Optimization of the Deposition Parameters of DLC Coatings with the IC-PECVD Method

Amorphous carbon film, also known as diamond-like carbon (DLC) film, is a promising material for tribological application. It is noted that properties relevant to tribological application change significantly depending on the method of preparation of these films. These properties are also altered by the composition of the films. In view of this, the purpose of the present study was to determine the optimal values of selected deposition parameters of hydrogenated DLC films on high-speed steel tool substrates with the inductively coupled plasma enhanced chemical vapor deposition (IC-PECVD) method. To optimize the deposition parameters for hydrogenated DLC films, Taguchi's method was used. Deposition parameters (bias voltage, bias frequency, deposition pressure, and gas composition) were optimized with consideration to hardness of the film. Based on the experimental results, the optimal parameter setting are ?50 V, 500 Hz, 4 µbar, and 90:10 for achieving maximum value of hardness. It was found that bias voltage has greater influence on hardness. At the optimum conditions, the conformance run resulted in a hardness value of 1580 KHN. Atomic force microscopy images showed that the DLC films are smooth with an average roughness (Ra) of 1.24 nm on silicon substrate.     

Optical and mechanical properties of diamond like carbon films deposited by microwave ECR plasma CVD

Diamond like carbon (DLC) films were deposited on Si (111) substrates by microwave electron cyclotron resonance (ECR) plasma chemical vapour deposition (CVD) process using plasma of argon and methane gases. During deposition, a d.c. self-bias was applied to the substrates by application of 13·56 MHz rf power. DLC films deposited at three different bias voltages (−60 V, −100 V and −150 V) were characterized by FTIR, Raman spectroscopy and spectroscopic ellipsometry to study the variation in the bonding and optical properties of the deposited coatings with process parameters. The mechanical properties such as hardness and elastic modulus were measured by load depth sensing indentation technique. The DLC film deposited at −100 V bias exhibit high hardness (∼ 19 GPa), high elastic modulus (∼ 160 GPa) and high refractive index (∼ 2·16–2·26) as compared to films deposited at −60 V and −150 V substrate bias. This study clearly shows the significance of substrate bias in controlling the optical and mechanical properties of DLC films.     

Improvement of adhesion of DLC coating on nitinol substrate by hybrid ion beam deposition technique

Diamond-like carbon (DLC) films were prepared for a protective coating on nitinol substrate by hybrid ion beam deposition technique with an acetelene as a source of hydrocarbon ions. An amorphous silicon (a-Si) interlayer was deposited on the substrates to ensure better adhesion of the DLC films followed by Ar ion beam treatment. The film thickness increased with increase in ion gun anode voltage. The residual stresses in the DLC films decreased with increase in ion gun anode voltage and film thickness, while the stress values were independent of the radio frequency (RF) bias voltage. The adhesion of the DLC film was improved by surface treatment with argon ion beam for longer time and by increasing the thickness of a-Si interlayer.     

基体负偏压对类金刚石涂层结构和性能的影响

采用直流等离子体增强化学气相沉积技术(DC-PECVD),通过控制基体负偏压的变化在YG8硬质合金基体上制备一系列类金刚石涂层。选用扫描电子显微镜、原子力显微镜、拉曼光谱、X射线光电子能谱、粗糙度仪对涂层形貌和结构进行表征测试。同时,利用显微硬度计、划痕测试仪系统地分析涂层的显微硬度和界面结合性能。结果表明:随着负偏压增大,涂层表面形貌逐渐平整光滑、致密,颗粒尺寸减小及数量降低。拉曼光谱表明,涂层具有典型的类金刚石结构,涂层中sp3键含量呈先增大后减小趋势,最大值约67.9%出现在负偏压为1000V左右,负偏压过大导致sp3键含量降低。显微硬度随负偏压变化规律与sp3键基本相符,sp3键含量决定显微硬度值大小。负偏压过大对吸附离子产生反溅射作用导致涂层厚度减小。当负偏压为1100V时,涂层与基体间的界面结合性能最优。     

类金刚石薄膜在不锈钢表面结合强度及耐腐蚀性研究

类金刚石(DLC)薄膜与不锈钢的结合强度是DLC薄膜应用于血管支架表面改性的关键技术问题.利用磁过滤阴极真空弧源沉积方法在316L不锈钢表面沉积DLC薄膜,研究沉积时基体偏压、薄膜厚度以及钛过渡层对DLC薄膜与基体结合强度的影响.研究结果表明,316L表面制备相同厚度的DLC薄膜,采用-1000V脉冲偏压制备的薄膜结合强度明显优于-80V直流偏压下制备的DLC薄膜;随着DLC薄膜厚度的增大,DLC薄膜与316L基体的结合力下降;316L不锈钢表面制备一层100nm的钛过渡层之后可以改善DLC薄膜的结合状况,并且经过20%的拉伸变形后,DLC薄膜完整,耐蚀性优于未表面处理的316L不锈钢.以上研究结果表明,磁过滤阴极真空弧源方法制备DLC薄膜与316L结合强度高,可以有效的提高316L的耐腐蚀性,是一种具有应用前景的血管支架表面改性方法.     

Deposition of boron doped DLC films on TiNb and characterization of their mechanical properties and blood compatibility

Abstract

Diamond-like carbon (DLC) material is used in blood contacting devices as the surface coating material because of the antithrombogenicity behavior which helps to inhibit platelet adhesion and activation. In this study, DLC films were doped with boron during pulsed plasma chemical vapor deposition (CVD) to improve the blood compatibility. The ratio of boron to carbon (B/C) was varied from 0 to 0.4 in the film by adjusting the flow rate of trimethylboron and acetylene. Tribological tests indicated that boron doping with a low B/C ratio of 0.03 is beneficial for reducing friction (μ = 0.1), lowering hardness and slightly increasing wear rate compared to undoped DLC films. The B/C ratio in the film of 0.03 and 0.4 exhibited highly hydrophilic surface owing to their high wettability and high surface energy. An in vitro platelet adhesion experiment was conducted to compare the blood compatibility of TiNb substrates before and after coating with undoped and boron doped DLC. Films with highly hydrophilic surface enhanced the blood compatibility of TiNb, and the best results were obtained for DLC with the B/C ratio of 0.03. Boron doped DLC films are promising surface coatings for blood contacting devices.     

Diamond like carbon coatings deposited by microwave plasma CVD: XPS and ellipsometric studies

Diamond-like carbon (DLC) films were deposited by microwave assisted chemical vapour deposition system using d.c. bias voltage ranging from −100 V to −300 V. These films were characterized by X-ray photoelectron spectroscopy (XPS) and spectroscopic ellipsometry techniques for estimating sp ³/sp ² ratio. The sp ³/sp ² ratio obtained by XPS is found to have an opposite trend to that obtained by spectroscopic ellipsometry. These results are explained using sub-plantation picture of DLC growth. Our results clearly indicate that the film is composed of two different layers, having entirely different properties in terms of void percentage and sp ³/sp ² ratio. The upper layer is relatively thinner as compared to the bottom layer.     

Comparing internal stress in diamond-like carbon films with different structure

Diamond-like carbon (DLC) films with different structures were deposited on Si (100) and stainless steel substrates in a hybrid deposition system with Ar and CH₄ as the feedstocks. The effects of the bias voltage, Ti-interlayer, Ti functional gradient layer and Ti-doping on the internal stress in DLC films were investigated. The results show that the internal stress in DLC films arises from both the intrinsic stress generated during the film growth and the thermal stress generated due to the mismatching of the thermal expansion coefficient between the DLC films and the substrate materials. The intrinsic stress can be released through doping titanium element at the expense of reducing the sp³/sp² ratio. The thermal stress in DLC films can be decreased through introducing Ti-interlayer or Ti functional gradient layer. Noticeably, DLC films with very low internal stress deposited on stainless steel can be obtained through the combination of Ti-doping and Ti functional gradient layer.     

脉冲偏压对等离子体沉积DLC膜化学结构的影响

以乙炔为气源，用等离子体基脉冲偏压沉积（plasma based pulsd bias deposition缩写PBPBD）技术进行了不同负脉冲偏压条件下制备DLC膜的试验，通过X射线光电子谱（XPS）、激光喇曼光谱[Raman]以及电阻分析方法考察了负脉冲偏压幅值对DLC膜化学结构的影响，结果表明由-50kV到-10kV随负脉冲偏压降低，DLC膜中SP^3键分数单调增加，但当脉冲偏压为0时形成高电阻的类聚合物膜，说明荷能离子的轰击作用形成DLC化学结构的必要条件，键角混乱度和SP^2簇团尺寸与脉冲偏压之间不具有单调关系，在中等幅值负脉冲偏压条件下，键用混乱度较大且SP^2簇团尺寸细小。     

Deuterium influence on optical gap of amorphous carbon diamond-like carbon (DLC) thin film

This present study aims to determine the hydrogen influence on the electrical gap of diamond-like carbon (DLC) film. DLC thin layers were deposited on silicon wafer by plasma enhanced chemical vapour deposition (PECVD). With this method we obtain a a-C:H film structure. To understand the mechanism of deposition, local structure and hydrogen effect in DLC we replace our methane plasma source by deuterated methane one. In this article, hydrogen rate is obtained by elastic recoil detection analysis (ERDA), electronic and bulk density is performed with X-ray reflectometry (XRR) and the determination of electrical gap is carried out using ultraviolet-visible absorption spectrometry. A specific attention is carried about the self-bias voltage and time variations to get different DLC and DDLC film compositions and also different electrical properties. We found that including deuterium in carbon increases the Tauc energy while keeping the same density. A comparison between these two sorts of film is expected to improve our understanding of the hydrogen role in the DLC films.     

脉冲真空弧源沉积类金刚石薄膜耐磨特性研究

本文利用脉冲真空弧源沉积技术在Cr17Ni14Cu4不锈钢和Si(100)基体上制备了类金刚石(DLC)薄膜,研究在不同基体偏压下,DLC薄膜的结构与性能.采用拉曼光谱和X射线光电子能谱(XPS)研究DLC薄膜的原子结合状态,利用CSEM销盘摩擦磨损试验机研究其耐磨性,利用HXD1000B显微硬度仪测试其显微硬度,并采用压痕法评价其结合力.研究结果表明:DLC薄膜与基体结合牢固.随着基体偏压的提高,DLC薄膜内sp3键含量增大,薄膜硬度提高.Cr17Ni14Cu4不锈钢表面沉积DLC薄膜后,耐磨性大幅度提高,本文探讨了DLC薄膜的耐磨机理.     

Low temperature crystallization of amorphous silicon carbide thin films for p–n junction devices fabrication

Metal induced crystallization technique was used to crystallize hydrogenated amorphous silicon carbide (a-SiC:H) thin films at low temperatures. Two types of substrates, silicon and silicon carbide were considered and the substrate effects on the final crystallized film were studied. About 200 nm a-SiC:H films were deposited and crystallized successfully on n-type Si and n-type 6H SiC substrates at a temperature of 600 °C. Fourier Transform Infrared (FTIR) spectroscopy and transmission electron microscopy (TEM) analysis confirmed the crystallization of a-SiC:H film. Current–voltage (I–V) and capacitance–voltage (C–V) measurement confirms the formation of p–n junction with rectification over five orders of magnitude from ?2 V to 2 V.     

直流负偏压对类金刚石薄膜结构和性能的影响

利用直流-射频-等离子体增强化学气相沉积技术在单晶硅表面制备了类金刚石薄膜，采用原子力显微镜、Raman光谱、X射线光电子能谱、红外光谱、表面轮廓仪和纳米压痕仪考察了直流负偏压对类金刚石薄膜表面形貌、微观结构、沉积速率和硬度等性能的影响。结果表明：无直流负偏压条件下，薄膜呈现有机类聚合结构，具有较低的SP3含量和硬度；叠加上直流负偏压后，薄膜具有典型的类金刚石结构特征，SP3含量和硬度得到了显著的提高；但随着直流负偏压的升高，薄膜的沉积速率和H含量逐渐降低，而SP3含量和硬度在直流负偏压为200V时出现最大值，此后逐渐降低。     

Microcrystalline silicon films fabricated by bias-assisted hot-wire chemical vapor deposition

Microcrystalline silicon films (μc-Si:H) were deposited on stainless steel substrates by bias-assisted hot-wire chemical vapor deposition. The effect of substrate bias and substrate temperature on the crystallinity of μc-Si:H films was studied by Raman spectroscopy, X-ray diffraction and scanning electron microscopy. The results show that both the Raman peak position and the crystalline fraction of the μc-Si:H films deposited at 200 °C were obviously improved by introducing ?800 V substrate bias. The films deposited at 200 °C with ?800 V substrate bias show strongly sharpened Si (111) peak together with Si (220) and Si (311) peaks, which was different from a weak Si (111) peak for those deposited without substrate bias. By increasing the substrate temperature from 200 to 300 °C, while keeping the substrate bias at ?800 V, the crystallinity of the silicon films was further improved, and μc-Si:H films with crystalline fraction of 74 % was obtained.     

Evaluation of microstructures and mechanical properties of diamond like carbon films deposited by filtered cathodic arc plasma

Diamond-like carbon (DLC) films were deposited by a cathodic arc plasma evaporation (CAPD) process, using a mechanical shield filter combined with a magnetic filter with enhanced arc structure at substrate-bias voltage ranging from − 50 to − 300 V. The film characteristics were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and high-resolution transmission electron microscopy (HRTEM). The mechanical properties were investigated by using a nanoindentation tester, scratch test and ball on disc wear test. The Raman spectra of the films showed that the wavenumber ranging from 900 to 1800 cm^− 1 could be deconvoluted into 1140 cm^− 1, D band and G band. The bias caused a significant effect on the sp³ content which was increased with the decreasing of I_D/I_G ratio. The XPS spectra data of the films which were etched by H⁺ plasma indicated the sp³ content are higher than those of the as-deposited DLC films. This implied that there is a sp²-rich layer present on the surface of the as-deposited DLC films. The nanoindentation hardness increased as the maximum load increased. A 380 nm thick and well adhered DLC film was successfully deposited on WC-Co substrate above a Ti interlayer. The adhesion critical load of the DLC films was about 33 N. The results of the wear tests demonstrated that the friction coefficient of the DLC films was between 0.12 and 0.2.     

Study of electrochemically grown copper indium diselenide (CIS) thin films for photovoltaic applications

CIS thin films have been grown electrochemically from an aqueous electrolyte at room temperature on fluorine doped tin oxide coated glass substrate at different deposition potentials ranging from ?0.7 to ?1.0 V versus Ag/AgCl reference electrode. Cyclic voltammetry was studied at slow scan rate to optimize the deposition potential. The thin film samples were selenized in a tubular furnace at 400 °C for 20 min. X-ray diffraction and Raman analysis was used to study the structural properties. Optical absorption, scanning electron microscopy and energy dispersive X-ray analysis (EDAX) have been used to investigate the band-gap, surface morphology and compositional analysis. Electrical properties were studied with the help of current–voltage measurements. Conductivity type for CIS thin films was studied by using photo-electrochemical study. The prominent reflections (112), (204/220) and (312/116) of tetragonal chalcopyrite CIS have been revealed for all as-grown and selenized samples. The energy band gap of the selenized CIS thin film deposited at various deposition potentials was found to be ~1.03 to 1.24 eV. Granular, uniform and void free surface was observed in as-prepared sample, while large clusters were noticed in selenized samples. EDAX results reveal that the stoichiometric CIS thin film are deposited ?0.8 V, however, Cu-rich and In-rich CIS layers were grown at lower and higher cathodic deposition potentials, deviated from ?0.8 V. The values ideality factor (η) calculated from I–V measurements were found to be decreased upon selenization. The Raman spectra of stoichiometric CIS thin film shows dominant A1 mode with spectral features sensitive to the microcrystalline quality of the layers. A ordered defect compound layer and secondary phases of CuSe are observed in In-rich and Cu-rich CIS layers, respectively.     

CVD of hard DLC films in a radio frequency inductively coupled plasma source

Chemical vapor deposition (CVD) of hard diamond-like carbon (DLC) films on silicon (100) substrates from methane was successfully carried out using a radio frequency (r.f.) inductively coupled plasma source (ICPS). Different deposition parameters such as bias voltage, r.f. power, gas flow and pressure were involved. The structures of the films were characterized by Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. The hardness of the DLC films was measured by a Knoop microhardness tester. The surface morphology of the films was characterized by atomic force microscope (AFM) and the surface roughness (R_a) was derived from the AFM data. The films are smooth with roughness less than 1.007 nm. Raman spectra shows that the films have typical diamond-like characteristics with a D line peak at 1331 cm⁻¹ and a G line peak at 1544 cm⁻¹, and the low intensity ratio of I_D/I_G indicate that the DLC films have a high ratio of sp³ to sp² bonding, which is also in accordance with the results of FTIR spectra. The films hardness can reach approximately 42 GPa at a comparatively low substrate bias voltage, which is much greater than that of DLC films deposited in a conventional r.f. capacitively coupled parallel-plate system. It is suggested that the high plasma density and the suitable deposition environment (such as the amount and ratio of hydrocarbon radicals to atomic or ionic hydrogen) obtained in the ICPS are important for depositing hard and high quality DLC films.     

Electrical percolation threshold in Ag–DLC nanocomposite films prepared by RF-sputtering and RF-PECVD in acetylene plasma

Silver–diamond like carbon (Ag–DLC) nanocomposite films were deposited on glass and silicon substrates by co-deposition of RF-sputtering and RF-PECVD method in acetylene plasma. The effects of deposition time on creation of conductive percolation pathway in Ag–DLC nanocomposite films were investigated. The films were characterized by XRD pattern, AFM images, UV–Vis and FTIR spectra. Pressure of chamber’s variation over time was illustrated the rate of carbon and silver deposition changing. The results showed that nanoparticles’ size and surface roughness was increased by increasing deposition time. Surface plasmon resonance peak’s red shift in optical absorption spectra of samples could be depends on silver nanoparticles’ scale up. Based on electrical measurements, electrical percolation threshold was observed only in the film with 35 min deposition time. Pathway was created for electric current by Ag nanoparticles’ moving in carbon matrix due to sp³ bonds and silver content in the films. The aging effect was studied for sample #2 in the threshold of percolation, where obtained Ag nanoparticles memorize its previous pathway. This investigation provides a better understanding for electric properties of Ag–DLC nanocomposite based on the percolation theory.     

金属等离子体浸没离子注入与沉积技术合成类金刚石薄膜研究

采用金属等离子体浸没离子注入与沉积技术在9Cr18轴承钢基体表面合成了类金刚石薄膜.研究了注入脉宽和工作气压对合成薄膜性能及化学组成的影响;通过激光Raman光谱、维氏硬度、针盘试验和电化学腐蚀等测试手段分别表征了合成薄膜后试样表面的化学组成和微观结构、显微硬度、摩擦磨损性能和抗腐蚀性能.结果表明:合成薄膜后,试样的显微硬度增大了88.7%,摩擦磨损和抗腐蚀性能也明显改善.     

Study of diamond-like carbon films on LiNbO3

Diamond-like carbon (DLC) films have been successfully deposited on Y-cut LiNbO₃ substrates using the plasma enhanced CVD technique. A thin interlayer of SiC between the DLC films and the LiNbO₃ is necessary to ensure a good adhesion of the DLC films to the LiNbO₃ substrate. The physical properties and structural network of the DLC films have been investigated in detail. It is observed that the film hardness is increased with increasing the film thickness, as is the adhesion of the DLC films to the LiNbO₃ substrates. The effect of accelerating surface acoustic wave by the DLC films has been confirmed.