Abstract: The concentration of chloride ion in an acid copper electroplating bath is determined from the effect that chloride exerts on the copper electrodeposition rate in the presence of organic additives. A cyclic voltammetric stripping (CVS) rate parameter is measured, before and after standard addition of a plating bath sample, in an acid copper electrodeposition solution containing little or no chloride and at least one organic additive. Cross contamination and waste disposal issues associated with the reagents and reaction products involved in chloride titration analyses are avoided. The method may also be applied to analysis of other halides (bromide and iodide) and other solutions.

Abstract: In the present invention, the test reference electrode used for voltammetric analysis of a plating bath is calibrated relative to the zero-current point between metal plating and stripping at a rotating platinum disk electrode in the plating bath supporting electrolyte. This calibration is readily performed during the normal course of cyclic voltammetric stripping (CVS) or cyclic pulse voltammetric stripping (CPVS) plating bath analysis the need for additional instrumentation or removal of the test reference electrode from the analysis equipment. Automatic calibration of the reference electrode enabled by the present invention, saves labor, time and expense, and minimizes errors in the plating bath analysis.

Abstract: Acid copper electroplating baths used to form ultra-fine circuitry features on semiconductor chips contain suppressor, anti-suppressor and leveler additives that must be closely controlled in order to obtain acceptable copper deposits. Cyclic voltammetric stripping (CVS) methods are available to measure the concentrations of the suppressor and anti-suppressor based on the effects of these additives on the copper electrodeposition rate. The present invention is a method that also uses measurements of the copper electrodeposition rate to determine the concentration of the leveler additive. The other two additives are included in the measurement solution at concentrations determined to provide the optimum compromise between minimal interference, high sensitivity and good reproducibility for the leveler analysis.

Abstract: Acid copper electroplating baths used to form ultra-fine circuitry features on semiconductor chips contain suppressor, anti-suppressor and leveler additives that must be closely controlled in order to obtain acceptable copper deposits. Cyclic voltammetric stripping (CVS) methods are available to measure the concentrations of the suppressor and anti-suppressor based on the effects of these additives on the copper electrodepositionrate. The present invention is a method that also uses measurements of the copper electrodepositionrate to determine the concentration of the leveler additive. The other two additives are included in the measurement solution at concentrations determined to provide the optimum compromise between minimal interference, high sensitivity and good reproducibility for the leveler analysis.