Thickness dependence of the structure of diamond-like carbon films by Raman spectroscopy

The thickness dependence on structure of Diamond-like carbon films of a-C:H deposited by ECR-CVD and ta-C by FCVA has been studied by visible and UV Raman spectroscopy. The results show that the evolution of structure as a function of the thickness for a-C:H films contains two stages: when thickness is less than 50 Å, the film contains less sp³ sites and not continuous; and when thickness is up to 50 Å, the film contains more sp³ sites and become continuous. However, for ta-C films, it includes three stages. In the first stage of thickness lower than 20 Å, the film is not continuous, and also contains less sp³. In the second stage of thickness between 20 Å and 50 Å, the sp³ site abruptly shifts a higher value in 20 Å and then keeps stable. In the third stage of thickness over 50 Å, the sp³ site has a little increase and then almost not changed. Thus, the fundamental limitation thickness in using DLC as an ultrathin overcoat for ta-C films is 20 Å (> 10 Å), and for a-C:H films is 50 Å. The implications of result on the mechanisms proposed for the film growth mode were also discussed.     

Structure and properties of silver-containing a-C(H) films deposited by plasma immersion ion implantation

In this study, we have grown silver-containing hydrogenated (a-C:H) and non-hydrogenated (a-C) amorphous carbon coatings by two plasma immersion ion implantation methods: I) chemical vapor deposition of methane combined with pulsed filtered cathodic arc deposition of silver, and II) by alternating arc pulses from graphite and silver in a dual cathodic arc plasma source. This unique “bias selective” feature of the deposition system allowed the deposition of silver with the substrates at ground and avoided the sputtering of the grown a-C film. Chemical composition of the samples was analyzed by acquiring their compositional depth-profiles using radio-frequency Glow Discharge Optical Emission Spectroscopy (rf-GDOES), while the microstructural properties were analyzed by X-ray absorption near edge spectroscopy (XANES) and Raman spectroscopy. In this contribution, we compare mechanical and biomedical properties by means of nanoindentation and cell viability tests, respectively, of a-C(H) films obtained by two different plasma immersion ion implantation techniques.     

Mechanical properties of high-density diamond like carbon (HD-DLC) films prepared using filtered arc deposition

Because high density DLC (HD-DLC) films prepared using filtered arc deposition (FAD) systems possess high hardness, low friction coefficients, and a smooth surface, they have been good candidates for use in tribological applications. The aim of present work is the investigation of the mechanical and structural properties of HD-DLC films.The experimental conditions were the following: arc current, 50 A; base pressure, less than 3 × 10^− 3 Pa; substrate bias, DC-100 V; substrate temperature, less than 100 °C. The HD-DLC films were formed on silicon wafers and tungsten carbide (WC) substrates. The film properties of hardness, composition, structure, and friction were analyzed.The film hardness is high, 80-90 GPa, with a low friction coefficient of less than 0.1.     

Influence of bias on properties of carbon films deposited by MCECR plasma sputtering method

The mirror-confinement-type electron cyclotron resonance(MCECR) plasma source has high plasma density and high electron temperature. It is quite useful in many plasma processing, and has been used for etching and thin-film deposition. The carbon films with 40 nm thickness were deposited by MCECR plasma sputtering method on Si, and the influence of substrate bias on the properties of carbon films was studied. The bonding structure of the film was analyzed by the X-ray photoelectron spectroscopy(XPS), the tribological properties were measured by the pin-on-disk(POD) tribometer, the nanohardness of the films was measured by the nanoindenter, and the deposition speed and the refractive index were measured by the ellipse meter. The better substrate bias was obtained, and the better properties of carbon films were obtained.     

Microstructure and mechanical properties of hard carbon films prepared by heat treatment of a polymer on steel substrate

Hard carbon films were prepared on steel substrates by heat treatment of a polymer-poly(phenylcarbyne) at various temperatures in an Ar atmosphere. The influence of heat treatment temperature on the microstructure, surface roughness and mechanical properties of the resulting films was investigated by Raman spectroscopy, atomic force microscopy (AFM), nanoindenter, scratch and ball-on-disk sliding tests. The sp² C fractions of the hard carbon films and the root mean square (RMS) roughness increased as the heat treatment temperature increased. The preparation at 800 °C gave rise to carbon films with the maximum hardness and the hardness dropped with the higher temperature due to graphitization. In addition, with increasing heat treatment temperature, critical load of the carbon films, the ability of friction reduction and wear resistance increased gradually. The influence of the heat treatment temperature on the mechanical properties of the hard carbon films is discussed in combination with the structural analysis.     

Magnetic and electric properties of C-Co thin films prepared by vaccum arc technique

Cobalt doped carbon thin films have been deposited by a pulsed anodic electric arc technique. The films were characterized by high resolution transmission electron microscopy, electric measurements under dc magnetic fields, and ac magnetic susceptibility measurements within a temperature range 15-300 K. An insulating to a metallic state transition at a critical temperature around 60 K was observed.     

靶电流对非平衡磁控溅射制备无氢碳膜结构与性能的影响

利用非平衡磁控溅射(UBMS)技术在硅基片上制备了无氢碳膜,并采用Raman光谱、X射线衍射、傅立叶变换光谱等手段对不同靶电流下沉积的薄膜的微观结构、沉积速率、粗糙度、表面接触角及红外透过率进行了研究.试验结果表明:随着靶电流的增大,薄膜的沉积速率增大,薄膜中sp3键含量增加,薄膜表面接触角增大,红外透过率增大;而薄膜的粗糙度随靶电流增加而减小.靶电流是影响非平衡磁控溅射制备无氢碳膜结构与性能的1个主要因素.     

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.     

Properties of nanostructured cubic boron nitride films prepared by the short-pulse laser plasma deposition techniques

Nanostructured cubic boron nitride (BN) films were synthesized on molybdenum substrates by using the short-pulse laser plasma deposition techniques. The surface morphologies, chemical compositions, bond structures, and mechanical properties of the obtained BN thin films have been investigated by scanning electron microscopy, Raman scattering, Fourier transform infrared spectroscopy (FTIR), energy dispersive spectra, and hardness measurements. High power density laser deposition yielded boron-rich BN nanorod arrays where tBN component dominates. Reducing power density down to 8 × 10⁷ W/cm² during laser plasma deposition produced flat cBN thin films. Typical TO and LO bands in the Raman and FTIR spectra of the cBN samples were identified. The cBN sample with hardness up to 40 GPa was obtained.     

Deposition of alpha-WC/a-C nanocomposite thin films by hot-filament CVD

Nanostructured tungsten carbide coatings containing amorphous carbon (a-C) phases are interesting composite materials. The incorporation of the a-C phase simultaneously improves the thermal stabilization of the carbide phase and the coatings' friction coefficient. Such nanocomposite coatings are also electrically conducting with resistivity values comparable to the transition metals, which make them useful for a number of electrochemical and electronic applications. Many deposition techniques have been used for the synthesis of these coatings. However, most of them lead to the formation of complex crystalline structures consisting of more than one carbide phase and varying amorphous contents.The novelty of this work is the formation of WC coatings with controllable film thickness and a-C content, almost fully composed by α-WC phase. Tungsten carbide coatings were deposited on silicon substrates using a hot filament chemical vapor deposition (HFCVD) equipment with hydrogen and methane as the deposition gasses. Two types of nanocomposite coatings were obtained with significant variations of the carbide phase and a-C contents.The results point to the W vaporization time as the main parameter influencing the film thickness. We also conclude that the formation of α-WC phase is the combining result of W filaments vaporization in vacuum and the carbon incorporation at low substrate temperature. The small crystallite size of the carbide grains (5-6 nm) could also explain the rapid diffusion of C through the tungsten-containing layer. Preliminary results show that the amount of a-C incorporated in the film is not only dependent on the CH₄/H₂ ratio but also on the substrate temperature.     

Adhesion improvement of hydrogenated diamond-like carbon thin films by pre-deposition plasma treatment of rubber substrate

For reduction of friction and enhancement of wear resistance of dynamic rubber seals, thin films of hydrogenated diamond-like carbon (DLC) have been deposited on hydrogenated nitrile butadiene rubber (HNBR) via magnetron-enhanced plasma chemical vapor deposition (ME-PCVD). Pre-deposition plasma treatment of HNBR substrate is proved to be crucial for the improvement of film performance due to enhanced interfacial adhesion. The columnar structure and the crack network formed during deposition enhance the flexibility of DLC thin films and exhibit strain tolerance up to 5%. Below 50% stretch strain and after unloading, thin DLC films of ∼ 300 nm thickness still adhere on the rubber substrates and no spallation or delamination is observed. The thin DLC film deposited on Ar-plasma pre-treated rubber at − 400 V substrate bias potential exhibits a very low coefficient of friction of 0.175 (compared to > 1 of uncoated HNBR rubber). After tribotests even under high normal load of 3 N, almost no wear can be seen on the films. Such tribological property is even better than that of 1 µm thick DLC or Me-DLC coated rubbers.     

Raman spectroscopy study of DLC films prepared by RF plasma and filtered cathodic arc

The build-up of intrinsic stress in carbon thin films deposited by vapour deposition can be a major cause of delamination. Arguably, this issue has been one of the main reasons why the industrial exploitation of carbon vapour deposited films has so far been of limited success. In the present study we deposited single and multilayer thin films of carbon and found that under certain deposition conditions, we were able to produce thin films free from delamination.Single and multilayer of films Diamond-like Carbon (DLC) were prepared by Plasma Immersion Ion Implantation and Deposition (PIIID) from two deposition systems: (1) Radio-Frequency (RF) plasma and (2) Filtered Cathodic Vacuum Arc (FCVA). Raman spectroscopy revealed a shift in the peaks previously identified as D and G band in the structures. The sp² and sp³ ratio contents were characterized by Raman spectroscopy.     

Use of diamond-like carbon with tungsten (W-DLC) films as biocompatible material

Diamond-like carbon (DLC), also known as amorphous hydrogenated carbon (a-C:H), are a class of materials with excellent mechanical, tribological and biological properties. When the DLC films are enhanced with other elements, all of these properties can be changed within a certain range.In this work, reactive magnetron sputtering was used to deposit W-DLC (hydrogenated tungsten carbide) films on Ti6Al4V (implant material). Many films were made using pure tungsten (99.99%) target and different plasmas processes, with different ratio among argon and methane. It was possible to change the films composition (from pure amorphous carbon to carbon enhanced with tungsten) according to ratio of argon and methane plasma. Between all films processed, the carbon films enhanced with tungsten showed good results in the “in vitro” cytotoxicity testing. Raman spectroscopy was used to analyze the chemical bonds kinds and the chemical bonds quantities. The Rutherford Back Scattering (RBS) was used to analyze the films compositions. The chemical inertness was analyzed by scanning voltametry. W-DLC thin films obtained in these processes have low roughness, high chemical resistance, good adhesion and show a high biocompatibility, when compared with common DLC thin films. Hence we have concluded that the tungsten concentrations in the DLC films make an important role to improve the properties of the DLC layers.     

氮化碳薄膜的电子结构和光学性质

在不同条件下用射频溅射方法制备了氮化碳薄膜。薄膜的电子结构和元素成分用傅里叶变换红外光谱(FTIR)和光电子能谱 (XPS)进行分析 ,薄膜的光学性质用紫外可见近红外光谱 (UV)进行检测。薄膜中的最大氮原子含量达到 0 .4 7,C1s和N1s电子的结合能产生了 2 .4 1～ - 1.7eV的移动 ,移动的大小取决于制备条件。UV谱表明氮化碳薄膜能强烈地吸收紫外光 ,而对红外光有较好的透明性 ,在 2 72 0nm附近存在一明锐的吸收峰 ,并给出了形成这一明锐吸收峰的适宜条件。这些结果对作为保护光学涂层的红外应用是有意义的。     

Photosensitivity and optical performance of hydrogenated amorphous carbon films processed by picosecond laser beams

In this work we investigate the photosensitivity of hydrogenated amorphous Carbon films (a-C:H) and the changes in their structural features and optical properties, when they are exposed to picosecond laser beams of various wavelengths (Nd:YAG, 1st harmonic, λ = 1064 nm and 4th harmonic, λ = 266 nm). The different light-matter interactions, which take place for the various laser wavelengths, are considered and discussed. The main findings include the formation of SiC at the a-C:H film/Si interface and the film graphitization, when the 1064 nm and 266 nm beams, respectively, are used. Finally we managed to vary locally the refractive index in the range of 1.60-1.95 (20% variations) by laser processing, a fact that is very important for various applications in photonics.     

Diamond-like carbon films synthesized on bearing steel surface by plasma immersion ion implantation and deposition

Diamond-like carbon (DLC) films were synthesized by plasma immersion ion implantation and deposition (PIIID) on 9Cr18 bearing steel surface. Influences of working gas pressure and pulse width of the bias voltage on properties of the thin film were investigated. The chemical compositions of the as-deposited films were characterized by Raman spectroscopy. The micro-hardness, friction and wear behavior, corrosion resistance of the samples were evaluated, respectively. Compared with uncoated substrates, micro-hardness results reveal that the maximum is increased by 88.7%. In addition, the friction coefficient decreases to about 0.1, and the corrosion resistance of treated coupons surface are improved significantly.     

The molecular structure of plasma polymerized thiophene and pyrrole thin films produced by double discharge technique

Production of polythiophene (PTH) and polypyrrole (PPY) thin films via double discharge plasma system has been studied. The double discharge system is a superposition of an ordinary low-pressure dc glow discharge and a high-current pulsed one. The glass substrates were located simultaneously at three different positions in the reactor and the thin films were synthesized at constant plasma parameters to evaluate the influence of the position on the molecular structure. And, the as-grown and iodine doped thin films were investigated to find out the correlation between molecular structure variation of the iodine–film interactions, too. The PTH (C₄H₄S) and PPY (C₄H₅N) monomers without using any carrier gases have been used as plasma precursors, each at 1 mbar operating pressure. The thin films were compared by using Fourier transform infrared (FTIR), X-ray photoelectron (XPS), and UV–visible absorption spectroscopy. It is found that the thin films obtained at the pulsed plasma region where the gas phase polymerization is dominated resemble to conventional polymeric structure. The XPS depth profiles revealed that while the stoichiometry of the monomer was almost preserved with the successive depth of PTH samples, but at the PPY one was not preserved. Moreover, the atomic concentration of oxygen and nitrogen observed at the surface of the films significantly drops down beneath the surface which indicates that they could be employed as anti-corrosive materials. It is found that chemical bonding with iodine take place after doping and the value of the optical band gap of polymers (E_g) are reduced proportionally with doping time.     

全方位离子注入与沉积类金刚石碳膜的结构与性能

用等离子体浸没离子注入与沉积(PIIID)复合强化新技术在AISI440C不锈钢表面制备了类金刚石(DLC)碳膜。膜层表面的原子力显微镜(AFM)形貌显示出DLC膜结构致密均匀。Raman光谱分析结果表明,制备的DLC主要是由金刚石键(sp3)和石墨键(sp2)组成的混合无定形碳膜,且sp3键含量大于10%。以纯石墨棒做阴极,C2H2为工作气体条件下合成的DLC薄膜中,sp3键含量总体上较单纯用石墨作阴极而无工作气体条件下合成的DLC薄膜中sp3键含量高。与基体相比,薄膜试样的显微硬度和摩擦磨损性能均得到了较大改善,最大硬度提高88.7%,磨损寿命延长超过4倍。     

Surface discharge characteristics of MgO thin films prepared by RF reactive magnetron sputtering

This paper describes the surface glow-discharge effect of MgO thin films prepared by reactive radio-frequency planar magnetron sputtering on the dielectric layer of an alternating-current plasma display panel. By introducing an MgO coating on the dielectric the discharge voltage decreases sharply, although the thickness is only a few tens of Ångstroms. The lowest discharge voltage is obtained for the sample prepared at a 30% O₂ content in an O₂+Ar gas mixture and at a sputtering gas pressure of about 5 mTorr. Moreover, high transparency (95%) is also obtained under the same experimental conditions. The samples prepared show more sputter-resistant properties than samples prepared by the electron-beam method and no cracks are observed on the surface after post-deposition annealing.