the ceramic must be achieved using adhesion promoters, such as the organosilanes. 

To an experienced operator trained in the handling of industrial chemicals, the dimers present Httle cause for concern in handling or storage. The finished polymer coating presents even less of a health problem contact with the reactive monomer is unlikely. In the ancillary operations, such as cleaning or adhesion promotion, the operator must observe suitable precautions. Before using the process chemicals, operators must read and understand the current Material Safety Data Sheets, which are available from the manufacturers. 

Additives. Because of their versatility, imparted via chemical modification, the appHcations of ethyleneimine encompass the entire additive sector. The addition of PEI to PVC plastisols increases the adhesion of the coatings by selective adsorption at the substrate surface (410). PEI derivatives are also used as adhesion promoters in paper coating (411). The adducts formed from fatty alcohol epoxides and PEI are used as dispersants and emulsifiers (412). They are able to control the viscosity of dispersions, and thus faciHtate transport in pipe systems (413). Eatty acid derivatives of PEI are even able to control the viscosity of pigment dispersions (414). The high nitrogen content of PEIs has a flame-retardant effect. This property is used, in combination with phosphoms compounds, for providing wood panels (415), ceUulose (416), or polymer blends (417,418) with a flame-retardant finish. 

AppHcation of an adhesion-promoting paint before metal spraying improves the coating. Color-coded paints, which indicate compatibiHty with specific plastics, can be appHed at 20 times the rate of grit blasting, typically at 0.025-mm dry film thickness. The main test and control method is cross-hatch adhesion. Among the most common plastics coated with such paints are polycarbonate, poly(phenylene ether), polystyrene, ABS, poly(vinyl chloride), polyethylene, polyester, and polyetherimide. 

Another market appHcation for naphthenic acid is the tire industry, where cobalt naphthenate is used as an adhesion promoter (see Adhesives Tire cords). Cobalt naphthenate improves the bonding of brass-plated steel cords to mbber, presumably by suppressing the de-zincification of brass (50). Its first reported use was in 1970 and the first patent for its use was issued in 1975 (51). About 900 t of cobalt naphthenate is used worldwide as an adhesion promoter, half of it in North America. The unit value fluctuates between 8.75—13.25 /kg because of the volatility of cobalt prices. Although it is the industry standard, the use of cobalt naphthenate is declining with the advent of more economical high metal-containing substitutes. 

Formulation. Polysulftde-based sealants are formulated with appropriate ingredients to obtain the desired properties for a particular appHcation. A typical formulation contains Hquid polysulftde polymer, curing agent, cure accelerators (bases) or retarders (acids), fillers, plasticizers, thixotropes, and adhesion promoters. 

Plasma processing technologies ate used for surface treatments and coatings for plastics, elastomers, glasses, metals, ceramics, etc. Such treatments provide better wear characteristics, thermal stability, color, controlled electrical properties, lubricity, abrasion resistance, barrier properties, adhesion promotion, wettability, blood compatibility, and controlled light transmissivity. 

Urethane sealants have good inherent adhesion to most substrates, but silane adhesion promoters are often used to improve this adhesion. Epoxy-, amino-, and mercapto-functional silanes are the most common because of their dual reactive nature. The silane end can react with surface hydroxyls the epoxy, amino, or mercapto end can react with the isocyanate. 

Adhesion promoting silanes are often added to improve adhesion to various substrates. As is the case with urethane sealants, silanes with a dual-reactive nature are typically used. Examples of such silanes are mercapto- and epoxy-functional silanes. Organic titanates may also be used. 

Silicone Heat-Cured Rubber. Sihcone elastomers are made by vulcanising high molecular weight (>5 x 10 mol wt) linear polydimethylsiloxane polymer, often called gum. Fillers are used in these formulations to increase strength through reinforcement. Extending fillers and various additives, eg, antioxidants, adhesion promoters, and pigments, can be used to obtain certain properties (59,357,364). 

---