Chemical diagnosis of DLC by ESR spectral analysis

Diamond-like carbon (DLC) films were deposited utilizing plasma enhanced chemical vapor deposition (PECVD) with four precursor gases such as methane, ethylene, acetylene and benzene in gas phase. Electron spin resonance (ESR) spectra showed that dangling-bond sites (DBSs) observed in all films were characterized by an isotropic broad single line. The DLC film with unsaturated precursor gases had the higher film growth rate and the higher DBS accumulative rate. Although the DBS in DLC films were quite stable at room temperature under anaerobic conditions, the DBS decayed rapidly to level off toward a limiting value when exposed to air. The stability and reactivity of the DBS in DLC film were assumed to depend on chemical structure of organic gas used as precursor. The detailed-ESR study on DBS of the DLC films could be one of the powerful tools for diagnosing the micro-structural properties and the quality of films.     

Annealing effect on the structural, mechanical and electrical properties of titanium-doped diamond-like carbon films

Titanium-doped diamond-like carbon (Ti-doped DLC) films with a Ti content of 1.1 at.% were synthesized on a Si substrate by a process that involves filtered cathodic vacuum arc (FCVA) and metal vapor vacuum arc (MeVVA) systems. The effect of annealing temperature on the microstructure, surface roughness, hardness and electrical resistivity of the resulting films was evaluated in this study. The Raman spectra revealed that the degree of graphitization of the Ti-doped DLC thin films was increased from 25 to 600 °C and the microstructure of the films is converted to a nano-crystalline graphite structure. The resulting films maintain a smooth surface after the annealing process. The hardness of the Ti-doped DLC films increases as the annealing temperature increases up to 400 °C because the induced defects and the inter-atomic bonds are repaired after the annealing process. But the hardness decreases at the higher temperature due to the increase of number and size of the nano-crystalline graphitic domains. Since the degree of graphitization of the thin films increases, the electrical resistivity of the Ti-doped DLC thin films decreases from 0.038 to 0.006 Ω cm.     

非平衡磁控溅射技术制备用于红外减反射的无氢碳膜

红外减反射保护膜具有特定的厚度要求,如能进一步减小无氢类金刚石膜(DLC)的光学吸收,就能使其在较大厚度时不过分损失光通量而得以广泛应用.从这点来讲,无氢类金刚石膜是一种极具开发潜力的材料.本文采用非平衡磁控溅射技术(UBMS)制备了无氢类金刚石膜,并研究了其厚度均匀性.研究结果表明:该非平衡磁控溅射装置有能力获得大于φ150 mm的均匀性范围.对DLC膜红外透射谱的分析表明,分别在Si和Ge基底表面单面制备的DLC薄膜,其峰值透射率在波数2983/cm时分别为68.83%和63.05%,这一结果接近无吸收碳材料理论上所能达到的值.同时,在5000到800/cm范围内,未发现明显的吸收峰.这些优良的光学特性表明,采用非平衡磁控溅射技术制备的无氢DLC膜可以作为窗口的红外增透保护膜使用.     

Low temperature annealing effects on the structure and optical properties of ZnO films grown by pulsed laser deposition

ZnO thin films were deposited on glass substrates at room temperature (RT) ∼500 °C by pulsed laser deposition (PLD) technique and then were annealed at 150-450 °C in air. The effects of annealing temperature on the microstructure and optical properties of the thin films deposited at each substrate temperature were investigated by XRD, SEM, transmittance spectra, and photoluminescence (PL). The results showed that the c-axis orientation of ZnO thin films was not destroyed by annealing treatments; the grain size increased and stress relaxed for the films deposited at 200-500 °C, and thin films densified for the films deposited at RT with increasing annealing temperature. The transmittance spectra indicated that E_g of thin films showed a decreased trend with annealing temperature. From the PL measurements, there was a general trend, that is UV emission enhanced with lower annealing temperature and disappeared at higher annealing temperature for the films deposited at 200-500 °C; no UV emission was observed for the films deposited at RT regardless of annealing treatment. Improvement of grain size and stoichiometric ratio with annealing temperature can be attributed to the enhancement of UV emission, but the adsorbed oxygen species on the surface and grain boundary of films are thought to contribute the annihilation of UV emission. It seems that annealing at lower temperature in air is an effective method to improve the UV emission for thin films deposited on glass substrate at substrate temperature above RT.     

Adhesion property of SiOx-doped Diamond-like Carbon Films Deposited on Polycarbonate by Inductively Coupled Plasma Chemical Vapor Deposition

SiO_x-DLC (diamond-like coating) films as candidates for protection coating of polymers were prepared by using a pulse-biased inductively coupled plasma chemical vapor deposition system with acetylene, tetramethylsilane and oxygen gasses. Effects of the gas composition and O₂ plasma pre-treatment on adhesion of the SiO_x-DLC films were investigated. Adhesion strength of Si-DLC films (with 0% oxygen) was almost the same to that of undoped DLC films. By employing O₂-plasma pre-treatment, adhesion strength of the Si-DLC films was considerably improved, while that of the undoped DLC films was not. The SiO_x-DLC films with the carbon to oxygen (O/C) ratio of 0.15 showed adhesion strength as high as that of the Si-DLC films on the O₂-plasma pre-treated substrate. However, further improvement of adhesion strength of the SiO_x-DLC was not realized by employing the O₂-plasma pre-treatment. On the other hand, the SiO_x-DLC films showed favorable feature of high deposition rate and large optical band gap although higher O/C ratio (> 0.15) brought about poor adhesion strength of the films.     

等离子体源离子注入法制备类金刚石薄膜

用等离子体源注入(PSII)在Si(100)上制备类金刚石膜，放电气体采用CH4，用微波电子回旋共振(ECR)产生等离子体。将-20～-30kV的高压加在衬底上，来提高离子的能量。通过Raman光谱和FT-IR光谱检测了类金刚石膜的化学组成及状态，并对其机械性能和表面形貌进行了检测。结果显示，硅片硬度和摩擦因数得到了改善，用PSII能够制备出性能优良的膜，可以将其应用到微电子器件(MEMS)上去。     

非平衡磁控溅射无氢DLC增透膜的研制

非平衡磁控溅射(UBMS)技术近年来得到了广泛地应用.采用该技术制备的类金刚石薄膜(DLC)具有许多独特的性质.本文利用正交实验方法,对非平衡磁控溅射技术制备无氢DLC膜增透膜进行了研究,得到了影响薄膜光学性能的主要因素和最佳的制备工艺.结果表明,非平衡磁控溅射制备的无氢DLC膜具有较宽的光谱透明区,锗基底单面沉积DLC膜,其峰值透射率达到61.4%,接近理论值.     

An examination of trace surface on diamond-like carbon film after ball-on disk measurement

Hydrogenated diamond-like carbon (DLC) films were prepared by the radio frequency plasma-enhanced chemical vapor deposition method on silicon substrates using methane (CH₄) and hydrogen (H₂) gas. The wear track on DLC films was examined after the ball-on disk (BOD) measurement with a Raman mapping method. The BOD measurement of DLC films was performed for 1 to 3 h with a 1-hour step time. The sliding traces on the hydrogenated DLC film after the BOD measurement were also observed using an optical microscope. The films synthesized in this work had a very low friction coefficient (about 0.06) and were adhered very well without peeling off during the BOD measurement even with very thin thickness. Energy dispersive X-ray spectra show the decrease of C atomic % and the increase of O atomic % according to the sliding time. The novel Raman mapping method effectively showed the graphitization of DLC films according to the sliding time.     

Characterization of iron oxide thin films prepared by sol-gel processing

Iron oxide thin films were prepared by spin-coating a gel solution of iron(III) nitrate dissolved in 2-methoxyethanol and acetylacetone on glass and quartz substrates. The film thickness was adjusted by changing the spinning rate of the spin coater. Annealing was carried out between 300 degrees C to 600 degrees C to investigate the phases present in the films. Viscosity of the main solution was found as 0.0035 Pa.s by viscosity measurement. TGA/DTA analyses showed that heat treatment should be done between 330 degrees C and 440 degrees C in order to produce maghemite thin films. SEM studies showed that single layer thickness of the films were between 65 and 80 nm. The structural characteristics were evaluated by changing the experimental parameters which are annealing temperature, annealing time and thickness of the films. From the X-ray diffraction analysis, maghemite formation was observed with decreasing annealing temperature, annealing time and film thickness. TEM results verified the presence of the maghemite phase by electron diffraction and selected area electron diffraction (SAED) methods. According to UV-Vis results transmittance of the films decreases with increasing annealing temperature.     

Friction force microscopy study of annealed diamond-like carbon film

In this paper we introduce mechanical and structural characteristics of diamond-like carbon (DLC) films which were prepared on silicon substrates by radio frequency (RF) plasma enhanced chemical vapor deposition (PECVD) method using methane (CH₄) and hydrogen (H₂) gas. The films were annealed at various temperatures ranging from 300 to 900 °C in steps of 200 °C using rapid thermal processor (RTP) in nitrogen ambient. Tribological properties of the DLC films were investigated by atomic force microscopy (AFM) in friction force microscopy (FFM) mode. The structural properties of the films were obtained by high resolution transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The wettability of the films was obtained using contact angle measurement. XPS analysis showed that the sp³ content is decreased from 75.2% to 24.1% while the sp² content is increased from 24.8% to 75.9% when the temperature is changed from 300 to 900 °C. The contact angles of DLC films were higher than 70°. The FFM measurement results show that the highest friction coefficient value was achieved at 900 °C annealing temperature.     

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.     

超高分子量聚乙烯表面金属化及类金刚石薄膜沉积复合处理研究

采用超高分子量聚乙烯(UHMWPE)表面金属化及类金刚石薄膜沉积复合处理工艺,提高超高分子量聚乙烯的耐磨性.首先采用磁过滤阴极真空弧源沉积技术(FCVA)在UHMWPE表面制备约30nm钛金属层,使UHMWPE表面金属化,然后再沉积DLC薄膜,研究结果表明,UHMWPE表面金属化后,DLC薄膜沉积过程中,电荷累积效应消...     

Characterization and tribological application of diamond-like carbon (DLC) films prepared by radio-frequency plasma-enhanced chemical vapor deposition (RF-PECVD) technique

Diamond-like carbon (DLC) films were successfully prepared on glass substrates and surfaces of selenium drums via radio frequency plasma enhanced chemical vapor deposition method. The microstructure, surface morphology, hardness, film adhesion, and tribological properties of the films were characterized and evaluated by X-ray photoelectron spectroscopy, atomic force microscopy, and micro-sclerometer and friction-wear spectrometer. The results showed that DLC films have smooth surfaces, homogeneous particle sizes, and excellent tribological properties, which can be used to improve the surface quality of the selenium drums and prolong their service life.     

类金刚石碳膜的结构特性与耐磨性能

采用双离子束增强沉积（IBED）和离子束直接沉积（IBD）技术，在CHn 能量为200~550eV和3～25keV范围内沉积的类金刚石薄膜具有光滑平坦的表面和非晶结构。X光电子谱和Raman光谱分析、以及显微硬度测量的结果表明，随着轰击离子能量的降低，薄膜的金刚石特性增强；在200～550eV能量范围内制备的DLC膜具有明显的sp3键特征和很高的显微硬度。沉积在GCr15钢上的DLC膜与GCr15钢的摩擦学对比实验表明，DLC膜具有很低的摩擦系数、比磨损率和高的抗磨损指数，这证明采用上述两种方法制备的DLC膜具有优良的抗摩擦磨损性能。     

Spatially resolved positron annihilation spectroscopy on friction stir weld induced defects

A friction stir welded (FSW) Al alloy sample was investigated by Doppler broadening spectroscopy (DBS) of the positron annihilation line. The spatially resolved defect distribution showed that the material in the joint zone becomes completely annealed during the welding process at the shoulder of the FSW tool, whereas at the tip, annealing is prevailed by the deterioration of the material due to the tool movement. This might be responsible for the increased probability of cracking in the heat affected zone of friction stir welds. Examination of a material pairing of steel S235 and the Al alloy Silafont36 by coincident Doppler broadening spectroscopy (CDBS) indicates the formation of annealed steel clusters in the Al alloy component of the sample. The clear visibility of Fe in the CDB spectra is explained by the very efficient trapping at the interface between steel cluster and bulk.     

类金刚石薄膜对轴承钢表面机械性能和滚动接触疲劳寿命的影响

使用等离子体浸没离子注入与沉积(PIII&D)技术在轴承钢基体表面合成类金刚石(DLC)薄膜,研究了薄膜的结构和性能,结果表明,所制备的DLC薄膜主要是由金刚石键(sp3)和石墨键(sp2)组成的混合无定形碳,且sp3键含量大于10%,DLC膜层致密均匀,与基体结合良好,DLC膜具有很高的硬度和杨氏模量,分别达到40 GPa和430 GPa;其最低摩擦系数由基体的0.87下降到0.2,被处理薄膜试件在90%置信区间下的L10、L50、La和平均寿命L较基体分别延长了10.1倍、4.2倍、3.5倍和3.4倍,PIII&D轴承钢滚动接触疲劳寿命的分散性得到了显著改善.     

Metal-doped diamond-like carbon films synthesized by filter-arc deposition

Diamond-like carbon (DLC) thin films are extensively utilized in the semiconductor, electric and cutting machine industries owing to their high hardness, high elastic modulus, low friction coefficients and high chemical stability. DLC films are prepared by ion beam-assisted deposition (BAD), sputter deposition, plasma-enhanced chemical vapor deposition (PECVD), cathodic arc evaporation (CAE), and filter arc deposition (FAD). The major drawbacks of these methods are the degraded hardness associated with the low sp³/sp² bonding ratio, the rough surface and poor adhesion caused by the presence of particles. In this study, a self-developed filter arc deposition (FAD) system was employed to prepare metal-containing DLC films with a low particle density. The relationships between the DLC film properties, such as film structure, surface morphology and mechanical behavior, with variation of substrate bias and target current, are examined. Experimental results demonstrate that FAD-DLC films have a lower ratio, suggesting that FAD-DLC films have a greater sp³ bonding than the CAE-DLC films. FAD-DLC films also exhibit a low friction coefficient of 0.14 and half of the number of surface particles as in the CAE-DLC films. Introducing a CrN interfacial layer between the substrate and the DLC films enables the magnetic field strength of the filter to be controlled to improve the adhesion and effectively eliminate the contaminating particles. Accordingly, the FAD system improves the tribological properties of the DLC films.     

Tribological properties of multilayer DLC/W-DLC films on Si

Multilayer films of diamond-like carbon (DLC) and tungsten-containing diamond-like carbon (W-DLC) films were deposited onto silicon wafers using radio frequency chemical vapor deposition (RFCVD) and a magnetron sputtering method. The W-DLC layer was deposited on the silicon wafer with less than 60 W magnetron output. The DLC layer was then deposited on the W-DLC layer.Surface morphology was investigated by atomic force microscopy and the film structure by transmission electron microscopy. Friction tests for multilayered films were performed in a nitrogen atmosphere at room temperature using a ball-on-disk tribometer. A conventional stainless steel ball was used for the test.The surface profiles seen by atomic force microscopy showed that round-shaped clusters of around 100 nm were observed in just the single W-DLC layer. These clusters were considered to be tungsten or tungsten-carbon composites. In the case of the DLC/W-DLC multilayered structure, the top DLC layer covered the W-DLC single layer and smoothed the surface of the W-DLC film.Friction tests demonstrated that the friction coefficient of the W-DLC single layer was above 0.6 and increased gradually as the number of cycle increased. The W-DLC films partially broke down during our measurements. However the DLC/W-DLC multilayer films showed stable friction properties and were observed for up to 100,000 cycles. Their friction coefficient was typically less than 0.1 at 10 cm/s rotating speed. The DLC/W-DLC multilayer films exhibited stable low friction properties in a long term test under a nitrogen atmosphere.     

Spatially resolved positron annihilation spectroscopy on friction stir weld induced defects

Abstract

A friction stir welded (FSW) Al alloy sample was investigated by Doppler broadening spectroscopy (DBS) of the positron annihilation line. The spatially resolved defect distribution showed that the material in the joint zone becomes completely annealed during the welding process at the shoulder of the FSW tool, whereas at the tip, annealing is prevailed by the deterioration of the material due to the tool movement. This might be responsible for the increased probability of cracking in the heat affected zone of friction stir welds. Examination of a material pairing of steel S235 and the Al alloy Silafont36 by coincident Doppler broadening spectroscopy (CDBS) indicates the formation of annealed steel clusters in the Al alloy component of the sample. The clear visibility of Fe in the CDB spectra is explained by the very efficient trapping at the interface between steel cluster and bulk.     

Diffusion and adhesion properties of Cu films on polyimide substrates

Copper thin films were prepared on polyimide (PI) substrates by physical vapor deposition (PVD) and chemical vapor deposition (CVD). Titanium nitride (TiN) diffusion barrier layers were deposited between the copper films and the PI substrates by PVD. Auger electron spectroscopy compositional depth profile showed that TiN barrier layer was very effective in preventing copper diffusion into PI substrate even after the Cu/TiN/PI samples were annealed at 300 °C for 5 h. For the as-deposited CVD-Cu/PI, CVD-Cu/TiN/PI, and as-deposited PVD-Cu/PI samples, the residual stress in Cu films was very small. Relatively larger residual stress existed in Cu films for PVD-Cu/TiN/PI samples. For PVD-Cu/TiN/PI samples, annealing can increase the peeling strength to the level observed without a diffusion barrier. The adhesion improvement of Cu films by annealing treatment can be attributed to lowering of the residual tensile stress in Cu films.