Multi-functional ECR plasma sputtering system for preparing amorphous carbon and Al–O–Si films

A design of cylindrical double-target source with shutter slider which can continuously change the target area ratio was applied to the divergent and mirror-confinement Electron Cyclotron Resonance (ECR) plasma sputtering system in the present study. The deposition process feasibility of several types of films (single-layer of pure and composite film as well as multi-layer film) can be realized by using this multi-functional system. The highly concerned amorphous carbon films were prepared with the Divergent ECR (DECR) and Mirror-Confinement ECR (MCECR) plasma sputtering systems. The tribological properties were compared, which both showed a normally friction coefficient around 0.15. Through adding substrate heating during film preparation, the tribological properties of DECR carbon films were improved with an obvious decreasing of friction coefficient to 0.05 and a much longer wear lifetime. The designed double-target source with shutter slider was used to prepare Al–O–Si films, by which the target area ratio of silicon to aluminum was changed from 0.5 to 2. A composite structure of Al–O–Si film with high transmittance up to 89% at 193 nm wavelength was obtained with the multi-functional ECR plasma sputtering system.     

X-ray reflectivity studies on DLC films deposited by microwave ECR CVD: Effect of substrate bias

Diamond like carbon (DLC) films were deposited at room temperature on Si (111) substrates by microwave electron cyclotron resonance (ECR) plasma chemical vapor deposition (CVD) process using plasma of methane diluted with argon gas. During deposition, dc self bias (− 25 V to − 200 V) on substrate was varied by application of RF power to the substrate. The influence of substrate bias on density of the deposited films was studied by X-ray reflectivity (XRR). The results from these measurements are further correlated with the results from UV and visible Raman spectroscopy. DLC film is modeled as a structure having three different layers such as low density surface, bulk and interface with the substrate. This three-layer model is used to fit the measured XRR data to evaluate the surface, interface and interlayer roughness, thickness and density of these films. The surface roughness obtained from XRR is correlated with the results from Atomic Force Microscopy (AFM) measurements. The observed results are explained based on the subplantation model for DLC film growth.     

Optical emission spectroscopy as a tool for designing and controlling the deposition of graded TiAlN layers by ECR-assisted reactive RF sputtering

Graded TiAlN layers were deposited by plasma reactive sputtering assisted by electron cyclotron resonance (ECR). For reactive sputtering, dual cathode radio-frequency (RF) magnetron targets, Ti and Al, were used. The deposition process was monitored by optical emission spectroscopy (OES). The OES results indicate that microwave excitation added to RF plasma has contrasting effects on Ti and Al concentration in the gas phase, enhancing titanium and quenching aluminium species reaching the deposited substrate. Thus, by the regulation of the ECR power and the ratio of the nitrogen flow to the nitrogen plus argon flow, the formation of graded layers is allowed. This approach was found to be appropriate for controlling and tailoring the interface between a metallic substrate and a hard coating. The layers were deposited on (100) oriented silicon and M2 steel tools using various combinations of variables, such as power input, bias substrate voltage and gas feed composition. The layers were characterized with regard to structure and composition using X-ray diffractometers and Auger electron spectroscopy. Layers deposited on grounded silicon at a low ECR power (≤100 W) were found to have a (111) oriented crystalline structure; the crystallographic orientation is affected by the bias voltage and substrate composition. Layers deposited at an ECR power >100 W had a random or amorphous structure. The relationship between the OES analyses of the plasma layer and the processing parameters, the structure and the composition of the layers formed are presented and discussed.     

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.     

The effect of applied substrate negative bias voltage on the structure and properties of Al-containing a-C:H thin films

Al-containing hydrogenated amorphous carbon (Al-C:H) films were prepared using a magnetron sputtering Al target in the CH₄ and Ar mixture atmosphere with various applied substrate pulse negative bias voltages. The hydrogen content and internal stress of the film decrease dramatically with the substrate pulse bias voltage increase. However, the hardness values of the films keep at high level (∼ 20 GPa) without any obvious changes with the increase of the applied substrate pulse bias voltages. The Al-C:H film prepared at applied substrate high bias voltage shows a long wear life and low friction coefficient.     

Composition and structure of Ti-C/DLC graded composite films

The Ti-C→DLC gradient composite films were characterized systematically.The elemental depth profile and elemental chemical state evolution were determined by X-ray photoelectron spectroscopy (XPS).The transmission electron microscope (TEM) and high-resolution transmission electron microscopy (HRTEM) were used to study the structure of interfacial zone between DLC film and Ti-C layers.Results show that there are composition transition zone between DLC film and either Ti-C layer or steel substrate on condition that pre-deposited Ti layers on the steel substrate then plasma based bias deposited DLC films.In Ti-C graded layer,the chemical state of titanium and carbon are changed gradually.The structures of zone in Ti-C layer near the DLC film is consisted of random oriented nanocrystallines TiC dispersed in amorphous DLC matrix.The structure of the zone between DLC film and Ti-C graded layer is gradually changed too.     

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.     

脉冲磁控溅射MoS2涂层的组织结构及摩擦学性能

采用单极性脉冲磁控溅射技术在A286基体表面制备MoS₂低摩擦系数涂层(LFC)。利用XRD、SEM等手段表征涂层的成分与微观组织;采用原位纳米力学测试系统、球-盘式摩擦磨损试验机分析涂层的力学和摩擦学性能,并探讨了脉冲偏压对涂层结构、力学和摩擦学性能的影响。结果表明,脉冲偏压由300V增加到600V,MoS₂涂层择优取向发生了(002)向(100)转变,当脉冲偏压增至800V时又恢复(002)择优取向,;随着脉冲偏压的增加,涂层的硬度及弹性模量出现先减少后增大趋势,摩擦系数在0.065~0.076范围内波动,呈现出先增加后减小趋势;偏压为800V的涂层摩擦学性能最佳,其磨损率仅为基体的13.5%。     

Plasma biasing to control the growth conditions of diamond-like carbon

It is well known that the structure and properties of diamond-like carbon, and in particular the sp³/sp² ratio, can be controlled by the energy of the condensing carbon ions or atoms. In many practical cases, the energy of ions arriving at the surface of the growing film is determined by the bias applied to the substrate. The bias causes a sheath to form between substrate and plasma in which the potential difference between plasma potential and surface potential drops. In this contribution, we demonstrate that the same results can be obtained with grounded substrates by shifting the plasma potential. This “plasma biasing” (as opposed to “substrate biasing”) is shown to work well with pulsed cathodic carbon arcs, resulting in tetrahedral amorphous carbon (ta-C) films that are comparable to the films obtained with the conventional substrate bias. To verify the plasma bias approach, ta-C films were deposited by both conventional and plasma bias and characterized by transmission electron microscopy (TEM) and electron energy loss spectrometry (EELS). Detailed data for comparison of these films are provided.     

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.     

Cathodic arc plasma deposition of nano-multilayered ZrN/AlSiN thin films

Thin films of ZrN/AlSiN were deposited on SKD 11 tool steel substrate using Zr and AlSi cathodes in an Ar/N₂ gas mixture in a cathodic arc plasma deposition system. The influence of the AlSi cathode arc current and the substrate bias voltage on the mechanical and structural properties of the films was investigated. X-ray diffraction, electron probe micro-analysis, high resolution transmission electron microscopy, nanoindentation and profilometry were used to characterize the films. The ZrN/AlSiN thin films had a multilayered structure by rotating the substrate in which nano-crystalline ZrN layers alternated with amorphous AlSiN layers. The hardness of the films increased as the AlSi cathode arc current was raised from 35 to 40 A, and then decreased with a further increase of the current. The hardness of the films increased with the increase of the bias voltage from − 50 to − 100 V. Further increase in the bias voltage decreased the hardness. The films exhibited a maximum hardness of 38 GPa. With the increase of bias voltage, the residual stress of the films correlated well with the hardness.     

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.     

Structure and blood compatibility of tetrahedral amorphous hydrogenated carbon formed by a magnetic-field-filter plasma stream

Tetrahedral amorphous hydrogenated carbon (ta-C:H) films with various substrate bias voltages were prepared using a magnetic-field-filter plasma stream deposition system. The microstructural and optical properties were studied using ellipsometric spectra. The refractive index n of each sample was obtained by simulating their ellipsometric spectral using Tauc-Lorentz oscillator model, and then the relative sp³ C ratio of each sample was calculated using Bruggeman effective medium approximation. The sp³ C fraction of each sample was quantified by using electron energy-loss spectroscopy (EELS). The blood compatibility of the samples was evaluated by tests of platelet adhesion, kinetic clotting time and thrombin time. The quantity and morphology of the adherent platelets on the surface of these samples were investigated using scanning electron microscopy. Results show that the spectroscopic ellipsometry is a helpful method to evaluate the sp³ carbon fraction of the carbon films. The substrate bias voltage has an obvious effect on sp³ content and blood compatibility of ta-C:H films. The sample prepared with substrate bias voltage of − 20 V showed the best blood compatibility. A simple bio-physical hypothetical model was proposed to explain the experiment results.     

Friction and wear characteristics of multi-layer graphene films investigated by atomic force microscopy

Friction and wear characteristics of multi-layer graphene films deposited on a Si substrate by mechanical exfoliation were investigated by atomic force microscopy (AFM). The graphene films consisted of a few layers of carbon basal plane. The number of graphene layers was determined by AFM and Raman spectroscopy. For the AFM friction measurement, loads in the range of − 5 to 30 nN were applied on the Si tip that slid against the graphene specimen. It was found that graphene films exhibited much lower friction (from 0.36 to 0.62 nN) than bare Si surface (from 1.1 to 4.3 nN) when the applied loads ranged from 3 to 30 nN. The wear characteristics were also assessed using the AFM. Detectable wear of graphene was generated when sliding was performed for 100 cycles under 5 μN applied load. The wear mechanism of graphene was proposed to be due to breakage of in-plane bonds between carbon atoms and shearing at the interface of graphene layers.     

Effect of substrate bias voltage on the texture and microstructure of Cu thin films deposited by ion beam deposition

Cu thin films deposited by non-mass separated ion beam deposition under various substrate bias voltages were investigated. The film textures and microstructure were analyzed by X-ray diffraction and field emission scanning electron microscopy, and the resistivity of the film was measured with the Van der Pauw method. It was found that the optimum negative substrate bias voltage for Cu films was −50 V. The Cu films deposited without substrate bias voltage showed a columnar grain structure with small grains and random orientation. However, when a substrate bias voltage of −50 V was applied, the Cu films had a non-columnar structure with a strong (111) texture and large grains. The electrical resistivity of the Cu films decreased remarkably with increasing negative substrate bias voltage, and reaching a minimum value of 1.8±0.13 μΩ cm at the substrate bias voltage of −50V.     

Influence of bias on properties of carbon films deposited by MCECR plasma sputtering method

The mirror-confinement-type electron cyclotron resonance(MCECR) plasma source has high plasma density and high electron temperature. It is quite useful in many plasma processing, and has been used for etching and thin-film deposition. The carbon films with 40 nm thickness were deposited by MCECR plasma sputtering method on Si, and the influence of substrate bias on the properties of carbon films was studied. The bonding structure of the film was analyzed by the X-ray photoelectron spectroscopy(XPS), the tribological properties were measured by the pin-on-disk(POD) tribometer, the nanohardness of the films was measured by the nanoindenter, and the deposition speed and the refractive index were measured by the ellipse meter. The better substrate bias was obtained, and the better properties of carbon films were obtained.     

Study on nanocrystalline Cr2O3 films deposited by arc ion plating: II. Mechanical and tribological properties

In this work, the influence of substrate bias voltage on the microhardness, adhesive strength, friction coefficient, and wear rate of AIP Cr₂O₃ films deposited on AISI 304 stainless steel substrates was investigated systematically. In the meantime, the wear failure mechanism of AIP Cr₂O₃ films in dry sliding contact was also analyzed and discussed. The results showed that the mechanical properties, adhesive behaviors, and tribological performance of AIP Cr₂O₃ films were greatly altered by applying a negative bias voltage. With increasing the bias voltage, the hardness, critical load, and tribological performance of AIP Cr₂O₃ films first were improved gradually, and then were impaired slightly again. When the bias voltage is − 100 V, the Cr₂O₃ film possessed the highest hardness, the strongest adhesion, and the best wear resistance. The essence of above phenomena was attributed to the variations of microstructure and defect density in the films induced by the substrate bias voltage increase. The main wear failure mechanism of AIP Cr₂O₃ films is crack initiation and propagation under the high contact stresses, inducing the local film with small area to flake off gradually, and eventually leading to the formation of a wear scar.     

Relation of the polymeric ion species in plasma to the hardness of a-C:H film made by PSII&D

The amorphous carbon (a-C:H) films formed by plasma source ion implantation and deposition (PSII&D) have expanded the tribological properties. Especially, the hardness can be widely changed by adequately selecting RF power, pulse bias voltage, gas species and gas pressure. Previously, we reported that a-C:H film hardness depended on the electron temperature in C₂H₂ plasma which was ignited with pulsed RF power, and that the hardness was in inverse proportion to the electron temperature in the range of less than 2.5 eV. We have discovered that the film hardness is, in some cases, changing even if the electron temperature is constant. This suggests that there are some new factors to determine the film hardness besides the electron temperature in the plasma. In this study, we employ a quadrupole mass spectrometer to measure the intensity of each polymeric ion in C₂H₂. The film hardness is determined by the synergy of the polymeric ion abundances and ion irradiation.     

Influence of dc bias on amorphous carbon deposited by pulse laser ablation

Amorphous carbon films were deposited on single-crystalline silicon and K9 glass by pulse laser ablation using different negative substrate bias.Scanning electron microscope(SEM) was used to observe morphology of the surface.Thickness and refractive index of the film deposited on K9 glass were measured by ellipsometry.Micro-hardness of films was measured relatively to single crystal silicon.All films deosited on silicon were analyzed by Raman spectra.All spectra were deconvoluted to three peaks.Line-width ratios varied similarly with bias voltage when the laser energy was kept invariant.     

自配对含氢类石墨碳薄膜超滑性能

采用等离子体增强化学气相沉积与原位渗氮复合技术在硅片和轴承钢球上制备了类石墨碳薄膜,将两者组成摩擦配伍对,并讨论自配对类石墨薄膜在氮气中摩擦学行为。利用往复摩擦机、扫描电子显微镜、三维表面轮廓仪考察自配对类石墨碳薄膜在不同载荷下摩擦磨损性能;采用高分辨透射电镜、拉曼光谱和红外吸收谱分析类石墨碳薄膜摩擦前后结构变化。摩擦测试结果表明：在载荷4 N时,薄膜摩擦因数为0.01;在8 N时,薄膜摩擦因数降低到0.005。这种变化归因于摩擦诱导薄膜结构进一步有序化以及沿滑动方向形成更加有序且更长石墨烯以及片状磨屑。证实了采用自配对碳薄膜方案是实现固体超滑一种有效途径。