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. (C) 2013 Elsevier B. V. All rights reserved.