PBII制备TiNx/DLC多层膜的结构及摩擦学性能

采用等离子体基离子注入技术在30CrMnSi钢上制备了TiNx/DLC多层膜，通过X射线光电子谱和激光喇曼光谱测试分析了膜的结构特征，TiNx/DLC膜大气下的摩擦性能和在球盘式摩擦磨损试验机上进行。结果表明：DLC膜的结构强烈依赖于基权脉冲偏压，－5kV制得的DLC膜具有较多的C－H键结构，因而硬度最低，仅有8.3GPa；而-15kV的DLC膜由于含有较多的sp^3键，获得了最高的显微努氏硬度（23.6GPa)。DLC膜与GCr15钢球大气下的摩擦因数为0.17左右，其磨损性能由于TiNx，过渡层引入而显著提高。     

用等离子体基脉冲偏压技术制备DLC膜

用等离子体基脉冲偏压技术制备了ＤＬＣ膜，ＤＬＣ膜硬度值达３０ＧＰａ，电阻值达１００ＭΩ以上。降低脉冲负压峰值及适量引入氢气可促进ＳＰ＾３结构的形成，但氢气量超过一定阈值后ＳＰ＾２束片尺寸细化，ＳＰ＾２键含量有增加的趋势。在ＧＣｒ１５轴承钢基体上经磁控溅射沉积约３００ｎｍ纯Ｔｉ层，再用脉冲偏压技术沉积ＤＬＣ膜的改性层，在ＤＬＣ膜与ＧＣｒ１５钢基体之间形成了Ｃ－Ｔｉ成分渐变的梯度层。     

脉冲偏压下沉积的立方氮化硼膜的断面结构研究

采用自行研制的磁增强活性反应离子镀系统，在脉冲偏压条件下成功地合成了高品质立方氮化硼（c-BN）薄膜。用傅立叶变换红外谱（FTIR）分析沉积膜的相结构，用透射电镜（TEM）及高分辨率透射电镜（HRTEM）分析膜的断面结构。FTIR结果表明：c-BN的纯度强烈地受基片负偏压 的影响，当基片负偏压为155V，c-BN膜的纯度高达90%以上，TEM及HRTEM对膜的断面结构分析表明，在膜与基片的界面处存在很薄的非晶氮化硼和六万氮化硼（h-BN）层，h-BN（0002）晶面垂直于基片段面，在界面层之上生长着单相c-BN层。     

脉冲偏压对磁过滤阴极电弧离子镀ta-C薄膜性能的影响

在不同脉冲偏压值下采用90°弯管磁过滤阴极电弧离子镀于硅片表面制备四面体非晶碳膜(Ta-C),研究了脉冲偏压对薄膜硬度、沉积速率、表面形貌及键价结构的影响。结论表明,薄膜沉积速率随脉冲偏压值的增加呈先增后减趋势,偏压值与膜层硬度值呈负相关性,高的偏压会抑制膜层中sp3键的形成,还能在一定程度上抑制大颗粒形成。本文研究内容为工业应用中通过脉冲偏压调整优化膜层综合性能提供参考。     

Co-Cr合金膜的X射线线形分析

利用近似函数法对Co－Cr合金薄膜的衍射线线形进行分析，并提出用“三线法”确定衍射线的函数类型及其积分宽度，由此可计算薄膜的晶粒尺寸和微观应变。理论计算和实验表明，“三线法”结合近似函数法在线形分析方面是简便、可靠的。通过分析Co－Cr膜在不同工艺条件下（膜厚、Ar工作气体压强和负偏压）的衍射线线形，发现衍射线的物理展宽（即有效晶粒尺寸的减小）与晶粒取向度的下降是相对应的。晶粒取向度的下降与结构缺陷密度的增大有关。负偏压溅射时由于Ar原子残留在膜内引起晶格膨胀，从而使微观应变有较大增加。     

不锈钢表面沉积DLC膜的结构和性能

应用线性离子束复合磁控溅射技术在不锈钢和硅片基体上制备DLC膜,研究了基体偏压和过渡层的厚度和结构对DLC薄膜结构和性能的影响。结果表明,在过渡层相同偏压为-200 V的条件下,薄膜中的sp3键含量更低,但是薄膜结构致密性的提高使其硬度和膜基结合力反而提高;在偏压为-200V的条件下,随着过渡层厚度及层数的增加DLC薄膜中sp3含量均降低,同时过渡层和多层薄膜的硬度减小;在偏压为-100V条件下,过渡层厚度和层数对DLC薄膜sp3的含量没有明显的影响。当过渡层厚度为1.7μm、结构为Cr/CrC时,在11Cr17不锈钢基体上可制备出厚度为4.92μm、硬度为29.4 GPa、摩擦系数小于0.1、结合力高于70 N综合性能最佳的DLC薄膜。     

负偏压对Be上磁控溅射离子镀Al膜结构影响的研究

以Be为基体，采用磁控溅射离子镀的在其上镀制Al膜，研究了负偏压对Al膜微结构的影响；研究表明，不加基体负偏压，Al膜在（111）面择优生长；随着基体负偏压升高Al膜在（111）面择优生长趋势减北，Al膜在（200）面生长趋势加强；当基体负偏压超过150V后，Al膜在（111）面择优生长的趋势又得到加强。晶粒在低负偏压时随负偏压增加而细化，当较高的负偏压引起基体温度升高时，此时晶粒又变大了。     

Co—Cr合金膜的X射线线形分析

利用近池数法对Ｃｏ－Ｃｒ合金薄膜的衍射线性形进行分析，并提出用“三线法”确定衍射线的函数类型及其积分宽度，由此可计算薄膜的晶粒尺寸和微观应变。理论计算和实验表明，“三线 法”结合近似函数在线形分析方面是简便，可靠的。通过分析Ｃｏ－Ｃｒ膜在不同工艺条件下（膜厚、Ａｒ工作气体压强和负偏压）的衍射线线形，发现衍射线的物理展宽（即有效晶粒尺寸的减小）是粒取向度的下降是相应的，晶粒取向度的下降与结构缺陷密度     

铝基复合材料表面多层复合厚膜的研究

对含50%AlN颗粒的铝基复合材料进行预处理后,在其表面依次采用浸锌化学镀镍工艺制备Ni-P过渡层,采用脉冲偏压磁过滤多弧离子镀工艺沉积硬质Ti/TiN调制周期膜,采用脉冲等离子体化学气相沉积工艺制备含氢类金刚石(DLC)膜等工艺最后形成了多层复合薄膜体系。利用X射线衍射仪、扫描电子显微镜、光谱仪、原子力显微镜、微载荷显微硬度仪、摩擦磨损试验机等设备分析了复合薄膜的组织结构、膜层形貌、截面形貌、显微硬度和摩擦系数等性能特点。测试表明:铝基复合材料/Ni-P层/Ti/TiN调制周期膜/含氢DLC膜这一梯度膜系具有结构交替变化,相邻界面形成混合层,性能梯度分布,硬度逐渐增加,摩擦系数小的特点。该复合工艺能够有效地解决铝基复合材料上制备硬质厚膜的热适配和晶格错配度大的难题,制备薄膜具有良好的膜基结合性能。     

衬底负偏压对线性离子束DLC膜微结构和物性的影响

采用一种新型线性离子束PVD技术制备出大面积类金刚石薄膜(DLC膜),研究了衬底负偏压对薄膜微结构和物性的影响.结果表明:制备出的类金刚石薄膜在300 mm×100 mm范围内纵向厚度均方差约10-12 nm,横向薄膜厚度均方差约2-4 nm.随着衬底偏压的提高,薄膜中sp~3键的含量先增加后减小,在衬底偏压为-100 V时sp~3键的含量最大;DLC膜的残余应力、硬度和弹性模量与sp~3键的含量呈近似线性的关系,在衬底偏压为-100 V时其最大值分别为3.1 GPa、26 GPa和230 GPa.DLC薄膜的摩擦学性能与薄膜中sp~3碳杂化键的含量密切相关,但是受衬底偏压的影响不大,其摩擦系数大多小于0.25.偏压对磨损的影响很大,在偏压比较低(0～-200 V)时,薄膜的磨损率约为10~(-8)mm~3/N·m,偏压升高到300 V磨损率急剧提高到10~(-7)mm~3/N·m.     

直流负偏压对类金刚石薄膜结构和性能的影响

利用直流-射频-等离子体增强化学气相沉积技术在单晶硅表面制备了类金刚石薄膜，采用原子力显微镜、Raman光谱、X射线光电子能谱、红外光谱、表面轮廓仪和纳米压痕仪考察了直流负偏压对类金刚石薄膜表面形貌、微观结构、沉积速率和硬度等性能的影响。结果表明：无直流负偏压条件下，薄膜呈现有机类聚合结构，具有较低的SP3含量和硬度；叠加上直流负偏压后，薄膜具有典型的类金刚石结构特征，SP3含量和硬度得到了显著的提高；但随着直流负偏压的升高，薄膜的沉积速率和H含量逐渐降低，而SP3含量和硬度在直流负偏压为200V时出现最大值，此后逐渐降低。     

Optimization of the Deposition Parameters of DLC Coatings with the IC-PECVD Method

Amorphous carbon film, also known as diamond-like carbon (DLC) film, is a promising material for tribological application. It is noted that properties relevant to tribological application change significantly depending on the method of preparation of these films. These properties are also altered by the composition of the films. In view of this, the purpose of the present study was to determine the optimal values of selected deposition parameters of hydrogenated DLC films on high-speed steel tool substrates with the inductively coupled plasma enhanced chemical vapor deposition (IC-PECVD) method. To optimize the deposition parameters for hydrogenated DLC films, Taguchi's method was used. Deposition parameters (bias voltage, bias frequency, deposition pressure, and gas composition) were optimized with consideration to hardness of the film. Based on the experimental results, the optimal parameter setting are ?50 V, 500 Hz, 4 µbar, and 90:10 for achieving maximum value of hardness. It was found that bias voltage has greater influence on hardness. At the optimum conditions, the conformance run resulted in a hardness value of 1580 KHN. Atomic force microscopy images showed that the DLC films are smooth with an average roughness (Ra) of 1.24 nm on silicon substrate.     

Influence of negative voltage on the structure and properties of DLC films deposited on NiTi alloys by PBII

Diamond-like carbon (DLC) films have been successfully deposited on Ti-50.8 at.%Ni using plasma based ion implantation (PBII) technique. The influences of the pulsed negative bias voltage applied to the substrate from 12 kV to 40 kV on the structure, nano-indentation hardness and Young’s modulus are investigated by the X-ray photoelectron spectroscopy (XPS) and nano-indentation technique. The results show that C 1s peak depends heavily on the bias voltage. With the increase of bias voltage, the ratio of sp²/sp³ first decreases, reaching a minimum value at 20 kV, and then increases. The DLC coating deposited at 20 kV shows the highest hardness and elastic modulus values as a result of lower sp²/sp³ ratio. The corrosion resistance of specimen deposited under 20 kV is superior to uncoated NiTi alloy and slightly better than those of the other samples deposited at 12 kV, 30 kV and 40 kV.     

脉冲真空弧源沉积类金刚石薄膜耐磨特性研究

本文利用脉冲真空弧源沉积技术在Cr17Ni14Cu4不锈钢和Si(100)基体上制备了类金刚石(DLC)薄膜,研究在不同基体偏压下,DLC薄膜的结构与性能.采用拉曼光谱和X射线光电子能谱(XPS)研究DLC薄膜的原子结合状态,利用CSEM销盘摩擦磨损试验机研究其耐磨性,利用HXD1000B显微硬度仪测试其显微硬度,并采用压痕法评价其结合力.研究结果表明:DLC薄膜与基体结合牢固.随着基体偏压的提高,DLC薄膜内sp3键含量增大,薄膜硬度提高.Cr17Ni14Cu4不锈钢表面沉积DLC薄膜后,耐磨性大幅度提高,本文探讨了DLC薄膜的耐磨机理.     

等离子体源离子注入法制备类金刚石薄膜

用等离子体源注入(PSII)在Si(100)上制备类金刚石膜，放电气体采用CH4，用微波电子回旋共振(ECR)产生等离子体。将-20～-30kV的高压加在衬底上，来提高离子的能量。通过Raman光谱和FT-IR光谱检测了类金刚石膜的化学组成及状态，并对其机械性能和表面形貌进行了检测。结果显示，硅片硬度和摩擦因数得到了改善，用PSII能够制备出性能优良的膜，可以将其应用到微电子器件(MEMS)上去。     

辅助气体组成对类金刚石薄膜结构和性能的影响

分别以氩气-甲烷、氩气-乙炔为辅助气体,高纯石墨为靶材,利用中频脉冲非平衡磁控溅射技术制备了类金刚石薄膜.采用Raman光谱、X射线光电子能谱、纳米压痕测试仪、原子力显微镜对所制备类金刚石薄膜的键结构、机械性能、表面形貌进行了分析.Raman光谱和X射线光电子能谱测试结果表明,以氩气-甲烷为辅助气体制备的类金刚石薄膜中sp3杂化键的含量比以氩气-乙炔为辅助气体制备的类金刚石薄膜的高.纳米压痕测试结果表明,以氩气-甲烷为辅助气体制备的类金刚石薄膜的纳米硬度比以氩气-乙炔为辅助气体的高.原子力显微镜测试结果表明,以氩气-甲烷为辅助气体制备的类金刚石薄膜的RMS表面粗糙度比以氩气-乙炔为辅助气体的低.以上结果说明辅助气体组成对类金刚石薄膜的键结构、机械性能、表面形貌有较大的影响.     

FCVA法制备的超薄类金刚石薄膜的结构分析

用真空阴极过滤电弧(Filtered Cathode Vacuum Arc,FCVA)法制备厚度分别为50 nm,30 nm,10 nm,5 nm,2 nm的类金刚石(DLC)薄膜,利用拉曼光谱和电子能量损失谱研究了薄膜的结构,分析了硬度和内应力的变化趋势。结果表明,随着薄膜厚度的减小,可见光拉曼光谱高斯分解的G峰位置向低波数方向移动,D峰和G峰强度之比Id/Ig不断增大,G峰面积与D峰面积之比Ag/Ad减小;说明随着薄膜厚度的减小,DLC薄膜中的sp3键含量减少,有序化的sp2团簇增加。电子能量损失谱的结果也表明薄膜厚度的减小会引起薄膜中sp3键含量的减少。当薄膜的厚度由50 nm变为30 nm时,薄膜硬度由53.85 GPa减小为39.64 GPa,内应力由4.63 GPa降低为3.47 GPa,随着厚度降低,薄膜的硬度和内应力呈下降趋势。     

X-ray reflectivity study of bias graded diamond like carbon film synthesized by ECR plasma

Diamond like carbon (DLC) coatings were deposited on silicon substrates by microwave electron cyclotron resonance (ECR) plasma CVD process using plasma of Ar and CH ₄ gases under the influence of negative d.c. self bias generated on the substrates by application of RF (13·56 MHz) power. The negative bias voltage was varied from ?60 V to ?150 V during deposition of DLC films on Si substrate. Detailed X-ray reflectivity (XRR) study was carried out to find out film properties like surface roughness, thickness and density of the films as a function of variation of negative bias voltage. The study shows that the DLC films constituted of composite layer i.e. the upper sub surface layer followed by denser bottom layer representing the bulk of the film. The upper layer is relatively thinner as compared to the bottom layer. The XRR study was an attempt to substantiate the sub-plantation model for DLC film growth.     

Growth and properties of the ion beam deposited SiOx containing DLC films

In the present study SiO_x containing diamond-like carbon (DLC) films were synthesized by the closed drift ion source from hexamethyldisiloxane vapor. Kinetics of the growth of DLC films was investigated using optical emission spectroscopy (OES). Structure, chemical composition, electrical and optical properties of the synthesized films were studied. The effects of ion beam energy were investigated. The main atomic hydrogen Balmer series lines and the intense broad CH group related peak were detected in the OES spectra registered in-situ during SiO_x containing diamond-like carbon film synthesis. The intensity ratio of H-β/CH peaks increased with the increase of applied ion beam energy. It was explained by activation of the dissociation of the hexamethyldisiloxane molecules. Changes of the structure of the diamond-like carbon films were observed for the films deposited under intense dissociation conditions.     

Chemical diagnosis of DLC by ESR spectral analysis

Diamond-like carbon (DLC) films were deposited utilizing plasma enhanced chemical vapor deposition (PECVD) with four precursor gases such as methane, ethylene, acetylene and benzene in gas phase. Electron spin resonance (ESR) spectra showed that dangling-bond sites (DBSs) observed in all films were characterized by an isotropic broad single line. The DLC film with unsaturated precursor gases had the higher film growth rate and the higher DBS accumulative rate. Although the DBS in DLC films were quite stable at room temperature under anaerobic conditions, the DBS decayed rapidly to level off toward a limiting value when exposed to air. The stability and reactivity of the DBS in DLC film were assumed to depend on chemical structure of organic gas used as precursor. The detailed-ESR study on DBS of the DLC films could be one of the powerful tools for diagnosing the micro-structural properties and the quality of films.