Study On DC Magnetron Sputtering Process And Structures Of Zr-Ni, Zr-Cu Amorphous Alloy Sputtering Films

Magnetron sputtering technique is a high speed and hypothermic method of sputtering film, which occupies a decisive position in the field of coating now. Amorphous alloys films have wide application prospect as functional materials for the special excellent properties of amorphous alloys. In this paper, regarding the Zr, Cu, Ni and their alloys as the main research object, the relationships between the deposition amount of sputtered films and the working gas pressure, sputtering power and sputtering method were studied separately. The effects of ions bombardment on the substrate and negative bias on adhesive force and growth pattern of thin films were also studied. The Zr-Ni, Zr-Cu binary amorphous alloy films were prepared by magnetron sputtering. The compositions, microstructures and thermal stability of films were researched and primarily compared with liquid quenched amorphous. It also presents the works on the exploring of preparing amorphous alloy by means of solid state amorphous reaction (SSAR) for multilayer sputtered films.The deposition amount of Zr, Cu single-metal films and Zr-Ni, Zr-Cu binary alloy films were measured using weighing method. The relationships between the deposition amount of sputtered films and the working gas pressure and sputtering power were analyzed. The results show that due to the impact of working gas pressure on electrons and gas molecules as well as on target atoms and gas molecules, the deposition amount of sputtered films does't decrease simply with the increasing of working gas pressure, but there is a best pressure range. The deposition amount of sputtered films increases with the increasing of sputtering power. Due to the superposition of glow discharge field increasing the ionization proportion of working gas pressure, the deposition amount of sputtered films by co-sputtering process is much larger than that of by layered sputtering process under the same sputtering power. The adhesive force of films on the substrate was measured with the adhesive tape pulling and stripper method. The microstructure of Cu film and the Al/Cu interface morphology were observed using the scanning electron microscopy. It is found that the ions bombardment on the substrate (Al foil) before the Cu film depositing and the bias voltage acted to the substrate during magnetron sputtering can improve the adhesive force of films on the substrate availably. The analysis indicates that ions bombardment on the substrate before the Cu film depositing can remove the oxide film from the surface of Al foil effectively, thereby the surface is cleaned. During magnetron sputtering, the higher bias voltage acted to substrate is able to induce a glow discharge and form magnetron sputtering ion plating, so as to form the "pseudo-diffusion layer" between the Cu film and the Al foil substrate and obtain the compact film that possess better adhesion and finer crystal grains.The Zr-Ni alloy sputtering films were made by magnetron co-sputtering technique with two targets at different sputtering powers. The compositions and microstructures were analyzed by EDS and XRD. The experimental results indicate that the films are amorphous basically in a wide composition range. The number, strength and location of the diffuse peaks change with compositions gradually, which is different from liquid quenched amorphous alloys in some aspects. It is considered through analysis that the two diffuse peaks in the XRD patterns are enriched by Zr and Ni atoms respectively. This is very likely to be related to the atoms trending to the equilibrium phase in the later period of flying and the initial stage of arriving substrate. The atoms do not have enough time to conduct long-range spread and are deposited on glass substrate presenting clusters-like when the gas phase turns into solid phase under quench conditions. They embed in each other and restrained diffusion and rearrangement, resulting in the segregation on a microscopic scale. The diffuse peak central position shifting and the strength increasing are related to the structures of amorphous films.The Zr-Ni-Cu alloy sputtering films were obtained by magnetron co-sputtering technique with three targets. It is found that the addition of Ni made the peak more diffuse, however, compared to the Zr-Ni binary amorphous alloy films, the diffuse peak strength increases on the X-ray diffraction patterns when the Cu atoms were used to replace the Ni atoms. Through analysis, the Cu, Ni and Zr atoms can not replace each other due to the glass-forming ability of Zr-Ni and Zr-Cu are different, although the atomic sizes of the Cu and Ni are similar. At the same time, the alloy composition changes when Cu, Ni and Zr atoms partially replace each other. These may result in the change of diffuse peak strength.The thermal analysis for Zr-Cu amorphous alloy sputtering films was conducted using differential scanning calorimeter (DSC). For the amorphous alloy film sputtered under cooling conditions, the obvious exothermic peaks are observed respectively at the high and low temperature in the DSC curves. The reason was unable to be determined by XRD analysis. In order to find the reason of the obvious exothermic peaks appearing in the DSC curves at the low temperature, the same experimental method above was applied to Fe-based (Fe78Si13B9) amorphous alloy sputtering films. The results show that the exothermic peaks also appeare at the low temperature in the DSC curves of Fe78Si13B9 amorphous sputtering film. The analysis indicates that the exothermic peaks appearing at the low temperature is due to the amorphous reaction among atoms. According to Kissinger equation, the crystallization activation energies of the Zri=0.40Cui=0.25 alloy films sputtered under cooling and non-cooling conditions have been calculated. The latter is slightly higher than the former, but their thermal stability are lower than that of the liquid quenched amorphous alloy.The Zr/Ni/Zr/Ni and Zr/Cu/Zr/Cu multilayered films were prepared by magnetron sputtering technique. Amorphous alloy layer is prepared based on the principle of solid state amorphous reaction (SSAR). Using SEM, a significant amorphous layer was found in the Zr/Cu/Zr/Cu multilayered films, corresponding to the parameters of diffusion annealing 260℃, 8h. Besides, the amorphous joining was explored by means of SSAR method.