Ag–Cu oxide nanoparticles with high oxidation states: towards new high Tc materials

Abstract

In Ag–Cu oxides possible to fabricate so far, superconductivity has not been detected, but high conductivity was. In the quest for superconductivity the demand is to create a high and peculiar copper–oxygen coordination. Such coordination makes it non-trivial to determine Cu oxidation states, which may be several and co-existing. Another reason for uncertainty is in oxygen deficiency typical for superconducting crystals. Finally, Cu oxidation is influenced by the other metals in the substance. For chemical fabrication the difficulty is to tune the relative abundances of elements in a fine way. Ag–Cu oxides have been also produced by reactive co-sputtering of Cu and Ag, but the composition with high Cu oxidation states necessary for high conductivity has not been realized. In the present work we have fabricated Ag–Cu-oxide nanoparticles containing Cu and Ag in high oxidation states actual for superconductivity. The fabrication includes reactive sputtering of Ag and Cu metals, their vapour oxidation and aggregation into nanoparticles. The ability to create different and high oxidation states, also co-existing, is demonstrated. The fabrication approach also allows overcoming the poor miscibility of Cu and Ag. The nanoparticle composition and the oxidation states could be determined due to an experimental arrangement in which photoelectron spectroscopy is applied to free nanoparticles in a beam in vacuum, what allows avoiding any contact of the particles to a substrate or atmosphere. The combination of the fabrication and characterization methods has proven to be a powerful approach when fine composition tuning and control are desirable.