脉冲偏压对等离子体沉积DLC膜化学结构的影响

以乙炔为气源，用等离子体基脉冲偏压沉积（plasma based pulsd bias deposition缩写PBPBD）技术进行了不同负脉冲偏压条件下制备DLC膜的试验，通过X射线光电子谱（XPS）、激光喇曼光谱[Raman]以及电阻分析方法考察了负脉冲偏压幅值对DLC膜化学结构的影响，结果表明由-50kV到-10kV随负脉冲偏压降低，DLC膜中SP^3键分数单调增加，但当脉冲偏压为0时形成高电阻的类聚合物膜，说明荷能离子的轰击作用形成DLC化学结构的必要条件，键角混乱度和SP^2簇团尺寸与脉冲偏压之间不具有单调关系，在中等幅值负脉冲偏压条件下，键用混乱度较大且SP^2簇团尺寸细小。     

微波ECR—CVD低温SiNx薄膜的氢含量分析

利用红外光谱技术研究了微波电子回旋共振（ＥＣＲ）等离子体化学气相沉积（ＣＶＤ）法在低温条件下制备的ＳｉＮ。膜的键的结构和氢含量，分析了微波 功率和后处理条件对膜含量的影响及其成因，提出适当提高微波功率是降低微波ＥＣＲ－ＣＶＤ低温ＳｉＮｘ膜中氢含量的可能途径。     

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。     

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。     

非平衡磁控溅射无氢DLC增透膜的研制

非平衡磁控溅射(UBMS)技术近年来得到了广泛地应用.采用该技术制备的类金刚石薄膜(DLC)具有许多独特的性质.本文利用正交实验方法,对非平衡磁控溅射技术制备无氢DLC膜增透膜进行了研究,得到了影响薄膜光学性能的主要因素和最佳的制备工艺.结果表明,非平衡磁控溅射制备的无氢DLC膜具有较宽的光谱透明区,锗基底单面沉积DLC膜,其峰值透射率达到61.4%,接近理论值.     

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。     

基于RFPECVD方法不锈钢上沉积类金刚石薄膜的机械与摩擦特性

讨论用射频等离子体增强化学气相沉积(RFPECVD)工艺,在室温下实现在1Cr18Ni9Ti不锈钢基底上镀类金刚石(DLC)膜.为提高DLC膜的结合力,首先在不锈钢基底上沉积Ti/TiN/TiC功能梯度膜.借助所设计的界面过渡层,成功地在不锈钢基底上沉积了一定厚度的DLC膜.通过优化沉积参数,所沉积的DLC膜在与100Cr6钢球对磨时摩擦系数低于0.020.在摩擦过程中DLC膜的磨损机制借助SEM、Raman分析进行了研究.     

脉冲阴极弧金属等离子体源的调试及其应用

对脉冲阴极弧金属等离子体源的工作参数进行了测量,研究了离子流与磁导管偏压以及磁场电流与离子流之间的关系,确定了其最佳工作参数.并应用该脉冲阴极弧金属等离子体源和等离子体浸没离子注入与沉积技术制备了TiC薄膜.对改性层的显微硬度、摩擦磨损性能和膜基结合力进行了测试分析.结果表明:合成TiC薄膜后,试样的显微硬度、摩擦磨损性能得到了明显的改善,并且膜层与基体之间的临界载荷为36.03 N.     

轮胎模具无氢DLC涂层的制备及表征

为探究轮胎模具类金刚石(DLC)涂层的应用前景,提高模具表面的硬度和疏水性,按照模具加工工艺制备35钢基体试样,利用电弧离子镀在基体上沉积无氢DLC涂层,对涂层粗糙度、三维表面形貌、断面结构、元素组成及含量、Raman光谱、纳米硬度和疏水性进行了分析.结果表明:通过改变粗糙度可以改善涂层的疏水性,涂层疏水性随粗糙度增大而显著增加,水接触角最高可达96°,且涂层硬度可达30.3 GPa.无氢DLC涂层可满足轮胎模具耐磨性和易清洁的使用要求,为制造高性能轮胎模具提供了一种可行的工艺选择.     

常温生长类金刚石薄膜的实验研究

利用射频等离子体增强化学气相沉积(RFPECVD)工艺在常温下实现在不锈钢、硅片、玻璃等基底上大面积沉积类金刚石(DLC)膜.薄膜表面光滑致密,与衬底的结合力较高.用Raman,FTIR,SEM,EDX研究了薄膜的形貌、结构与组分.用栓-盘摩擦磨损试验机测试了薄膜的摩擦系数.通过优化沉积参数,所沉积的DLC膜在与100Cr6钢球对磨时摩擦系数低于0.01.在摩擦过程中DLC膜的磨损机制借助SEM进行了研究.     

CVD of hard DLC films in a radio frequency inductively coupled plasma source

Chemical vapor deposition (CVD) of hard diamond-like carbon (DLC) films on silicon (100) substrates from methane was successfully carried out using a radio frequency (r.f.) inductively coupled plasma source (ICPS). Different deposition parameters such as bias voltage, r.f. power, gas flow and pressure were involved. The structures of the films were characterized by Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. The hardness of the DLC films was measured by a Knoop microhardness tester. The surface morphology of the films was characterized by atomic force microscope (AFM) and the surface roughness (R_a) was derived from the AFM data. The films are smooth with roughness less than 1.007 nm. Raman spectra shows that the films have typical diamond-like characteristics with a D line peak at 1331 cm⁻¹ and a G line peak at 1544 cm⁻¹, and the low intensity ratio of I_D/I_G indicate that the DLC films have a high ratio of sp³ to sp² bonding, which is also in accordance with the results of FTIR spectra. The films hardness can reach approximately 42 GPa at a comparatively low substrate bias voltage, which is much greater than that of DLC films deposited in a conventional r.f. capacitively coupled parallel-plate system. It is suggested that the high plasma density and the suitable deposition environment (such as the amount and ratio of hydrocarbon radicals to atomic or ionic hydrogen) obtained in the ICPS are important for depositing hard and high quality DLC films.     

利用前后处理技术改进钛／硅基板上的类金刚石场发射特性

采用微波等离子体化学气相沉积系统存钛/硅基板上沉积类金刚石薄膜,并利用拉曼光谱仪、扫瞄式电子显微镜及原子力显微镜研究了氢等离子体前处理及快速退火后处理对类金刚石薄膜场发射特性之影响.在沉积类金刚石薄膜之前,钛/硅基板使用了两种前处理技术:第一种为研磨金刚石粉末,第二种为研磨金刚石粉末后外加氢等离子体刻蚀处理.成长类金刚石薄膜后进行快速退火处理.发现不论是氢等离子体前处理还是快速退火后处理皆能改善场发射特性,其中经退火后处理的场发射特性比氢等离子体前处理的场发射特性改善更明显.其因之一在于快速退火后处理可在类金刚石薄膜表而形成sp2丛聚,提供了很多的场发射子,也同时增加了表面粗糙度;另一个原因可能是在快速退火后处理期间会使类金刚石薄膜进一步石墨化,因而提供了许多电子在通过类金刚石薄膜时的传输路径.研究结果表明:利用适当的前后处理技术可改进类金刚石薄膜的场发射特性,进而做为冷阴极材料之应用.     

Influence of hydrogen on the mechanical properties and microstructure of DLC films synthesized by r.f.-PECVD

This paper aims to investigate the influence of hydrogen on the variation of mechanical properties and microstructure of diamond-like carbon (DLC) films synthesized by radio frequency plasma chemical vapor deposition (r.f.-PECVD). The DLC films were deposited on a silicon substrate (p-type). The reactant gases employed in this paper are a mixture of acetylene and hydrogen. The ratio of hydrogen in the gas mixture was successively varied to clarify its influence on the roughness, thickness, microstructure, hardness, modulus, residual stress and wear depth for the DLC films. The results reveal that increasing the concentration of hydrogen decreases thickness and roughness. Meanwhile, increasing the hydrogen concentration causes the decrease of sp³ ratio, hardness as well as modulus. Finally, wear behavior is correlated to the surface morphology and hydrogen concentration for deposition with hydrogen-containing reactant gas.     

瓶体内表面制备类金刚石膜流场结构的格子波尔兹曼模拟

类金刚石膜(Diamond-like Carbon,DLC)具有优异的气体阻隔性能.在PET瓶体内表面制备DLC阻隔涂层时,阻隔涂层的均匀性会受到瓶体内流场结构(气压分布、速度分布等)的显著影响.本文应用格子波耳兹曼方法(Lattice Boltzmann Method/Model,LBM)对PET瓶体内制备DLC阻隔涂层时的流场结构进行模拟,研究了送气速度、气体运动粘度系数和装置结构变化时瓶体内部流场结构的变化.研究结果表明,降低进气速度和提高气体运动粘度系数有利于减弱回流而获得层流结构;装置结构的调整能够改变瓶体内的流场结构,采用恰当的异型装置可以获得较理想的流场结构,对实验工作具有一定的指导意义.     

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.     

脉冲真空放电离子密度的测量

由于采用脉冲放电沉积技术能够克服连续电弧离子镀沉积时产生的液滴及负偏压放电的缺点，特别是它在镀制类金刚石薄膜中显示出来的独特性能：不含氢和硬度高，使其在薄膜沉积技术中越来越受到广大研究者的重视。为了更深入地研究薄膜的沉积工艺和薄膜性能之间的关系，迫切需要对脉冲真空放电等离子体的微观参数进行深入透彻的研究，如离子密度及其空间分布等。本文介绍了测量脉冲真空电弧离子源离子密度的方法，并采用该方法测量了脉冲真空电弧离子源离子密度及其空间分布，分析和研究了影响离子空间分布的各种参数。     

Hydrogen induced microstructural variation in diamond and diamond like carbon thin films

Hydrogen plays a crucial role in the growth of micro-crystalline diamond (MCD) and diamond like carbon (DLC) thin films grown by plasma assisted chemical vapour deposition (PACVD) processes. It selectively etches graphite phase and helps in stabilizing the diamond phase. The presence of various hydrocarbon species in the plasma and their reaction with atomic, excited or molecular hydrogen on the substrate surface decide the mechanism of diamond nucleation and growth. Several mechanisms have been proposed but the process is still not well understood. Control of hydrogen and other deposition parameters in the PACVD process leads to deposition of yet another class of materials called diamond like carbon. By varying the concentration of hydrogen it is possible to produce purely amorphous carbon films on the one hand and amorphous hydrogenated carbon films (with as high as 60% hydrogen) on the other. Very hard, optically transparent and electrically insulating films characterize the diamond like behaviour. The proportion of hydrogen and its bonding with carbon or hydrogen in the film can be varied to obtain very hard to very soft films which could be optically transparent or opaque. The microstructure of these films have been investigated by a large number of techniques. The results show interesting situations. This paper reviews the work on the role of hydrogen on the growth, structure and properties of MCD and DLC thin films.     

Abscheidung superharter Kohlenstoffschichten mittels Laser‐Arco® auf dem Weg vom Labor in die industrielle Serienfertigung

Superhard carbon film deposition by means of Laser‐Arco® on the way from the Laboratory into the industrial series coating Diamond‐like carbon films (DLC) are more and more applied as wear protection coatings for components and tools due to their unique combination of high hardness, low friction and sticking tendency to metallic counter bodies. Up to now applied DLC films are hydrogen containing (a‐C:H) or metal carbon films (Me‐C:H) deposited by a plasma assisted CVD process from carbon‐hydrogen gas mixtures. Their wide industrial effort results from that the can be deposited with slowly modified coating machines for classical hard coating (e.g. TiN or CrN). A new generation DLC films are the hydrogen‐free ta‐C films (ta‐C = tetrahedral bounded amorphous carbon) with a between two and three‐times higher hardness and with a resulting higher wear resistance under extreme condition than classical DLC films. They have excellent emergency running properties at lubrication break down. Their industrial application is more difficult due to that they cannot deposited with modified coating machines for classical hard and DLC coating and a new technology with corresponding equipment was not available up to now. The laser controlled, pulsed arc deposition technology (Laser‐Arco®) of the Fraunhofer IWS Dresden has this potential. In kind of a Laser‐Arc‐Module‐source the ta‐C film deposition can be integrated in every industrial used deposition machine.     

Investigation of the properties of diamond-like carbon thin films deposited by single and dual-mode plasma enhanced chemical vapor deposition

In this study diamond-like carbon (DLC) films were deposited by a dual-mode (radio frequency/microwave) reactor. A mixture of hydrogen and methane was used for deposition of DLC films. The film structure, thickness, roughness, refractive index of the films and plasma elements were investigated as a function of the radio frequency (RF) and microwave (MW) power, gas ratio and substrate substance. It was shown that by increasing the H₂ content, the refractive index grows to 2.63, the growth rate decreases to 10 (nm/min) and the surface roughness drops to 0.824 nm. Taking into consideration the RF power it was found that, as the power increases, the growth rate increases to 11.6 (nm/min), the variations of the refractive index and the roughness were continuously increasing, up to a certain limit of RF power. The Raman G-band peak position was less dependent on RF power for the glass substrate than that of the Si substrate and a converse tendency exists with increasing the hydrogen content. Adding MW plasma to the RF discharge (dual-mode) leads to an increase of the thickness and roughness of the films, which is attributed to the density enhancement of ions and radicals. Also, optical emission spectroscopy is used to study the plasma elements.