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Polyvinylpyrrolidone (PVP) is studied in this paper as an inhibitor of cobalt electrodeposition. The suppression effect of PVP was analyzed through electrochemical methods, including cyclic voltammetry (CV) and galvanostatic measurements (GM) tests. It is indicated that PVP effectively suppresses the electrodeposition of cobalt and chloride ion accelerates this suppression. Further experiments verify that PVP inhibits the deposition of cobalt through the adsorption on the electrode surface. Quantum chemical calculations were employed to calculate the molecular orbitals of PVP and the electrostatic potential (ESP) energy of the involved molecules. The simulation results imply that the amide group acts as the main electrophilic attack region and facilitates nucleophilic reactions to bond with cobalt. High aspect ratio trench filling on silicon wafer was achieved with the addition of PVP, which confirms that PVP is an applicable inhibitor for the practical electrodeposition of cobalt filling. The mechanism of cobalt trench filling was proposed to explain the role of PVP in the electroplating filling. Besides, crystalline and morphological characterizations reveal that PVP is able to inhibit the specific crystal growth of cobalt, especially the growth of 220 crystal plane, affect the crystal morphology of cobalt and improve surface compactness.

A novel additive system comprising bis-(sodium sulfopropyl)-disulfide, polyethylene glycol and hydroquinone (HQ) was developed and investigated to achieve high rate copper electrodeposition at high temperature. HQ, as the key additive compound in this system, refines the Cu grain, makes the coating surface bright and smooth at high current density. The underlying mechanism of the additive-assisted electroplating was investigated through electrochemical, morphological characterizations and molecular dynamics simulation. Nanocubical copper particles were found through chronoamperometry tests, which explains the fine crystalline Cu grains and the bright coating surface. Additionally, the formation of the nanocubical copper particles is caused by the different adsorption energies of HQ on (311), (111) and (220) crystal faces and further leads to a strong suppression on the (220) orient crystal faces. Moreover, the electroplating results of through-holes illustrate the feasibility of this additive system in practical applications.