Corrosive behavior of chromium carbide-based films formed on steel using a filtered cathodic vacuum arc system

The formation of chromium carbide-based hard-coatings on steels using a 90°-bend filtered cathodic vacuum arc (FCVA) has extensive industrial applications; such coatings are free of macroparticles and exhibit excellent characteristics. In this investigation, a working pressure of C₂H₂/Ar was adopted to synthesize amorphous chromium carbide film (a-C:Cr) and crystalline chromium carbide film (cryst-Cr₃C₂) from a Cr target (99.95%) at 500 °C under a substrate voltage of −50 V. The corrosion behavior of a-C:Cr coated on steel (a-C:Cr/steel) and cryst-Cr₃C₂ coated on steel (cryst-Cr₃C₂/steel) were compared in terms of open-circuit potentials (OCP) and polarization resistance (R_p) in an aerated 3.5 wt% NaCl aqueous solution, as determined by electrochemical impedance spectroscopy (EIS). The XRD results indicated that the transformation of a-C:Cr to cryst-Cr₃C₂ is distinct as the working pressure declines from 1.2 × 10⁻² to 2.9 × 10⁻³ Torr. The OCP of a-C:Cr/steel and cryst-Cr₃C₂/steel resemble each other and both assembly are nobler than uncoated steel. The R_p of the coatings exceeds that of the uncoated steel. The SEM observation and the EIS results demonstrate that the cryst-Cr₃C₂/steel more effectively isolates the defects than dose a-C:Cr/steel.     

Synthesis and characterization of tantalum nitride films prepared by cathodic vacuum arc technique

Tantalum nitride films were deposited on silicon wafer and steel substrates by cathodic vacuum arc in N₂/Ar gas mixtures. The chemical composition, crystalline microstructure and morphology of the films were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), respectively. According to the results, film composition and microstructure depends strongly on the N₂ partial pressure and the applied negative bias (V_s).     

Influence of oxygen pressure of ZnO/glass substrate produced by pulsed filtered cathodic vacuum arc deposition

The effects of oxygen pressure on the structural and optical properties of high quality transparent conductive ZnO thin films were studied in detail. ZnO thin films were prepared by pulsed filtered cathodic vacuum arc deposition system under various oxygen pressures on glass substrate at room temperature. With increasing oxygen pressure, the structure and optical properties of films change. The structural and optical properties of the ZnO thin films were investigated using X-ray diffraction, transmittance spectrometry, refractive index, oscillator parameters, energy band gap and Urbach tail. The films show c-axis oriented (0 0 2) hexagonal wurtize crystal structure. It has been found that the grain size of ZnO thin films increases from 16.9 to 22.6 nm with the increase of oxygen pressure from 3.8×10⁻⁴ to 6.9×10⁻⁴ Torr and the crystallinity is enhanced. Average transmittance is about 90% in the visible region of the ZnO thin films. From optical transmittance spectra of ZnO films, the absorption edge shifts towards the taller wavelength with an increase in oxygen pressure. The energy band gap decreases from 3.31 to 3.20 eV with an increase in oxygen pressure. The packing density investigation shows in ZnO films high packing densities (above 0.78) can be obtained.     

Effect of pulsed bias on properties of ZrN/TiZrN films deposited by cathodic vacuum arc

ZrN/TiZrN multilayer are deposited by cathodic vacuum arc method with different substrate bias (from 0 to -800 V), using Ti and Zr plasma flows in residual N₂ atmosphere, combined with ion bombardment of sample surfaces. The effect of pulsed bias on structure and properties of films is investigated. Microstructure of the coating is analyzed by X-ray diffraction (XRD), and scanning electron microscopy (SEM). Meanwhile, the nanohardness, Young's modulus, and scratch tests are performed. The experimental results show that the films exhibit a nanoscale multilayer structure consisting of TiZrN and ZrN phases. Solid solutions are formed for component TiZrN films. The dominant preferred orientation of TiZrN films is (111) and (220). At pulsed bias of -200 V, the nanohardness and the adhesion strength of ZrN/TiZrN multilayer reach a maximum of 38 GPa, and 78 N, respectively. The ZrN/TiZrN multilayer demonstrates an enhanced nanohardness compared with binary TiN and ZrN films deposited under equivalent conditions.     

Micromechanical properties of carbon nitride films deposited by radio-frequency-assisted filtered cathodic vacuum arc

Super-hard and elastic carbon nitride films have been synthesized by using an off-plane double-bend filtered cathodic vacuum arc combined with a radio-frequency nitrogen-ion beam source. A nanoindenter was used to determine the micromechanical properties of the deposited films. X-ray photoelectron spectroscopy was used to study the composition and bonding structure of the deposited films. The influence of nitrogen ion energy on the structure and micromechanical properties of the deposited films was systematically studied. As the nitrogen ion energy is increased, the microhardness, Young’s modulus and elastic recovery also increase, reaching a maximum of 47 GPa, 400 GPa, and 87.5%, respectively, at a nitrogen ion energy of 100 eV. Further increase in nitrogen ion energy results in a decrease in microhardness, Young’s modulus and elastic recovery of the deposited films. The formation of five-membered rings, as indicated by XPS, which causes bending of the basal planes and forms a three-dimensional rigid covalent bond network, contributes to the super-hardness, Young’ s modulus and high elastic recovery of the films deposited at a nitrogen ion energy of 100 eV. Revised version: 29 October 2001 / Accepted: 7 November 2001 / Published online: 2 May 2002     

Effect of pulsed bias on the properties of ZrN/TiZrN films deposited by a cathodic vacuum arc

ZrN/TiZrN multilayers are deposited by using the cathodic vacuum arc method with different substrate bias(from 0 to 800 V),using Ti and Zr plasma flows in residual N 2 atmosphere,combined with ion bombardment of sample surfaces.The effect of pulsed bias on the structure and properties of films is investigated.Microstructure of the coating is analyzed by X-ray diffraction(XRD),and scanning electron microscopy(SEM).In addition,nanohardness,Young’s modulus,and scratch tests are performed.The experimental results show that the films exhibit a nanoscale multilayer structure consisting of TiZrN and ZrN phases.Solid solutions are formed for component TiZrN films.The dominant preferred orientation of TiZrN films is(111) and(220).At a pulsed bias of 200 V,the nanohardness and the adhesion strength of the ZrN/TiZrN multilayer reach a maximum of 38 GPa,and 78 N,respectively.The ZrN/TiZrN multilayer demonstrates an enhanced nanohardness compared with binary TiN and ZrN films deposited under equivalent conditions.     

Characterization of Ti-Zr-N films deposited by cathodic vacuum arc with different substrate bias

Ti-Zr-N (multi-phase) films were prepared by cathodic vacuum arc technique with different substrate bias (0 to −500 V), using Ti and Zr plasma flows in residual N₂ atmosphere. It was found that the microstructure and mechanical properties of the composite films are strongly dependent on the deposition parameters. All the films studied in this paper are composed of ZrN, TiN, and TiZrN ternary phases. The grains change from equiaxial to columnar and exhibit preferred orientation as a function of substrate bias. With the increase of substrate bias the atomic ratio of Ti to Zr elements keeps almost constant, while the N to (Ti + Zr) ratio increases to about 1.1. The composite films present an enhanced nanohardness compared with the binary TiN and ZrN films deposited under the same condition. The film deposited with bias of −300 V possesses the maximum scratch critical load (L_c).     

Field emission from awl-shaped diamond-like carbon by using filtered cathodic arc plasma technique on anodic aluminum oxide template

Awl-shaped diamond-like carbon (DLC) was directly grown on anodic aluminum oxide (AAO) template by using filtered cathodic arc plasma (FCAP) technique at room temperature. The awls of DLC were about 250 nm in the height and the diameters of the awls were ∼100 nm at the top. The awl density was estimated to be ∼10⁸ cm⁻². A broad asymmetric band ranging from 1100 to 1800 cm⁻¹ was detected by Raman spectrum. This asymmetric band was characteristic band of DLC. The sp³/(sp³+sp²) ratio of C-C bond of the awl-shaped DLC was measured by X-ray photoelectron spectrum, and it was about 68.3%. Field-emission properties of the awl-shaped DLC were investigated. A low turn-on field of 2.6 V/μm at 10 μA/cm² with an emission area of 3.14 mm² was achieved, and the emission current stability was very good. The results indicated that the electrons were emitted under both the effect of enhanced field because of the geometry and the work function of the DLC sample. Based on Fowler-Nordheim plot, the values of work function for the awl-shaped DLC were estimated in ranges of 0.23-1.08 from a linearity plot.     

Research on the properties of ZnO thin films deposited by using filtered cathodic arc plasma technique on glass substrate under different flow rate of O2

ZnO thin film has been deposited on the glass substrate at a temperature of 200 °C using the filtered cathodic arc plasma (FCAP) technique with the oxygen flow rate of 1.0, 3.0, 5.0, 7.0, 9.0 and 10.0 sccm. The deposition processes are only held in pure oxygen atmosphere. The as-grown films exhibit a polycrystalline hexagonal wurtzite structure. With the oxygen flow rate increase, the crystallinity of the samples first increases and then decreases as measured by X-ray diffractometry (XRD). And the tensile stress exists in all the as-grown thin films. The small grain with a mean diameter of 13 nm is observed by the field emission scanning electron microscopy (FESEM). The electrical resistivity values of the thin films are very low ranging from 5.42 × 10⁻³ Ω cm to 4.0 × 10⁻² Ω cm. According to the result from room temperature photoluminescence spectra measurement, the luminescent bands also depend on the oxygen supply.     

Optical and electrical properties of BaSnO3 and In2O3 mixed transparent conductive films deposited by filtered cathodic vacuum arc technique at room temperature

For the crystalline temperature of BaSnO$_{3}$ (BTO) was above 650 ℃, the transparent conductive BTO-based films were always deposited above this temperature on epitaxy substrates by pulsed laser deposition or molecular beam epitaxy till now which limited there application in low temperature device process. In the article, the microstructure, optical and electrical of BTO and In$_{2}$O$_{3}$ mixed transparent conductive BaInSnO$_x$ (BITO) film deposited by filtered cathodic vacuum arc technique (FCVA) on glass substrate at room temperature were firstly reported. The BITO film with thickness of 300 nm had mainly In$_{2}$O$_{3}$ polycrystalline phase, and minor polycrystalline BTO phase with (001), (011), (111), (002), (222) crystal faces which were first deposited at room temperature on amorphous glass. The transmittance was 70%-80% in the visible light region with linear refractive index of 1.94 and extinction coefficient of 0.004 at 550-nm wavelength. The basic optical properties included the real and imaginary parts, high frequency dielectric constants, the absorption coefficient, the Urbach energy, the indirect and direct band gaps, the oscillator and dispersion energies, the static refractive index and dielectric constant, the average oscillator wavelength, oscillator length strength, the linear and the third-order nonlinear optical susceptibilities, and the nonlinear refractive index were all calculated. The film was the n-type conductor with sheet resistance of 704.7 $\Omega /\Box $, resistivity of 0.02 $\Omega \cdot$cm, mobility of 18.9 cm$^{2}$/V$\cdot$s, and carrier electron concentration of $1.6\times 10^{19}$ cm$^{-3}$ at room temperature. The results suggested that the BITO film deposited by FCVA had potential application in transparent conductive films-based low temperature device process.     

Low-temperature deposited ZnO thin films on the flexible substrate by cathodic vacuum arc technology

In this paper, un-doped zinc oxide (ZnO) films with various thicknesses (150, 250, 350, 450 and 550 nm) were successfully prepared onto PET substrates using cathodic vacuum arc technique at low-temperature (<40 °C). Their microstructure, optical and electrical properties were investigated and discussed. The films showed (0 0 2) peaks, an average transmittance over 80% in the visible region. Calculated values of the band gap are around 3.29-3.33 eV when the film thickness increased, indicating a slight blue shift of optical transmission spectra. The lowest resistivity about 5.26 × 10⁻³ Ω cm could be achieved for the un-doped ZnO film with thickness of 550 nm.     

不同能级加速过滤电弧沉积四面体非晶碳膜的结构和性能

采用过滤阴极真空电弧技术，通过施加0—2000 V衬底负偏压使沉积离子获得不同能级的入射能量，在单晶硅上制备了四面体非晶碳薄膜.拉曼光谱分析表明，薄膜的结构为非晶sp³骨架中镶嵌着平面关联长度小于1 nm的sp²团簇.原子力显微镜研究表明：在低能级、富sp³能量窗口和次高能级，薄膜中sp³的含量越多，其表面就越光滑，应用sp³浅注入生长机制能够圆满地解释薄膜表面形态与离子入射能量之间的关系；但在高 关键词： 四面体非晶碳 过滤阴极真空电弧 能级     

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.     

X-ray photoelectron spectroscopy of nano-multilayered Zr-O/Al-O coatings deposited by cathodic vacuum arc plasma

Nano-multilayered Zr-O/Al-O coatings with alternating Zr-O and Al-O layers having a bi-layer period of 6-7 nm and total coating thickness of 1.0-1.2 μm were deposited using a cathodic vacuum arc plasma process on rotating Si substrates. Plasmas generated from two cathodes, Zr and Al, were deposited simultaneously in a mixture of Ar and O₂ background gases. The Zr-O/Al-O coatings, as well as bulk ZrO₂ and Al₂O₃ reference samples, were studied using X-ray photoelectron spectroscopy (XPS). The XPS spectra were analyzed on the surface and after sputtering with a 4 kV Ar⁺ ion gun. High resolution angle resolved spectra were obtained at three take-off angles: 15°, 45° and 75° relative to the sample surface.It was shown that preferential sputtering of oxygen took place during XPS of bulk reference ZrO₂ samples, producing ZrO and free Zr along with ZrO₂ in the XPS spectra. In contrast, no preferential sputtering was observed with Al₂O₃ reference samples. The Zr-O/Al-O coatings contained a large amount of free metals along with their oxides. Free Zr and Al were observed in the coating spectra both before and after sputtering, and thus cannot be due solely to preferential sputtering.Transmission electron microscopy revealed that the Zr-O/Al-O coatings had a nano-multilayered structure with well distinguished alternating layers. However, both of the alternating layers of the coating contained of a mixture of aluminum and zirconium oxides and free Al and Zr metals. The concentration of Zr and Al changed periodically with distance normal to the coating surface: the Zr maximum coincided with the Al minimum and vice versa. However the concentration of Zr in both alternating layers was significantly larger than that of Al. Despite the large free metal concentration, the Knoop hardness, 21.5 GPa, was relatively high, which might be attributed to super-lattice formation or formation of a metal-oxide nanocomposite within the layers.     

Argon-dominated plasma beam generated by filtered vacuum arc and its substrate etching

A new technique to etch a substrate as a pre-treatment prior to functional film deposition was developed using a filtered vacuum arc plasma. An Ar-dominated plasma beam was generated from filtered carbon arc plasma by introducing appropriate flow rate of Ar gas in a T-shape filtered arc deposition (T-FAD) system. The radiation spectra emitted from the filtered plasma beam in front of a substrate table were measured. The substrate was etched by the Ar-dominated plasma beam. The principal results are summarized as follows. At a high flow rate of Ar gas (50 ml/min), when the bias was applied to the substrate, the plasma was attracted toward the substrate table and the substrate was well etched without film formation on the substrate. Super hard alloy (WC), bearing steel (SUJ2), and Si wafer were etched by the Ar-dominated plasma beam. The etching rate was dependent on the kind of substrate. The roughness of the substrate increased, when the etching rate was high. A pulse bias etched the substrate without roughening the substrate surface excessively.     

Comparative study of titanium carbide and nitride coatings grown by cathodic vacuum arc technique

Titanium nitride (TiN), titanium carbide (TiC) thin films and TiC/TiN bilayers have been deposited on AISI 304 stainless steel substrates by plasma assisted physical vapor deposition technique—reactive pulsed vacuum arc method. The coatings were characterized in terms of crystalline structure, microstructure and chemical nature by X-ray diffraction and X-ray photoelectron spectroscopy, respectively. Tribological behavior was investigated using ball on disc technique. The average coefficient of friction was measured, showing lower values for the TiN/TiC bilayer. Dynamic wear curves were performed for each coating, observing a better wear resistance for TiN/TiC bilayers, compared to TiN and TiC monolayers. On the other hand, the TiCN formation in the TiN/TiC bilayer was observed, being attributed to the interdiffusion between TiN and TiC at the interface. Moreover, the substrate temperature influence was analysing observing a good behavior at T_S = 115 °C.     

Synthesis of titanium nitride thin films deposited by a new shielded arc ion plating

Thin films of titanium nitride (TiN) were deposited on stainless steel substrates by a modified deposition technique, double-layered shielded arc ion plating with vicarious circular holes (DL-SAIP). The results show that the TiN film with the distance of 10 mm between the double-layered shield plates had the least droplets. The deposition rate of the films prepared with the new technique was more homogeneous than that of all the other shielded arc ion plating. The film/substrate adhesion and microhardness values of the TiN films were higher than 40 N and 18 GPa, respectively. Thus such TiN thin films can be expected in applications.     

Characterization of Zr-Si-N films deposited by cathodic vacuum arc with different N2/SiH4 flow rates

Zr-Si-N films were deposited on silicon and steel substrates by cathodic vacuum arc with different N₂/SiH₄ flow rates. The N₂/SiH₄ flow rates were adjusted at the range from 0 to 12 sccm. The films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), hardness and wear tests. The structure and the mechanical properties of Zr-Si-N films were compared to those of ZrN films. The results of XRD and XPS showed that Zr-Si-N films consisted of ZrN crystallites and SiN_x amorphous phase. With increasing N₂/SiH₄ flow rates, the orientation of Zr-Si-N films became to a mixture of (1 1 1) and (2 0 0). The column width became smaller, and then appeared to vanish with the increase in N₂/SiH₄ flow rates. The hardness and Young's modulus of Zr-Si-N films increased with the N₂/SiH₄ flow rates, reached a maximum value of 36 GPa and 320 GPa at 9 sccm, and then decreased 32 GPa and 305 GPa at 12 sccm, respectively. A low and stable of friction coefficient was obtained for the Zr-Si-N films. Friction coefficient was about 0.1.     

The effect of applied negative bias voltage on the structure of Ti-doped a-C:H films deposited by FCVA

Ti-doped hydrogenated diamond-like carbon (DLC) films were deposited on Si(1 0 0) substrates by a filtered cathodic vacuum arc (FCVA) method using Ar and CH₄ as the feedstock. The composition and microstructure of the films were investigated by Raman spectroscopy, X-ray photoelectron spectroscopy and IR spectroscopy. The internal stress was determined by the radius of curvature technique. The influence of the bias voltage on the microstructure of the as-deposited films was investigated. It was found that the graphite-like bonds was dominated in the Ti-doped DLC film deposited at 0 V bias voltage. When bias voltage was increased to −150 V, more diamond-like bond were produced and the sp³ content in film reached the maximum value, after which it decreased and more graphite-like bonds feature produced with further increase of the negative bias voltage. The compressive internal in the Ti-doped DLC films also exhibited a maximum value at −150 V bias voltage. IR results indicated that CH bonded intensity reduced, and H atoms bonded with C atoms were substituted for the Ti atoms as the negative bias voltage increasing. All the composition and microstructure change can be explained by considering the plasma conditions and the effect of negative bias voltage applied to the substrate.     

Structure and properties of zirconium oxide thin films prepared by filtered cathodic vacuum arc

Zirconium oxide (ZrO₂) thin films deposited at room temperature by the filtered cathodic vacuum arc (FCVA) technique are detailed in terms of the film structure, composition, morphology, and optical and mechanical properties, which are tailored by the oxygen (O₂) flow rate during deposition. The relationships between the film structure, composition, morphology, and properties are emphasized. With an increasing O₂ flow rate, the film evolves in structure from amorphous, through a pure monoclinic phase with varying preferential orientation, to amorphous again, accompanied by an increase in the O/Zr atomic ratio and a conversion of Zr ions from low oxidation states into Zr⁴⁺. Such a structural trend arises from the change in composition, and influences the film morphology and mechanical properties so that the amorphous films exhibit small clusters on the surface and smoother morphology as well as lower hardness compared with the polycrystalline films. The film composition rather than the density dominates the optical properties, where the transmittance and the optical band gap increase with increasing O/Zr values, while the refractive index and extinction coefficients behave conversely with the lowest refractive index (2.16 at 550 nm) approaching the bulk value (2.2) . PACS  68.55.Jk; 78.66.Nk; 68.37.Ps