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2/ Electroless Plating 27.1. Introduction 27-1 27.2. Plating Systems, 27-2 27.3. Electroless Plating Solutions. 27-3 Deposition Rate» Solution Life Reducing Agent Eiiency Factor + Solution Sensitivity to Activation 27.4. Practical Applications 27-4 27.5. Mechanisms of Autocatalytic Metal fon Reduction ....27-5 27.6 Stability of Plating Solutions. 27-7 27.7. Electroless Plating. 27-7 Copper Deposition + Nick Plating» Cobalt, on, and Tin lating » Deposition of Precious Metals Deposition of Metal ‘Alloys A. Vakelis, 27.8. Properties of Chemically Deposited Metal Coatings...27-10 “echuanin Academy of Scences References 27-11 27.1 Introduction In electroless plating, metallic coatings are formed as a result of a chemical reaction between the reducing, agent present in the solution and metal ions. The metallic phase that appears in such reactions may be obtained either in the bulk of the solution or as a precipitate in the form of a film on a solid surface. Localization of the chemical process on a particular surface requires that the surface must serve as a catalyst. Ifthe catalyst isa reduction product (metal) itself, autocatalysis is ensured, and in this case, it is possible to deposit a coating, in principle, of unlimited thickness. Such autocatalytic eactio the essence of practical processes of electroless plating. For this reason, these plating processes are sometimes called autocatalyti, Electroless plating may include metal plating techniques in which the metal is obtained as a result of the decomposition reaction of a particular compound; for example, aluminum coatings are deposited during decomposition of complex aluminum hydrides in organic solvents. However, such methods are rate, and their practical significance is not great. Ina wider sense, electroless plating also includes other metal deposition processes from solutions in Which an external electrical curtent is not used, such as immersion, and contact plating methods in which another more negative (active) metal is used as a reducing agent. However, such methods havea limited, application; they are not suitable for metallization of dielectric materials, and the reactions taking place are not catalytic. Therefore, they usually are not classified as electroless plating. Electroless plating now is widely used in modifying the surface of various materials, such as noncon- ductors, semiconductors, and metals. Among the methods of applying metallic coatings, itis exceeded. in volume only by electroplating techniques, and itis almost equal to vacuum metallization. Electroless plating methods have some advantages over similar electrochemical methods. These are as follows: constitute 271 272. Coatings Technology Handbook, Third Edition 1. Coatings may be deposited on electrically nonconductive materials (on almost any surface that is stable in electroless plating solutions). Coatings have more uniform thickness, irrespective of the shape of the produet to be plated. 3. Deposition is simple — itis enough to immerse the (pretreated) product in the electroless plating, solution, 4, Itis possible to obtain coatings that have unique mechanical, magnetic, and chemical properties. Application of electroless plating, in comparison with electroplating techniques, is limited by two factors: (a) it is more expensive because the reducing agent costs more than an equivalent amount of electricity, and (b) it is less intensive because the metal deposition rate is limited by metal ion reduction in the bulk of the solution. 27.2 Plating Systems “To ensure chemical reduction of metal ions in a solution, the solution must contain a sufficiently strong and active reducing agent; that is, it must have a sufliciently negative redox potential. The more easily the metal ions are reduced, the greater is the number of available reducing agents. Because only auto catalytic reduction reactions may be used successfully for deposition of coatings, the number of electroless plating Me-Red (metal-reducing agent) systems suitable for practice is not great (see Table 27.1). Currently known electroless plating methods may be used to deposit 12 different metals, including metals belonging to the groups of iron, copper, and platinum (the well-known catalysts of various reactions) as well as tin and lead (only one solution has been published for deposition of the latter) Although deposition of chromium and cadmium coatings is described in the patent literature, toca alytic reduction is not realized in these cases. Coatings are deposited on some metals by immersion plating only. Insome widely used processes, the deposition of metal is accompanied by precipitation ofthe reducing agent decomposition products — phosphorus and boron — and so, the respective alloys are obtained. tis not difficult to deposit two or more metals ata time; electroless plating methods are known for deposition of more than 50 alloys of different qualitative composition, mostly based on nickel, cobalt, and copper. ‘The majority of reducing agents used in electroless plating are hydrogen compounds, in which H is ked to phosphorus, nitrogen, and carbon. It isin the reactions of these compounds that significant lytic effects are possible because in the absence of catalysts, these reactions proceed slowly. ‘The most effective autocatalysis is obtained when the strongest reducer — hypophosphite — is used. In the absence of catalyst, the reducer is inert and does not react even with the strong oxidants; only a lis ‘TABLE 27.1. Coatings Obtained by Electroless Plating Reducing Agent Ment 7H Na COB, _AB, ‘Oihers NON OW NEB Ni Co CoP Co CoCo Fe Fee cu a a @ @ Ms Ag Ag ARR Ag au au AN ADA au PooomeP PP Rh Rh Rh Ru Rw Pr Pe me Pe si sn Pb Pb Electroless Plating 27.3 few catalysts ae suitable for it (eg, Ni, Co, and Pd), but they provide ora catalytic proces of the highest rate without reduction i the bulk of a solution. Other reducers ate more versatile, for example, by using borohydride, we may deposit coatings of almost all the metals mentioned. The reducing capacity of hydrogen compounds increases with an increase in pH of a solution. For this reason, the majority of electroless plating solutions are allaline. Such simple reducing agents as metal ions of variable valenees (Fe, Ce", and 7) usualy are not suitable for deposition of coatings, because noncatalytic reduction oceuss rather easily. Recently, condi tions have been established for autocataytic deposition of tin and silver coatings using as reducing agents such metal complexes as Sn(OH)? and Co(NH,) Depositons of some metals (Ag, Au, Cu) by chemical reduction techniques was known as long ago 2s the 19th century, but it became popular after Brenner found (in 1945) avery ecient electroless nickel plating process using hypophosphite. It was then that the term “electroless plating” was coined 27.3 Electroless Plating Solutions ‘The electroless plating solutions used in practice, in addition to the basic components (the salt of the ‘metal tobe deposited and a reducing agent), contain other substances a well. Usually these areas follows: 1. Ligands, which form soluble complexes with metal ions, are necessary for alkaline solutions. Also, the use of stable complexes sometimes enhances the autocatalytc elect, 2. Substances controlling and maint n pH value of the solution are used: buffer addi- tions ae especialy important, because in the course of metal eduction, hydrogen ions ae formed, 3, Stabilizers that decelerate reduction reaction in the bulk of a solution and, hence, enhance auto- catalysis can be used. ning a cert Sometimes, agents such as brighteners are also added to the solution. ‘The basic technological parameters of electroless plating solutions are discussed in Sections 27.3.1 through 27.3.4. 27.3.1 Deposition Rate Deposition rate usualy is expressed in micrometers per hour (jim/h; oF mil/h, tn./h, mgfem*h). In the course of deposition, ifthe concentrations of reacting substances are not maintained at a constant level, this rate decreases. The values given in the literature are ofien averages, rellecting only the initial period. Such average rates depend on the ratio of the surface to be plated to the solution volume (dm*/). ‘The dependence of the deposition rate (») on the concentration of reacting substances for a general case is rather complicated. It is often deseribed by empirical equations, for example: [Me [Real [HY (1) (ay Where kis the rate constant (a constant value fora system of the given type), and [Lis the concentration of a fiee ligand (not bound with metal ions in a complex). The exponents a and b are usually smaller than unity, which cis a negative value (in alkaline solutions OH-ion concentration is used, and in such a case, the exponent is often positive, O < ¢ < 1). Exponent d is usually close to zeros when the ligand. is substituted, however, the deposition rate may change substantially. With constant concentrations of other solution components, the deposition rate decreases when the stability of a metal complex increases (when the concentration of free metal ions is lowered); however, this relationship for a general case is not rigorous ‘The electroless deposition rate of most metals under suitable conditions is about 2 to 5 jm/h, and only electroless nickel plating rate may be as high as 20 jm/h (this corresponds to an electroplating process at current densities of 200 A/m:)