Electroless Copper

Many electroless coppers also have extended process Hves. Bailout, the process solution that is removed and periodically replaced by Hquid replenishment solution, must still be treated. Better waste treatment processes mean that removal of the copper from electroless copper complexes is easier. Methods have been developed to eliminate formaldehyde in wastewater, using hydrogen peroxide (qv) or other chemicals, or by electrochemical methods. Ion exchange (qv) and electro dialysis methods are available for bath life extension and waste minimi2ation of electroless nickel plating baths (see... 

Electroless copper solutions underwent similar development during the same period (10). Early printed circuit boards used mechanically attached eyelets to provide electrical conductivity between the copper sheathing laminated on two sides of a plastic board. Electroless copper plating provided a less expensive, better conductive path, allowing much greater numbers and smaller sizes of holes. Later, electroless coppers even replaced the laminated bulk copper sheathing in the semiadditive and additive processes (see Copper). 

The ideal electroless solution deposits metal only on an immersed article, never as a film on the sides of the tank or as a fine powder. Room temperature electroless nickel baths closely approach this ideal electroless copper plating is beginning to approach this stabiHty when carefully controUed. Any metal that can be electroplated can theoretically also be deposited by electroless plating. Only a few metals, ie, nickel, copper, gold, palladium, and silver, are used on any significant commercial scale. 

Electroless reactions must be autocatalytic. Some metals are autocatalytic, such as iron, in electroless nickel. The initial deposition site on other surfaces serves as a catalyst, usually palladium on noncatalytic metals or a palladium—tin mixture on dielectrics, which is a good hydrogenation catalyst (20,21). The catalyst is quickly covered by a monolayer of electroless metal film which as a fresh, continuously renewed clean metal surface continues to function as a dehydrogenation catalyst. Silver is a borderline material, being so weakly catalytic that only very thin films form unless the surface is repeatedly cataly2ed newly developed baths are truly autocatalytic (22). In contrast, electroless copper is relatively easy to maintain in an active state commercial film thicknesses vary from <0.25 to 35 p.m or more. 

Process Control. Some hot nickel and flash electroless copper solutions are plated to the point of exhaustion and then discarded. Most baths are formulated to give bath fives of >6 turnovers of the bath constituents some reach steady-state buildup of the by-products and can be used indefinitely. AU. regenerable solutions should be filtered to remove particulates that can cause deposit roughness and bath instability. 

Adequate ventilation is necessary for aH process lines to ensure worker safety. Electroless copper baths must have good ventilation to remove toxic formaldehyde vapors and caustic mist generated by the hydrogen evolution reactions and air sparging. Electroless nickels need adequate ventilation to remove nickel and ammonia vapors. Some states and municipalities requite the removal of ammonia from wastewaters. A discussion of printed circuit board environmental issues and some sludge reduction techniques is avaHable (25). 

Electroless nickel or nickel—lead alloys can improve the solderabiUty and braisabiUty of aluminum even when a continuous film is not present. Electroless nickel systems based on dimethylaminehorane reduciag agents are used to coat aluminum contacts and semiconductors (qv) ia the electronics iadustry. Newer uses iaclude corrosion-resistant electroless nickel topcoatings on electroless copper plating for radio frequency... 

Numerous variations exist in the electroless plating solutions, processes, and techniques employed both in laboratory and commercial form, to create a great variety of products (39). AH produce a layer of highly conductive copper in specified areas. Modem electroless copper films have a ductiHty and conductivity identical to that of electrolytic copper (40). The three basic classes of copper baths are... 

Fig. 2. Multilayer printed circuit board composite. Constmction is multiple layers of epoxy—glass and foil copper. Foil copper outermost layer and drilled through-holes are sequentially plated with electroless copper, electrolytic copper, electroless nickel, and electroless gold.

The cost of the chemicals used in electroless copper plating is very low, rarely exceeding 2.78/m, except for fully additive processes. The principal costs of printed circuit board production arise mainly from handling steps and other operations. 

SemiadditiveMethod. The semiadditive method was developed to reduce copper waste. Thin 5.0 lm (4.5 mg/cm ) copper foil laminates are used, or the whole surface may be plated with a thin layer of electroless copper. Hole forming, catalysis, and electroless copper plating are done as for subtractive circuitry. A strippable reverse—resist coating is then appHed. Copper is electroplated to 35 p.m or more, followed by tin or tin—lead plating to serve as an etch resist. The resist is removed, and the whole board is etched. The original thin copper layer is quickly removed to leave the desired circuit. This method wastes less than 10% of the copper. 

Yullj Additive Method. No electrolytic plating step is used ia the fully additive process. The copper circuit is formed directly on the board without a continuous copper film. Heavy-build electroless coppers are used to iacrease the final thickness of the entire circuit. This process is much more difficult to control than the others. Additive processiag is becoming increasingly important ia high aspect ratio, very small diameter through-holes that caimot be easily electrolyticaHy plated. 

Electroless Copper. Electroless copper, iatroduced ia the mid-1950s (41,43), is available commercially ia great variety. Eormaldehyde is usually the reduciag agent, copper sulfate (occasionally copper nitrate or copper chloride) is the metal salt, and sodium hydroxide is used to control pH. 

Chemical reduction is used extensively nowadays for the deposition of nickel or copper as the first stage in the electroplating of plastics. The most widely used plastic as a basis for electroplating is acrylonitrile-butadiene-styrene co-polymer (ABS). Immersion of the plastic in a chromic acid-sulphuric acid mixture causes the butadiene particles to be attacked and oxidised, whilst making the material hydrophilic at the same time. The activation process which follows is necessary to enable the subsequent electroless nickel or copper to be deposited, since this will only take place in the presence of certain catalytic metals (especially silver and palladium), which are adsorbed on to the surface of the plastic. The adsorbed metallic film is produced by a prior immersion in a stannous chloride solution, which reduces the palladium or silver ions to the metallic state. The solutions mostly employed are acid palladium chloride or ammoniacal silver nitrate. The etched plastic can also be immersed first in acidified palladium chloride and then in an alkylamine borane, which likewise form metallic palladium catalytic nuclei. Colloidal copper catalysts are of some interest, as they are cheaper and are also claimed to promote better coverage of electroless copper. 

Electroless nickel baths are usually preferred to electroless copper, since they tend to be more stable and are less likely to deposit metal on unwanted areas, such as plating racks. Electrolytic copper is then plated before the final application of nickel and chromium, where this is the required finish, as it... 

Under micro-discontinuous chromium coatings, copper undercoats improve corrosion resistance. On non-conductors, especially on plastic substrates, copper is often applied before nickel-chromium plating over the initial electroless copper or nickel deposit in order to improve ductility and adhesion, e.g. as tested by the standard thermal-cycling test methods ... 

Thorough rinsing between the pretreatment steps is essential to prevent carry-over of solutions. The commonest plastic plated is ABS (acrylonitrile butadiene styrene copolymer) but procedures are also available for polypropylene and other plastics. In some proprietary processes, electroless copper solutions are used to give the initial thin conducting layer. 

More recently, Wiese and Weil" reported a detailed study of the mechanism of electroless copper deposition with formaldehyde from alkaline ethylenediamine-tetraacetate (EDTA)-containing solutions. The partial reactions were expected to be... 

DSA-02 oxide-coated Ti anode (DSA = Dimensionally Stable Anode) is placed, thus creating a large cathode volume. The effluent solution flows perpendicularly through the electrodes with a typical flow rate of 0.5 dm3 s-1. The flowthrough metal electrodes have an active area approximately 15 times their geometric area. The cell allows air sparging to increase the mass-transfer. The current efficiency is about 40% when the inlet concentration of the metal ions is 150 to 1500 ppm and the concentration at the out-let is about 50 ppm. The cell is currently used for the treatment of recirculated wash-waters from acid copper, copper cyanide, zinc cyanide, zinc chloride, cadmium sulphate, cadmium cyanide and precious metal plating and washwaters from electroless copper deposition. Since the foam metal electrodes are relatively expensive the electrodes... 

Peng, Y. and Q. Chen, Fabrication of copper/multi-walled carbon nanotube hybrid nanowires using electroless copper deposition activated with silver nitrate. Journal of The Electrochemical Society, 2012.159(2) p. D72-D76. 

Electroless Deposition of Copper. The basic ideas of the mixed-potential theory were tested by Paunovic (10) for the case of electroless copper deposition from a cupric sulfate solution containing ethylenediaminetetraacetic acid (EDTA) as a complexing agent and formaldehyde (HCHO) as the reducing agent (Red). The test involved a comparison between direct experimental values for and the rate of deposition with those derived theoretically from the current-potential curves for partial reactions on the basis of the mixed-potential theory. 

Thus, one concludes that the mixed-potential theory is essentially verified for the case of electroless copper deposition. These conclusions were later confirmed by Donahue (15), Molenaar et al. (25), and El-Raghy and Abo-Salama (33). The mixed-potential theory has been verified for electroless copper deposition as well using hypophosphite as the reducing agent (72). 

Interaction Between Partial Reactions. The original mixed-p)otential theory assumes that the two partial reactions are independent of each other (1). In some cases this is a valid assumption, as was shown earlier in this chapter. However, it was shown later that the partial reactions are not always independent of each other. For example, Schoenberg (13) has shown that the methylene glycol anion (the formaldehyde in an alkaline solution), the reducing agent in electroless copper deposition, enters the first coordination sphere of the copper tartrate complex and thus influences the rate of the cathodic partial reaction. Ohno and Haruyama (37) showed the presence of interference in partial reactions for electroless deposition of Cu, Co, and Ni in terms of current-potential curves. 

Kinetic Scheme. Generally, metal ions in a solution for electroless metal deposition have to be complexed with a ligand. Complexing is necessary to prevent formation of metal hydroxide, such as Cu(OH)2, in electroless copper deposition. One of the fundamental problems in electrochemical deposition of metals from complexed ions is the presence of electroactive (charged) species. The electroactive species may be complexed or noncomplexed metal ion. In the first case, the kinetic scheme for the process of metal deposition is one of simple charge transfer. In the second case the kinetic scheme is that of charge transfer preceded by dissociation of the complex. The mechanism of the second case involves a sequence of at least two basic elementary steps ... 

Figure 8.7. Potential sweep function for the partial cathodic process in electroless copper deposition dissociation and reduction of Cu(II)EDTA complex. (From Ref. 31, with permission from the Electrochemical Society.)...

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