刻蚀工艺对四面体非晶碳膜生长及其性能的影响

目的研究不同等离子体刻蚀工艺对基体和四面体非晶碳膜(ta-C)的影响,并进一步考察不同电弧等离子体刻蚀时间对ta-C薄膜结构的影响。方法采用自主设计研制的45°单弯曲磁过滤阴极真空电弧镀膜设备,进行不同等离子体刻蚀以及ta-C薄膜的沉积。使用等离子体发射光谱仪表征离子种类及其密度,使用椭偏仪表征薄膜厚度,原子力显微镜表征刻蚀后的基体粗糙度,拉曼光谱仪和XPS表征薄膜结构,TEM分析薄膜的膜基界面结构。结果辉光刻蚀工艺中,作用的等离子体离子以低密度的Ar离子为主;而电弧刻蚀时,作用的等离子体离子为高密度的Ar离子和少量的C离子,并且能够在基体表面形成约15 nm的界面层,并实现非晶碳膜(a-C)的预沉积。随电弧等离子体刻蚀时间增加,ta-C薄膜的sp3含量有所降低。结论相比于辉光刻蚀,电弧刻蚀利于制备较厚的ta-C薄膜。这主要是因为电弧刻蚀时,基体表面形成良好的界面混合层,并预沉积了非晶碳膜,形成a-C/ta-C的梯度结构,有助于增强膜基结合力。     

Corrosion protection of ultra-thin ta-C films for recording slider applications at varied substrate bias

Ultra-thin tetrahedral amorphous carbon (ta-C) films have been prepared by filtered catholic vacuum arc system for recording slider applications. In order to study the corrosion behavior of the slider coatings deposited at different substrate bias, the micro-structure and surface properties of the ta-C films were respectively investigated in terms of Raman spectroscopy, atomic force microscopy, water contact angle and corrosion measurements. Results showed that a very smooth ta-C film with lowest surface energy and highest sp³ bonding content was obtained at the medium bias voltage of 100 V. However, as to the protection against corrosion, the optimum bias was found to be greater than that giving the maximum diamond-like properties.     

Plasma biasing to control the growth conditions of diamond-like carbon

It is well known that the structure and properties of diamond-like carbon, and in particular the sp³/sp² ratio, can be controlled by the energy of the condensing carbon ions or atoms. In many practical cases, the energy of ions arriving at the surface of the growing film is determined by the bias applied to the substrate. The bias causes a sheath to form between substrate and plasma in which the potential difference between plasma potential and surface potential drops. In this contribution, we demonstrate that the same results can be obtained with grounded substrates by shifting the plasma potential. This “plasma biasing” (as opposed to “substrate biasing”) is shown to work well with pulsed cathodic carbon arcs, resulting in tetrahedral amorphous carbon (ta-C) films that are comparable to the films obtained with the conventional substrate bias. To verify the plasma bias approach, ta-C films were deposited by both conventional and plasma bias and characterized by transmission electron microscopy (TEM) and electron energy loss spectrometry (EELS). Detailed data for comparison of these films are provided.     

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.     

Effect of the carbon ion energy on the microstructure of ta-C/Cr multilayers

The effect of the carbon ion energy applied in a pulsed arc deposition process on the morphology of the interface between Cr layers and subsequently deposited tetrahedral bonded carbon (ta-C) coatings was investigated. The carbon ion energy was varied through the bias voltage between ~ 25 and 500 eV. Small-angle and wide-angle X-ray scattering (SAXS and WAXS), high resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS) were used as the central experimental methods for microstructure analysis. In order to improve the scattering power of the ta-C/Cr interfaces for SAXS, the samples were prepared in the form of ta-C/Cr multilayers. SAXS revealed density and thickness of individual layers in the multilayer stack, and the roughness and morphology of the ta-C/Cr interfaces. The density of ta-C layers ranged between 2.72 and 3.15 g/cm³, which was related to the amount of sp³ bonds between 37% and 71%. The amount of the sp³ bonds calculated from the density of the ta-C layers agreed well with the amount of the sp³ bonds determined using EELS. HRTEM confirmed both the increase of the interface roughness with increasing carbon ion energy and the changes in the correlation of the interface corrugations observed by SAXS. Furthermore, HRTEM approved the crystallinity of Cr layers revealed by WAXS.     

Effect of high substrate bias and hydrogen and nitrogen incorporation on spectroscopic ellipsometric and atomic force microscopic studies of tetrahedral amorphous carbon films

The influence of substrate bias and hydrogen/nitrogen incorporation on the optical properties [studied by spectroscopic ellipsometry (SE)] and surface morphology [studied by atomic force microscopy] of tetrahedral amorphous carbon (ta-C) films, deposited by S bend filtered cathodic vacuum arc (FCVA) process, is reported. SE spectra of the imaginary part of the dielectric constant are used to estimate carbon bonding ratios. In ta-C films, optical constants increase with substrate bias and hydrogen/nitrogen incorporation. The optical band gap (E_g) and sp³ content increase up to −200 V substrate bias and then decrease. E_g increases with hydrogen incorporation but is unchanged by nitrogen incorporation.     

Effect of substrate bias on microstructure and tribological performance of GLC films using hybrid HIPIMS technique

The Cr-doped hydrogen-GLC films were prepared by a hybrid magnetron sputtering system composed of a direct current magnetron sputtering (DC-MS) source of carbon and a high power impulse magnetron sputtering (HIPIMS) source of Cr with reactive gas of C2H2.The hydrogen-free GLC and Cr-doped GLC films were also prepared for comparison.The influence of substrate bias on the Cr-doped hydrogen-GLC films was investigated.With the increase of substrate bias from 100 V to 250 V,the re-sputtering of weak bonding sp2 firstly occurred and induced an increased sp3 bonding.However,the following sp3 to sp2 transformation resulted in a decreased sp3 bonding.The change trends of surface roughness and friction coefficient with the increased bias voltages were the same as those of sp3 bond.The lowest surface roughness and lowest friction coefficient corresponded to the highest sp3 with the Cr-GLC-H films at the bias voltage of-100 V.     

Structural analysis for the stress variation of ta-C film with deposition energy: A molecular dynamics simulation

Molecular dynamics simulations are performed on the atomic origin of the evolution of residual stress in tetrahedral amorphous carbon (ta-C) film using the empirical Tersoff potential. The densities of and residual stresses in the amorphous films generated by molecular dynamics simulations were found to be in good agreement with the corresponding experimental results. A radial distribution function analysis shows that the peak at approximately 2.1 Å found in high-stress configurations, which is referred to as a satellite peak, is closely linked with the variation of the residual stress in ta-C film.     

Effect of substrate bias voltage on the texture and microstructure of Cu thin films deposited by ion beam deposition

Cu thin films deposited by non-mass separated ion beam deposition under various substrate bias voltages were investigated. The film textures and microstructure were analyzed by X-ray diffraction and field emission scanning electron microscopy, and the resistivity of the film was measured with the Van der Pauw method. It was found that the optimum negative substrate bias voltage for Cu films was −50 V. The Cu films deposited without substrate bias voltage showed a columnar grain structure with small grains and random orientation. However, when a substrate bias voltage of −50 V was applied, the Cu films had a non-columnar structure with a strong (111) texture and large grains. The electrical resistivity of the Cu films decreased remarkably with increasing negative substrate bias voltage, and reaching a minimum value of 1.8±0.13 μΩ cm at the substrate bias voltage of −50V.     

Effect of negative substrate bias voltage on the nucleation and growth of Cu films during the initial stage of ion beam deposition

We focused the effect of a negative substrate bias voltage on the nucleation and growth of Cu films during the initial stage of ion beam deposition. The resultant microstructure of Cu films was observed by atomic force microscopy (AFM). It was found that Cu films with or without a negative substrate bias voltage have a different dependence of nucleation and growth. It was established that the mechanism of nucleation and growth of Cu films is changed to a progressive nucleation and lateral growth by a sufficient migration of adatoms accelerated by applying a negative substrate bias voltage.     

偏压对离子源辅助HiPIMS制备纳米TiN薄膜力学性能和耐蚀性能的影响

为提高磁控溅射制备薄膜的致密度,减少结构缺陷,研究薄膜显微结构对硬度、韧性及耐蚀性能的影响,尝试在改变离子源和基材偏压的条件下,采用离子源辅助HiPMIS技术在304不锈钢和P型（100）晶向硅片上制备TiN纳米薄膜。采用扫描电子显微镜、小角X射线衍射仪对薄膜的形貌和晶体结构进行分析;采用纳米压痕仪和维氏硬度计分别测量计算薄膜的硬度和韧性,并通过电化学工作站对薄膜的耐蚀性能进行检测。结果表明：随着偏压的增加以及离子源的引入,离子的轰击效应增强,薄膜的沉积速率下降,致密度增加。偏压为-200 V时,薄膜的硬度达到最大值16.2 GPa,且对应的晶粒尺寸最小,（111）晶面衍射峰的强度最高。离子源的加入使所制备薄膜的硬度略有下降。此外,随着偏压的增加,薄膜的韧性和耐腐蚀性能也有一定提高。     

Effects of tetrahedral amorphous carbon film deposited on dental cobalt–chromium alloys on bacterial adhesion

The dental cobalt–chromium alloys are an important biomaterial used in making artificial dentures. Bacterial adhesion to cobalt–chromium alloys usually results in severe complications such as periodontal infection, secondary caries, and denture stomatitis, which have severe adverse impacts on human health. Therefore, an effective method is needed to reduce the bacterial adhesion to dental cobalt–chromium alloys. The aim of this study was to investigate the effects of ta-C films deposited on a dental cobalt–chromium alloy on the adhesion of Streptococcus mutans (ATCC175), Actinomyces viscosus (ATCC19246) and Candida albicans (ATCC76615). A filtered cathodic vacuum arc (FCVA) technique was used to coat the cobalt–chromium alloy with a ta-C film. Atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to analyze the surface characteristics of the coating. Surface roughness was detected. Surface free energy and its components were calculated by measuring the contact angle. The results showed that the maximum sp³ fraction was achieved at 200 V substrate bias voltage. Compared with uncoated specimens, the ta-C film coated specimens had a lower surface roughness, a higher surface energy and a higher hydrophilicity. Most importantly, the adhesion of the three tested bacterial strains to the ta-C film coated cobalt–chromium alloy was significantly decreased. These results showed that ta-C film surface treatment could significantly reduce the bacterial adhesion to dental cobalt–chromium alloys, suggesting the potential of ta-C film surface treatment in artificial denture applications.     

真空阴极弧离子镀类金刚石碳膜Raman光谱研究

分别采用带有和不带有弯曲弧磁过滤器的真空阴极弧离子镀方法，在不同镀膜电流以及不同基片偏流下分别制备了类金刚石碳膜，对比了不同结构下类金刚石碳膜的Raman光谱特点对其Raman光谱的D峰和G峰采用Gaussian-Lorentzion的几率分布进行了分峰，并着重讨论了基片偏流、弯曲磁场等沉积参数对膜结构的影响结果表明，氩分压对膜结构影响不大，较大的偏流以及弯曲磁场的加入均有利于sp^3杂化碳键的形成。     

Preparation of ZrO<Subscript>2</Subscript> dielectric layers by subsequent oxidation after Zr film deposition with negative substrate bias voltage

ZrO₂ dielectric layers were prepared by a two-step process, a deposition of pure Zr film with and without a negative substrate bias voltage and a subsequent oxidation of the Zr films. We focused on the effect of the negative substrate bias voltage on the Zr film deposition and the subsequent oxidation of the Zr films. As a result, the Zr film deposited at the substrate bias voltage of −50 V (Vs = −50 V) was found to have a high intensity peak of Zr (100) and a uniform and smooth surface. From the capacitance-voltage and current-voltage measurements of the ZrO₂ films, a high dielectric constant of 21 and the equivalent oxide thickness (EOT) of 2.6 nm were obtained on the oxidation layer of the Zr film deposited at Vs = −50 V. On the other hand, a low dielectric constant of 15 and the EOT of 3.6 nm was obtained on that of the Zr film deposited at Vs = 0 V. The leakage current density of the ZrO₂ film (Vs = −50 V) was 5.69×10⁻⁴ A/cm², and this value was much lower than the 1.21×10⁻⁴ A/cm² for the ZrO₂ film (Vs = 0 V). It was found that the two-step process by subsequent oxidation after film deposition using a negative substrate bias voltage is useful for obtaining high-quality dielectric layers.     

基片偏压对电弧离子镀ZrN薄膜微结构和表面形貌的影响(英文)

在不同的基片偏压下利用电弧离子镀技术制备氮化锆薄膜,以考察基片偏压对氮化锆薄膜微结构和表面形貌的影响。利用XRD、EPMA和FE-SEM等技术对不同偏压时得到ZrN薄膜的相结构、成分和表面形貌进行表征。结果表明,薄膜中存在立方氮化锆和六方纯锆相;随着基片偏压的增大,薄膜的择优取向由(111)变为(200),最后变为(111),晶粒尺寸由30nm减小至15nm。同时发现,随着基片偏压的增大,薄膜微结构由明显的柱状特征变为致密的等轴晶特征,表明由偏压增强的离子轰击能有效抑制柱状晶生长;薄膜沉积速率和锆氮摩尔比随着基片偏压的增大先增大后减小,在-50V时达到最大。     

掺磷四面体非晶碳薄膜的电学性能

采用过滤阴极真空电弧技术以PH_3为掺杂源,施加0—200 V基底负偏压,制备了掺磷四面体非晶碳(ta-C:P)薄膜,利用X射线光电子能谱(XPS)和Raman光谱研究ta-C:P薄膜的微观结构,通过测定变温电导率和电流-电压曲线,考察ta-C:P薄膜的导电行为。结果表明,磷掺入增加了薄膜中sp~2杂化碳原子含量和定域电子π/π~*态的数量,提高了薄膜的导电能力,且以-80 V得到的ta-C:P薄膜导电性能最好,在293—573 K范围内ta-C:P薄膜中的载流子表现出跳跃式传导和热激活传导两种导电机制,电流-电压实验证明ta-C:P薄膜为n型半导体材料。     

Influence of substrate bias on microstructure and morphology of ZrN thin films deposited by arc ion plating

Zirconium nitride thin films were fabricated using arc ion plating under negative substrate biases to investigate the influence of substrate bias on the ZrN films. The phase, composition, and surface morphology of the ZrN ?lms, with respect to substrate bias, were studied by XRD, EPMA, and FE-SEM, respectively. The results show that cubic ZrN and hexagonal Zr phases form in the ZrN films. The competition between surface energy and strain energy makes the preferred orientation change from (111) to (200) and then back to highly (111) preferred orientation as a function of substrate bias. With the increase of bias voltage, the crystallite size of ZrN films reduces from 30 to 15 nm. Meanwhile, the film microstructure evolves from an apparent columnar structure to a highly dense equiaxed structure, indicating that the ion bombardment enhanced by substrate bias can suppress the columnar growth in the ZrN films. Deposition rate and mole ratio of Zr to N increase with the increase of bias voltage and reach the maximum at –50 V, and then show a decline trend when bias voltage further increases.     

Cathodic arc plasma deposition of nano-multilayered Zr-O/Al-O thin films

Thin films of Zr-O/Al-O were deposited on SKD 11 tool steel substrate using Zr and Al cathodes in a cathodic arc plasma deposition system. The substrates were mounted on a rotating holder which alternatively exposed them to plasma from the two cathodes. The influence of the Zr and Al cathode arc currents and the substrate bias on the mechanical and the structural properties of the films were investigated. Films with a nano-layered structure of alternating Al-rich and Zr-rich layers were obtained. The Zr layers contained nano-crystallites of (101) oriented t-ZrO structure. Crystallites with α-Al₂O₃ structure were observed only when the substrate was negatively biased in the 100-150 V range. The hardness of the film decreased with the increase of Zr cathode current from 60 to 80 A, increased when the Al cathode current increased from 25 to 30 A, and decreased when the Al cathode current increased from 30 to 35 A. The hardness of the film increased with the increase of bias voltage up to − 150 V and then decreased with further increase of the negative bias. The film structure was elucidated by HRTEM microscopy. Good correlation between the residual stress and the hardness enhancement of the films was observed.     

Influence of deposition parameters on the internal stress in a-C:H films

Amorphous hydrogenated carbon (a-C:H) films were deposited from a mixture of C₂H₂ and Ar by the r.f. plasma-enhanced chemical vapor deposition technique. The internal stress was measured by the substrate bending method. The films were characterized by IR and positron annihilation spectroscopies. The influence of substrate bias and C₂H₂ content in the feedgas on the internal stress and structure were studied. It was found that the hydrogen content and sp³/sp² ratio decrease with an increase in substrate bias and a decrease in C₂H₂ content in the feedgas. However, the variations in H content and sp³/sp² ratio with C₂H₂ content are much less than that with substrate bias. The void density, which increases monotonically with the increase of C₂H₂ content, initially decreases and then increases with the increase of substrate bias. The internal stress in a-C:H films decreases with the increase of substrate bias and C₂H₂ content in the feedgas. The decreases of the H content and sp³/sp² ratio in the films are the main factors that cause the reduction in internal stress. The void density has a minor effect on the internal stress.     

偏压类型对磁过滤等离子体制备优质类金刚石膜的影响

采用自行研制的磁过滤等离子体装置在单晶Si基底上制备了优质类金刚石(DLC)薄膜.运用红外光谱(IR)、扫描电镜(SEM),原子力显微镜(AFM)和纳米压痕仪对样品进行了表征和分析,着重研究了衬底偏压类型对制备薄膜的影响.结果表明:在无偏压或周期性负偏压下制备的DLC薄膜的sp3含量比连续负偏压下制备的薄膜的sp3含量要高;同时在周期性偏压下制备的薄膜表面较光滑,其表面粗糙度仅为0.1 nm,sp3含量达到66.8%,相应的纳米硬度也较高(达到80GPa).同时对相应的成膜机理进行了讨论.