Effect of Counter Ions in a Diallylamine-type Copolymer Additive on Via-filling by Copper Electrodeposition

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In previous studies of additives for via-filling by copper deposition, we succeeded in the complete filling of via holes by copper deposition through the use of a single diallylmethylamine-type additive instead of the conventional combination of four different additives. However, work had yet to be started on analyzing the structure and function of the polymer additive. Therefore, we synthesized a series of diallylmethylamine-type polymers with different polymer counter ions, and used these polymers as single additives in the basic bath for the copper electrodeposition. We studied the characteristics of the action of these additives using an optical microscope to observe the filling of the vias in the substrate, and by performing cyclic voltammetry (CV) and linear sweep voltammetry (LSV) measurements with a rotating disk electrode. Via-filling was not possible with the diallylmethylamine-type polymers containing counter ions such as acetate ions, but with polymers containing halogen counter ions, we achieved good via-filling and were able to observe clear hysteresis in the CV curves.
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