Copper electroplating additives

The first commercial boards usiag electroless plating for connection between the sides were made by Motorola ia 1953 (41). An unclad plastic board was coated with electroless silver, a reverse resist appHed, and copper electroplated to the required circuit thickness. The resist and excess silver were removed. This semi-additive process is stiU used, with copper replacing the silver. 

Copper sulfate can be described as a by-product of copper refining that is obtained by crystallization of the weak liquor. The copper sulfate precipitate formed is centrifuged, dried, screened, and finally packaged in bags and drum. However, it is produced in some chemical industries by reacting copper shot with sulfuric acid, air, and water. It is widely used as an insecticide, additive nutrients (for soils that are deficient in copper), copper electroplating, wood preservation, and in petroleum refining. 

Metal Coatings. Tellurium chlorides, as well as tellurium dioxide in hydrochloric acid solution, impart permanent and attractive black antique finish to silverware, aluminum, and brass. Anodized aluminum is colored dark gold by tellurium electro deposition. A solution containing sodium tellurate and copper ions forms a black or blue-black coating on ferrous and nonferrous metals and alloys. Addition of sodium tellurite improves the corrosion resistance of electroplated nickel. Tellurium diethyldithiocarbamate is an additive in bright copper electroplating (see Electroplating). 

Anodes. There are two types of anodes soluble and insoluble. Most electroplating baths use one or the other specifically however, a few baths use either or both. Chromic acid plating baths use insoluble anodes alkaline zinc cyanide baths use both noncyanide alkaline zincs may use either. Soluble anodes are designed to dissolve efficiendy with current flow and preferably, not to dissolve when the system is idle. A plating solution having the anode efficiency close to the cathode efficiency provides a balanced process that has fewer control problems and is less cosdy. If the anode efficiency is much greater than the cathode efficiency and there are only small solution losses, the dissolved metal concentration rises until at some time the bath has to be diluted back or the excess metal has to be reduced by some other means. If the anode efficiency is less than the cathode efficiency, the dissolved metal decreases, pH decreases, and eventually metal salt additions and other solution corrections are required. Based on the cost of metal, it is usually considerably more economical to plate from the anode rather than add metal salt. Copper cyanide, for example, costs about twice as much to add than to dissolve a comparable amount of copper anode. Additionally, the anion added with the metal salt may build up in the plating solution. 

Pyrobrite [ATOTECH]. TM for a bright-leveling, pyrophosphate copper electroplating process. The materials used are copper pyrophosphate trihydrate, potassium pyrophosphate, ammonium hydroxide, and addition agents. 

Healy, J.P., Pletcher, D., and Goodenough, M. (1992) The chemistry of the additives in an acid copper electroplating bath part I. Polyethylene glycol and chloride ion. Electroanal. Chem., 338 (1), 155-165. 

The negative resist pattern is used to selectively build up the circuit by copper electroplating. When the required conductor thickness (typically 17 or 35 pm) is reached, it is plated with tin, tin-lead or gold as a positive resist. Removal of the resist is followed by rapid etching of the electroless copper layer. The remainder of the process is similar to that for subtractive methods. In the "folly additive method, the full conductor thickness may be built up in a single, long (24 h) electroless deposition stage. 

There has been a continual increase in size and complexity of PCBs with a concurrent reduction in conductor and hole dimensions. Conductors can be less than 250 p.m wide some boards have conductors less than 75 pm wide. Multilayer boards greater than 2.5 mm thick having hole sizes less than 250 pm are being produced. This trend may, however, eventually cause the demise of the subtractive process. It is difficult to etch such fine lines using 35-pm copper foils, though foils as thin as 5 pm are now available. It is also difficult to electroplate holes having high aspect ratio. These factors may shift production to the semiadditive or fully additive processes. 

On ferrous metals immersion deposition in the copper sulphate bath produces non-adherent deposits, and a cyanide copper undercoat is therefore normally used. Where the use of a cyanide strike cannot be tolerated, an electroplated or immersion nickel deposit has been used . Additions of surface-active agents, often preceded by a sulphuric acid pickle containing the same compound, form the basis of recent methods for plating from a copper sulphate bath directly on to steel ". 

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