T-shape filtered arc deposition system with built-in electrostatic macro-particle trap for DLC film preparation

A T-shape filtered arc deposition system (T-FAD) is a powerful tool to prepare high-quality diamond-like carbon (DLC) films. Most macro-particles (droplets) emitted from the graphite cathode are caught at the extension duct of the droplet catcher or collector facing the cathode, and then the clean plasma bent 90° is transported toward the substrate. However, further droplet reduction is still required in order to realize a higher quality film without droplet incorporation. In the present study, T-FAD employed an electrostatic droplet trap (ES-trap). A cylindrical ES-trap was placed in the extension duct part of the T-shape duct of an electromagnetic plasma transportation and droplet filter. The ion current at the exit of the T-filter duct and the current flowing to the ES-trap were measured as a function of the ES-trap bias voltage for various ES-trap positions. The deposition rate and number of droplets were also measured. As a result, it was found that the optimum voltage of the ES-trap was + 35 V and that it was better to place the ES-trap closer to the plasma beam in order to obtain fewer droplets on the film without an excessive decrease in the deposition rate. In the optimum condition, the number of droplets on the DLC film prepared with ES-trap was reduced to 1/3 of that without the ES-trap.     

Preparation of various DLC films by T-shaped filtered arc deposition and the effect of heat treatment on film properties

Different types of diamond-like carbon (DLC) films (ta-C, a-C, ta-C:H and a-C:H) were prepared on super hard alloy (WC-Co) substrate using a T-shape filtered arc deposition (T-FAD) system. At first, the film properties, such as structure, hydrogen content, density, hardness, elastic modulus, were measured. Ta-C prepared with a DC bias of −100 V showed the highest density (3.1 g/cm³) and hardness (70-80 GPa), and the lowest hydrogen content (less than 0.1 at. %). It was found that the hardness of the DLC film is proportional to approximately the third power of film density. The DLC films were then heated for 60 min in an electric furnace at 550 °C in N₂. Only the ta-C film hardly change its structure, although other films were graphitized. The 200-nm thick ta-C film was then heated for 60 min through the temperature range from 400 to 800 °C in N₂ with 2 vol.% of O₂ and the film structure found to be stable up to 700 °C. The substrate was oxidized at 800 °C, indicating the ta-C film had a thermal barrier function up to that temperature.     

Fabrication of diamond-like carbon film on rubber by T-shape filtered-arc-deposition under the influence of various ambient gases

Diamond-like carbon (DLC) films were prepared on rubber substrates using T-shape filtered-arc-deposition (T-FAD), which effectively removes the macrodroplets emitted from the graphite cathode spot from the processing plasma. In the present study, the influence of ambient gas (no gas, Ar, H₂, C₂H₂, C₂H₄, CH₄) was investigated. The DLC films adhered well to the rubber substrate. When the substrate was stretched, the small DLC islands were separated and clefs were opened. The deposition rate on rubber was approximately twice higher than that on a Si substrate. When hydrocarbon gas was introduced as an ambient gas, the deposition rate became higher than that for no gas and H₂ gas. In the cases of C₂H₄ and CH₄ gases, the DLC film was considered to contain a considerable amount of hydrogen. When C₂H₂ gas was used, the highest deposition rate with less surface roughness was achieved.     

Microstructure of interface for high-adhesion DLC film on metal substrates by plasma-based ion implantation

The diamond-like carbon (DLC) film was prepared on various metal substrates with a plasma-based ion implantation and deposition using superimposed RF and negative high-voltage pulses. The adhesion strength of DLC film was enhanced above the epoxy resin strength by implantation of carbon ions or mixed ions of carbon and silicon to the substrate surface before DLC deposition. In order to clarify the mechanism for improvement in adhesive strength, the microstructure of an interface between DLC film and substrate was examined in detail by transmission electron microscopy (TEM) observations in combination with EDS analysis. As a result, the enhancement in adhesion strength of DLC film by C ion implantation resulted from the formation of amorphous-like phase in the ion-implanted region of substrate, the production of carbon-component graded interface, the destruction of the oxide layer on the top surface of substrate, and the reduction of residual stress in DLC film by ion implantation during the deposition. The production of stress-free DLC film allowed us to demonstrate a supra-thick DLC film of more than 400 μm in thickness.     

Evaluation of pinhole defect in DLC film prepared by hybrid process of plasma-based ion implantation and deposition

Pinhole defect in diamond-like carbon (DLC) film prepared by a hybrid process of plasma-based ion implantation and deposition using toluene plasma was evaluated by the critical passivation current density in the anodic polarization method. The area ratio of pinhole defects to the SUS304 bare substrate was decreased exponentially with increasing DLC film thickness and reached about 3×10^-6% at film thickness. As a result, it is found that the corrosion resistance of DLC-coated specimens was improved with increasing film thickness. The production of an interfacial mixing layer by ion implantation from methane and acetylene plasmas between the DLC film and the substrate material reduced pinhole defects in the film.     

TiNi合金表面沉积类金刚石薄膜的性能评价

类金刚石膜作为新型的生物材料得到了广泛的关注。本实验制备的薄膜为典型的类金刚石膜,膜层比较致密、均匀和光滑。膜层硬度随离子束能量变化,在束电源为750V附近出现峰值,硬度达到了15GPa,该膜的摩擦系数为0.124。在Troyde’s模拟体液中的电化学分析表明,类金刚石膜显著提高了TiNi合金表面抗点蚀能力。     

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.     

真空磁过滤电弧离子镀沉积Ti-O薄膜及其血液相容性

采用真空磁过滤电弧离子镀技术在单晶硅(100)和载玻片表面沉积Ti-O薄膜,研究了不同氧分压(0.08、0.13、0.2Pa)对薄膜结构及血液相容性的影响.研究结果表明,随着氧分压的提高,Ti-O薄膜相结构从三氧化二钛转变为金红石结构二氧化钛.扫描电子显微镜观察表明,所制备薄膜表面结构致密,与基体结合紧密.血小板粘附实验结果表明,0.13Pa下制备的薄膜血液相容性优异,优于临床应用的热解碳材料.     

衬底偏压对四面体非晶碳膜结构和性能的影响

采用过滤阴极真空电弧技术并施加一定的衬底负偏压,在P(100)单晶硅片上制备出四面体非晶碳薄膜利用可见光Raman光谱研究薄膜的结构,通过BWF函数描述的单斜劳伦兹曲线拟合数据并获得表征曲线非对称性的耦合系数,从而反映了薄膜中sp3杂化的含量分别用原子力显微镜和纳米压入仪研究薄膜的表面形态和力学性能.结果表明:当衬底偏压为-80V时,薄膜中sp3杂化的含量最多,均方根表面粗糙度值最低(Rq=0.23nm),硬度、杨氏模量和临界刮擦载荷也最大,分别为51.49GPa、512.39GPa和11.72mN.随着衬底偏压的升高或降低,sp3键的含量减少,其它性能指标也分别降低.     

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.     

Characterization and tribological application of diamond-like carbon (DLC) films prepared by radio-frequency plasma-enhanced chemical vapor deposition (RF-PECVD) technique

Diamond-like carbon (DLC) films were successfully prepared on glass substrates and surfaces of selenium drums via radio frequency plasma enhanced chemical vapor deposition method. The microstructure, surface morphology, hardness, film adhesion, and tribological properties of the films were characterized and evaluated by X-ray photoelectron spectroscopy, atomic force microscopy, and micro-sclerometer and friction-wear spectrometer. The results showed that DLC films have smooth surfaces, homogeneous particle sizes, and excellent tribological properties, which can be used to improve the surface quality of the selenium drums and prolong their service life.     

真空阴极弧离子镀类金刚石碳（DLC）膜的碳弧稳定性研究

选用氩气、氩气加氢气、氩气加乙炔等气体作为介质，石墨作为靶材进行真空阴极弧离子镀来制备类金刚石碳膜。石墨电弧有其独特的电弧特性曲线，不同气体介质对碳弧特性的影响不同，磁场的大小对电弧的稳定性有很大作用，碳弧下基片偏流随电弧电压的增加而减小，试验得到表面光滑的类金刚石碳（DLC）膜，对膜的表面进行了SEM分析。     

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。     

Effect of gas introduction position on substrate etching by means of Ar-dominated graphite-cathodic-arc plasma beam in μT-FAD

Substrate etching by means of Ar-mixed graphite-cathodic-arc plasma beam was investigated in a newly-developed compact-type μT-FAD. The surface level and roughness change were measured as a function of the Ar gas flow rate, when Ar gas was introduced into the arc generation zone and in the vicinity of the substrate. When Ar gas was introduced to the arc generation zone, the etching rate was lower but the surface was relatively not roughened. When Ar gas was introduced in the vicinity of the substrate, the etching rate was higher but the surface was roughened. At the same gas flow rate (and pressure), the substrate was etched more than three times faster when Ar gas was introduced into the arc generation zone than to the vicinity of the substrate. After measuring the discharge and plasma conditions, the results were considered to be caused by the difference in the amount of plasma transported to the substrate.     

Annealing effect on the structural, mechanical and electrical properties of titanium-doped diamond-like carbon films

Titanium-doped diamond-like carbon (Ti-doped DLC) films with a Ti content of 1.1 at.% were synthesized on a Si substrate by a process that involves filtered cathodic vacuum arc (FCVA) and metal vapor vacuum arc (MeVVA) systems. The effect of annealing temperature on the microstructure, surface roughness, hardness and electrical resistivity of the resulting films was evaluated in this study. The Raman spectra revealed that the degree of graphitization of the Ti-doped DLC thin films was increased from 25 to 600 °C and the microstructure of the films is converted to a nano-crystalline graphite structure. The resulting films maintain a smooth surface after the annealing process. The hardness of the Ti-doped DLC films increases as the annealing temperature increases up to 400 °C because the induced defects and the inter-atomic bonds are repaired after the annealing process. But the hardness decreases at the higher temperature due to the increase of number and size of the nano-crystalline graphitic domains. Since the degree of graphitization of the thin films increases, the electrical resistivity of the Ti-doped DLC thin films decreases from 0.038 to 0.006 Ω cm.     

Effect of annealing on diamond-like carbon characteristics by electron spin resonance spectral analysis

We have examined the effect of annealing on physicochemical properties of the diamond-like carbon (DLC) films to produce higher quality films by the electron spin resonance spectral analyses of the immobilized dangling-bond sites (DBS), since amount of DBS reflects the characteristics of DLC films. On heat treatment of DLC deposited from ethylene monomer under anaerobic condition, the DBS decay was clearly shown, as the temperature raised. The decay described by second-order kinetics indicated that the recombination reaction of DBS progressed on heat treatment, suggesting that annealing treatment would accelerate the carbon-carbon covalent bonding network to produce harder films. In fact, the resulted DLC film derived from ethylene monomer showed non-existence of any type of oxygen atom based on X-ray photoelectron spectrum measurement, and water contact angle measurement showed higher hydrophobic surface of the DLC films.     

多弧离子镀沉积过程中等离子体参数对薄膜沉积的影响

采用平面探针测试了衬底附近的电流密度，弧电流和衬底偏压的增加均有助于增加到达衬底附近的离子的数量。弧电流增加引起村底的温升，衬底偏压对衬底温度影响较小。采用多弧离子镀技术沉积Cr-N薄膜，衬底偏压对薄膜的硬度影响较小；弧电流增大，薄膜的硬度随之降低。XRD分析表明，弧电流较高时，不利于Cr—N相的形成，薄膜中以Cr的宏观液滴为主，薄膜硬度较低。     

The influence of deposition rate on the stress and microstructure of AlN films deposited from a filtered cathodic vacuum arc

Aluminium nitride (AlN) thin films have been reactively deposited using a filtered cathodic vacuum arc system. A pulsed substrate bias was applied in order to increase the average energy of the depositing species. The stress and microstructure of the films were determined as a function of the deposition rate and pulse bias amplitude/frequency. The stress generated in films grown with high voltage pulsed bias depended on the deposition rate and a transition from tensile stress to compressive stress occurred as the deposition rate increased. This trend was accompanied by progressive changes in the microstructure. In order of increasing deposition rate, the films exhibited: a porous structure with tensile stress; a dense AlN film with compressive stress; and a dense AlN film showing evidence of a thermally induced reduction in stress.     

Influence of substrate bias voltage on properties of Pt thin films deposited by non-mass separated ion beam deposition method

Pt thin films were deposited on Si substrates by applying a negative substrate bias voltage using a non-mass separated ion beam deposition method. The effect of the substrate bias voltage on the properties of the deposited films was investigated. In the case of Pt thin films deposited without the substrate bias voltage, a columnar structure and small grains were observed. The electrical resistivity of the deposited Pt films was very high (49.3 ± 0.65 µΩ cm). By increasing the substrate bias voltage, no clear columnar structure was observed. At the substrate bias voltage of − 75 V, the resistivity of the Pt film showed a minimum value of 16.9 ± 0.2 µΩ cm closed to the value of bulk (10.6 µΩ cm).     

Adhesion property of SiOx-doped Diamond-like Carbon Films Deposited on Polycarbonate by Inductively Coupled Plasma Chemical Vapor Deposition

SiO_x-DLC (diamond-like coating) films as candidates for protection coating of polymers were prepared by using a pulse-biased inductively coupled plasma chemical vapor deposition system with acetylene, tetramethylsilane and oxygen gasses. Effects of the gas composition and O₂ plasma pre-treatment on adhesion of the SiO_x-DLC films were investigated. Adhesion strength of Si-DLC films (with 0% oxygen) was almost the same to that of undoped DLC films. By employing O₂-plasma pre-treatment, adhesion strength of the Si-DLC films was considerably improved, while that of the undoped DLC films was not. The SiO_x-DLC films with the carbon to oxygen (O/C) ratio of 0.15 showed adhesion strength as high as that of the Si-DLC films on the O₂-plasma pre-treated substrate. However, further improvement of adhesion strength of the SiO_x-DLC was not realized by employing the O₂-plasma pre-treatment. On the other hand, the SiO_x-DLC films showed favorable feature of high deposition rate and large optical band gap although higher O/C ratio (> 0.15) brought about poor adhesion strength of the films.