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。     

Ar/N2气体比例对ZrN/WN纳米多层膜的结构和性能的影响

选择Zr和W的氮化物作为个体层材料,利用FJL560CI2型超高真空射频磁控与离子束联合溅射系统制备ZrN,WN及一系列的ZrN/WN多层薄膜.通过X射线衍射仪,俄歇电子能谱和纳米力学测试系统分析了该体系合成中Ar/N2气体比例对多层膜结构与机械性能的影响.结果表明多层膜的纳米硬度值普遍高于两种个体材料混合相的硬度值;当流量比FArFN2=5时W2N的(111)峰加强并出现(200)峰,结晶出现多元化,多层膜体系的硬度、应力、弹性模量以及膜基结合性能均达到最佳效果.     

非平衡磁控溅射制备氮化硅薄膜及其性能研究

采用非平衡磁控溅射技术,通过改变氮气和氩气分压比P(N2)/P(Ar),在钛合金(Ti6Al4V)表面制备出不同结构及性能的氮化硅薄膜.结果显示,制备的氮化硅薄膜为非晶态结构,随着氮气分压的增加,Si-N键的含量增加,其对应的红外吸收峰逐渐变宽,并向高波数偏移.氮化硅薄膜的显微硬度、耐磨性随着P(N2)/P(Ar)的增加而先增加,当P(N2)/P(Ar)为0.25时,随着P(N2)/P(Ar)的增加,薄膜硬度及耐磨性稍有降低.氮化硅薄膜具有较好的膜/基结合力,当增大氮气和氩气分压比,薄膜的脆性随之增加.     

高功率脉冲磁控溅射制备TiNx涂层研究

采用高功率复合脉冲磁控溅射技术(HPPMS)在316不锈钢、硬质合金基体上沉积了TiN薄膜,研究不同N2流量下TiNx膜层的沉积速率、硬度、晶体生长取向、摩擦磨损等性能,并在相同的平均靶电流下与直流磁控溅射制备的TiN薄膜对比.结果表明:HPPMS制备的膜层更加致密,在氩氮流量比为7.4∶1时膜层显微硬度达2470 HV,晶粒尺寸也明显小于直流磁控溅射制备的TiN,摩擦磨损性能也得到了改善.     

微波-ECR等离子体辅助沉积Zr-N薄膜结构和性能研究

在不同氮流量下,利用微波-ECR等离子体溅射沉积技术在45#钢基体上制备了ZrN薄膜.XRD、TEM分析结果表明:随着充入N2流量的改变,薄膜结构由单一的ZrN结构向ZrN和ZrNx复合结构转变,然后出现非晶态结构.当N2流量在(2～8) sccm之间,薄膜为ZrN结构;在(10～12) sccm时,为ZrN和正交的ZrNx(a=0.3585 nm,b=0.4443 nm,c=0.5798 nm)混合型结构;14 sccm时出现非晶化趋势.俄歇电子谱仪(AES)和探针分析表明:薄膜中氮含量为7.73%～66.96%.同时对薄膜的硬度进行了测试,薄膜硬度在19.82 GPa～26.32 GPa之间,随氮值的变化,先增加后降低.对硬度最高的4#样品进行了摩擦性能测试,磨损率约4.5×10-8 mg/min.薄膜这些性能的变化是由于不同氮流量下薄膜结构发生变化造成的.     

射频磁控溅射制备（AlCrTiZrNb）N高熵合金薄膜的微观组织和力学性能

研究了氮含量对(AlCrTiZrNb)N高熵合金薄膜微观结构和力学性能的影响,利用射频磁控溅射工艺在不同N₂和Ar流量比下制备了(AlCrTiZrNb)N高熵合金薄膜。结果表明,随着氮气流量的升高,(AlCrTiZrNb)N薄膜的沉积速率逐渐下降,AlCrTiZrNb合金薄膜的结构由非晶态转变为由Me-N(金属氮化物)构成的面心立方固溶体结构,(AlCrTiZrNb) N薄膜的择优生长取向为(200)晶面。同时随着N₂流量的增加,(AlCrTiZrNb) N高熵合金薄膜的硬度首先快速升高,随后略微降低。当N₂:Ar=1:1时,(AlCrTiZrNb)N薄膜硬度最大值28.324 GPa,此时(AlCrTiZrNb) N薄膜呈现单一的面心立方固溶体结构,饱和Me-N相的形成与各元素的固溶强化作用是其硬度的增长的主要原因。     

镍基合金基体上离子镀TiN薄膜的制备及性能

在镍基合金Inconel 740H基底上通过多弧离子镀制备Ti N薄膜.控制温度、气体流量、过渡层成分等重要参数,研究其对Ti N薄膜的表面形貌、力学性能以及耐腐蚀性的影响.多弧离子镀沉积过程中,沉积温度分别为200、250、300℃;过渡层成分分别为Al、Cr、Ti;气体流量分别为Ar 5 Sccm∶N240 Sccm,Ar 6 Sccm∶N248 Sccm,Ar 8 Sccm∶N264 Sccm.实验结果表明:在本实验的温度范围内,Ti N薄膜的致密度、结合力以及表面硬度均随着沉积温度的提高而提高;Cr作为过渡层的效果优于Al和Ti,薄膜成分均匀、表面致密,硬度更高,且耐腐蚀性能优异;在Ar、N2流量比一定的情况下,气体流量对Ti N薄膜的表面形貌和力学性能影响不大.本实验的最佳参数是:沉积温度300℃,过渡层成分为Cr,气体流量为Ar 6 Sccm、N248 Sccm.     

氮流量对孪生靶磁控溅射沉积氮化铬薄膜性能的影响

采用中频孪生靶反应磁控溅射在金属镍基底上制备氮化铬薄膜。利用X射线衍射仪、显微硬度计、扫描电子显微镜、原子力显微镜、磨擦磨损试验仪和电化学工作站等系统研究了氮气流量(即氮/氩流量比)对薄膜的相结构、显微硬度、表面形貌、附着力、耐磨性和耐腐蚀性的影响。结果得到随氮/氩流量比的增加,CrN_x薄膜成分经历了一个由Cr→Cr+Cr N→Cr+Cr_2N+Cr N的演化过程,薄膜形貌由致密、球状颗粒向类长方体规则形状的面心结构转化;而薄膜的表面粗糙度则呈现出在低氮时稍微下降,高氮含量时又快速增加的趋势,在N_2/Ar流量比为23/53时,粗糙度达到最小;耐磨性、硬度都呈现随着氮流量的增加先上升后下降;薄膜耐腐蚀性能随氮的加入明显得到改善。综合性能分析认为,制备2.5μm厚的氮化铬薄膜时在N_2/Ar(流量比)为23/53较为合适。     

离子轰击能量对ZrN/TiAlN纳米多层膜性能的影响

使用超高真空离子束辅助沉积系统(IBAD)制备一系列具有纳米调制周期的ZrN/TiAlN多层膜,研究了离子辅助轰击对薄膜性能的影响.结果表明:离子辅助轰击使大部分ZrN/TiAlN多层膜的纳米硬度和弹性模量值高于两种个体材料硬度的平均值;离子的轰击和薄膜表面原子与轰击离子之间的动量传输提高了薄膜的致密度;当轰击能量为200 eV时,多层膜的硬度最高(30.6 GPa),弹性模量、表面粗糙度和摩擦系数等也明显改善.     

反应溅射Zr-Si-N复合膜的微结构与力学性能

在Ar、N2混合气氛中，通过双靶反应磁控溅射方法制备了一系列不同Si含量的Zr-Si-N复合薄膜，采用EDS、XRD、SEM、AFM和微力学探针表征了复合膜的成分、相组成、微结构和力学性能。结果表明：随着Si的加入，Si3N4界面相形成于ZrN晶粒表面并阻止其长大。低Si含量下，晶粒的细化使Zr-Si-N薄膜得到强化，在Si含量为6．2at％时其硬度和弹性模量分别达到最高值29．8GPa和352GPa。继续增加Si的含量，薄膜逐渐向非晶态转变，同时产生ZrxSiy相，并伴随有明显的力学性能降低。Zr-Si-N薄膜力学性能增加受到限制，可能与Si3N4界面相和ZrN晶粒之间的低润湿性有关。     

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。     

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.     

直流反应磁控溅射法注积ZrN薄膜

采用直流反应磁控溅射法淀积ZrN薄膜发现在（100）晶向硅片上ZrN薄膜按（111）晶向生长，控制生长工艺可以获得ZrN（111）晶向的外延生长膜．     

扩散阻挡层对Cu-Zr合金膜表面形貌与结构的影响

用磁控溅射和离子束溅射共沉积的方法，分别以TiN,TaN,ZrN为扩散阻挡层，在单晶硅片上制备了Cu-Zr合金膜，膜在400℃氮气中退火1h，研究表明，不同扩散阻挡层上Cu-Zr膜的形貌不同，沉积态膜的组成颗粒以ZrN为扩散阻挡层的最小，退火后膜的颗粒长大，且Zr向膜表面和界面处扩散，沉积态的膜具有强的（111）取向，峰形宽化明显，退火后又出现（200）、（220）、（311）衍射峰，扩散阻挡层不同时Cu-Zr合金膜的（200）与（111）的强度比值不同。     

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。     

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.     

Wear behavior of HPPMS deposited (Ti,Al,Si)N coating under impact loading

Over the last decade the interest in High Power Pulse Magnetron Sputtering (HPPMS) and High impulse Magnetron Sputtering (HiPIMS) has undergone a considerable increase. This is mainly due to the fact that several researchers have shown that in these processes a distinct increase of the ionization of deposition species is observable. However, there is only little known about the performance of these films with regard to applications. Recently Hovsepian et al. [1] and Bobzin et al. [2] presented cutting results of different films. Both authors show that films deposited using HPPMS or HiPIMS outperform state‐of‐the‐art coatings. Depending on the cutting process, besides hardness and adhesion also excellent impact behavior is required. Therefore this work deals with the impact behavior of (Ti,Al,Si)N which was deposited using HPPMS for the application in interrupted cutting process. The impact behavior of HPPMS coating under normal and tangential loads is analyzed. During impact tests number of impacts, loads and inclination angle of the samples with regard to the load direction are varied. (Ti,Al,Si)N shows an excellent endurance even at very high loads causing Hertzian stresses in the range of 10–13 GPa. At an inclination angle of 10° and an impact load of 100 N, which corresponds to app. 10 GPa initial Hertzian stress, no damage was observed after 800×10³ impacts.     

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.