Toward Preeminent Throwing Power from a Novel Alkaline Copper Electronic Electroplating Bath with Composite Coordination Agents

Graphical Copper Electronic Electroplating : A novel copper electroplating bath in weak alkalinity and containing citrate (Cit) and ethylenediamine (En) in the through-hole thickening of printed circuit board (PCB) was presented. The selective adsorption of Cit−Cu and En−Cu coordination ions at different sites was driven by respective overpotential in TH of PCB for conformal copper electroplating. In this work, an electronic copper electroplating bath with low copper ion concentration and preeminent throwing power in through hole (TH) thickening of the printed circuit board (PCB) was successfully developed. Based upon the weak alkaline bath containing the composite complexants of citrate (Cit) and ethylenediamine (En), their synergistic effects on the preeminent bath throwing power were carefully investigated and theoretically proved. The UV-vis spectroscopy results illustrated that En exhibited a stronger coordination ability with Cu (II) ion than citrate, and the stoichiometric coordination ratio between En and Cu (II) ion was 2 : 1. The linear sweep voltammetry (LSV) results showed that the electro-reduction peak potential of Cit−Cu coordination ion was −0.55 V (vs. Hg/HgO), whereas that of En−Cu ion was at a more negative potential of −0.82 V. The in situ Fourier transform infrared (FTIR) spectroscopy revealed that the adsorptions of the Cit−Cu and En−Cu coordination ions were potential dependent on the copper electrode. The Cit−Cu coordination ion was easily adsorbed at the interior sites of through holes with lower over-potential to promote the growth of copper coating. Moreover, the En−Cu coordination ion adsorbed preferably on the surface and the edge of through hole for its higher electro-reduction overpotential, to hinder the germinating of copper nuclear. The cross-section observation of optical microscope proved that the throwing power of novel copper electroplating bath behaved surpassingly, up to 105.8 %.