Strong adhesion between a deposited copper film and an alumina substrate takes place when the substrate is laser-irradiated prior to deposition. A post-deposition annealing is required to achieve the strong bonding. In this work, the interfacial region between the copper film and the alumina substrate was analyzed using Auger Electron Spectroscopy (AES). It was found that a transitional region is always present in couples that have a high adhesion strength, while little or no transitional region was found in weakly bonded couples. The transitional region depends on the laser irradiation atmosphere. In the case of laser irradiation in air, oxygen excess was found on the surface of the alumina substrate, and in the copper/alumina couple the transitional region consists of a copper oxide and a Cu–Al double oxide. When the laser irradiation was performed in a reducing atmosphere (Ar–4% H2), substoichiometric alumina and metallic aluminum were found on the surface of the substrate and also a reaction between copper and the substoichiometric aluminum oxide was detected in the subsurface. Although the substoichiometric alumina is formed on the surface irradiated in Ar–4% H2, a stable Al2O3 thin layer is formed on the outmost surface because the irradiated substrate is exposed to the atmosphere before deposition. This reoxidized layer remains whole at the interface of the couple upon low temperature (at least up to 300 °C) annealing, while it is ruptured upon higher temperature annealing (500 °C in this work). In the latter case, the copper film can contact and react with the substoichiometric alumina formed in the subsurface of the substrate irradiated in the Ar–4% H2 atmosphere. It is concluded that the Cu–Al–O interfacial compound formed in the transitional region causes the strong adhesion between the copper film and the alumina substrate.
Resin-supported iridium complex for low-temperature vanillin hydrogenation using formic acid in water