Structure and blood compatibility of tetrahedral amorphous hydrogenated carbon formed by a magnetic-field-filter plasma stream

Tetrahedral amorphous hydrogenated carbon (ta-C:H) films with various substrate bias voltages were prepared using a magnetic-field-filter plasma stream deposition system. The microstructural and optical properties were studied using ellipsometric spectra. The refractive index n of each sample was obtained by simulating their ellipsometric spectral using Tauc-Lorentz oscillator model, and then the relative sp³ C ratio of each sample was calculated using Bruggeman effective medium approximation. The sp³ C fraction of each sample was quantified by using electron energy-loss spectroscopy (EELS). The blood compatibility of the samples was evaluated by tests of platelet adhesion, kinetic clotting time and thrombin time. The quantity and morphology of the adherent platelets on the surface of these samples were investigated using scanning electron microscopy. Results show that the spectroscopic ellipsometry is a helpful method to evaluate the sp³ carbon fraction of the carbon films. The substrate bias voltage has an obvious effect on sp³ content and blood compatibility of ta-C:H films. The sample prepared with substrate bias voltage of − 20 V showed the best blood compatibility. A simple bio-physical hypothetical model was proposed to explain the experiment results.     

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.     

Load-carrying capacity evaluation of coating/substrate systems for hydrogen-free and hydrogenated diamond-like carbon films

Diamond-like carbon (DLC) coatings have shown excellent tribological properties in laboratory tests. The coatings have also been introduced to several practical applications. However, the functional reliability of the coatings is often weakened by adhesion and load-carrying capacity related problems. In this study the load-carrying capacity of the coating/substrate system has been evaluated. The DLC coatings were deposited on stainless steel, alumina and cemented carbide with two different deposition techniques: the tetrahedral amorphous carbon (ta-C) coatings were deposited by a pulsed vacuum arc discharge deposition method and the hydrogenated carbon (a-C:H) films by radio frequency (r.f.) plasma deposition method. The load-carrying capacity of the coated systems was evaluated using a scratch test, Rockwell C-indentation test and ball-on-disc test. The effect of substrate material, substrate hardness, coating type and coating thickness was studied. An increase in substrate hardness increased the load-carrying capacity for the coated systems, as expected. The two coating types exhibited different performance under load due to their different physical and mechanical properties. For the load-carrying capacity evaluations the ball-on-disc configuration was found to be most suitable. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

厚度对真空电弧制备传感器用非晶ta-C膜性能的影响

采用双弯曲磁过滤阴极真空电弧沉积方法在传感器用P型单晶硅上制备ta-C膜,并通过实验测试的手段研究厚度对其组织及性能的影响。研究结果表明:逐渐延长沉积时间后,沉积速率始终保持1.6 nm/min的稳定状态。分别运用椭偏仪和光度计测定ta-C膜的厚度结果基本一致,差值小于2 nm。随着膜厚的增加,sp³C比例发生了减小,原先的sp³结构逐渐转变为sp²结构。当膜厚增大后,ta-C膜内形成了更高比例的sp³C。当膜厚增大后,G峰发生了低位移动,此时膜内的sp³C比例发生了降低。当膜厚增大后,ta-C膜色散值和残余压应力发生了不断减小,表明膜获得了更小的拓扑无序度。不同厚度的涂层粗糙度基本接近,都在0.6 nm以内。膜表面呈现光滑的连续分布形态,粗糙度保持基本恒定。     

超薄四面体非晶碳膜的结构和性能

使用磁过滤阴极真空电弧(FCVA)技术制备不同厚度的超薄四面体非晶碳膜(ta-C)，研究了表征和测量超薄ta-C碳膜微观结构和性能的方法以及膜厚的影响。使用X射线衍射仪验证椭圆偏振光谱仪联用分光光度计表征膜厚度的可靠性并测量了膜密度；用拉曼谱分析薄膜的内在结构，验证用椭偏联用分光光度计表征sp³ C含量的可靠性；用Stoney^，s公式计算了薄膜的残余应力。结果表明，薄膜的厚度由7.6 nm增大到33.0 nm其沉积速率变化不大，为1.7±0.1 nm/min；根据椭偏联用分光光度计的表征结果，薄膜中sp³ C的含量逐渐减少，拓扑无序度降低，与拉曼谱的表征结果一致；厚度为7.6 nm的超薄ta-C碳膜中p³ C的含量最高；随着厚度的增大薄膜中的残余压应力从14 GPa降低到5 GPa；厚度为11.0 nm的薄膜主体层密度最大，为3070 kg/m³，致密性较好；厚度对薄ta-C碳膜表面粗糙度的影响较小。用椭偏和分光光度计测量超薄ta-C碳膜的厚度和表征显微结构是可行的，X射线反射法可用于测量超薄ta-C碳膜密度和表面粗糙度，但是对薄膜的质量要求较高。     

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.     

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.     

超薄四面体非晶碳膜光学常数的精确测定

目的联合使用光谱型椭偏仪(SE)和分光光度计,精确测定超薄四面体非晶碳薄膜(ta-C)的光学常数。方法由于该薄膜的厚度对折射率、消光系数有很大的影响,仅采用椭偏参数拟合,难以准确得到该薄膜的光学常数,椭偏法测定的未知参数数量大于方程数,椭偏方程无唯一解。因此,加入透过率与椭偏参数同时进行拟合(以下简称SE+T法),以简单、快速、准确地得到该薄膜的光学常数。结果薄膜具有典型的非晶碳膜特征,SE和SE+T两种拟合方法得到的光学常数具有明显的差异,消光系数k在可见以及红外区最大差值可达0.020,紫外区最大的偏差约为0.005;折射率n在500 nm波长以上最大差值为0.04,在紫外光区和可见光区两种方法得到的n趋于一致。联用时的拟合结果具有更好的唯一性,而且拟合得到的光学常数变得平滑。结论椭偏与分光光度计联用适合精确测定测量范围内的超薄四面体非晶薄膜的光学常数。     

氩气流量对四面体非晶碳膜结构和摩擦性能的影响

利用自主研制的45°单弯曲阴极电弧沉积系统,通过改变Ar流量(2,5以及10 ml/min),在p型(100)硅基底上制备了四面体非晶碳膜。借助表面轮廓仪测定薄膜厚度和粗糙度变化;采用X射线光电子谱获得薄膜微结构信息,利用残余应力仪和摩擦磨损试验机测定薄膜的内应力和摩擦学性能。实验结果表明:随Ar流量增加,薄膜的沉积速率降低,表面趋于光滑;薄膜中sp3含量由2 ml/min时的68%下降至10 ml/min时的55%;薄膜应力值随Ar流量的增大而减小,在10 ml/min处取得最小值;不同Ar流量条件下所制备薄膜的摩擦系数在0.024~0.045之间,且随Ar流量增加而增大。