Analysis And Control Of Copper Plating Bath Additives And By-Products

New copper plating bath chemisties are being developed to meet the emerging need of plating copper into submicron features on semiconductor wafers. These chemistries are designed to provide a fast, efficient, fill for even the most challenging wafer terrain. It has been found that maintaining the concentration of the additives in these plating baths at certain levels is critical to the performance of the bath. Plating technology for semiconductor applications requires rigid bath control and disciplined methodology. Establishing correlations between what is found in the plated film and bath chemistry control parameters is fundamental in producing interconnects that are consistent and reliable. To establish these correlations, it is important to have a clear understanding of the chemical composition of the bath. It is theorized that the "suppressor" bath components help moderate the deposition rate of the copper fill and the "leveler" additives improve the topology of the copper overfill. Too much or too little of these components in the bath can be detrimental to the quality of the copper deposition and may result in "fill failure" leading to a higher than necessary scrap rate for the wafers. Indirect bath measurements, such as Cyclic Voltammetric Stripping (CVS), tell an incomplete story as these techniques only measures the combined effect of the additives and by-products on the plating quality. High Performance Liquid (HPLC) and Ion Chromatography are analytical techniques which provide important information on the concentration, chemical balance and trend measurement of major constituents such as additives, brighteners, boosters, stabilizers, carriers, levelers, inhibitors, accelerators, transition metals, metal complexes and contaminants in the plating bath. This information provides for improved device quality, reduced scrap rate and reduced costs of bath maintenance. This, however, is not the end of the story. In addition to additives, copper plating baths also contain process byproducts. This paper will cover the development of analytical methods using metal free liquid chromatography to quantify the components and any related by-products found in copper plating baths used for small-featured semiconductors..