Morphological Stability Limits of Ag–Cu–Al Nanocrystalline Thin Films Prepared via Reactive Sputtering in Ar–O2 Mixed Gas

Abstract

As a first step toward developing a downsized and high-performance O₂ separator suitable for large-scale industrial applications, such as steelmaking, we have studied nanocrystalline Ag alloy thin films with high O₂ permeability via rapid diffusion at Ag grain boundaries, operating at plant-waste heat temperatures (200 °C to 500 °C). In the present study, fabrication of nanocrystalline Ag–2at. pctCu–10at. pctAl alloy thin films with Ag grain size below 10 nm was attempted via reactive sputtering in Ar–O₂ using grain boundary pinning force of a large number of alumina particles. Cross-sectional observation of the fabricated thin film showed that the Ag grain size ranged from 4 to 15 nm when the film thickness was less than 200 nm, but when the film thickness exceeded 200 nm, the Ag grains abruptly coarsened, reaching a maximum grain size of 214 nm. Furthermore, large surface irregularities with sizes of up to 500 to 600 nm (equivalent to 2/3 of the film thickness) were also observed. Heat transfer analysis revealed that the Ag film partially melted because of the large amount of heat released by the oxidation of Al during sputtering deposition. The conditions necessary for the fabrication of high-Al nanocrystalline Ag alloy thin films via reactive sputtering in Ar–O₂ gas without film melting were clarified.