Investigation of the influence of a model additive system on copper electrodeposition: Integration of experiments on the surface morphology evolution with multiscale simulation

A novel procedure was applied to develop two multiscale simulation models for the simulation of copper trench infill and copper nucleation on foreign substrates. In the development of the copper trench infill model, two sets of sophisticated chemistry models that included series of chemical reactions and assumptions were proposed to account for additive chemistry when copper was electrodeposited on a copper surface. The chemistry models were successfully embedded into previously developed simulation codes. A high throughput impinging jet cell was constructed to perform all the copper electrodeposition experiments based on D-optimal design. The root mean square surface roughness of each copper deposit that was measured from AFM images, together with potential responses, was used to estimate the sensitive kinetic parameter values associated with the multiscale simulation model. Successful simulation of copper trench infill process was accomplished with use of the estimated parameter values. Final simulation results were carefully analyzed and the detailed mechanisms of trench infill process were discussed.; In the development of copper nucleation model, a chemistry model describing the influences of additives on copper electroplating kinetics on polycrystalline gold was proposed, which was mostly derived from experimental results. This model was written into a multiscale simulation code to simulate surface kinetics controlled copper nucleation behaviors on foreign substrates. Copper was galvanostatically deposited onto a rotating gold disk electrode according to the conditions set by an appropriate D-optimal experimental design matrix, and transient potential responses were recorded. A high throughput bipolar electrochemical cell was constructed so that copper can be deposited onto a bipolar gold electrode under various conditions by following the same experimental design matrix. Copper nuclei along the gold electrode were examined by AFM and further characterized by ImagePro software. The potential responses obtained from gold rotating disk electrode and copper nuclei characterizations from AFM images will be used in future work to estimate the unknown kinetic parameters in the multiscale simulation model.; In the last chapter, copper electroplating behavior on electrodeposited ruthenium surface was briefly discussed.