Chemical and morphological difference between TiN/DLC and a-C:H/DLC grown by pulsed vacuum arc techniques

In order to improve the adherence of DLC films, interlayers of amorphous hydrogenated carbon (a-C:H) and titanium nitride (TiN) were deposited by means of the pulsed vacuum arc technique. Bilayers were obtained by using a carbon target of 99.98% of purity in mixtures of (Ar + CH₄) and (Ar + H₂) for producing a-C and DLC, respectively and a target of titanium of 99.999% in a mixture of (Ar + N₂) for growing TiN. After the deposition, chemical and morphological differences between TiN/DLC and a-C:H/DLC bilayers grown on silicon and stainless steel 304 were studied using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and scanning probe microscopy (SPM) techniques. XPS analysis showed a difference in sp³/(sp²+sp³) bonds ratio for each bilayer, being 0.67 for TiN/DLC and 0.45 for a-C:H/DLC bilayers. sp³ and sp² bonds were also observed by the FTIR technique. SPM images, in atomic force microscopy (AFM) and lateral force microscopy (LFM) modes were carried out for illustrating the comparison between TiN/DLC and a-C/DLC morphologic characteristics. Roughness and grain size were studied as a function of the H₂ concentration for both bilayers.     

Deposition of a-C:H films on UHMWPE substrate and its wear-resistance

In prosthetic hip replacements, ultrahigh molecular weight polyethylene (UHMWPE) wear debris is identified as the main factor limiting the lifetime of the artificial joints. Especially UHMWPE debris from the joint can induce tissue reactions and bone resorption that may lead to the joint loosening. The diamond like carbon (DLC) film has attracted a great deal of interest in recent years mainly because of its excellent tribological property, biocompatibility and chemically inert property. In order to improve the wear-resistance of UHMWPE, a-C:H films were deposited on UHMWPE substrate by electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-PECVD) technology. During deposition, the working gases were argon and acetylene, the microwave power was set to 800 W, the biased pulsed voltage was set to −200 V (frequency 15 kHz, duty ratio 20%), the pressure in vacuum chamber was set to 0.5 Pa, and the process time was 60 min. The films were analysed by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, nano-indentation, anti-scratch and wear test. The results showed that a typical amorphous hydrogenated carbon (a-C:H) film was successfully deposited on UHMWPE with thickness up to 2 μm. The nano-hardness of the UHMWPE coated with a-C:H films, measured at an applied load of 200 μN, was increased from 10 MPa (untreated UHMWPE) to 139 MPa. The wear test was carried out using a ball (Ø 6 mm, SiC) on disk tribometer with an applied load of 1 N for 10000 cycles, and the results showed a reduction of worn cross-sectional area from 193 μm² of untreated UHMWPE to 26 μm² of DLC coated sample. In addition the influence of argon/acetylene gas flow ratio on the growth of a-C:H films was studied.     

高增透的类金刚石碳膜的红外吸收特性研究

利用射频等离子体分解甲烷的技术在锗片上沉积了非晶结构的类金刚石碳膜,傅里叶红外光谱仪测量显示镀覆的类金刚石碳膜的锗片在红外范围内具有高增透作用,特别在１７４０～！２０４４ｃｍ＾－１其峰值透过率高达９９％,在９４５．７ｃｍ＾－１（１０．６ｕｍ）处透过率为９４．５％。利用实测的液内的吸收系数接近于０,在１０．６ｕｍ的吸收系数为２３０ｃｍ＾－１,膜主要由ｓｐ＾３的Ｃ＿Ｈ键结构组成,各吸收峰均得到了很好的     

Transport and optical properties of amorphous carbon and hydrogenated amorphous carbon films

In this paper we report on the electrical and optical properties of amorphous carbon (a-C) and hydrogenated amorphous carbon (a-C:H) films. Resistivity of both types of films decreases with increase in temperature. At lower temperatures (60-250 K) the electron transport is due to variable range hopping for the a-C films. At higher temperatures (300-430 K) it is thermally activated for both types of films. Analysis of the heterojunction between diamond-like carbon (DLC) and bulk silicon (Si) leads to the conclusion that our a-C films are of n-type and our a-C:H films are of p-type. The optical measurements with DLC revealed a Tauc bandgap of 0.6 eV for the a-C films and 1-1.2 eV for the a-C:H films. An Urbach energy around 170 meV could be determined for the a-C:H films. Strain versus resistance plots were measured resulting in piezoresistive gauge factors around 50 for the a-C films and in between 100 and 1200 for the a-C:H films.     

Opto-electrical properties of amorphous carbon thin film deposited from natural precursor camphor

A simple thermal chemical vapor deposition technique is employed for the pyrolysis of a natural precursor “camphor” and deposition of carbon films on alumina substrate at higher temperatures (600-900 °C). X-ray diffraction measurement reveals the amorphous structure of these films. The carbon films properties are found to significantly vary with the deposition temperatures. At higher deposition temperature, films have shown predominately sp²-bonded carbon and therefore, higher conductivity and lower optical band gap (Tauc gap). These amorphous carbon (a-C) films are also characterized with Raman and X-ray photoelectron spectroscopy. In addition, electrical and optical properties are measured. The thermoelectric measurement shows these as-grown a-C films are p-type in nature.     

铜上采用过渡层沉积类金刚石薄膜的研究

将等离子增强非平衡磁控溅射物理气相沉积(PEUMS-PVD)和电子回旋共振-微波等离子体增强化学气相沉积(MW-ECRPECVD)技术相结合，通过制备不同的过渡层，在铜基上成功地制备了类金刚石膜.拉曼光谱分析表明，所制备的碳膜具有典型的类金刚石结构特征.检测结果表明，随着沉积偏压的增大，D峰和G峰均向高波数漂移，I_D/I_G值增大，表面粗糙度减小，而平均硬度和弹性模量呈先增大后减小的趋势. 关键词： 铜基体 类金刚石膜 过渡层 拉曼光谱     

Thermal stability of ultrathin amorphous carbon films synthesized by plasma-enhanced chemical vapor deposition and filtered cathodic vacuum arc

Abstract

Ultrathin hydrogenated amorphous carbon (a-C:H) films deposited by plasma-enhanced chemical vapor deposition (PECVD) and hydrogen-free amorphous carbon (a-C) films of similar thickness deposited by filtered cathodic vacuum arc (FCVA) were subjected to rapid thermal annealing (RTA). Cross-sectional transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) were used to study the structural stability of the films. While RTA increased the thickness of the intermixing layer and decreased the sp³ content of the a-C:H films, it did not affect the thickness or the sp³ content of the a-C films. The superior structural stability of the FCVA a-C films compared with PECVD a-C:H films, demonstrated by the TEM and EELS results of this study, illustrates the high potential of these films as protective overcoats in applications where rapid heating is critical to the device functionality and performance, such as heat-assisted magnetic recording.     

Nanocomposite TiC/a-C：H film prepared on titanium aluminium alloy substrates by PSII assistant MW-ECRCVD

Thin films of titanium carbide and amorphous hydrogenated carbon have been synthesized on titanium aluminium alloy substrates by PSII assisted MW-ECRCVD with a mirror field. The microstructure, chemical composition and mechanical property were investigated. Using XPS and TEM, the films were identified to be a-C：H film containing TiC nanometre grains （namely, the so-called nanocomposite structure）. The size of TiC grains of nanocomposite TiC/DLC film is about 5 nm. The nanocomposite structure has obvious improvement in the mechanical properties of DLC film. The hardness of a-C：H film with Ti is enhanced to 34 G Pa~ while that of a-C：H film without Ti is about 12 G Pa, and the coherent strength is also obviously enhanced at the critical load of about 35N.     

Preparation and Thermal Characterization of Diamond-Like Carbon Films

Diamond-like carbon （DLC） films are prepared on silicon substrates by microwave electron cyclotron resonance plasma enhanced chemical vapor deposition. Raman spectroscopy indicates that the films have an amorphous structure and typical characteristics. The topographies of the films are presented by AFM images. Effective thermal conductivities of the films are measured using a nanosecond pulsed photothermal reflectance method. The results show that thermal conductivity is dominated by the microstructure of the films.     

Structural and optical properties of Fe-doped hydrogenated amorphous carbon films prepared from trans-2-butene by plasma enhanced metal organic chemical vapor deposition

Fe-doped hydrogenated amorphous carbon (a-C:H:Fe) films were deposited from a gas mixture of trans-2-butene/ferrocene/H₂ by plasma enhanced metal organic chemical vapor deposition. X-ray photoelectron spectroscopy, Fourier transform infrared spectra and Raman spectra were used to characterize the composition and the bonding structure of the a-C:H:Fe and a-C:H films. Optical properties were investigated by the UV–visible spectroscopy and the photoluminescence (PL) spectra. The Fe-doped films contain more aromatic structures and C=C bonds than the undoped films. The sp ² carbon content and sp ² clustering of the films increase, and aromatic-like rings’ structures become richer after Fe-doping. The Tauc optical gap of the a-C:H:Fe films become narrower by 0.3 eV relative to the value of the a-C:H films. The PL peak shifts from 2.35 eV of the a-C:H films to 1.95 eV of the a-C:H:Fe films, and the PL intensity of the a-C:H:Fe films is greatly enhanced. A deep level emission peak around 2.04 eV of the a-C:H:Fe films is observed.     

Fe纳米颗粒嵌埋对类金刚石薄膜结构及电学性能的影响

 采用脉冲激光气相沉积方法制备了不同Fe嵌埋浓度的Fe: DLC多层纳米复合薄膜。用X射线光电子能谱仪(XPS)对薄膜的组成成分进行分析。利用透射电子显微镜（TEM）、拉曼光谱、电流-电压曲线研究Fe纳米颗粒嵌埋对薄膜的微观结构及电学性能的影响。XPS和TEM表明,Fe纳米颗粒周期性地均匀地嵌埋在碳薄膜中。拉曼光谱表明薄膜中的C为典型的类金刚石结构,Fe纳米颗粒促进芳香环式结构的形成,薄膜结构的有序度提高。电流 电压曲线表明,Fe纳米颗粒的嵌埋导致薄膜的室温电导率增加。     

DLC coating of textile blood vessels using PLD

Textile blood vessels with a length of 30 cm were coated with amorphous diamond-like carbon (DLC) layers with thicknesses up to 200 nm. The layers were created by pulsed laser deposition in vacuum or argon ambient. The percentage of sp³ carbon was evaluated using X-ray photoelectron spectroscopy, X-ray excited Auger electron spectroscopy and Raman spectroscopy. Depending on the deposition conditions the sp³ content varied from ∼40% to 60%. The adhesion of the DLC layers to the textile vessels was checked. The preliminary biocompatibility results from in vivo tests with sheep are also given.     

Comparison of the X-ray photoelectron and electron-energy-loss spectra of the nitrogen-doped hydrogenated amorphous carbon bond

The composition of nitrogen-doped hydrogenated amorphous carbon (a-C : H : N) films grown in a magnetically confined rf plasma-enhanced chemical vapour deposition system has been determined by X-ray photoelectron spectroscopy (XPS) and compared with that determined using a combination of elastic recoil detection analysis, Rutherford back-scattering and nuclear reaction analysis. The importance of nitrogen doping or 'incorporation' in hydrogenated amorphous carbon (a-C : H) films is discussed in relation to the significant variation in the sp 2 -to-sp 3 ratio that takes place. At 7 at.% N in the a-C : H matrix, a critical change in the microstructure is observed, which governs the resulting mechanical, optical and electronic properties. Finally, the correlation between the sp 2 and sp 3 fractions determined by a non-destructive method of obtaining the bond fractions (XPS) and by electron-energy-loss spectroscopy is discussed, with a view to evaluating accurately the sp 2 fraction in a-C : H : N films.     

Simultaneous interaction of methyl radicals and atomic hydrogen with amorphous hydrogenated carbon films, as investigated with optical in situ diagnostics

Methyl radicals (CH₃) and atomic hydrogen (H) are dominant radicals in low-temperature plasmas from methane. The surface reactions of these radicals are believed to be key steps leading to deposition of amorphous hydrogenated carbon (a-C:H) films or polycrystalline diamond in these discharges. The underlying growth mechanism is studied, by exposing an a-C:H film to quantified radical beams of H and CH₃. The deposition or etching rate is monitored via ellipsometry and the variation of the stoichiometry is monitored via isotope labeling and infrared spectroscopy. It was shown recently that, at 320 K, methyl radicals have a sticking coefficient of 10^-4 on a-C:H films, which rises to 10^-2 if an additional flux of atomic hydrogen is present. This represents a synergistic growth mechanism between H and CH₃. From the interpretation of the infrared data, a reaction scheme for this type of film growth is developed: atomic hydrogen creates dangling bonds by abstraction of bonded hydrogen within a surface layer corresponding to the range of H in a-C:H films. These dangling bonds serve at the physical surface as adsorption sites for incoming methyl radicals and beneath the surface as radicalic centers for polymerization reactions leading to carbon–carbon bonds and to the formation of a dense a-C:H film. Received: 18 July 2000 / Accepted: 12 December 2000 / Published online: 3 April 2001     

Structural and tribological properties of nitrogen doped amorphous carbon thin films synthesized by CFUBM sputtering method for protective coatings

Nitrogen doped amorphous carbon (a-C:N) films are a material that may successfully compete with DLC coatings, which have high hardness, high wear resistance, and a low friction coefficient. The a-C:N films were prepared on silicon substrate by a closed-field unbalanced magnetron sputtering method with a graphite target and using the Ar/N₂ mixture gases. And, we investigated the effects of various DC bias voltages from 0 to −300 V on the structural and tribological properties of the a-C:N films. This study was focused on improving physical properties of the a-C:N film by controlling process parameters like negative substrate DC bias voltage. The maximum hardness of the a-C:N film was 23 GPa, the friction coefficient was 0.08, and the critical load was 25 N on a Si wafer. Consequently, the structural and tribological properties of the a-C:N film showed a clear dependence on the energy of ions bombardment and the density of the sputtering and the reaction gases during film growth.     

Controllable fabrication of self-organized nano-multilayers in copper–carbon films

In order to clarify the influence of methane concentration and deposition time on self-organized nano-multilayers,three serial copper-carbon films have been prepared at various methane concentrations with different deposition times using a facile magnetron sputtering deposition system. The ratios of methane concentration(CH4/Ar+CH4) used in the experiments are 20%, 40%, and 60%, and the deposition times are 5 minutes, 20 minutes, and 40 minutes, respectively.Despite the difference in the growth conditions, self-organizing multilayered copper-carbon films are prepared at different deposition times by changing methane concentration. The film composition and microstructure are investigated by x-ray photoelectron spectroscopy(XPS), x-ray diffraction(XRD), field emission scanning electron microscopy(FESEM), and high-resolution transmission electron microscopy(HRTEM). By comparing the composition and microstructure of three serial films, the optimal growth conditions and compositions for self-organizing nano-multilayers in copper-carbon film are acquired. The results demonstrate that the self-organized nano-multilayered structure prefers to form in two conditions during the deposition process. One is that the methane should be curbed at low concentration for long deposition time,and the other condition is that the methane should be controlled at high concentration for short deposition time. In particular, nano-multilayered structure is self-organized in the copper-carbon film with copper concentration of 10-25 at.%.Furthermore, an interesting microstructure transition phenomenon is observed in copper-carbon films, that is, the nanomultilayered structure is gradually replaced by a nano-composite structure with deposition time and finally covered by amorphous carbon.     

氢的强化刻蚀对金刚石薄膜品质的影响与sp2杂化碳原子的存在形态

用化学气相沉积方法制备了金刚石薄膜.在制备过程中，通过间歇式关闭甲烷气体，强化了氢对sp2杂化碳原子的刻蚀.用拉曼光谱和金相显微镜对薄膜进行了分析表征.结果表明，氢对sp2杂化碳原子的强化刻蚀并未影响金刚石薄膜的品质和微观结构.这一结论说明，在金刚石薄膜中，sp2杂化碳原子主要存在于金刚石晶粒表面和晶界碳原子之间,而不是以石墨或无定形碳颗粒为主要存在方式. 关键词： 化学气相沉积 金刚石薄膜 拉曼光谱 强化刻蚀     

Effects of flow ratios on surface morphology and structure of hydrogenated amorphous carbon films prepared by microwave plasma chemical vapor deposition

A series of hydrogenated amorphous carbon (a-C:H) films were deposited on silicon substrates by microwave plasma chemical vapor deposition technique with a mixture of hydrogen and acetylene. The effects of flow ratio of hydrogen to acetylene on surface morphology and structure of a-C:H films were investigated using surface-enhanced Raman spectroscopy and scanning probe microscope (SPM) in the tapping AFM mode. Raman data imply a transition from graphite-like phase to diamond-like bonding configurations when the flow ratio increases. AFM measurements show that the increase in hydrogen content, to some extent, can smoothen the surface morphology and decrease the RMS roughness. Excessive hydrogen is found to cause the formation of polymeric hydrocarbon clusters in the films and reduce deposition rate.     

Preparation and tribological properties of DLC/Ti filmby pulsed laser arc deposition

This paper reports that DLC (diamond like carbon)/Ti and DLC films were prepared by using pulsed laser arc deposition. R-ray diffraction, Auger electron spectroscopy, Raman spectroscopy, atomic force microscopy, nanoindenter, spectroscopic ellipsometer, surface profiler and micro-tribometer were employed to study the structure and tribological properties of DLC/Ti and DLC films. The results show that DLC/Ti film, with $I(D)/I(G)$ 0.28 and corresponding to 76{\%} sp$^{3}$ content calculated by Raman spectroscopy, uniform chemical composition along depth direction, 98 at{\%} content of carbon, hardness 8.2 GPa and Young's modulus 110.5 GPa, compressive stress 6.579 GPa, thickness 46~nm, coefficient of friction 0.08, and critical load 95mN, exhibits excellent mechanical and tribological properties.     

Incorporation of nitrogen into amorphous-hydrogenated carbon (diamond-like) films

Nitrogen-doped amorphous hydrogenated carbon films (a-C:H) were prepared by mixing nitrogen gas and benzene during dc plasma discharge deposition. The growth rate of the film decreases strongly with increasing nitrogen content in the mixture. The nitrogen concentration in the films was determined by nuclear reaction analysis (NRA) and Auger electron spectroscopy (AES) using suitable calibration samples. The results of AES measurements are generally consistent with NRA values. Nitrogen incorporation in the a-C:H films shows pronounced doping effects as reflected in their optical and electrical properties.Dedicated to Professor J. P. F. Sellschop for his 60^th birthday