Adhesion improvement of hydrogenated diamond-like carbon thin films by pre-deposition plasma treatment of rubber substrate

For reduction of friction and enhancement of wear resistance of dynamic rubber seals, thin films of hydrogenated diamond-like carbon (DLC) have been deposited on hydrogenated nitrile butadiene rubber (HNBR) via magnetron-enhanced plasma chemical vapor deposition (ME-PCVD). Pre-deposition plasma treatment of HNBR substrate is proved to be crucial for the improvement of film performance due to enhanced interfacial adhesion. The columnar structure and the crack network formed during deposition enhance the flexibility of DLC thin films and exhibit strain tolerance up to 5%. Below 50% stretch strain and after unloading, thin DLC films of ∼ 300 nm thickness still adhere on the rubber substrates and no spallation or delamination is observed. The thin DLC film deposited on Ar-plasma pre-treated rubber at − 400 V substrate bias potential exhibits a very low coefficient of friction of 0.175 (compared to > 1 of uncoated HNBR rubber). After tribotests even under high normal load of 3 N, almost no wear can be seen on the films. Such tribological property is even better than that of 1 µm thick DLC or Me-DLC coated rubbers.     

Deposition of dense and smooth Ti films using ECR plasma-assisted magnetron sputtering

We report high quality Ti films grown in a novel electron cyclotron resonance (ECR) plasma-assisted magnetron sputtering (PMS) deposition system. The films are compared with films deposited by conventional direct current (DC) magnetron sputtering. Using ECR-PMS, the argon plasma bombardment energy and Ti film deposition rate can be controlled separately, with the substrate bias voltage under feedback control. Results from SEM, AFM, XRD and PAS (scanning electron microscopy, atomic force microscopy, X-ray diffraction and positron annihilation spectroscopy) show that the properties of Ti films prepared by ECR-PMS are greatly improved compared with conventional sputtering. SEM and AFM confirmed that ECR-PMS Ti films have a dense, smooth, mirror-like surface. Increasing the substrate bias of the ECR plasma from − 23 V to − 120 V while keeping a fixed sputtering bias voltage of − 40 V, the intensity of the (100) reflection of Ti film was a little strengthened, but (002) remained strongly preferred orientation. The XRD peak broadening of ECR-PMS Ti films is more than for conventional magnetron sputtering, due to grain refinement induced by Ar ion bombardment. Doppler broadening of PAS analysis reveals that the Ti films have fewer vacancy defects compared with films prepared by the conventional magnetron.     

Hexagonal diamond formation on steel substrates by negative bias microwave plasma enhanced chemical vapor deposition

This paper reports for the first time the synthesis of hexagonal diamond thin films on high-speed steel substrates by multi-mode microwave plasma enhanced chemical vapor deposition. Before deposition of the films, the substrate surface was treated by scratching with diamond powder. The deposited films were characterized by X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy. The XRD patterns of (100) and (101) planes and the Raman peaks at ~ 1317-1322 cm^− 1 were observed, confirming the formation of hexagonal diamond phase in the prepared films. The effects of voltage bias on the phase formation, microstructure and hardness of the films were also studied by setting the voltage to 0, − 70, − 150 and − 190 V. The highest hardness of 23.8 GPa was found in the film having clusters of size about 550 nm deposited under a bias voltage of − 150 V. These clusters were built up of grains of size about 14 nm.     

Properties of Zr-ZrC-ZrC/DLC gradient films on TiNi alloy by the PIIID technique combined with PECVD

The Zr-ZrC-ZrC/DLC gradient composite films were prepared on TiNi alloy by the techniques combined plasma immersion ion implantation and deposition (PIIID) and plasma enhanced chemical vapor deposition (PECVD). With this method, the Zr-ZrC intermixed layers can be obtained by the ion implantation and deposition before the deposition of the ZrC/DLC composite film. In our study, an optimal gradient composite film has been deposited on the NiTi alloys by optimizing the process parameters for implantation and deposition. The surface topography was observed through AFM and the influence of the deposition voltage on the surface topography of the film was investigated. XPS results indicate that on the outmost layer, the Zr ions are mixed with the DLC film and form ZrC phase, the binding energy of C 1s and the composition concentration of ZrC depend heavily on the bias voltage. With the increase of bias voltage, the content of ZrC and the ratio of sp³/sp² firstly increases, reaching a maximum value at 200 V, and then decreases. The nano-indentation and friction experiments indicate that the gradient composite film at 200 V has a higher hardness and lower friction coefficient compared with that of the bare NiTi alloy. The microscratch curve tests indicate that gradient composite films have an excellent bonding property comparing to undoped DLC film. Based on the electrochemical measurement and ion releasing tests, we have found that the gradient composite films exhibit better corrosion resistance property and higher depression ability for the Ni ion releasing from the NiTi substrate in the Hank's solution at 37°C.     

Influence of substrate bias on the composition of SiC thin films fabricated by PECVD and underlying mechanism

The influence of the substrate bias on the composition of SiC thin films synthesized by plasma-enhanced chemical vapor deposition was studied. Our results indicate that the ratio of Si to C in the thin films is almost stoichiometric at a bias of − 300 V, whereas excessive carbon is observed in the films if the bias is lower or higher. Very little oxygen can be detected in the film produced without biasing. The effects of the bias on the composition of the thin films can be attributed to the interaction between the positive ions in the plasma and the surface atoms. The underlying mechanism is also discussed.     

Structural and optical properties of diamond like thin films deposited by asymmetric bipolar pulsed-DC reactive magnetron sputtering

In contrast with PECVD technology, reactive sputtering of graphite allows an independent control of the substrate bias. This characteristic permits the modification of film properties without varying the plasma composition. In the present study, the characteristics of DLC films grown by pulsed-DC reactive sputtering were determined as a function of substrate bias. Asymmetric bipolar pulsed-DC in a gas mixture of Ar and 7.5% CH₄ with substrate bias in the range of − 300 V to 0 V, provided wear resistant a-C:H films with wear rate values in the range of 15 to 23 · 10^− 15 m³ m^− 1 N^− 1. DLC exhibit characteristics associated to hydrogenated DLC films (DLCH), namely: moderate sp³ content and mass density (up to 1.8 g/cm³), low hydrogen content (∼ 30%) and high transparency (> 90%) up to wavelengths of 700 nm with a Tauc gap energy up to 1.9 eV. Moreover, they also showed low stress values and moderate wear rates, as shown in previous studies.     

Mechanical properties of high-density diamond like carbon (HD-DLC) films prepared using filtered arc deposition

Because high density DLC (HD-DLC) films prepared using filtered arc deposition (FAD) systems possess high hardness, low friction coefficients, and a smooth surface, they have been good candidates for use in tribological applications. The aim of present work is the investigation of the mechanical and structural properties of HD-DLC films.The experimental conditions were the following: arc current, 50 A; base pressure, less than 3 × 10^− 3 Pa; substrate bias, DC-100 V; substrate temperature, less than 100 °C. The HD-DLC films were formed on silicon wafers and tungsten carbide (WC) substrates. The film properties of hardness, composition, structure, and friction were analyzed.The film hardness is high, 80-90 GPa, with a low friction coefficient of less than 0.1.     

偏压对DLC薄膜结构及摩擦学性能的影响

目的通过调节偏压,改善无氢DLC薄膜的微观结构,提高其力学性能和减摩抗磨性能。方法采用离子束辅助增强磁控溅射系统,沉积不同偏压工艺的DLC薄膜。采用原子力显微镜(AFM)观察薄膜表面形貌,采用拉曼光谱仪对薄膜的微观结构进行分析,采用纳米压痕仪测试薄膜硬度及弹性模量,采用表面轮廓仪测定薄膜沉积前/后基体曲率变化,并计算薄膜的残余应力,采用大载荷划痕仪分析薄膜与不锈钢基体的结合力,采用TRB球-盘摩擦磨损试验机评价薄膜的摩擦学性能,采用白光共聚焦显微镜测量薄膜磨痕轮廓,并计算薄膜的磨损率。结果偏压对DLC薄膜表面形貌、微观结构、力学性能、摩擦学性能都有不同程度的影响。偏压升高导致碳离子能量升高,表面粗糙度呈现先减小后增加的趋势,-400V的薄膜表面具有最小的表面粗糙度且C─C sp^3键含量最多,这也导致了此偏压下薄膜的硬度最大。薄膜的结合性能与碳离子能量大小呈正相关,-800 V时具有3.98 N的最优结合性能。不同偏压工艺制备的薄膜摩擦系数随湿度的增加,均呈现减小的趋势,偏压为-400V时,薄膜在不同湿度环境中均显示出最优的摩擦学性能。结论偏压为-400 V时,DLC薄膜综合性能最优,其表面粗糙度、硬度、结合力和摩擦系数分别为2.5 nm、17.1 GPa、2.81 N和0.11。     

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.     

Cathodic arc plasma deposition of nano-multilayered Zr-O/Al-O thin films

Thin films of Zr-O/Al-O were deposited on SKD 11 tool steel substrate using Zr and Al cathodes in a cathodic arc plasma deposition system. The substrates were mounted on a rotating holder which alternatively exposed them to plasma from the two cathodes. The influence of the Zr and Al cathode arc currents and the substrate bias on the mechanical and the structural properties of the films were investigated. Films with a nano-layered structure of alternating Al-rich and Zr-rich layers were obtained. The Zr layers contained nano-crystallites of (101) oriented t-ZrO structure. Crystallites with α-Al₂O₃ structure were observed only when the substrate was negatively biased in the 100-150 V range. The hardness of the film decreased with the increase of Zr cathode current from 60 to 80 A, increased when the Al cathode current increased from 25 to 30 A, and decreased when the Al cathode current increased from 30 to 35 A. The hardness of the film increased with the increase of bias voltage up to − 150 V and then decreased with further increase of the negative bias. The film structure was elucidated by HRTEM microscopy. Good correlation between the residual stress and the hardness enhancement of the films was observed.     

钛合金表面大气压等离子体枪制备类金刚石薄膜

在大气下,采用大气压介质阻挡放电(DBD)等离子体枪在低温下(350℃),以甲烷为单体,氩气为工作气体,在Ti6Al4V钛合金表面制备一层类金刚石薄膜(DLC),以期改善钛合金表面摩擦学性能。利用激光拉曼(Raman)光谱和X射线光电子能谱(XPS)分析了所制备DLC薄膜的结构;利用扫描电子显微镜(SEM)观察DLC薄膜的表面形貌;利用划痕仪测量了DLC薄膜与基体的结合力;利用球-盘摩擦磨损实验仪对DLC薄膜的耐磨性能进行了研究。结果表明:在本实验工艺条件下沉积的类金刚石薄膜厚度约为1.0μm,薄膜均匀且致密,表面粗糙度Ra为13.23nm。类金刚石薄膜与基体结合力的临界载荷达到31.0N。DLC薄膜具有优良的减摩性,Ti6Al4V表面沉积DLC薄膜后摩擦系数为0.15,较Ti6Al4V基体的摩擦系数0.50明显减小,耐磨性能得到提高。     

Deposition of nanolayered CrN/AlBN thin films by cathodic arc deposition: Influence of cathode arc current and bias voltage on the mechanical properties

Thin films of CrAlBN were deposited on SKD 11 tool steel substrate using Cr and AlB cathodes in a cathodic arc plasma deposition system. The influence of AlB cathode arc current and substrate bias voltage on the mechanical and the structural properties of the films was investigated. The CrAlBN thin films had a multilayered structure in which the nano-crystalline CrN layer alternated with the amorphous AlBN layer. The hardness of the films increased as the AlB cathode arc current was raised from 35 to 45 A, and then decreased with further increase of the current. The hardness of the films increased rapidly with the increase of the bias voltage from − 50 to − 150 V. Further increase in the bias voltage decreased the hardness. The maximum hardness of 48 GPa was obtained at the bias voltage of − 150 V. With the increase of bias voltage, a good correlation between the residual stress and the hardness of the films was observed.     

Characteristics of copper oxide films deposited by PBII&D

Copper oxide films were deposited by plasma based ion implantation and deposition using a copper antenna as rf sputtering ion source. A gas mixture of Ar + O₂ was used as working gas. During the process, copper that was sputtered from the rf antenna reacted with oxygen and was deposited on a silicon substrate. The composition and the chemical state of the deposited films were analyzed by XPS. The structure of the films was detected by XRD. It is observed that Cu₂O film has been prepared on the Si substrate. It is found that the microstructure of the deposited film is amorphous for the applied voltage of − 5 kV. The surface layer of the deposited films is CuO. This is because the surface layer absorbs the oxygen from ambient air after the treated sample was removed from the vacuum chamber. An appropriate applied voltage, 2 kV under the present conditions, brings the lowest resistance. It is also seen that the maximum absorbance of the deposited films moves to a lower wavelength with increased applied voltage.     

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.     

Characteristics and tribological performance of DLC and Si-DLC films deposited on nitrile rubber

The characteristics and tribological performance of DLC and Si-DLC films with and without Si–C interlayers were studied in this paper. The films were deposited on nitrile rubber using a closed field unbalanced magnetron sputtering ion plating system. The film properties and characteristics were determined by scanning electron microscopy (SEM), hydrophobicity studies, Raman spectroscopy and tribological investigations. Tribological performance of these films was investigated using a pin-on-disc tribometer under applied loads of 1 N and 5 N under conditions of dry and wet sliding. The effect of immersing the films in water on tribological performance was also examined. The results show that the morphology of the films had a crack-like network. At a substrate bias of − 30 V, the coatings were characterised by a very dense non-columnar microstructure. The highest value of the ratio of intensities of the D and G peaks (I_D/I_G) was 1.2 for Si-DLC film with Si–C interlayer. The lowest value of 0.7 was observed for DLC film. The contact angle (CA) of water droplets showed that the films were hydrophobic. These results are interpreted in terms of hybridisation of carbon in these coatings. The tribological investigation showed a dependence on both the tribological condition under investigation and the atomic percentage of Si in the films. At 5 N normal load the lowest wear depth was observed for DLC films.     

Exploring the potential of high power impulse magnetron sputtering for growth of diamond-like carbon films

Amorphous carbon films are deposited employing high power impulse magnetron sputtering (HiPIMS) at pulsing frequencies of 250 Hz and 1 kHz. Films are also deposited by direct current magnetron sputtering (dcMS), for reference. In both HiPIMS and dcMS cases, unipolar pulsed negative bias voltages up to 150 V are applied to the substrate to tune the energy of the positively charged ions that bombard the growing film. Plasma analysis reveals that HiPIMS leads to generation of a larger number of ions with larger average energies, as compared to dcMS. At the same time, the plasma composition is not affected, with Ar⁺ ions being the dominant ionized species at all deposition conditions. Analysis of the film properties shows that HiPIMS allows for growth of amorphous carbon films with sp³ bond fraction up to 45% and density up to 2.2 g cm^− 3. The corresponding values achieved by dcMS are 30% and 2.05 g cm^− 3, respectively. The larger fraction of sp³ bonds and mass density found in films grown by HiPIMS are explained in light of the more intense ion irradiation provided by the HiPIMS discharge as compared to the dcMS one.     

The effect of substrate bias voltage on PbTe films deposited by magnetron sputtering

The PbTe films were deposited onto ITO glass substrate by radio frequency magnetron sputtering. Effect of external direct current electrical field applied between substrate and target on the quality of films was investigated. Stylus surface profile, X-ray diffraction (XRD), atomic force microscope (AFM) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the films. The film thickness was measured by a conventional stylus surface profile. The crystal structure and lattice parameters of films were determined by using XRD. The surface morphology of the films was measured by AFM. The absorption coefficients and optical band gaps of films were found from FTIR. The sheet resistance of the samples was measured with a four-point probe and the resistivity of the film was calculated. All the obtained films were highly textured with a strong (2 0 0) orientation. With increasing bias voltage to −30 V, the property of crystal structure, surface morphology and absorption coefficients and resistivity were improved. However, further increase of substrate bias leads to transformation of the property.     

Preparation of ZrO<Subscript>2</Subscript> dielectric layers by subsequent oxidation after Zr film deposition with negative substrate bias voltage

ZrO₂ dielectric layers were prepared by a two-step process, a deposition of pure Zr film with and without a negative substrate bias voltage and a subsequent oxidation of the Zr films. We focused on the effect of the negative substrate bias voltage on the Zr film deposition and the subsequent oxidation of the Zr films. As a result, the Zr film deposited at the substrate bias voltage of −50 V (Vs = −50 V) was found to have a high intensity peak of Zr (100) and a uniform and smooth surface. From the capacitance-voltage and current-voltage measurements of the ZrO₂ films, a high dielectric constant of 21 and the equivalent oxide thickness (EOT) of 2.6 nm were obtained on the oxidation layer of the Zr film deposited at Vs = −50 V. On the other hand, a low dielectric constant of 15 and the EOT of 3.6 nm was obtained on that of the Zr film deposited at Vs = 0 V. The leakage current density of the ZrO₂ film (Vs = −50 V) was 5.69×10⁻⁴ A/cm², and this value was much lower than the 1.21×10⁻⁴ A/cm² for the ZrO₂ film (Vs = 0 V). It was found that the two-step process by subsequent oxidation after film deposition using a negative substrate bias voltage is useful for obtaining high-quality dielectric layers.     

High adhesion of diamond-like carbon thin film to an aluminum alloy achieved by substrate sputtering and redeposition method

A novel technique to improve the adhesion of a diamond-like carbon (DLC) film to an Al alloy was demonstrated in this study. DLC films were deposited by diode rf bias sputtering. The Al component in the substrate was initially deposited on a graphite target during the sputter-cleaning of the substrate. Then the graphite target and the deposited Al were simultaneously sputtered to form an interface layer between the DLC film and the substrate in the early stage of deposition. We call this method substrate sputtering and redeposition (SSRD), which enhanced the antiwear lifetime of DLC/Al alloy samples. X-ray photoelectron spectroscopy clarified that a thicker mixed layer of Al and C was formed around the interface in the case of a longer substrate sputtering duration in the SSRD method. This interface structure could account for the strong adhesion of the DLC film to the substrate and the reduced delamination of the film obtained using the SSRD method.     

High-repetition rate pulsed laser deposition of ZrC thin films

ZrC thin films were grown on (100) Si substrates by the pulsed laser deposition (PLD) technique using a high-repetition rate excimer laser working at 40 Hz. The substrate temperature during depositions was set at 300 °C and the cooling rate was 5 °C/min. X-ray diffraction investigations showed that the films were crystalline. Films deposited under residual vacuum or 2 × 10^− 3 Pa of CH₄ atmosphere exhibited a (200)-axis texture, while those deposited under 2 × 10^− 2 Pa of CH₄ atmosphere were found to be equiaxed. The surface elemental composition of as-deposited films, analyzed by Auger electron spectroscopy (AES), showed the usual high oxygen contamination of carbides. Once the topmost − 3-5 nm region was removed, the oxygen concentration rapidly decreased, being around 3-4% only in bulk. Scanning electron microscopy (SEM) investigations showed a smooth, featureless surface morphology, corroborating the roughness values below 1 nm (rms) obtained from simulations of the X-ray reflectivity (XRR) curves. From the same simulations we also estimated films mass density values of around 6.32-6.57 g/cm³ and thicknesses that correspond to a deposition rate of around 8.25 nm/min. Nanoindentation results showed a hardness of 27.6 GPa and a reduced modulus of 228 GPa for the best quality ZrC films deposited under an atmosphere of 2 × 10^− 3 Pa CH₄.