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.     

V and N co-doped diamond-like carbon films deposited by pulsed bias arc ion plating

V and N co-doped diamond-like carbon (DLC–VN) composite films were deposited on cemented carbide substrates by pulsed bias arc ion plating. The effects of V and N contents on the structures and properties of the films were investigated by X-ray photoelectron spectroscopy (XPS), Raman spectra, grazing incident X-ray diffraction (GIXRD), transmission electron microscopy (TEM) and nano-indentation, respectively. The as-deposited films consist of a DLC–VN nanocomposite, where VN nanograins are embedded in an amorphous carbon matrix. The V and N contents have significant influences on the relative proportion of VN with respect to DLC. A proper concentration of VN nanocrystals in DLC induces even the formation of nano-diamond. The DLC–VN films have higher hardnesses than pure DLC films, which could be attributed to the nanocomposite structure.     

Tribological behaviors of hydrogenated diamond-like carbon films in different testing environments

Hydrogenated diamond-like carbon (DLC) films were deposited on Si substrate using plasma enhanced chemical vapor deposition(PECVD) technique with CH4 plus H2 as the feedstock. The tribological properties of the hydrogenated DLC films were measured on a ball-on-disk tribometer in different testing environments (humid air,dry air, dry O2, dry Ar and dry N2 ) sliding against Si3 N4 balls. The friction surfaces of the films and Si3 N4 balls were observed on a scanning electron microscope (SEM) and investigated by X-ray photoelectron spectroscopy (XPS). The results show that the tribological properties of the hydrogenated DLC films are strongly dependent on the testing environments. In dry Ar and dry N2 environments, the hydrogenated DLC films provide a superlow friction coefficient of about 0. 008 -0.01 and excellent wear resistance (wear life of above 56 km). In dry air and dry O2, the friction coefficient is increased to 0. 025 - 0.04 and the wear life is decreased to about 30 km. When sliding in moist air, the friction coefficient of the films is further increased to 0. 08 and the wear life is decreased to 10. 4 km. SEM and XPS analyses show that the tribological behaviors appear to rely on the transferred carbon-rich layer processes on the Si3 N4 balls and on the friction-induced oxidation of the films controlled by the nature of the testing environments.     

Influence of substrate surface topography in the deposition of nanostructured diamond-like carbon films by high density plasma chemical vapor deposition

In this work, we have studied the influence of the substrate surface condition on the roughness and the structure of the nanostructured DLC films deposited by High Density Plasma Chemical Vapor Deposition. Four methods were used to modify the silicon wafers surface before starting the deposition processes of the nanostructured DLC films: micro-diamond powder dispersion, micro-graphite powder dispersion, and roughness generation by wet chemical etching and roughness generation by plasma etching. The reference wafer was only submitted to a chemical cleaning. It was possible to see that the final roughness and the sp³ hybridization degree strongly depend on the substrate surface conditions. The surface roughness was observed by AFM and SEM and the hybridization degree of the DLC films was analyzed by Raman Spectroscopy. In these samples, the final roughness and the sp³ hybridization quantity depend strongly on the substrate surface condition. Thus, the effects of the substrate surface on the DLC film structure were confirmed. These phenomena can be explained by the fact that the locally higher surface energy and the sharp edges may induce local defects promoting the nanostructured characteristics in the DLC films.     

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.     

Electrodeposition of DLC films on carbon steel from acetic acid solutions

In this paper the electrodeposition of DLC films on carbon steel from aqueous acetic acid solutions and their structural and mechanical characterization are reported. The process is performed at room temperature at relatively low cell voltages (from ?8 to ?20 V) with entirely environmentally friendly chemicals. Qualitative and quantitative evaluation of C hybridisation type have been performed by Raman spectroscopy. Microhardness and adhesion of the supported electrodeposited films have been measured by micro-indentation and scratch-testing. Notably, ductile failure was found to correspondence to a wide range of film growth conditions. The corrosion resistance of DLC-coated steel has been assessed by electrochemical impedance spectrometry in a neutral chloride solution. Optimal electrodeposition conditions were identified for the formation of high-quality DLC films ca. 270 nm thick with a high content of diamond-coordinated carbon and an ideal combination of hardness and adhesion; films formed under these conditions also confer some degree of corrosion protection to the steel substrate.     

AZ31表面混合碳源制备DLC薄膜的结构和性能

为了提高镁合金的耐蚀性和耐磨性,扩大镁合金的应用,节能减排,保护环境,采用绿色环保的磁控溅射技术在AZ31表面制备了强保护性的DLC薄膜。采用X射线小角掠入射研究薄膜的物相结构,借助扫描电镜观察薄膜表面形貌、横截面形貌和腐蚀形貌,采用纳米压痕仪测试薄膜的力学性能,分别采用电化学工作站和摩擦磨损试验机研究薄膜的耐蚀性和耐磨性,膜基的结合性能采用划痕试验评估。结果表明,薄膜为无定形碳结构,随着活性气体流量的增加,薄膜结构由非晶向纳米晶转变。薄膜与基体结合良好,结合力19~25 N。薄膜表面具有弥散分布的不规则颗粒,且表面粗糙度受活性气体流量影响明显。薄膜厚度1.15~1.18μm,活性气体流量对薄膜厚度影响很小。随着活性气体流量的增加,DLC薄膜的硬度和杨氏模量增大,其最大值分别为17.35 GPa和94 GPa;摩擦系数和磨损率降低,其最小值分别为0.103和6.45×10^-10mm³/(N·m)。活性乙炔流量5 mL/min时,薄膜的耐蚀性能最好,活性乙炔流量10 mL/min时,薄膜的耐磨性能最好。     

Influence of nitrogen gas on structure and properties of DLC films prepared by XeCl pulsed laser deposition

Diamond-like carbon （DLC） films were prepared by PLD process using 308 nm（XeCl） laser beam with high power （500 W） and high fi＇equency（300 Hz）. The effects of nitrogen pressure on the structure and properties of the DLC films under such extremely high power and repetition rate were studied. The results indicate that the microstructures of the films are varied fi＇om amorphous carbon to graphitized carbon in long-order with the increase of N2 pressure, and the optical properties of the films are deteriorated as compared to that of DLC films without nitrogen.     

Facile synthesis of CNTs-doped diamond-like carbon film by electrodeposition

A simple and effective process for synthesis of carbon nanotubes (CNTs)-doped diamond-like carbon (DLC) film via electrodeposition has been reported. Transmission electron microscope (TEM), Raman, X-ray photoelectron spectroscopy (XPS), and Fourier transformation infrared spectrometry (FTIR) were employed to investigate the microstructure, chemical composition, and various carbon phases of the films. The experimental results clearly showed that the CNTs were well dispersed in the carbon film and the D and G bands of the composite carbon film both downshifted comparing with those of the undoped carbon film. The hardness of the carbon film was improved with the incorporation of CNTs from 10.28 to 12.47 GPa, while the Young's modulus was decreased from 253.64 to 206.66 GPa. Simultaneously, the residual stress of the carbon film was greatly reduced from 1.2 to 0.83 GPa after the incorporation of CNTs.     

类金刚石膜在模具中的应用

阐述了类金刚石膜的结构和力学性能,介绍了类金刚石膜在各种模具上的应用。类金刚石膜能有效提高模具使用寿命,降低模具使用成本。分析了目前类金刚石膜在模具上的应用和推广中存在的障碍。     

中频对靶磁控溅射制备含铬类金刚石薄膜

利用新型中频对靶磁控溅射在硅和M2高速钢基体上沉积了一系列无氢含铬类金刚石膜.考察了类金刚石膜的表面形貌、显微结构、硬度、结合力和摩擦磨损性能.结果表明：合成的类金刚石薄膜具有优良的综合性能,硬度为30-46GPa、结合力Lc达50-65N、大气环境下摩擦系数约为0.1.     

Effect of laser fluences on the structure of carbon nitride films deposited by direct current plasma assisted pulsed laser ablation

Carbon nitride films were deposited by direct current plasma assisted pulsed laser ablation of a graphite target under a nitrogen atmosphere at room temperature. The surface morphology, composition and bonding structure of the deposited films were characterized by atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, Raman, and X-ray photoelectron spectroscopy (XPS). The effect of laser fluences in the range 0.5–3 J/cm² on the surface morphology, composition and bonding structure of the carbon nitride films were systematically studied. As laser fluence is increased, AFM results show a great decrease in the surface roughness of carbon nitride films. FTIR and XPS results indicate an increase in the N/C ratio and the content of N atoms bonded to sp³ C, as well as a decrease in the content of H atoms and the content of N atoms boned to sp² C in the deposited films, and Raman spectra indicate an increase in the content of disordered sp² C atoms and the sp² cluster size. The increase in the film density and the decrease in the particle fraction contribute to the decrease of surface roughness with increasing laser fluence.     

Electrodeposition of B,Ni co-doped diamond-like carbon films on AZ91D magnesium alloy: Corrosion and wear resistance

Diamond-like carbon (DLC) possesses brilliant and excellent properties, including excellent corrosion resistance as well as outstanding wear resistance. Ni and B co-doped DLC films were deposited on AZ91D magnesium alloy by electrodeposition under mild conditions (300 V and 25°C). Uniform and dense morphology of co-doped DLC films were observed, and Ni and B were uniformly incorporated into the carbon-based films. Among all the electrodeposits, the appearance of D and G peaks near 1330 and 1570 cm⁻¹ revealed that the as-deposited films were typical DLC films. As the addition of Ni was increased to 0.05 g, the highest microindentation hardness, the lowest friction coefficient, and wear loss were achieved to be 164.5 HV, 0.3, and 0.6 × 10⁻⁵ kg/m, respectively. The amorphous carbon films fabricated at 0.05 g Ni had the lowest corrosion current density and the most positive corrosion potential, which was mainly due to the small and dense granular structure effectively hindering the penetration of corrosion media.     

Physical properties of chemical vapour deposited nanostructured carbon thin films

A simple thermal chemical vapour deposition technique is employed for the deposition of carbon films by pyrolysing the natural precursor “turpentine oil” on to the stainless steel (SS) and FTO coated quartz substrates at higher temperatures (700-1100 °C). In this work, we have studied the influence of substrate and deposition temperature on the evolution of structural and morphological properties of nanostructured carbon films. The films were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), contact angle measurements, Fourier transform infrared (FTIR) and Raman spectroscopy techniques. XRD study reveals that the films are polycrystalline exhibiting hexagonal and face-centered cubic structures on SS and FTO coated glass substrates respectively. SEM images show the porous and agglomerated surface of the films. Deposited carbon films show the hydrophobic nature. FTIR study displays C-H and O-H stretching vibration modes in the films. Raman analysis shows that, high ID/IG for FTO substrate confirms the dominance of sp³ bonds with diamond phase and less for SS shows graphitization effect with dominant sp² bonds. It reveals the difference in local microstructure of carbon deposits leading to variation in contact angle and hardness, which is ascribed to difference in the packing density of carbon films, as observed also by Raman.     

不同沉积气压对MPCVD法制备的类金刚石膜性能的影响

采用微波等离子体化学气相沉积法,以玻璃作为基底,通入CH4和H2,在改变沉积气压的条件下研究类金刚石(DLC)薄膜的生长情况。再利用紫外–可见–近红外分光光度计、激光Raman光谱仪和场发射扫描电子显微镜分别对制备出的DLC薄膜的光透过率、质量以及表面形貌进行表征与分析。结果表明:随着沉积气压的逐渐增大,可见光范围内的光透过率随之增大,类金刚石粒径逐渐减小,膜表面的团聚体尺寸逐渐减小、平整度提高。     

Hydrogen-free carbon thin films prepared by new type surface-wave-sustained plasma (SWP)

In this paper is described the simple structure of a new type surface-wave-sustained plasma (SWP) source without a magnetic field surrounding the chamber wall. In the source, the plasma is excited and sustained by 2.45 GHz microwaves, and the plasma density is measured by a single Langmuir probe in the target direction. The results indicate that the electron density obtained in this system is as high as 9 × 10¹¹ cm^− 3 even at a low pressure of 2.8 Pa. A graphite target (99.998%) and argon (99.999%) are used for depositing hydrogen-free amorphous carbon films by the new SWP source. The Raman spectra of the carbon films were obtained, and the results denote that the structure of the carbon films prepared by SWP is typical of diamond-like carbon; the Raman intensity ratio I_D/I_G is 2.97. The surface morphology was investigated by using an atomic force microscope (AFM). The images demonstrate that the hydrogen-free carbon films deposited by SWP have a very smooth surface, with a grain size of about 20 nm and surface roughness R_a of about 0.778 nm.     

Mechanical properties of silicon-doped diamond-like carbon films prepared by pulse-plasma chemical vapor deposition

Silicon-doped diamond-like carbon (Si-DLC) films were prepared by dc pulse-plasma chemical vapor deposition (CVD), using a mixture of acetylene (C₂H₂) and tetramethylsilane (TMS) as the material gas. The pulse voltage was varied from − 2 to − 5 kV, and the TMS flow ratio (TMS/(C₂H₂ + TMS)) was varied from 0 to 40%. At a pulse voltage of − 2 kV, an increase in TMS flow ratio leads to a decrease in hardness. In contrast, at a pulse voltage of − 5 kV, an increase in TMS flow ratio leads to a slight increase in hardness. The high hydrogen concentration in the films due to an increase in TMS flow ratio promotes the formation of polymeric sp³ C―H bonds, resulting in the fabrication of soft films at a low pulse voltage of − 2 kV. However, an increase in the effect of ion peening on the growth face results in the formation of hard films at a high pulse voltage of − 5 kV. Then, at a pulse voltage of − 5 kV fabricating hard Si-DLC films, an increase in TMS flow ratio leads to an increase in the silicon content in the films, resulting in a decrease in the friction coefficient. Therefore, it is clarified that Si-DLC films fabricated by dc pulse-plasma CVD under a high pulse voltage and high TMS flow ratio exhibit high hardness and a low friction coefficient. Moreover, to investigate the friction coefficient of Si-DLC films fabricated by dc pulse-plasma CVD, films deposited by dc plasma CVD were also evaluated. To obtain the same low friction coefficient, dc pulse-plasma CVD requires less TMS than dc plasma CVD. Hence, it is also clarified that Si-DLC films can be fabricated at a low cost by dc pulse-plasma CVD.     

Fabrication of carbon nanotube based transparent conductive thin films using layer-by-layer technology

This paper presents a simple and convenient process for the fabrication of carbon nanotube based optically transparent and electrically conductive thin films. Single-walled carbon nanotubes (SWNTs) are chemically treated to introduce negatively charged carboxylic groups on their surfaces, so that a stable SWNT aqueous dispersion can be obtained without any surfactant. The substrate surface is modified by a layer-by-layer nanoassembly technique, in which a positively charged hydrophilic polymer molecular layer is formed on the top of the substrate. This helps the SWNT dispersion to be cast onto the substrate using convenient wet coating techniques and increases the bonding force between the thin films and the substrates. Using the developed process, large sizes of conductive pure SWNT thin films that are uniform and highly transparent have been fabricated.     

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.     

Thermal stability studies of atmospheric plasma deposited siloxane films deposited on Vycor™ glass

The thermal stability of siloxane films deposited on Vycor glass and silicon substrates using atmospheric pressure plasma was studied. Siloxane films were deposited from a liquid tetraethyl orthosilicate (TEOS) precursor which was nebulised into a helium/oxygen plasma. The thickness of the siloxane films was in the range 1-12 nm as measured using both ellipsometry and X-ray reflectometry. Film composition and chemical properties were examined using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis. The thermal stability of the films was evaluated under argon atmosphere at temperatures up to 700 °C. The films were found to exhibit good adhesion without cracks or delamination after the thermal treatment. A decrease in coating thickness and a reduction in surface roughness was however observed indicating, a change in coating chemistry. This was confirmed by the reduction in carbon concentration observed by XPS. Particulates generated by excess gas phase reaction of TEOS were observed on the surface of the coating. A larger reduction in particulates size was observed after thermal treatment compared with the reduction in thickness of the bulk coating. This indicates that the particulates may have a different composition to that of the coating.