There are a variety of different electrolyte chemistries that can be used for copper electroplating, but most can be broadly characterized into five general categories based on the complexing agent: • Alkaline
cyanide • Alkaline non-cyanide • Acid
sulfate • Acid
fluoroborate •
Pyrophosphate Alkaline cyanide Alkaline cyanide baths have historically been one of the most commonly used plating chemistries for copper electrodeposition. Cyanide copper baths typically provide high covering and
throwing power, allowing uniform and complete coverage of the substrate, but often plate at lower
current efficiency. Baths may also contain
Rochelle salts and
sodium or
potassium carbonate, as well as a variety of proprietary additives. with industrial applications that include decorative plating,
electroforming,
rotogravure, and
printed circuit board and semiconductor fabrication. Acid sulfate baths contain
cupric sulfate as the source of copper(II) ions;
sulfuric acid to increase bath conductivity, ensure copper salt solubility, decrease anode and cathode polarization, and increase throwing power; and a source of
chloride ions such as
hydrochloric acid or
sodium chloride, which helps reduce anode polarization and prevents striated deposits from forming. Variations of the acid copper electrolyte include general-purpose baths, high-throw baths, and high-speed baths. The high-throw and high-speed baths are used when greater throwing power and faster plating rates are required, including for printed circuit board fabrication where high throw is required to plate the low-current-density areas in the through holes. • Suppressors (also known as inhibitors or carriers) (typically polyethers such as
polyethylene glycol or
polypropylene glycol) • Accelerators (also known as brighteners) (typically thiols or disulfides such as
3-Mercapto-1-propanesulfonic acid or
bis-(3-sodium sulfopropyl) disulfide) • Levelers (examples include dyes such as
Janus Green B,
Alcian Blue, and Diazine Black) Without these additives, copper will preferentially deposit on the surface near the top of the vias instead of inside the vias due to the lower local current density inside the vias, leading to top-down via filling and undesirable voids. The suppressor inhibits plating near the top of the via and the surface, while the brightener accelerates plating near the bottom of the via. The leveler helps prevent buildup at the via opening and creates a smoother surface finish.
Acid fluoroborate Copper fluoroborate baths are similar to acid sulfate baths, but they use fluoroborate as the anion rather than sulfate. Pyrophosphate baths contain cupric pyrophosphate as a source of copper(II) ions, potassium pyrophosphate as a source of free
pyrophosphate that increases bath conductivity and helps with anode dissolution,
ammonia for increased anode dissolution and deposit grain refinement, and a source of
nitrate ions such as
potassium or
ammonium nitrate to decrease cathode polarization and increase the maximum allowed current density. When the bath is made up, the copper pyrophosphate and potassium pyrophosphate react to form a complex, [K6Cu(P2O7)2], which dissociates to form the Cu(P2O7)26− anion from which copper deposits. Variations of the pyrophosphate electrolyte include general-purpose baths, strike baths, and printed circuit baths. Printed circuit baths typically contain organic additives to improve ductility and throwing power. In pyrophosphate baths,
orthophosphate ions are formed from the hydrolysis of pyrophosphate and tend to build up in the electrolyte over time, which presents maintenance challenges. Orthophosphate ions decrease bath throwing power and deposit ductility at concentrations above 40–60 g/L, and they lead to lower solution conductivity, banded deposits, and lower bright current density range at concentrations beyond 100 g/L. Orthophosphate is removed from the bath by either doing partial bails and dilutions or by completely dumping and remaking the bath. ==Current control==