高功率脉冲磁控溅射氩氮比对ZrN薄膜结构及性能的影响

采用高功率复合脉冲磁控溅射的方法(HPPMS)在不锈钢基体上制备ZrN薄膜,对比DCMS方法制备的ZrN薄膜,得出HPPMS制备的薄膜表面更平整光滑、致密,既无空洞、又无大颗粒等缺陷。Ar/N对薄膜相结构及硬度、耐磨耐蚀等有较大影响。XRD结果显示,薄膜主要以ZrN(111)和ZrN(220)晶面择优生长,并呈现出多晶面竞相生长的现象。制备的ZrN薄膜的硬度最高可达33.1 GPa,同时摩擦系数小于0.2,耐腐蚀性也有很大提高,腐蚀电位比基体提高了0.27 V,腐蚀电流下降到未处理工件的1/5。存在一个合适的Ar/N比,使得制备的ZrN薄膜具有较好的耐磨性和耐腐蚀性。     

钽基体上铜薄膜微观结构的分子动力学模拟

运用分子动力方法模拟了铜薄膜在钽（100）及（111）基体上沉积过程。结果表明沉积过程中铜薄膜的晶格位向取决于钽基体的晶格位向．在钽（100）面上，铜薄膜在不同的温度下分别沿（111）或（110）面生长，所形成的晶界与住错沿着薄膜的生长方向发展，薄膜表面的粗糙度与沉积温度有关，低温时表面粗糙度较大。而在钽（100）面上，铜薄膜的外延生长面为（100）面，位错沿（111）面分布，并只存在于界面附近，在铜薄膜的内部仅有少量的点缺陷，薄膜表面粗糙度较小并与沉积温度无关。     

CVD金刚石薄膜(111)与(100)取向生长的热力学分析

用非平衡热力学耦合模型计算了CVD金刚石薄膜生长过程中C2H2与CH3浓度之比[C2H2]/[CH3]随衬底温度和CH4浓度的变化关系,从理论上探讨了金刚石薄膜（111）面和（100）面取向生长与淀积条件的关系。在衬底温度和CH4浓度由低到高的变化过程中,[C2H2]/[CH3]逐渐升高,导致金刚石薄膜的形貌从（111）晶面转为（100）晶面。添加氧后C2H2与CH3浓度都将下降,但C2H2下降得更多,因而添加氧也使[C2H2]/[CH3]下降,从而有利于生长（111）晶面的金刚石薄膜。     

热丝CVD法低温制备的多晶硅薄膜质量对衬底依赖性的研究

以SiH4和H2作为反应气体,采用HWCVD的方法分别在石英玻璃、AZO、Si（100）和Si（111）衬底上制备了多晶硅薄膜。利用X射线衍射（XRD）,拉曼（Raman）光谱和傅里叶红外（FT-IR）吸收光谱研究了不同衬底对多晶硅薄膜的择优取向、晶化率和应力的影响,用SEM观察了多晶硅薄膜的表面形貌。研究发现在4种衬底上生长的多晶硅薄膜均为（111）择优取向。单晶硅片对多晶硅薄膜有很强的诱导作用,并且Si（111）的诱导作用优于Si（100）的诱导作用。AZO对多晶硅薄膜生长也有一定的诱导作用。通过计算薄膜晶态比,得到除以石英为衬底的样品外,其它3种样品的晶态比均在90%以上,尤其以单晶硅片为衬底的样品更高。石英玻璃、AZO和Si（100）上生长的多晶硅薄膜中均存在压应力。     

多晶硅薄膜的铝诱导晶化法制备及其晶粒的择优取向特性

采用铝诱导非晶硅薄膜晶化技术制备了多晶硅薄膜,并研究了多晶硅的成核和生长特性。非晶硅薄膜采用等离子体增强化学气相沉积法制备,其表面沉积铝薄膜后经不同温度的氮氛围退火处理。结果表明,退火后的硅薄膜层与铝层发生置换,所生长的多晶硅颗粒的平均尺寸约为150nm。X射线衍射分析结果揭示,薄膜的晶向显著依赖于退火温度,较低温度下,铝诱导晶化速率较慢,薄膜的优化晶向与非晶硅薄膜中团簇的初始原子排列趋势紧密相关。而较高温度下,铝诱导晶化促使多晶硅(111)择优成核及随后的固相生长。     

不同衬底制备稀土Nd+3掺杂SnO2薄膜的XRD、SEM分析

采用真空气相沉积法在玻璃和单晶硅衬底[111]上制备纳米SnO2及稀土金属钕掺杂薄膜，并对薄膜进行热处理。对薄膜进行XRD、SEM测试。实验显示，不同衬底制备SnO。薄膜在未掺钕时结构有明显区别，采用同样工艺条件在玻璃衬底上制备的SnO2薄膜没有显示择优生长；在硅衬底上制备未掺钕SnO2薄膜显示出沿[101]晶向择优生长趋势。掺钕（5at％）玻璃衬底制备的薄膜沿[110]衍射峰较强，但薄膜基本呈现自由生长；掺钕后硅衬底制备的薄膜则强烈沿[110]晶向择优生长，随掺钕含量增加择优生长趋势消失，当掺钕含量为（5at％）时薄膜呈自由生长结构较完善。SEM给出在玻璃基片生长的薄膜表面形貌呈均匀小颗粒状，平均晶粒尺寸在30nm左右。硅基片制备的薄膜表面则呈紧密均匀带孔颗粒状；颗粒尺寸约1000nm与计算值相差较大。两种衬底制备的SnO2薄膜经稀土钕掺杂可抑制晶粒生长。本实验中钕掺杂量为5at％（热处理T=500℃，t=45min）时薄膜结构特性最佳。     

氮分压对ZrN薄膜结构及颜色的影响

采用直流反应磁控溅射法,通过改变反应气体N2分压(5%、10%、20%、30%、40%、50%、60%),在SiO2/Si(111)基片上制备ZrN薄膜。利用XRD、SEM、EDS分析了薄膜的物相、结构、形貌以及成分,使用分光光度计测量了薄膜的反射光谱,并进一步确定了薄膜颜色在L*a*b*色度坐标中的位置,研究了氮分压对薄膜颜色的影响,以及ZrN薄膜颜色与薄膜成分、结构之间的关系。分析结果表明:在不同的氮分压下,ZrN薄膜具有较好的成膜质量;随着氮分压的增加,薄膜沉积速率降低、N含量增加;薄膜结晶度先升高后降低、且在氮分压为10%时,薄膜出现(111)的择优取向;薄膜颜色随薄膜成分结构的改变而发生明显的变化(颜色由银色向金色、暗金、深褐色以及非本征颜色转变)。当反应气体N2分压较低时,分压的增加使得锆与氮更容易键合,导致薄膜中N含量增加,使ZrN结晶度增大并出现择优取向。当N2分压超过10%后,薄膜中多余的氮处于晶格的间隙位置,使得薄膜晶格间距变大且结晶度降低,薄膜成分结构的改变导致了薄膜颜色的变化。     

真空蒸发制备Sb掺杂CdTe薄膜

采用真空蒸发技术在玻璃衬底上制备了Sb掺杂的CdTe薄膜,薄膜为沿(111)晶向择优生长的立方闪锌矿结构的CdTe,结果表明Sb掺杂使得薄膜表面更加均匀致密,改善了薄膜的结晶状况,增大了薄膜的光吸收范围,同时也使薄膜的带隙宽度有所减小,大大降低了薄膜的电阻率.     

直流反应磁控溅射法淀积ZrN薄膜

采用直流反应磁控溅射法淀积ＺｒＮ薄膜，发现在晶向硅片上ＺｒＮ薄膜按晶向生长。控制生长工艺可以获得ＺｒＮ晶向的外延生长膜。     

偏压对反应磁控溅射TiN薄膜结构以及性能的影响

本文采用直流反应磁控溅射技术,以Ar和N2为反应前驱气体制备了TiN功能装饰薄膜.重点研究了衬底负偏压对沉积TiN薄膜的色泽、性能及微结构的影响.采用台阶轮廓仪、X射线衍射仪、EDS能谱仪、纳米压痕仪等分析了薄膜的粗糙度、晶相、组分、纳米硬度以及弹性模量.结果表明,采用适宜的衬底负偏压调控轰击离子能量,能够有效阻止薄膜结构中空位以及缺陷的产生,从而有效避免薄膜表面的紫黑色氧化钛的生成,有利于表面光滑的金黄色TiN薄膜制备,同时使薄膜具备更优异的力学性能.实验结果还表明基体偏压可显著影响TiN薄膜的择优生长取向:随偏压增加,薄膜由(111)晶相择优生长转变为(200)晶相的择优生长,(200)晶相的薄膜比(111)晶相薄膜具有更佳的力学性能.     

工艺参数对阴极电弧离子镀ZrN薄膜表面形貌及结构的影响

本文采用阴极电弧离子镀技术制备了ZrN膜层,研究了工作气压、偏压、弧流等工艺参数对ZrN膜层表面形貌和结构的影响,分别用扫描电镜(SEM)、X射线衍射仪(XRD)分析了膜层的表面形貌及相结构。结果表明:工作气压、偏压、弧电流等工艺参数对ZrN膜层的表面形貌有较大的影响,在本实验内适当提高N2压强、偏压以及在稳弧前提下降低弧流有利于减少大颗粒,改善ZrN膜层表面形貌,提高膜层综合性能;不同工艺参数下制备的ZrN膜层均具有典型的面心立方结构,工作气压和弧电流对ZrN膜层晶体生长方向的影响较小,偏压对晶体生长方向的影响显著,在20 V偏压下,晶体呈(200)面择优取向,继续提高偏压(100 V~300 V),晶体生长呈(111)面择优取向。     

高功率脉冲磁控溅射ZrN纳米薄膜制备及性能研究

采用高功率复合脉冲磁控溅射的方法(HPPMS)在不锈钢基体上制备ZrN纳米薄膜,并研究了不同的工作气压对薄膜形貌、相结构及各种性能的影响。采用SEM、XRD对其表面形貌和结构进行分析,发现制备的薄膜表面光滑、致密,无大颗粒,主要以ZrN(111)和ZrN(220)晶面择优生长,并呈现出多晶面竞相生长的现象。对薄膜硬度、弹性模量、耐磨性和耐腐蚀性的测试发现薄膜具有很高的硬度,最高可达33.1 GPa,同时摩擦系数均小于0.2,耐腐蚀性也都有很大提高,腐蚀电位比基体提高了0.28 V,腐蚀电流下降到未处理工件的1/5。工作气压较低时,薄膜耐磨耐蚀性能都较好,但在较高气压时,耐磨耐蚀性能出现一定的下降。     

Influence of the aluminum incorporation on the structure of sputtered ZrNx films deposited at low temperatures

We have studied the influence of the Al incorporation in the crystalline structure of ZrN thin films deposited by dc magnetron sputtering processes at low temperature. The incorporation of the aluminum in the films depends directly on the Ar/N₂ ratio in the gas mixture and the power applied to the aluminum cathode during the deposition. The chemical composition and the crystalline structure of the films were analyzed by Energy Dispersive X-ray (EDX) spectroscopy and X-ray Diffraction (XRD), respectively. When Al atoms are incorporated into the ZrN coatings, the strong ZrN (200) preferred orientation is modified to a combination of phases related to (111) ZrN with a contribution of cubic (111) AlN and possibly (211) Zr₃N_4, which are detected by XRD for high aluminum concentrations. Fourier Transform Infrared (FTIR)spectroscopy allowed us to complete the identification of the nitrides and oxides incorporated into the deposited films. The effect of a bias voltage applied to the substrate has also been investigated and related to the changes in the microstructure and in the nanohardness values of the ZrAlN films.     

Optimizing surface morphologies for ceramic films prepared using a magnetron sputtering

This article presents the application of the response surface methodology for yielding the optimal conditions and for developing robust surface morphologies of zirconium nitride (ZrN) films. In this research, the ZrN films with (Ti, Cr) interfaces ((Ti, Cr)ZrN) were prepared by an unbalanced magnetron (UBM) sputtering. Two kinds of zirconium nitride films, with and without Ti additives, were reported. An orthogonal array for reducing the large number of experiments was introduced. The significant parameters from an analysis of variance for the (Ti, Cr)ZrN films were clearly observed. Furthermore, a quadric model was constructed efficiently. The predicted values and experimental results were close, which confirmed that the quadric model can be effectively used to predict the surface morphologies of the (Ti, Cr)ZrN films in the UBM sputtering. The experimental results were consistent with the response surface predictions. Therefore, it was concluded that the surface morphologies on multilayered films can be accurately predicted by response surface analysis, thereby justifying the reliability and feasibility of the approach.     

Analysis of the oxidation kinetics and barrier layer properties of ZrN and Pt/Ru thin films for DRAM applications

ZrN and Pt/Ru thin films have been grown by an automated ion beam sputter-deposition system. Both materials were evaluated for use as barrier layers (ZrN) and bottom electrodes (Pt/Ru) in dynamic random access memory (DRAM) applications. The ZrN films had resistivities on the order of 250–300 μω cm. The ZrN films were (002) oriented and were rather smooth with an average surface roughness of ±17 Å. Analysis of the oxidation kinetics of the ZrN thin films reveals a thermally activated, diffusion-limited oxidation process with an activation energy of 2.5 eV in the temperature range of 500–650 ° C. This implies that there is an advantage in using ZrN as a barrier layer instead of TiN since the activation energy for oxidation of TiN is 2.05 eV. In addition, preliminary data suggest that a Pt/Ru double layer may be a promising bottom electrode and oxygen diffusion barrier for use in DRAMs with high-permitivity dielectrics.     

Vacuum arc deposition of nanostructured multilayer coatings for biomedical applications

In recent years, the smart materials have attracted much attention due to their unusual properties such as shape memory effect and pseudoelasticity, being widely used for biomedical implants. These materials contain certain amounts of nickel, titanium and others which are not adequate for surgical implants and prosthesis. In the work reported here, two types of nonostructured multilayer coatings (TiN/ZrN, ZrN/Zr) used to prevent the ions release from shape memory alloys were investigated. For comparison, the TiN and ZrN monolayers were also examined. The films were deposited onto nickel-titanium based alloy (Ti-Ni-Nb) and Ni substrates by vacuum arc deposition technique under various deposition conditions. The concentrations of dissolved ions in Ringer solution for uncoated and coated Ni samples were determined to examine the benefic barrier effect of these coatings for ions release from shape memory alloys. In order to have a more complete characterization of the investigated coatings, other properties such as elemental and phase composition, morphology, texture, microhardness, and adhesion were studied. For all coatings, the concentrations of dissolved ions were lower that those measured in the case of the uncoated specimens. The nanostructured multilayer films exhibited the best mechanical and anticorrosive properties.     

室温磁控溅射制备(Ti,Zr)N薄膜及其性能研究

采用直流反应磁控溅射工艺,在载波片和Al基材上制备出金黄色的(Ti,Zr)N薄膜.(Ti,Zr)N薄膜具有比TiN薄膜更高的硬度和更强的耐腐蚀性能.用XRD衍射方法和扫描隧道显微镜对薄膜的晶体结构、微观表面形貌和电子结构进行了测试分析.XRD结果表明,(Ti,Zr)N薄膜为多晶态,存在TiN和ZrN两种分离相;从表面形貌可知,薄膜表面平整,晶粒排列致密且无连接松散的大颗粒;STS谱表明,Zr掺杂后,禁带宽度仍为1.64eV,但在禁带内增加了新能级,新能级的宽度分别为0.33eV和0.42eV,这也正是掺杂Zr后,薄膜仍呈现金黄色的主要原因.     

Structure and tribological properties of reactively sputtered Zr-Si-N films

Zr-Si-N films were deposited on silicon and steel substrates by magnetron sputtering of a Zr-Si composite target in Ar-N₂ reactive mixtures. The silicon concentration in the films was adjusted in the 0-7.6 at.% range by varying the surface of Si chips located on the erosion zone of the target. The films were characterised by X-ray diffraction, electron probe microanalysis, atomic force microscopy and wear tests. The structure and the tribological properties of Zr-Si-N films were compared to those of ZrN coatings. Depending on the silicon concentration, the films were either nanocomposites (nc-ZrN/a-SiN_x) or amorphous. Introduction of silicon into the zirconium nitride coatings induced a change in the preferential orientation of the ZrN grains: [111] for ZrN films and [100] for Zr-Si-N ones. This texture modification was also observed for a ZrN film deposited on an amorphous SiN_x layer. Thus, within our deposition conditions, the occurrence of a-SiN_x enhanced the [100] preferred orientation. Friction and wear behaviour of the films were carried out against spheres of alumina or 100 Cr6 steel by using a ball-on-disc tribometer. The results showed that addition of silicon into ZrN-based coating induced a strong decrease in the friction coefficient and in the wear rate compared to those of ZrN films. These results were discussed as a function of the films structure and composition.