掺磷四面体非晶碳薄膜电极的电化学伏安特性

采用过滤阴极真空电弧技术, 以高纯磷烷气体为掺杂源制备掺磷四面体非晶碳(ta-C:P)薄膜. 利用X射线光电子能谱和激光拉曼光谱表征薄膜的成分和结构, 采用循环伏安和微分脉冲伏安分析薄膜的电化学行为. 结果表明, 磷的掺入没有引起薄膜非晶结构的明显变化, 只是促进了sp²杂化碳原子的团簇. 经过酸预处理的ta-C:P薄膜在硫酸溶液中有宽的电势窗口和低的背景电流; 对Cl^-有催化活性; 薄膜表面电子传输速度快; 对水溶液中Cu²⁺和Cd²⁺有检测活性. 因此具有良好导电性的ta-C:P薄膜适于作为电极并有望用于污水中重金属离子的分析检测等领域.     

离子束辅助磁控溅射制备类石墨碳膜的结构与性能研究

采用离子束辅助磁控溅射技术(IBMSD)制备了高硬度、低电阻率的类石墨碳膜(GLC), 用TEM和XRD考察其组成相, 用XPS、FTIR和电阻率间接确定其碳键结构, 并测定了不同气体和离子能 量辅助轰击下制备的几组薄膜的沉积速率、成分、硬度和粗糙度等. 结果表明: 采用IBMSD制备的GLC是一种以sp²键为主的非晶硬质碳膜. CH₄辅助轰击较Ar有利于提高沉积速率. 辅助轰击能量的增大使薄膜表面粗糙度先减小后增大, 硬度的变化一定程度上与粗糙度相关.     

电压对中频脉冲非平衡磁控溅射类金刚石薄膜结构与性能的影响

制备参数对类金刚石(DLC)薄膜的性能和结构有显著影响。利用中频脉冲非平衡磁控溅射新技术制备了DLC薄膜,采用Raman光谱、X射线光电子能谱仪、纳米压痕仪、光谱型椭偏仪研究了溅射电压对DLC薄膜微观结构、力学性能和光学性能的影响。结果表明:当溅射电压由550 V增加到750 V时,DLC薄膜中sp3杂化碳含量随溅射电压的增加而增加,当溅射电压超过750 V时,薄膜中sp3杂化碳含量随溅射电压的增加而减少;DLC薄膜的纳米硬度、折射率均随溅射电压的增加先增加而后减小,溅射电压为750 V时制备薄膜的纳米硬度及折射率最大。     

常压化学气相沉积方法制备非晶硅薄膜及其光致发光性能研究

使用改进的常压化学气相沉积(APCVD)系统制备了非晶硅薄膜,测量了样品的光致发光特性,使用Raman光谱和X射线光电子能谱(XPS)谱测量了薄膜的微结构特征.样品在523 nm出现发光峰,Raman光谱和XPS谱表明制备的薄膜结构中存在富氧相和富硅相的分相现象,分析认为相界面的存在是产生发光的原因.Raman光谱分峰结果表明薄膜中存在纳米晶粒.     

硼掺杂四面体非晶碳薄膜的光学特性研究

采用过滤阴极真空电弧技术制备了不同硼含量的掺杂四面体非晶碳薄膜(ta-C:B)。使用椭偏仪和紫外-可见光分度计测试了薄膜的折射率、消光系数、透过率和反射率。结果表明,硼含量小于2.13%时,硼含量增加,薄膜折射率缓慢增大;消光系数基本保持不变。当硼含量继续增加到3.51%和6.04%时,折射率分别迅速增加至2.65和2.71,相应的消光系数增大至0.092和0.154;而薄膜的光学带隙从2.29eV缓慢减小至1.97eV,后又迅速降至1.27eV。同时ta-C:B膜的透过率逐渐减小,反射率逐渐增大,表明硼的掺入降低了薄膜的透光性能。ta-C:B膜光学性能的变化,除了与sp3杂化碳的含量有关外,还取决于薄膜中sp2杂化碳的空间分布特点。     

磁过滤阴极弧制备四面体非晶碳膜热稳定性研究

为研究磁过滤阴极弧制备的四面体非晶碳(tetrahedral amorphous carbon, ta-C)膜在自然环境中使用的热稳定性, 将ta-C膜在空气中退火3h, 退火温度分别为200、400和500℃. 用XPS和Raman谱对膜的微观结构进行表征. 结果表明, 在400及400℃以下退火, XPS谱C1_s峰和Raman谱都没有明显变化. 当退火温度为500℃时, C1_s峰峰形仍然没有变化; Raman峰I_D/I _G增大, G峰峰位未变, 峰的对称性变好. 分析显示膜中石墨颗粒长大, 但没有发生石墨化. 说明磁过滤阴极弧制备的ta-C膜因不含氢和结构致密而表现出良好的热稳定性. 另外, 在退火温度为500℃时, 样品边缘已经氧化挥发.     

溅射靶功率对氮化碳薄膜结构的影响

利用双放电腔微波ECR等离子体增强非平衡磁控溅射技术,在Si(100)上制备氮化碳薄膜,并对薄膜进行了拉曼(Raman)、原子力显微镜(AFM)、X射线光电子谱(XPS)等结构的表征.发现溅射靶功率对制膜工艺、薄膜的结构和表面形貌产生很大影响.随着溅射靶功率的增大,薄膜的沉积速率减小,表面粗糙度增大,薄膜结构中的sp2含量增加.     

射频磁控溅射制备类金刚石薄膜的特性

采用射频磁控溅射技术,用高纯石墨靶在单晶硅片、抛光不锈钢片上制备了类金刚石薄膜(DLC)。采用Raman光谱、原子力显微镜、显微硬度分析仪,表征了类金刚石薄膜的微观结构、表面形貌、硬度。结果表明,制备的类金刚石薄膜中含sp2、sp3杂化碳键,具有典型的类金刚石结构特征。计算表明,对应sp3杂化碳原子含量的ID1IG为3.18;薄膜的表面十分平整光滑,表面粗糙度极低,平均粗糙度Ra为0.17 nm;薄膜硬度可以高达30.8 GPa。     

基体温度对中频脉冲非平衡磁控溅射技术沉积类金刚石薄膜结构与性能的影响

利用中频脉冲非平衡磁控溅射技术在不同的基体温度下制备了类金刚石(DLC)薄膜,采用Raman光谱、X射线光电子能谱(XPS)、纳米压痕测试仪、椭偏仪对所制备DLC薄膜的微观结构、机械性能、光学性能进行了分析。Raman光谱和XPS结果表明,当基体温度由50℃增加到100℃时,DLC薄膜中的sp3杂化键的含量随基体温度的升高而增加,当基体温度超过100℃时,DLC薄膜中的sp3杂化键的含量随基体温度的升高而减少。纳米压痕测试表明,DLC薄膜的纳米硬度随基体温度的增加先增加而后减小,基体温度为100℃时制备的薄膜的纳米硬度最大。椭偏仪测试表明,类金刚石薄膜的折射率同样随基体温度的增加先增加而后减小,基体温度为100℃时制备的薄膜的折射率最大。以上结果说明基体温度对DLC薄膜中的sp3杂化键的含量有很大的影响,DLC薄膜的纳米硬度、折射率随薄膜中的sp3杂化键的含量的变化而变化。     

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。     

Relative fraction of sp bonding in boron incorporated amorphous carbon films determined by X-ray photoelectron spectroscopy

Boron incorporated amorphous carbon (a-C:B) films were deposited by a filtered cathodic vacuum arc system using various percentage of boron mixed graphite cathodes. X-ray photoelectron spectroscopy (XPS) was employed to determine the properties of the films as a function of boron concentration. Deconvolutions of the XPS C 1s core level spectra were carried out using four different components. The relative fraction of sp³ bonding was then evaluated from the area ratio of the peaks at 285.0, 284.1 eV which were individually attributed to sp³ C-C, sp² CC hybridizations. The results showed that the sp³ content of a-C:B film decreases from 73.8 to 58.6% for the films containing boron from 0.59 to 2.13 at.%, and then gradually reduced to 42.5% at a slower rate with boron concentration up to 6.04 at.%. Furthermore, a series of a-C:B films with fixed boron content (2.13 at.%) were prepared to identify the relationship between sp³ bonding and substrate bias. It was found that the fraction of sp³ bonding increased from 50.28% at the bias voltage of 0 V and reached a maximum value of 66.3% at −150 V. As the bias voltage increased up to −2000 V, the sp³ content decreased sharply to 43.9%.     

Studying the high-field electron conduction of tetrahedral amorphous carbon thin films by conducting atomic force microscopy

The high-field electron conduction of tetrahedral amorphous carbon (ta-C) thin films substrate has been studied using a conducting atomic force microscope (C-AFM). The ta-C thin films with a high concentration of sp³ bonding (80–90%) were deposited on Si by field arc deposition (FAD). The high-field “conductance” and surface morphology were mapped simultaneously. At low bias, the “conductance” exhibits inhomogeneities on a large scale, presumably due to thickness variations or interface defects. However, at high bias, the small difference in “conductance” due to thickness variations or interface defects was buried by the high intrinsic “conductivity.” It has also been shown that high field causes electric breakdown in these films by converting sp³ bonding to sp² at high electric field.     

Thickness dependent electronic structure of ultra-thin tetrahedral amorphous carbon (ta-C) films

Microstructural properties of ultrathin (1-10 nm) tetrahedral amorphous carbon (ta-C) films are investigated by Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, X-ray Photoelectron Spectroscopy, Raman spectroscopy and Atomic Force Microscopy (AFM). The CK-edge NEXAFS spectra of 1 nm ta-C films provided evidence of surface defects (C―H bonds) which rapidly diminish with increasing film thickness. A critical thickness for stabilization of largely sp³ matrix structure distorted by sp² sites is observed via the change of π*C═C peak behavior. Meanwhile, an increase in the film thickness promotes an enhancement in sp³ content, the film roughness remains nearly constant as probed by spectroscopic techniques and AFM, respectively. The effect of thickness on local bonding states of ultrathin ta-C films proves to be the limiting factor for their potential use in magnetic and optical storage devices.     

Characterization of boron-doped diamond-like carbon prepared by radio frequency sputtering

Instead of the sophisticated deposition processes and boron sources reported in literature, the study used the radio frequency magnetron sputtering method to prepare boron-doped diamond-like carbon (DLC) films with p-type conduction. The adopted sputtering targets were composed of boron pellets buried in a graphite disc. The undoped DLC films prepared exhibited n-type conduction, based on the Hall-effect measurement. For boron content ≥ 2.51 at.%, the films showed semiconductor behavior converted from n-type to p-type conduction after annealing at 450 °C. B-DLC films with a boron content of 5.91 at.% showed a maximum carrier concentration of 1.2 × 10¹⁹ cm⁻³, a mobility of 0.4 cm²/V s, and an electrical resistivity of 1.8 Ω cm. The results of XPS and Raman spectra indicated that the motion of boron atoms was thermally activated during post-annealing, helping promote the formation of C-B bonds in the films. Moreover, the doping of boron in DLC films decreased sp³ bonding and facilitated carbon atoms to form sp² bonding and graphitization.     

Structural and surface energy analysis of nitrogenated ta-C films

Surface and bulk properties of the Filtered Cathodic Vacuum Arc prepared nitrogenated tetrahedral amorphous carbon (ta-C:N) films were characterized by X-ray Photoelectron Spectroscopy (XPS), Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS), Raman spectroscopy, Atomic Force microscopy and contact angle techniques. An increase in the Nitrogen (N) content of the films is accompanied by a reduction in the sp³ fraction, confirmed via the deconvolution of the C 1 s XPS spectra. Critical Raman parameters such as peak position and peak width of the G band, defect ratio, I_D/I_G and skewness of the G line were analyzed as a function of N content. ToF-SIMS showed the variance of chemical composition with the increase in the sputtering depth. While some amount of incorporated oxygen and hydrogen were observed for all films; for high N content ta-C:N films signature of CN bonds was evident. Surface energies (both polar and dispersive components) for these ta-C:N films were analyzed in a geometric mean approach. Contact angle measurements using both deionized water and ethylene glycol reveal that upon the insertion of nitrogen into ta-C films, the initial change in the contact angle is sharp, followed by a gradual decrease with subsequent increase in N content. The variation of contact angle with increasing N content corresponds to an increase of the total surface energy with an increase of the polar component and a decrease of the dispersive component.     

Superior wear resistance of diamond and DLC coatings

As the hardest known material, diamond and its coatings continue to generate significant attention for stringent applications involving extreme tribological conditions. Likewise, diamond-like carbon (DLC, especially the tetragonal amorphous carbon, ta-C) coatings have also maintained a high level interest for numerous industrial applications where efficiency, performance, and reliability are of great importance. The strong covalent bonding or sp³-hybridizaiton in diamond and ta-C coatings assures high mechanical hardness, stiffness, chemical and thermal stability that make them well-suited for harsh tribological conditions involving high-speeds, loads, and temperatures. In particular, unique chemical and mechanical nature of diamond and ta-C surfaces plays an important role in their unusual friction and wear behaviors. As with all other tribomaterials, both diamond and ta-C coatings strongly interact with the chemical species in their surroundings during sliding and hence produce a chemically passive top surface layer which ultimately determines the extent of friction and wear. Thick micro-crystalline diamond films are most preferred for tooling applications, while thinner nano/ultranano-crysalline diamond films are well-suited for mechanical devices ranging from nano- (such as NEMS) to micro- (MEMS and AFM tips) as well as macro-scale devices including mechanical pump seals. The ta-C coatings have lately become indispensable for a variety of automotive applications and are used in very large volumes in tappets, piston pins, rings, and a variety of gears and bearings, especially in the Asian market. This paper is intended to provide a comprehensive overview of the recent developments in tribology of super-hard diamond and DLC (ta-C) films with a special emphasis on their friction and wear mechanisms that are key to their extraordinary tribological performance under harsh tribological conditions. Based on the results of recent studies, the paper will also attempt to highlight what lies ahead for these films in tribology and other demanding industrial applications.     

Relationships between the fretting wear behavior and mechanical properties of thin carbon films

Mechanical load can drastically affect the properties of orthopedic implant materials. Damage of these materials usually occurs in contact surfaces, caused by abrasion, adhesion, fretting, delamination, pitting and fatigue depending on friction, lubrication, contact area, surface finish and level of loads (stresses).Carbon-based films are biocompatible with good bearing capacity, wear resistance, corrosion resistance and have a low coefficient of friction. However, great intrinsic stress prevents their wider application, mainly as implant coatings. To reduce this undesirable effect special deposition procedures are under development and/or the films are doped with suitable elements. It must be emphasized that DLC is not a material but a group of materials with a variety of properties. The relationships between the fretting wear behavior and mechanical properties of films based on carbon deposited by DC using the pulsed arc discharge PVD nitrogen doped (a-C) and the filtered pulsed arc discharge deposition system (ta-C) were tested.The composition of carbon films (sp³, sp²) was determined by Raman spectroscopy. Mechanical properties of elastic modulus and hardness were determined by a NanoTest apparatus with diamond Berkovich tip using the Oliver-Pharr procedure and adhesion was measured by nanoscratch tests. Tribological behavior was analyzed by fretting tests with a corundum ball under dry sliding lubricated conditions.The good performance of the hard carbon coatings is often discussed. Results from this study of fretting and the associated lubrication (bovine serum) show that ta-C coatings, despite their high hardness, have very low friction coefficients and low volume losses.     

Plasma-assisted deposition of BN thin films from B(N3)3

Thin boron nitride films have been deposited via plasma-assisted dissociation of the single-source precursor boron triazide. Infrared absorption and X-ray photoelectron spectroscopic studies have shown that the films are composed of sp²-bonded boron nitride, with a B/N ratio very near 1:1. The films are significantly more resistant to degradation in air and contain fewer impurities than those previously grown from dissociation of boron triazide. The film growth mechanism is discussed, along with information on the role ion bombardment plays in the resultant properties of the films.     

Correlations between substrate bias, microstructure and surface morphology of tetrahedral amorphous carbon films

The microstructure and surface morphology of ta-C films deposited on p-type (1 0 0) single crystal silicon with the substrate negative bias varying from 0 to 2000 V by the filtered cathodic vacuum arc technology have been investigated by means of Raman spectroscopy and atomic force microscope. The optimal deposition process of sp³-rich ta-C films can be confirmed in light of the relations between the coupling coefficients or full-width at half-maximum and the substrate negative bias. The surfaces of these films are uniform and smooth and RMS surface roughness is less than 0.4 nm. At the lower energetic grades, the more the content of sp³ is in the film, the smoother the surface of the film is. The dependence of the surface morphology and the impinging energy of the species can be illustrated according to the subimplantation growth mechanism. Nevertheless at the high energetic grade, the impinging ions with appropriate energy sputter and smoothen the surface so that the roughness might be even lower than the one of the films with the richest sp³ component.