Electrodeposition is a prevailing method in fabrication of Cu interconnects in microelectronics due to its ability to fill complex structures having a wide range of critical dimensions. A typical acidified Cu electrolyte contains a number of additives, organic and inorganic species in ppm amounts, with a specific role in the plating process. The additives in Cu plating have been extensively studied in the past couple of decades, and grouped according to their role in filling/creating features for microelectronics applications. This categorization is not a uniform one, and it might differ from author to author. In one popular convention, organic additives in the so-called three-component plating bath are named accelerator, suppressor and leveler, with their names hinting at how they influence Cu deposition. Ultimately, it is thanks to these additives that defect-free Cu features ranging from tens of nanometers to hundreds of micrometers can be economically fabricated.

However, it is not enough to successfully fill a given single feature. The same has to be done for all the features on a 300 mm wafer, and then performed reproducibly over and over again. So, one needs to monitor the state of the electrolyte, i.e. of all the bath constituents, and either replace or replenish the electrolyte when the need arises. Additives could also have a strong influence on the physical properties of the deposit and therefore have a strong influence on the post-plating processing results. An additive that promotes void-free deposition of Cu structures in the end might not be used in a production line if it creates issues in the processing steps following electrodeposition.

In our presentation we focus on a number of specific examples showing the effect of additives on nucleation and growth of Cu, propagation of Cu fronts on resistive substrates, post-plating processing, and their use in substrate surface modifications. A closer look is taken into in situ microscopic and electrochemical techniques and their use in studies of electrochemical nucleation and growth of Cu. We discuss advantages and drawbacks of potential step and galvanostatic deposition techniques in determining nucleation and growth parameters, and selection criteria for additive sets for a given plating task. We demonstrate that substrate surface modifications prior to plating could help simplify bath composition, i.e. eliminate need for some additives in the electrolyte, or improve the filling performance of the given plating bath. We also give examples of additives that promoted void-free filling of features but also influenced physical/mechanical properties of the final product in such a way that rendered it unusable in a specific application.