62 Parylene Coating 621. Process 62-1 62.2. Properties. 62-2 William F. Beach 62.3. Applications. 62-3 Consultant References, 62-3 62.1 Process ‘The parylene process'? isa means of applying a pinhole-free coating with exceptional conformality and control of thickness. The coatings so produced have excellent dielectric as well as barrier properties. The parylene coating, composed solely of poly (p-xylylene) (PPX), a family of linear, high molecular weight organic polymers, is grown directly on a substrate by vapor deposition polymerization (VDP). The gaseous p-xylylene monomer (PX) is transformed into a solid polymer coating without passing through, an intermediate liquid stage. Since surface forces have no opportunity to alter the cross-sectional profile, the result isa coating of extraordinary uniformity of thickness and continuity. No postdeposition eure is necessary to complete the coating chemistry. The parylene process affords exceptional control of coating, thickness. While typically used in thicknesses of 1 to 10 jum, continuous parylene films have been demonstrated at thicknesses under 500 (0.05 um). In principle, there is no upper limit to the thickness towhicha parylene film might be grown, but practical constraints of time and cost place an upper bound in the vicinity of 100 um, ‘The parylene process is further distinguished by the fact that itis conducted at room temperature. Parylene growth rates actually decrease at high temperatures. There is an advantage in operating the process at subambient temperatures, if such operation is feasible. Another distinguishing feature of the parylene process is that it proceeds without the assistance ofa catalyst. Thus, the coating is of remarkable chemical purity with respect to catalyst residues, which in other coating systems can be ionic or ionogenic, ot leachable. ‘The monomer is exceptionally reactive. It cannot be stored. It can be handled only as a rarefied, low pressure gas. It is therefore necessary to generate monomer as it is required by the coating process. Monomer is conveniently generated by the pyrolytic cleavage of its dimer, di-p-xylylene (DPX), a [2.2] paracyclophane. Monomer generation from dimer proceeds in quantitative yield with no by-products. Because the temperatures for monomer generation and consumption are so different, monomer trans port from one site to the other during deposition is a practical necessity. Such transport is done most ficiently when all other gases are absent. For this reason, the commercial process is conducted within. a vacuum system, ‘The composition of the coating can be modified to some extent by attaching substituents to the ring carbons of the DPX molecule. Although many versions of parylene process feedstock DPX are known, those that are commercially available at this time include DPXN, the base hydrocarbon; DPXC, with an average of one chlorine atom per aromatic ring; and DPXD, averaging two chlorine atoms per aromatic ring. The coatings prepared starting with these dimers are called Parylene N, Parylene C, and Parylene 621622. Coatings Technology Handbook, Third Edition Px Px. Pex -200"¢ 680°C 250 “tor “05 torr “0.1 toe <7ee ~2.008 torr lO Vaporizer Pyroysis Deposition Thimble Mechanical Chamber Cold Vacuum Trp Pump FIGURE 62.1. Schematic of parylene deposition apparatus , respectively. Substituents reduce the volatility of the monomer, causing the proce of the modified versions to be somewhat different ‘The discovery of the base member ofthe family, poly(p-xylylene), was first reported in 1947. However, it was not until 1965, when the Gorham process starting with DPX was announced; that the polymer family became industrially viable, Figure 62.1 is a schematic of the patylene equipment, with typical ‘operating conditions indicated. ing characteristics 62.2 Properties ‘The glass transition temperatures of the parylenes are in the vicinity of room temperature, However, the parylenes are crystalline polymers, and as such retain substantial physical strength and solvent resistance at temperatures approaching their crystalline melting points (for Parylenes N, C, and D: 420, 290, and 380°C, respectively). Long-term contact with solvents results in a mere few percent swelling. Equilibrium, ‘moisture absorption is very low. Significantly, no mode of moisture-induced degradation is chemically feasible, The dielectric constants and loss factors of the parylenes are low and invariant over a wide range of frequencies. Although permeable, the parylenes at a given thickness are superior as barriers to other corganie polymers that can conveniently be prepared as coatings. “The parylenes are vulnerable to attack by oxygen, particularly at elevated temperatures and in the presence of ultraviolet radiation. In ait, 10-year use temperatures for Parylenes N, C, and D ate projected. to be 60, 80, and 110°C, respectively. In oxygen-free environments, the thermal endurance of each is substantially better. ‘While it is tempting to categorize the parylene vapor deposition polymerization process with the superficially similar processes of evaporation, sputtering, or chemical vapor deposition of metals or inorganics, there are important distinctions to be made. In the latter processes, the growth action isParylene Coating 623, confined tothe outer substrate surfaces, while the parylene polymerization chemistry actually occurs under the surface of the growing coating, As. result, the parylenes deposit in a condition of compressive stress and adhete to organi substrates, which are permeable to monomer by an interpenetration mechanism, Adhesion to impermeable metallic or inorganic substeates such as aluminum or silica can be achieved by pretreatment with an organosilane primer such as jtmethacryloxypropyl trimethoxysilane (A-174). 62.3. Applications ‘The parylenes first found use in electronics construction, Because ofits exceptionally low and frequency- independent dielectric constant, Parylene N continues to be used as the functional dielectric in high quality miniature film capacitors. Very early on, the parylenes were qualified under MIL-1-46058, the specification for coating printed circuit assemblies. Parylene C continues to enjoy a reputation as a high performance coating for military circuitry, particulaely in avionics. Parylene C is also an Underwriters Laboratories (UL) approved conformal coating, The use ofthe parylenes as circuit coatings has extended. to hybrids. The exceptional conformality of the parylenes has served them wel in these applications, but so far has impeded their use in multilevel interconnection schemes, where a planarizing dielectric is sought. In the manufacture of miniature electric motors, such as those used in wristwatches, parylene is used as an insulating coating on the armature. Parylene’s exceptional thickness contzol permits the winding of a maximum number of turns, and therefore superior motor performance, Furthermore, a parylene process variation in which the parts are tumbled during deposition permits economies through the coating of thousands of parts at atime. Parylene’s use today has broadened to such diverse missions as the immobilization of loose particles that otherwise would result in early device failure (Winchester drives and hybrids), the modification of surface abrasiveness on ferrite toroids, and the reinforcement and preservation of embrittled paper in old books and museum artifacts References 1. WEE Beach, C. Lee, D. R Basset, T. M. Austin, and R. Olson, “Xylylene polymers,” in Eneyelopedia of Polymer Science and Engineering, 2nd ed, New York: Wiley-Interscience, 1988. 2. (a) S. M. Lee, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed., Vol. 24. New York: Wiley-Interscience, 1983, pp. 744-771. (b) M. Saware, Polym. Eng. SCE, 16(7), 473-479 (1976) (c) W.F. Gorham and W. D. Niegisch, in Encyclopedia of Polymer Science and Technology, Vol, 15. 1971, pp. 98-124. (d) L.A. Errede and M. Saware Q. Rev. 12, 301-320 (1958). 3. W.E Gorham, U. S. Patent 3,342,754 (September 19, 1967); Union Carbide Corp. ©2009 Tyr Ar Gap.