Aging influence of poly(ethylene glycol) suppressors of Cu electrolytes on gaps filling

In this study, we investigate how the degradation of poly(ethylene glycol) (PEG) additives in Cu electroplating electrolytes influences the gaps filling of damascene features and the roughness of plated surfaces. The cleavage of PEG, whose reaction is enhanced by a high bias current and more plating cycles, not only diminishes the inhibition effect of the electrolytes, but also enables the formation of enormous complexes of short-chain PEG-Cu far from the reacting surfaces. Hence, the more plating cycles performed, the worse the gaps filling characteristic and the rougher the plated surfaces. Furthermore, an overshoot phenomenon on the transient cells voltage for PEG-containing electrolytes is observed and explained well by a dynamic equilibrium between PEG absorption ability and Cu reduction speed. Accordingly, the change in overshoot shape is closely related to PEG aging and this fact is employed to examine the reliability of electrolytes.