ISSN 0018-1439 Russian Original Vol. 20, No. 3 May-June, 1986 November, 1986 HIECAP 20(3) 145-222 (1986) HIGH ENERGY CHEMISTRY XMMUA BbICOKMX 3HEPIMA (KHIMIYA VYSOKIKH ENERGII) TRANSLATED FROM RUSSIAN CONSULTANTS BUREAU, NEW YORKPLASMA POLYMERIZATION (REVIEW) Une $39.216.2:678,026 G. K. Vinogradov The term "plasma (gaseous discharge) polymerization" is widely used to denote the pro- cess of forming high molecular weight products in electrical discharges. In its traditional sense the word "polymerization" means the synthesis of a polymer by successive joining of mole- cules of a initial low molecalar substance (monomer) to the active center at the end of a growing chain. thus, ‘the chemical structure of the polymer can be described in terms of the structare of the monomer, 1-e., in the ordinary context it is molecular polymerization that is meant. Yasuda [1], in analyzing the difference in polyaerization processes in electrical discharges, has proposed referring to plasna polymerization as "elementary" or "atomic," since the feed materiel, referred to as a “nononer," may undergo substantial destruction in @ plas- ma and the polymer may not be made up of elenents or parts of the "monomer" which simultane- ously play an inportant role in maintaining the discharge. In our opinion it fe appropriate to datroduce a special term which substantially restricts the content of the term “plasma polymerization", since this process encompasses both the synthesis of a high molecular prod- uct and its modification during the formation process. In addition, the mechanism for this effect is known only in general ovt2ine and different particle species (uncharged molecules and radicals, positive and negative tons, electrons, etc.) may participate in it depending fon the conditions. We shall designate by plasma polymerization a process in witich an initial Jow molecular substance introduced into an electrical discharge is converted into high molec- ular products in the gas phase or on the reactor walls. In this case we shall refer to the initial low molecular material from which the high molecular product is mainly formed as the monomer. Plasma polymerization is usually done in glow discharges at low pressures (2-10" Pa). As a result of the polymerization of, for example, organic compounds on surfaces adjacent to the active zones of a discharge or its afterglow, polymer fiims are formed and powders may be deposited. Substantial interest in polymerization in plasmas, which was apparently first observed in 1874 [2], developed in the end of the 1950's and beginning of the 1960's in connection with the development of electronics, where polymer films obtained in plasmas were used as dielectrics in the manufacture of condensers. ‘The number of papers dealing with the forma- tion of polymer films has subsequently increased up to the present time owing to their ex- panding practical application in such areas as electronics, optics, the production of bio- medical materials, the textile industry, the manufacture of semipermeable membranes for sep- aration of Liguid and gaseous mixtures, corrosion protection, instrument manufacture, chemical technology, and so on. The widespread uses are explained by the valuable, often unique, properties of these polymer films: chemical stability, structural continuity, good adhesion, high optical and electrical parameters, mechanical strength, etc., in a thin (0-01-10 uy) ma- terial that 1s relatively simple to ob¢ain. It is important that the chemical composition and structure and, therefore the properties of a polymer film can be varied over wide limits. Although the plasma chemical technology for producing thin polymer filas has entered widespread use in industry and a large amount of information on che growth kinetics and prop- erties of polymer films hag been accumulated, the mechanism for their formation has not yet been clarified. This is explained by the extreme complexity of plasma chemical processes in a {Lim-producing plasma, by the variety of reactions, end products, and intermediate products, by the inadequate development of experimental methods for studying such systems, and by the small amount of research that has been done both on the properties of low-temperature non- equilibrium plasmas in molecular gases and on the processes that cake place on surfaces. the properties of polymer films, their practical applications, and the possible mechan- isms for their formation are rather fully reflected in a cumber of reviews and books [3-18]; K.-V> Topeliev thst itute of Petrochemical Synthesis, USSR Academy of Sciences. Trans=— lated from Khimiya Vysokikh Energii, Vol. 20, No. 3, pp. 195-214, May-June, 1986. Original article submitted January 5, 1984. 0018-1439/86/2003-0145$12-50© 1986 Plenum Publishing Corporation 145ae pdty => (4 Fig. 1. The most widely used types of laboratory plas~ ma chemical glow-discharge reactors for studying poly- merization processes in plasmas: a) dc discharge tubes b) rf discharge tube with exzernal electrodes; ¢) c} Lindtical rf reactor with inductive excitation; 4) tubu- lar rf reactor with internal electrodes and a rectangu- lar channel; ¢, £) "plane condenser" type reactors under bell jars. lus, the purpose of the present review is primarily to analyze the state and methodology f research on gaseous discharge polymerization aud ¢o clarify the main approaches and trends mn the Literature. EXPERIMENTAL FOUNDATIONS OF GASEOUS DISCHARGE POLYMERIZATION 2. Experimental apparatus. atus, Low-temperature nonequilibrium plasmas are usually produced n dey Comercial and low Frequency (<10 kitz) ac, rf (1-50 Milz), or microwave (1-5 Giz) elec- rical discharges in gases (vapors) at low pressures (1-10° Pa) or atmospheric pressure. The onequilibrium plasma is an ionized gas (degree of Jontzation 107+-10-*) in which the tenpera~ ure (translational energy) of the heavy pare{cles (atons, molecules, radicals, ions) is sev- ral orders of magnitude lower than the temperature (translational energy) of the electrons. nthe plasmas the gas is cold (300-1000°K) and the electrons are "heated" to 10*-107*K. Thus, he plasma contains excited and charged particles and radicals in suprathermal concentrations. body placed in this plasma is subject only to surface interaction and its volume properties re not changed. ‘The surface of a body in contact with the plasma is subject to intense bombardment by etive particles and UV radiation. Each of these particles can produce some local effect on he surface material depending on its translational or internal energy: transfer energy to he surface, kaock off one atom or a group of atoms, remove an adsorbed particle, form a free tence (surface radical) on the surface, form a chemical bond between neighboring atoas in the urface layer, and a particle from the gaseous phase may be joined to the surface by a chem- cal bond. These processes can be controlled by varying the chemical composition of the {ni- ial gas, the pressure, the discharge power, the surface potential, etc. From this it is lear that this kind of plasma 1s a uniquely delicate instrument for acting on material sur- Polymer films are usually obtained and studied in low-pressure glow discharges, and some- Imes in Low-power atmospheric-pressure corona discharges [19]. These discharges ave distin- ulshed bya greater disequilibrium, by a wide range of parameters of the plasma generated in tem, and by ease of control. RE discharges occur most widely. They are used both in labor- vory studies and in industrial technology. dc and low-frequency ac discharges are less often sed, since formation of polymer films on the electrodes inhibits stable operation of the dis- arge and requires the use of specially-designed electrodes, such as heated electrodes. Mi- rowave dischargeshave not as yet found wide application, low-pressure glow-discharge apparatus consist of a vacuum system, a reactor, and a gen- rator (discharge power supply). The reactor is usually a metallic or glass bell jar with a lameter of 0.2-0.5 mand internal electrodes or a glass (quartz alundum) cylinder with an ceerual excitation winding or external or internal electrodes. Plasma chemical apparatus pr production vf polymer films are compatible with existing equipment for vacuum metalliza- lon, reactive sputtering, etc, Different types of reactor have beendescribed inRefs. 5 and16, 6