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     

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     

Tribological characterization of chromium nitride coating deposited by filtered cathodic vacuum arc

CrN coatings were prepared by filtered cathodic vacuum arc (FCVA) technique. The influence of the deposition parameters (nitrogen partial pressure PN₂, substrate bias voltage V_s and preheating of the substrate) on the structural, mechanical and tribological properties of the FCVA CrN coatings was investigated. Further, the FCVA CrN coating was compared in dry reciprocating sliding with commercial multi-arc ion plating (MAIP) CrN coating as to friction and wear properties. Profilometer, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDX) were used to evaluate the wear scars and the wear mechanisms were discussed. The results showed that the structural, mechanical and tribological properties of the FCVA CrN coatings were significantly dependent on the deposition parameters. The FCVA CrN coating deposited with PN₂ of 0.1 Pa, V_s of −100 V and without preheating exhibited the optimal mechanical and tribological properties. The FCVA CrN coating exhibited much better anti-abrasive and anti-spalling properties than the MAIP CrN coating, which was resulted from significant reduction of macroparticles and pitting defects by the FCVA technique. The MAIP CrN coating suffered severe concentrated wear by a combination wear mechanisms of delamination, abrasive and oxidative wear when high normal load was applied, while for the FCVA CrN coating the wear mechanisms were ultra-mild abrasive and oxidative wear.     

Plasma motion in a filtered cathodic vacuum arc

A model is proposed for the flow of a plasma originating from a cathodic vacuum arc into a curvilinear magnetic field. The model gives good agreement with measurements obtained from a filtered cathodic-arc thin film deposition system. The important parameters involved in the motion of a vacuum arc plasma beam through a magnetic filter are examined. The analysis is based on the use of the guiding center approximation to describe the motion of the charged particles produced in the plasma where the thermal energy is negligible compared to the mass flow energy. Electron-ion collision effects are included within the framework of the drift model. It is shown that under the limiting condition of a collision frequency which is much higher than the cyclotron frequency of the electron, the motion of the plasma ions around the bend becomes independent of the magnetic field, with the number of ions traversing the filter significantly reduced. However, in the collisionless plasma case (cyclotron frequency higher than the collision frequency), the model predicts a square-law relationship between ion-saturation current and magnetic field , I_p ∞B²     

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.     

Characteristics of filtered vacuum arc deposited ZnO-SnO2 thin films on room temperature substrates

ZnO, SnO₂ and zinc stannate thin films were deposited using filtered vacuum arc deposition (FVAD) system on commercial microscope glass and UV fused silica substrates (UVFS) at room temperature (RT). The structural and morphological analyses were performed using X-ray diffraction (XRD) and Atomic Force Microscopy (AFM), respectively. XRD patterns of ZnO films deposited at RT had strongly c-axis orientation, whereas SnO₂ and zinc stannate films had amorphous structure as they did not have any defined patterns. Average crystalline size and surface grain size of ZnO films were ∼16 nm, as determined from diffraction line broadening and AFM images, respectively. Optical constants in the 250-1100 nm wavelength range were determined by variable angle spectroscopic ellipsometry and transmission measurements. The transmission of the deposited films in the VIS was 80-90%, affected by interference. The refractive indices and the extinction coefficients of deposited ZnO, SnO₂ and zinc stannate films were in the range 1.87-2.15 and 0.02-0.04, depending on wavelengths and deposition parameters. The optical band gap (E_g) was determined by the dependence of the absorption coefficient on the photon energy at short wavelengths. Its values for ZnO, SnO₂ and zinc stannate were in the range 3.25-3.30 eV, 3.60-3.98 eV and 3.43-3.52 eV, respectively, depending on the deposition pressure.     

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.     

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).     

Optical and structural parameters of the ZnO thin film grown by pulsed filtered cathodic vacuum arc deposition

Transparent conductive ZnO film was deposited on glass substrate by pulsed filtered cathodic vacuum arc deposition (PFCVAD). Optical parameters such as absorption coefficient α, the refractive index n, energy band gap E_g and dielectric constants have been determined using different methods. Kramers-Kronig and dispersion relations were employed to determine the complex refractive index and dielectric constants using reflection data in the ultraviolet-visible-near infrared regions. The spectra of the dielectric coefficient were used to calculate the energy band gap and the value was 3.24 eV. The experimental energy band gap was found to be 3.22 eV for 357 nm thick ZnO thin film. The envelope method was also used to calculate the refractive index and the data were consistent with K-K relation results. The structure of the film was analyzed with an x-ray diffractometer and the film was polycrystalline in nature with preferred (002) orientation.     

Properties of boron and phosphorous incorporated tetrahedral amorphous carbon films grown using filtered cathodic vacuum arc process

This paper reports the electrical, mechanical, structural and field emission properties of as grown and also boron and phosphorous incorporated tetrahedral amorphous carbon (ta-C) films, deposited using a filtered cathodic vacuum arc process. The effect of varying boron and phosphorous content (up to 2.0 at.% in to ta-C) on the conductivity (σ_D), activation energy (ΔE₁), hardness, microstructure, emission threshold (E_turn-ON) and emission current density (J) at 12.5 V/μm of ta-C: B and ta-C: P films deposited at a high negative substrate bias of −300 V are reported. It is observed that both boron and phosphorous incorporation leads to a nearly an order increase in σ_D and corresponding decrease in ΔE₁ and a slight increase in hardness as compared to as grown ta-C films. In the case of field assisted electron emission, it is observed that E_turn-ON increases and J decreases. The changes are attributed to the changes in the sp³/sp² ratio of the films due to boron and phosphorous incorporation. The effect of boron on ta-C is to give a p-type effect whereas the effect of phosphorous gives n-type doping effect.     

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.     

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.     

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.     

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.     

Superhard nanocomposite nc-TiC/a-C:H film fabricated by filtered cathodic vacuum arc technique

Superhard nanocomposite nc-TiC/a-C:H films, with an excellent combination of high elastic recovery, low friction coefficient and good H/E ratio, were prepared by filtered cathodic vacuum arc technique using the C₂H₂ gas as the precursor. The effect of C₂H₂ flow rate on the microstructure, phase composition, mechanical and tribological properties of nanocomposite nc-TiC/a-C:H films have been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy disperse spectroscopy (EDS), microindentation and tribotester measurements. It was observed that the C₂H₂ flow rate significantly affected the Ti content and hardness of films. Furthermore, by selecting the proper value for C₂H₂ flow rate, 20 sccm, one can deposit the nanocomposite film nc-TiC/a-C:H with excellent properties such as superhardness (66.4 GPa), high elastic recovery (83.3%) and high H/E ratio (0.13).     

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.     

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.     

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).     

Electrical and optical properties of vacuum deposited MnPc thin films

Sandwich and planar structures were fabricated using manganese phthalocyanine (MnPc) as active layer and gold (Au) as electrodes by thermal evaporation method. The permittivity ε of MnPc was determined from the dependence of capacitance on film thickness. J-V characteristics of Au/MnPc/Au structure at room temperature were performed. Thermally generated hole concentration p₀, hole mobility μ_p, total trap concentration N_t and depth of the trap level were estimated. The activation energies of MnPc films were determined from the Arrhenius plots of ln σ versus 1000/T. The absorption and reflectance spectra of MnPc thin film deposited at room temperature were recorded in the spectral range 300–900 nm. The optical band gap of MnPc thin film was determined from the α² versus hν graph. The optical constants n and k were found. The real and imaginary parts of the optical dielectric constant ε₁ and ε₂ were calculated.