Substrate effects on the microstructure of hydrogenated amorphous carbon films

In this work, plasma enhanced chemical vapour deposition was used to prepare hydrogenated amorphous carbon films (a-C:H) on different substrates over a wide range of thickness. In order to observe clear substrate effect the films were produced under identical growth conditions. Raman and near edge X-ray absorption fine structure (NEXAFS) spectroscopies were employed to probe the chemical bonding of the films. For the films deposited on silicon substrates, the Raman I_D/I_G ratio and G-peak positions were constant for most thickness. For metallic and polymeric substrates, these parameters increased with film thickness, suggesting a change from a sp³-bonded hydrogenated structure to a more sp² network, NEXAFS results also indicate a higher sp² content of a-C:H films grown on metals than silicon. The metals, which are poor carbide precursors, gave carbon films with low adhesion, easily delaminated from the substrate. The delamination can be decreased/eliminated by deposition of a thin (∼10 nm) silicon layer on stainless steel substrates prior to a-C:H coatings. Additionally we noted the electrical resistivity decreased with thickness and higher dielectric breakdown strength for a-C:H on silicon substrate.     

Correlation of sp and sp fraction of carbon with electrical, optical and nano-mechanical properties of argon-diluted diamond-like carbon films

In the present work the correlation of electrical, optical and nano-mechanical properties of argon-diluted diamond-like carbon (Ar-DLC) thin films with sp³ and sp² fractions of carbon have been explored. These Ar-DLC thin films have been deposited, under varying C₂H₂ gas pressures from 25 to 75 mTorr, by radio frequency-plasma enhanced chemical vapor deposition technique. X-ray photoelectron spectroscopy studies are performed to estimate the sp³ and sp² fractions of carbon by deconvoluting C 1s core level spectra. Various electrical, optical and nano-mechanical parameters such as conductivity, I-V characteristics, optical band gap, stress, hardness, elastic modulus, plastic resistance parameter, elastic recovery and plastic deformation energy have been estimated and then correlated with calculated sp³ and sp² fractions of carbon and sp³/sp² ratios. Observed tremendous electrical, optical and nano-mechanical properties in Ar-DLC films deposited under high base pressure conditions made it a cost effective material for not only hard and protective coating applications but also for electronic and optoelectronic applications.     

Diamond-like-carbon films produced by magnetically guided pulsed laser deposition

We have compared the quality of carbon films deposited with magnetically guided pulsed laser deposition (MGPLD) and conventional pulsed laser deposition (PLD). In MGPLD, a curved magnetic field is used to guide the plasma but not the neutral species to the substrate to deposit the films while, in conventional PLD, the film is deposited with a mixture of ions, neutral species and clusters. A KrF laser pulse (248 nm) was focused to intensities of 10 GW/cm² on a carbon source target and a magnetic field strength of 0.3 T was used to steer the plasma around a curved arc to the deposition substrate. Electron energy loss spectroscopy was used in order to measure the fraction of sp³ bonding in the films produced. It is shown that the sp³ fraction, and hence the diamond-like character of the films, increased when deposited only with the pure ion component by MGPLD compared with films produced by the conventional PLD technique. The dependence of film quality on the laser intensity is also discussed. Received: 7 December 2000 / Accepted: 20 August 2001 / Published online: 2 October 2001     

Hydrogenated diamond-like carbon film deposited on UHMWPE by RF-PECVD

In this work, investigations were conducted to analyze the properties of diamond-like carbon (DLC) film deposited on ultra-high molecular weight polyethylene (UHMWPE) by radio frequency plasma enhanced chemical vapor deposition (RF-PECVD) at a low temperature of 50 °C. Composition and structure of the films were characterized by scanning electron microscopy (SEM) and Raman spectroscopy. Hardness and wettability of the film were tested. Tribological characterizations were carried out on a universal micro-tribometer, and reciprocating friction against ZrO₂ ball was adopted with 25% bovine serum as lubrication. Results show that DLC film was successfully deposited on UHMWPE surface by RF-PECVD and the sp³ content was about 20% in the film. The film increased the macrohardness of the substrate by about 42% and the wettability was improved too. Tribology test showed a higher friction coefficient but a much smaller wear volume after the deposition due to the surface roughening and strengthening.     

Photoluminescence of amorphous carbon films fabricated by layer—by—layer hydrogen plasma chemical annealing method

A method in which nanometre-thick film deposition was alternated with hydrogen plasma annealing (layer-by-layer method) was applied to fabricate hydrogenated amorphous carbon films in a conventional plasma-enhanced chemical vapour deposition system.It was found that the hydrogen plasma treatment could decrease the hydrogen concentration in the films and change the sp^2/sp^3 ratio to some extent by chemical etching.Blue photoluminescence was observed at room temperature,as a result of the reduction of sp^2 clusters in the films.     

The influence of the structures and compounds of DLC coatings on the barrier properties of PET bottles

To reduce the oxygen transmission rate through a polyethylene terephthalate (PET) bottle (an organic plastic) diamond-like carbon (DLC) coatings on the inner surface of the PET bottle were deposited by radio frequency plasma-enhanced chemical vapour deposition (RF-PECVD) technology with C₂H₂ as the source of carbon and Ar as the diluted gas. As the barrier layer to humidity and gas permeation, this paper analyses the DLC film structure, composition, morphology and barrier properties by Fourier transform infrared, atomic force microscopy, scanning electron microscopy and oxygen transmission rate in detail. From the spectrum, it is found that the DLC film mainly consists of sp³ bonds. The barrier property of the films is significantly relevant to the sp³ bond concentration in the coating, the film thickness and morphology. Additionally, it is found that DLC film deposited in an inductively coupled plasma enhanced capacitively coupled plasma source shows a compact, homogeneous and crack-free surface, which is beneficial for a good gas barrier property in PET bottles.     

不同射频输入功率下制备的氟化类金刚石碳膜疏水性研究

以高纯石墨作靶、氩气（Ar）和三氟甲烷（CHF₃）为源气体,用反应磁控溅射法在不同射频功率下制备了氟化类金刚石碳（F-DLC）膜,并对其疏水性进行研究.双蒸水液滴与膜表面接触角的测试结果表明,所制备薄膜表面的最大水接触角可达115°左右.通过原子力显微镜获得的薄膜表面AFM图谱、拉曼光谱以及傅里叶变换红外光谱探讨了影响薄膜的疏水性的因素.结果表明,薄膜的疏水性与薄膜的表面粗糙度和表面键结构直接相关,表面粗糙度越大,疏水性越好,但与薄膜中的F含量和sp³/sp²的比值并未呈单调增加或减小的对应关系.射频输入功率影响着薄膜的沉积速率,与薄膜表面粗糙度、薄膜中芳香环单核的比例以及薄膜表面的键结构（F的接入方式）直接相关. 关键词： 疏水性 反应磁控溅射 氟化类金刚石膜 射频功率     

含氮氟化类金刚石(FN-DLC)薄膜的研究：(Ⅰ) sp结构与化学键分析

以CF₄，CH₄和N₂为源气体，利用射频等离子体增强化学气相沉积法，在不同功率下制备了含氮氟化类金刚石膜.用俄歇电子能谱、拉曼光谱、X射线光电子能谱和傅里叶变换红外光谱对薄膜的电子结构和化学键进行了表征，并结合高斯分峰拟合方法分析了薄膜中sp²，sp³结构比率.结果表明，制备的薄膜属于类金刚石结构，不同沉积功率下，薄膜内的sp²/sp³值在2.0—9.0之间，随着沉积功率的增加薄膜内sp²的相对含量增加.膜内主要有C—F_x(x=1，2)，C—C，C=C和C≡N等化学键.沉积功率增加，C—C基团增加，膜内F的浓度降低，C—F基团减少，薄膜的关联加强，稳定性提高. 关键词： 含氮氟化类金刚石膜 sp结构 化学键结构 射频功率     

Mechanical properties and platelet adhesion behavior of diamond-like carbon films synthesized by pulsed vacuum arc plasma deposition

Diamond-like carbon (DLC) is an attractive biomedical material due to its high inertness and excellent mechanical properties. In this study, DLC films were fabricated on Ti6Al4V and Si(1 0 0) substrates at room temperature by pulsed vacuum arc plasma deposition. By changing the argon flow from 0 to 13 sccm during deposition, the effects of argon flow on the characteristics of the DLC films were systematically examined to correlate to the blood compatibility. The microstructure and mechanical properties of the films were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) surface analysis, a nano-indenter and pin-on-disk tribometer. The blood compatibility of the films was evaluated using in vitro platelet adhesion investigation, and the quantity and morphology of the adherent platelets was investigated employing optical microscopy and scanning electron microscopy.The Raman spectroscopy results showed a decreasing sp³ fraction (an increasing trend in I_D/I_G ratio) with increasing argon flow from 0 to 13 sccm. The sp³:sp² ratio of the films was evaluated from the deconvoluted XPS spectra. We found that the sp³ fraction decreased as the argon flow was increased from 0 to 13 sccm, which is consistent with the results of the Raman spectra. The mechanical properties results confirmed the decreasing sp³ content with increasing argon flow. The Raman D-band to G-band intensity ratio increased and the platelet adhesion behavior became better with higher flow. This implies that the blood compatibility of the DLC films is influenced by the sp³:sp² ratio. DLC films deposited on titanium alloys have high wear resistance, low friction and good adhesion.     

Low energy repetitive miniature plasma focus device as high deposition rate facility for synthesis of DLC thin films

Diamond-like carbon (DLC) films were deposited on Si (1 0 0) substrate using a low energy (219 J) repetitive (1 Hz) miniature plasma focus device. DLC thin film samples were deposited using 10, 20, 50, 100 and 200 focus shots with hydrogen as filling gas at 0.25 mbar. The deposited samples were analyzed by XRD, Raman Spectroscopy, SEM and XPS. XRD results exhibited the diffraction peaks related to SiO₂, carbon and SiC. Raman studies verified the formation amorphous carbon with D and G peaks. Corresponding variation in the line width (FWHM) of the D and G positions along with change in intensity ratio (I_D/I_G) in DLC films was investigated as a function of number of deposition shots. XPS confirmed the formation sp² (graphite like) and sp³ (diamond like) carbon. The cross-sectional SEM images establish the 220 W repetitive miniature plasma focus device as the high deposition rate facility for DLC with average deposition rate of about 250 nm/min.     

Substrate temperature influence on the trombogenicity in amorphous carbon nitride thin coatings

Carbon nitride thin films were obtained through plasma assisted physical vapor deposition technique by pulsed arc, varying the substrate temperature and investigating the influence of this parameter on the films hemocompatibility. For obtaining approaches of blood compatibility, environmental scanning electron microscopy (ESEM) was used in order to study the platelets adherence and their morphology. Moreover, the elemental chemical composition was determined by using energy dispersive spectroscopy (EDS), finding C, N and O. The coatings hemocompatibility was evaluated by in vitro thrombogenicity test, whose results were correlated with the microstructure and roughness of the films obtained.During the films growth process, the substrate temperature was varied, obtaining coatings under different temperatures, room temperature (T_room), 100 °C, 150 °C and 200 °C. Parameters as interelectrodic distance, voltage, work pressure and number of discharges, were remained constant. By EDS, carbon and nitrogen were found in the films.Visible Raman spectroscopy was used, and it revealed an amorphous lattice, with graphitic process as the substrate temperature was increased. However, at a critical temperature of 150 °C, this tendency was broken, and the film became more amorphous. This film showed the lowest roughness, 2 ± 1 nm. This last characteristic favored the films hemocompatibility. Also, it was demonstrated that the blood compatibility of carbon nitride films obtained were affected by the I_D/I_G or sp³/sp² ratio and not by the absolute sp³ or sp² concentration.     

Laser fluence dependence of the elastic properties of diamond-like carbon films prepared by pulsed-laser deposition

We studied the temperature dependence of internal friction of variety of amorphous diamond-like carbon films prepared by pulsed-laser deposition. Like the most of amorphous solids, the internal friction below 10 K exhibits a temperature independent plateau, which is caused by the atomic tunnelling states—a measure of structure disorder. In this work, we have varied the concentration of sp³ versus sp² carbon atoms by increasing laser fluence from 1.5 to 30 J/cm². Our results show that the internal friction has a nonmonotonic dependence on sp³/sp² ratio with the values of the internal friction plateaus varying between 6×10⁻⁵ and 1.1×10⁻⁴. We explain our findings as a result of a possible competition between the increase of atomic bonding and the increase of internal strain in the films, both of which are important in determining the tunneling states in amorphous solids. The importance of the internal strain in diamond-like carbon films is consistent with our previous study on laser fluence, doping, and annealing, which we will review as well. In contrast, no significant dependence of laser fluence is found in shear moduli of the films, which vary between 220 and 250 GPa.     

类金刚石薄膜力学特性的分子动力学模拟

基于Brenner的REBO势函数,利用分子动力学方法模拟了含氢量不同的类金刚石薄膜的纳米压痕过程,依据得到的加载卸载曲线,计算了薄膜的刚度、硬度以及弹性模量.结果表明:类金刚石薄膜的硬度由氢含量和sp³键含量两个因素共同决定;当薄膜中氢含量小于39% 时,薄膜硬度主要取决于sp³键含量,sp³键越多,硬度越高;当薄膜中氢含量达到52%,薄膜硬度则显著下降,此时氢的作用占据主导地位. 关键词： 类金刚石薄膜 分子动力学模拟 纳米压痕 硬度     

Influence of the plasma parameters and nitrogen addition on the electrical characteristics of DLC films deposited by inductively coupled plasma deposition

This work has been based on studies of the plasma parameters influence and nitrogen addition over on the electrical characteristics of diamond-like carbon (DLC) films deposited by inductively coupled plasma deposition (ICP) system. For these studies, it was used a mixture of methane with different flows of nitrogen, two different pressure processes and three different coil powers. The nitrogenated DLC films, had presented a great variation in their electric and structural properties with the nitrogen variation in the plasma. With the nitrogen addition, an increase in its dielectric constant of 1.7-7.4 to concentration of the 40% of the nitrogen has occurred. For high nitrogen concentrations (80% of nitrogen), the dielectric constant decreases (of 7.4 for 5.0). The resistivity of the films decreases with the nitrogen concentration increase (1.2 × 10⁹ Ω cm). Attributing semiconductors characteristics to DLC films. With the increase of nitrogen concentration, the sp³ hybridization increases, too. These characteristics were excellent for innumerable applications in electronic devices.     

Optical and Electrical Properties Evolution of Diamond-Like Carbon Thin Films with Deposition Temperature

Optical and electrical properties of diamond-like carbon （DLC） films deposited by pulsed laser ablation of graphite target at different substrate temperatures are reported. By varying the deposition temperature from 400 to 25℃, the film optical transparency and electrical resistivity increase severely. Most importantly, the transparency and resistivity properties of the DLC films can be tailored to approaching diamond by adjusting the deposition temperature, which is critical to many applications. DLC films deposited at low temperatures show excellent optical transmittance and high resistivity. Over the same temperature regime an increase of the spa bonded C content is observed using visible Raman spectroscopy, which is responsible for the enhanced transparency and resistivity properties.     

Fabrication of DLC films by pulsed ion beam ablation in a dense plasma focus device

The pulsed intense ion beam, emitted from a dense plasma focus (DPF) discharges performed with hydrogen gas, has been used to ablate the graphite target depositing diamond-like carbon (DLC) films on Si substrates. The substrates were mounted on a holder, which allowed for deposition at positions between normal and 20° off-normal to the target. The samples were removed for analysis after 10 and 20 shots. Nano-particles were observed in the films by a field-emission scanning electron microscope. Raman spectra indicate that sample deposited at 20° off-normal with 20 shots possesses the highest sp³ content among the samples. The film deposited at this position was also found has the highest hardness.     

Comparison and semiconductor properties of nitrogen doped carbon thin films grown by different techniques

Amorphous carbon nitride (a-CN_x) thin films have been synthesised by three different deposition techniques in an Ar/N₂ gas mixture and have been deposited by varying the percentage of nitrogen gas in the mixture (i.e. the N₂/Ar + N₂ ratio) from 0 to 10%. The variation of the electrical conductivity and the gap values of the deposited films versus the N₂/Ar + N₂ ratio were investigated in relation with their local microstructure. Film composition was analysed using Raman spectroscopy and optical transmission experiments. The observed variation of electrical conductivity and optical properties are attributed to the changes in the atomic bonding structures, which were induced by N incorporation, increasing both the sp² carbon content and their relative disorder. The low N content samples seem to be an interesting material to produce films with interesting properties for optoelectronic applications considering the facility to control the gas composition as a key parameter.     

Electrochemical corrosion behaviors of a-C:H and a-C:NX:H films

The a-C:H and a-C:N_X:H films were deposited onto silicon wafers using radio frequency (rf) plasma enhanced chemical vapor deposition (PECVD) and pulsed-dc glow discharge plasma CVD, respectively. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize chemical nature and bond types of the films. The results demonstrated that the a-C:H film prepared by rf-CVD (rf C:H) has lower I_D/I_G ratio, indicating smaller sp² cluster size in an amorphous carbon matrix. The nitrogen concentrations of 2.9 at.% and 7.9 at.% correspond to carbon nitride films prepared with rf and pulse power, respectively.Electrochemical corrosion performances of the carbon films were investigated by potentiodynamic polarization test. The electrolyte used in this work was a 0.89% NaCl solution. The corrosion test showed that the rf C:H film exhibited excellent anti-corrosion performance with a corrosion rate of 2 nA cm⁻², while the carbon nitride films prepared by rf technique and pulse technique showed a corrosion rate of 6 nA cm⁻² and 235 nA cm⁻², respectively. It is reasonable to conclude that the smaller sp² cluster size of rf C:H film restrained the electron transfer velocity and then avoids detriment from the exchange of electrons.     

Evaluation of bacterial adhesion on Si-doped diamond-like carbon films

Diamond-like carbon (DLC) films as biomaterial for medical devices have been attracting great interest due to their excellent properties such as hardness, low friction and chemical inertness. It has been demonstrated that the properties of DLC films can be further improved by the addition of silicon into DLC films, such as thermal stability, compressive stress, etc. However no research work on anti-bacterial properties of silicon-doped diamond-like carbon films has been reported. In this paper the surface physical and chemical properties of Si-doped diamond-like carbon films with various Si contents on 316 stainless steel substrate prepared by a magnetron sputtering technique were investigated, including surface topography, surface chemistry, the sp³/sp² ratio, contact angle, surface free energy, etc. Bacterial adhesion to Si-doped DLC films was evaluated with Pseudomonas aeruginosa, Staphylococcus epidermidis and Staphylococcus aureus which frequently cause medical device-associated infections. The experimental results showed that bacterial adhesion decreased with increasing the silicon content in the films. All the Si-doped DLC films performed much better than stainless steel 316L on reducing bacterial attachment.     

Electrochemical synthesis and STM-STS studies of thin diamond-like films on the surface of oxidized aluminum

Thin carbon films on the surface of aluminum containing native oxide were prepared at room temperature by electrochemical deposition from a solution of lithium acetylenide in dimethylsulfoxide. The structure of the coatings obtained was studied by scanning tunnel microscopy and spectroscopy. The mechanical characteristics of carbon coatings were found to depend strongly on the main parameters determining deposition conditions. The presence of a considerable amount of sp ³ carbon (diamond-like phases) in the films was substantiated.