[en] Additives having azole groups with different numbers of nitrogen atoms, such as indole, benzimidazole, indazole, benzotriazole (BTA), and 1H-benzotriazole-methanol (BTA-MeOH) were adopted to improve the mechanical hardness of electrodeposited Cu films. The effects of these additives on the film properties were elucidated in relation to their number of nitrogen atoms. Electrochemical current–potential behaviors showed that the additives containing three nitrogen atoms (BTA and BTA-MeOH) more effectively inhibited Cu electrodeposition. The inhibition strongly affected the film properties, resulting in reduced grain size and surface roughness, and increased resistivity and hardness. Cu films deposited with BTA or BTA-MeOH also exhibited 35% reduced grain size and 1.5-time higher hardness than Cu films deposited in electrolyte containing other BTA-derivatives having fewer nitrogen atoms. This notable grain refining effect of BTA and BTA-MeOH can be evaluated with respect to the strong interaction of their nitrogen atoms with the substrate and the copper ions, as well. - Highlights: • Additives of similar structure containing 1, 2, and 3 nitrogen atoms were used. • Additives with 3 nitrogen atoms more strongly inhibited Cu deposition than others. • Additives containing 3 nitrogen atoms efficiently affected film properties. • Additives having 3 nitrogen atoms remarkably improved film hardness

[en] Electrodeposition of Cu-based alloys has been researched for a variety of applications due to Cu-based alloys having superior properties compared to pure Cu, including higher chemical resistance, mechanical hardness, and electrocatalytic activity. Cu-Ag is the most electrically conductive among Cu-based alloys, and it has higher mechanical hardness and oxidation resistance compared to pure Cu. Cu-Ag co-deposition in cyanide-based electrolytes has been previously reported; however, the toxicity of cyanide limited its use. In this study, we introduce an ammonium hydroxide-based electrolyte for Cu-Ag electrodeposition and the properties of Cu-Ag films deposited in this electrolyte. Electrochemical measurements were performed to determine the potential range for co-electrodeposition of Cu and Ag, and the effect of nitrate reduction on the film deposition was examined. The effects of deposition potential and concentration of Ag ions in the electrolytes on the electrical resistivity and Ag contents of the films were investigated. The modulation of Ag ion concentration was found to be a more effective way to control Ag contents in the deposited films. Co-deposition of 4 at% Ag with Cu in the ammonium-hydroxide electrolyte markedly improved mechanical hardness and oxidation resistance compared to a pure Cu film without severe deterioration of electrical conductivity.

[en] Highlights: • The choline-based leveler having two quaternary ammoniums was synthesized. • The adsorption of this leveler with suppressor and accelerator was examined. • Galvanostatic Cu bottom-up filling was achieved with three-additive system. • The mechanism of gap-filling was elucidated based on the additive adsorption. - Abstract: Through Silicon Via (TSV) technology is essential to accomplish 3-dimensional packaging of electronics. Hence, more reliable and faster TSV filling by Cu electrodeposition is required. Our approach to improve Cu gap-filling in TSV is based on the development of new organic additives for feature filling. Here, we introduce our achievements from the synthesis of choline-based leveler to the feature filling using a synthesized leveler. The choline-based leveler, which includes two quaternary ammoniums at both ends of the molecule, is synthesized from glutaric acid. The characteristics of the choline-based additive are examined by the electrochemical analyses, and it is confirmed that the choline-based leveler shows a convection dependent adsorption behavior, which is essential for leveling. The interactions between the polymeric suppressor, accelerator, and the choline-based leveler are also investigated by changing the convection condition. Using the combination of suppressor, accelerator, and the choline-based leveler, the extreme bottom-up filling of Cu at trenches with dimensions similar to TSV are fulfilled. The mechanism of Cu gap-filling is demonstrated based on the results of electrochemical analyses and feature filling