【作者】 李海凤；

【导师】 牛玉超；

【作者基本信息】 山东建筑大学 ， 材料学， 2010， 硕士

【摘要】 磁控溅射技术作为一种高速、低温溅射镀膜方法,目前已经在镀膜领域占有举足轻重的地位。非晶合金溅射薄膜凭借其诸多优良性能,在作为功能材料方面具有广阔的应用前景。本文以Zr、Cu、Ni及它们间的合金为主要研究对象,具体研究了直流磁控溅射镀膜工艺中工作气体压强、溅射功率、溅射方式与膜层沉积量之间的关系以及反溅射和负偏压对膜基间结合力、膜层生长方式的影响；利用磁控溅射工艺制备了一系列Zr基非晶合金薄膜,对其成分、结构、热稳定性等进行了研究,并与液淬非晶进行了初步对比；另外,还进行了多层溅射膜间的固态非晶化反应(SSAR)来制备非晶合金层的初步探索。使用称重法对一系列单元(Ni、Cu)和二元(Zr-Ni、Zr-Cu)合金薄膜的沉积量进行测量记录,分析了溅射膜沉积量随工作气体压强、溅射功率的变化规律。结果表明,由于工作气体压强对电子与气体分子以及对靶材原子与气体分子碰撞几率的影响,使得膜层的沉积量不是随着工作气体压强的升高单纯地呈下降趋势,而是有一最佳压强范围；随着溅射功率的增大,膜层沉积量增加；在溅射功率相等的条件下,由于辉光放电电场叠加增大了工作气体的离化率,共溅膜比分层溅射膜的沉积量大得多。采用胶粘带拉剥法测试了膜基间的结合力,使用SEM观察了Cu膜的组织和Al/Cu的界面形貌,发现镀Cu前对Al箔进行反溅射和溅射沉积过程中对工件施加负偏压都可有效地提高膜基间的结合力,且施加较高负偏压比镀前反溅射对膜层质量影响更大。分析认为,镀Cu前反溅射,可有效地去除Al箔表面的氧化膜,使Al箔表面得到净化,磁控溅射沉积过程中对工件施加较高负偏压将产生辉光放电,使工艺转化成溅射离子镀,在Cu膜与Al箔基体之间形成明显的“伪扩散层”,从而获得与基体结合良好、晶粒细小、致密的镀层。采用两靶共溅镀膜工艺,制备了不同成分的Zr-Ni合金溅射膜,利用EDS和XRD对其进行了成分和结构分析,结果显示,在较宽的成分范围内,制备的合金溅射膜均为非晶态,且随着成分的变化,非晶漫射峰的数量、强度和位置逐渐发生变化,表现出与液淬非晶合金的不同。分析认为,X射线衍射图上不同的非晶漫射峰,分别富集着Zr原子和Ni原子,这极有可能与两种溅射原子在飞行后期和到达基底表面初期趋向当时温度下的平衡相有关,同时在气相直接凝聚成固相的剧冷条件下,两种溅射原子没有充分的时间进行长程扩散,会分别呈团簇状沉积在基体上,且相互嵌入抑制扩散和重排,造成了微观尺度上的偏聚；漫射峰中心位置的偏移和峰强度的改变与非晶膜此时形成的结构有关。采用三靶共溅镀膜工艺,制备了Zr-Ni-Cu合金溅射膜。用Ni元素部分取代Cu元素,使得X射线衍射图中漫射峰更加弥散,而用Cu元素部分取代Ni元素,与原来的Zr-Ni二元非晶膜相比,发现其X射线衍射图中漫射峰的强度增大。分析认为,尽管Cu和Ni在尺寸上相近,但由于Cu原子和Zr原子之间、Ni原子和Zr原子之,间形成非晶合金的能力不同,Cu和Ni因此不能互相等同取代,同时Cu和Ni相互部分取代后,合金系的成分也会随之改变,这些都会导致溅射合金膜漫射峰的变化。使用差示扫描量热仪对不同基底温度溅射沉积而成的Zr-Cu非晶合金膜进行热分析,发现基底水冷的非晶合金膜DSC曲线上除高温处有一个晶化放热峰外,在低温处还有一个放热峰,通过XRD分析后仍不能判定其起因。采用以上同样的实验方法,用典型的Fe基非晶合金(Fe78Si13B9)溅射膜对比分析确定Zr-Cu非晶合金膜DSC曲线上低温处放热峰的成因。结果显示,Fe78Si13B9非晶合金溅射膜同样在其DSC曲线上呈现出低温处放热峰。分析认为,两非晶合金薄膜DSC曲线上低温处放热峰是合金原子间非晶化反应的结果。通过Kissinger方程计算合金膜的晶化激活能,得出非水冷基底非晶合金膜比水冷基底非晶合金膜的晶化激活能稍高,但它们均比液淬非晶合金的稳定性低。磁控溅射制备了Zr/Ni/Zr/Ni和Zr/Cu/Zr/Cu多层膜,利用固态非晶化反应(SSAR)原理制备非晶合金层。SEM观察发现,在Zr/Cu/Zr/Cu多层膜中得到了非晶合金层,对应其扩散退火参数为260℃、8h,并通过固态非晶化反应实验对非晶合金的连接进行了探索。更多还原

【Abstract】 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.更多还原