The electrochemical deposition of copper ͑Cu͒ thin film on polycrystalline ruthenium ͑Ru͒ electrode surface was investigated in a sulfuric acid plating bath. Scanning electron microscopic characterization indicated that a continuous thin Cu film ͑150 Å and above͒ could be conformally coated on Ru with good control of thickness. The nucleation and growth of Cu on Ru was studied using the potentiostatic current-transient method. The results support a predominantly progressive nucleation of Cu on the Ru surface. In addition, X-ray diffraction patterns indicated ͑i͒ a principally ͑111͒ texture of the electrochemically grown Cu on Ru and ͑ii͒ the absence of any new phase or compound formation between the two metals, even after annealing up to 800°C. Scotch tape peel tests showed that Cu films adhered strongly to Ru, both before and after the annealing treatments. The lack of metallurgical interaction and strong adhesion between Cu and Ru at elevated temperatures underscore the potential application of Ru as a new Cu diffusion barrier.

Interfacial stability of electroplated copper on a 5nm ruthenium film supported by silicon, Cu∕(5nmRu)∕Si, was investigated using Rutherford backscattering and high-resolution analytical electron microscopy. Transmission electron microscopy (TEM) imaging shows that a 5nm Ru film is amorphous in contrast to the columnar microstructures of thicker films (20nm). Direct Cu plating on a 5nm Ru film yielded a homogeneous Cu film with over 90% plating efficiency. It is demonstrated that 5nm Ru can function as a directly plateable Cu diffusion barrier up to at least 300°C vacuum anneal. TEM reveals an interlayer between Ru∕Si, which expands at the expense of Ru upon annealing. Electron energy loss spectroscopy analyses show no oxygen (O) across the Cu∕(5nmRu)∕Si interfaces, thereby indicating that the interlayer is ruthenium silicide (RuxSiy). This silicidation is mainly attributed to the failure of the ultrathin Ru barrier at the higher annealing temperature.

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The structure and electrochemical properties of arrayed nitrogen-containing carbon nanotube (CN x NT)−platinum nanoparticle (Pt NP) composites directly grown on Si substrates have been investigated. The CN x nanotube arrays were grown by microwave-plasma-enhanced chemical vapor deposition first and then acted as the template and support for Pt dispersion in the following sputtering process. Under the same sputtering conditions, it was found that well-separated Pt NPs would form with an average diameter of 2 nm on the arrayed NTs while a continuous Pt thin film was observed on the bare Si substrate. X-ray photoelectron spectroscopy (XPS), X-ray diffraction, and electron microscopy were employed to study bonding and structure changes with increasing deposition time. Implications of the C1s and N1s bonding changes in XPS and their possible relation to the NT−Pt composite structures with self-limited size distribution are discussed. Cyclic voltammograms show well-behaved curves in methanol oxidation, suggesting an efficient electronic conduction mechanism from the substrate via CN x NTs to reach individual Pt NPs is in operation. Such an integrated nanocomposite approach possesses a high potential for micro direct methanol fuel cell applications.