[en] The uniformity of Cu growth on Pd nanocatalysts was controlled by using organic additives in the formation of electroless Cu seed layers. Polyethylene glycol (PEG, Mw. 8000) not only reduced the deposition rate but also improved the uniformity of Cu growth on each Pd nanocatalyst during the seed layer formation. The stronger suppression effect of PEG on Cu than on Pd reduced the difference in the deposition rate between the two surfaces, resulting in the uniform deposition. Meanwhile, bis(3-sulfopropyl) disulfide degraded the uniformity by strong and nonselective suppression. The sheet resistance measurement and atomic force microscopy imaging revealed that the uniform Cu growth by PEG was more advantageous for the formation of a thin and smooth Cu seed layer than the non-uniform growth. The uniform Cu growth also had a positive influence on the subsequent Cu electrodeposition: the 60-nm-thick electrodeposited Cu film on the Cu seed layer showed low resistivity (2.70 μΩ·cm), low surface roughness (6.98 nm), and good adhesion strength. - Highlights: • Uniform Cu growth on Pd was achieved in formation of electroless Cu seed layer. • PEG addition to electroless bath improved the uniformity of Cu growth on Pd. • A thin, smooth and continuous Cu seed layer was obtained with PEG. • Adhesion strength of the Cu seed layer was also improved with PEG. • The uniformity improvement positively affected subsequent Cu electrodeposition

[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] Cu growth phenomena during electroless deposition (ELD) on Ru substrate were investigated in this study. Different to the formaldehyde based Cu ELD bath, the use of hydrazine based Cu ELD bath facilitated the observation of Cu growth phenomena during ELD. The whole surface-catalyzed ELD occurred on Ru, and electrochemical quartz crystal microbalance as well as linear sweep voltammetry studies revealed that Cu covered Ru surface within a few seconds of ELD. Measurement of sheet resistance change confirmed that Cu nucleation on Ru was continuous with forming a film. During the period, Cu film growth was monitored by an atomic force microscope imaging, indicating that Cu was deposited on Ru preferentially, rather than on the deposited Cu at the initial stage of the deposition. The whole surface-catalyzed ELD achieved 55 nm gap-filling, and this showed the possibility of the practical adoption of ELD as a method for metallization in ultralarge-scale integration