09-Electrolytic_Copper_Plating_Additives_and_Contaminants.pdf

Electrolytic Copper Plating Additives and Contaminants Wayne Jones 2Electrolytic Copper Plating Chemistry Typical DC Acid Copper Electroplating Solution contains: Inorganic ? Sulfuric Acid (180 - 250 g/l) ? Copper Sulfate (40 - 100 g/l) ? Hydrochloric Acid (25 - 100 mg/l) Organic ? Brightener (2 - 10 mls/l) ? Leveler (5 - 15 mls/l) ? Carrier (25 - 100 mls/l) Water (Balance) 3Electrolyte Control Sulfuric Acid – Virtually unconsumed…Dragout Titration or Specific Gravity Copper Sulfate – Maintained by Anode Erosion Titration, UV/Vis Chloride – Maintained by chemical analysis Titration, Ion Specific Electrode, UV/Vis 4Additives – Mostly Proprietary Brighteners – are plating accelerators, which act as a micro-leveler and impact grain refinement. They tend to be attracted to cathode induction zone points of higher electro- potential, temporarily packing the area and forcing copper to deposit elsewhere. As the copper deposit levels, the local point of high potential disappears and the brightener drifts away, as well as depleting (hydrolysis) to a higher level of activity. Chemical Family - Organic Sulfides, Disulfides, Thioethers, Thiocarbamates. Levelers – are strong secondary plating inhibitors, which typically co-function with Brighteners to reduce copper growth at protrusions and edges. They improve mass transfer to localized sites of lesser electro-potential or feature height. Chemical Family – Quaternary Nitrogen Cmpd. Carriers – are plating inhibitors or suppressors, they create and maintain a defined diffusion layer at the Anode (which regulate the flow of Cu+2 ions into the electrolyte and ultimately to the cathode (board surface). Carrier depletion occurs as the PEG cleaves. Chemical Family – Polyethylene Glycol (PEG), Polyalkylene Glycol (PAG) Chlorides – mild plating inhibitors, which stabilizes the Cu+1 ion that serves as an intermediate in the electro-deposition process during reduction to Cu +2. Additionally they modify adsorption pr