Electrochemical properties of boron-carbon-nitride films formed by magnetron sputtering

The electrochemical behavior of B_1.0C_2.4N_1.0 thin film was investigated in acidic, neutral and alkaline solutions. The anodic polarization curve of the film in 1 M NaOH showed the anodic dissolution of the film. The curve of the film in 1 M HCl showed no anodic dissolution. The cathodic polarization curve in 1 M NaCl showed shift to a negative potential side, but the anodic polarization curve was the same as that of Pt. The anodic dissolution in 1 M NaOH depended on potentials, that is, no anodic dissolution was recognized in a potential range of −0.2 to 0.1 V but the dissolution rate increased with increasing potential in a range of 0.1-0.6 V. The anodic current density of the film is directly proportional to the dissolution rate at potentials higher than 0.1 V. The dissolution rate of the film was increased with increasing solution pH.     

Large-area uniform hydrogen-free diamond-like carbon films prepared by unbalanced magnetron sputtering for infrared anti-reflection coatings

The hydrogen-free diamond-like carbon (DLC) films are potential materials to be used as infrared anti-reflection protective coatings if their optical absorption can be reduced to get relatively thick films needed. In this study, hydrogen-free DLC films were deposited by the physical vapor deposition (PVD) method in an unbalanced magnetron sputtering (UBMS) system with a rectangle graphite target of 440 × 80 mm in the argon atmosphere. The UBMS system was described in detail and the magnetron field distribution of the target was denoted in this work. The film thickness uniformity was investigated and the results showed that this system is capable of depositing uniform films larger than 150 mm in diameter. The infrared transmission spectra of DLC films were analyzed by a FTIR spectrometer, the results indicating that transparent films were obtained in the infrared region for the single side DLC coated on the silicon and germanium substrates, and about 68.83% and 63.05% transmittance were achieved respectively at the wave number of 2983 /cm, close to theoretical value for non-absorption carbon material. No obvious absorption peaks were found between 5000 and 800 /cm. The refractive index and extinction coefficient of the DLC films deposited under optimized conditions were about 2.08 and 0.067 respectively at the wavelength of 1600 nm. These important optical characteristics showed that the hydrogen-free DLC films prepared in the UBMS system were suitable for infrared transmission enhancement applications.     

Improved physical properties of Al-doped ZnO thin films deposited by unbalanced RF magnetron sputtering

Room temperature Al-doped ZnO (AZO) thin films with improved crystalline and optical properties were grown on normal glass substrates using unbalanced RF magnetron sputtering technique. To modify the plasma density towards the substrate and enhance the crystalline nature, an additional magnetic field ranging from 0 to 6.0 mT has been applied to the AZO target by proper tuning of solenoid coil current from 0 to 0.2 A respectively, which plays a significant role for controlling the physical properties of AZO films. The results from XRD studies indicate that all AZO films were composed of hexagonal wurtzite structure with better crystal quality through the applied magnetic field, ZnO (002) plane as a preferred growth. Furthermore, XPS studies suggested that symmetric chemical shifts in the binding energies for the Zn 2p and O1s levels with applied magnetic field. SEM analysis revealed the formation of a smooth, homogeneous and dense morphological surface with applied magnetic field. From AFM analysis, it was observed that the applied magnetic field strongly influenced the grain size and the films showed decreasing tendency in electrical resistivity. Films exhibited superior optical transmittance more than 94% in the visible region essentially due to the formation of better crystalline nature. The results indicate that improved band gap from 3.10 to 3.15 eV with additional magnetic field varied from 0 to 6.0 mT respectively.     

Corrosion performance of thin hydrogenated amorphous carbon films prepared by magnetron sputtering

Hydrogenated amorphous carbon (a-CH_x) films were prepared by magnetron sputtering at different H₂/Ar gas flow ratios. Several sets of perpendicular magnetic recording disks with a-CH_x overcoats of 5 nm were prepared for accelerated environmental corrosion test. The corrosion spots on the disks and the corrosion products were analyzed using optical surface analyzer and time-of-flight secondary ion mass spectroscopy, respectively. Other techniques, such as Raman spectroscopy, atomic force microscopy nano-scratch and contact angle measurement, were used to characterize the properties of a-CH_x films. Compared to pure carbon overcoat, all the a-CHx overcoats have better corrosion resistance and higher polar component of surface free energy. The a-CH_x film with appropriate H content shows the highest scratching resistance, and the corresponding disk has the lowest corrosion area on the disk surface after the accelerated corrosion.     

Structure and high-temperature tribological properties of Pb-Cr-O composite films prepared by reactive magnetron sputtering

The formation of ternary composite oxides in a high-temperature environment has laid the foundation for the design of high-temperature wear-resistant self-lubricating film. A series of Pb-Cr-O films with different Cr contents were prepared by incorporating different ratios of Pb-Cr into a target in the reactive magnetron sputtering system. The results showed that the hardness of the Pb-Cr-O films is greatly improved compared to the pure Pb-O film. In addition, the Pb₂₉Cr₄O₆₇ film with the highest Cr content forms an amorphous structure due to the accumulation of Cr⁶⁺ at the grain boundary, which improves the H/E and H³/E² of the film. At 600 °C, in contrast with the single PbO lubricating phase formed by pure Pb₃₃O₆₇ film, the Pb₂₉Cr₄O₆₇ film forms a composite lubricating phase of Pb₅CrO₈ and PbO. This leads to a decreased wear rate as low as 7.2 × 10^?6 mm³N^?1m^?1 while maintaining low coefficient of friction comparable to pure Pb₃₃O₆₇ film. At higher temperature of 700 °C, Cr element in Inconel 718 matrix diffuses into the Pb-based oxide film and forms Pb₅CrO₈ phase similar to Pb₂₉Cr₄O₆₇ film, which improves the wear resistance of the Pb₃₃O₆₇ film while maintaining low friction coefficient of 0.15.     

Mechanical characterization of ultra-thin fluorocarbon films deposited by R.F. magnetron sputtering

Fluorocarbon films were deposited on silicon substrate by R.F. magnetron sputtering using a polytetrafluoroethylene (PTFE) target. Structure of the deposited films was studied by X-ray photoelectron spectroscopy (XPS). Hardness, elastic modulus and scratch resistance were measured using a nanoindenter with scratch capability. -CF_x (x = 1, 2, 3) and C-C units were found in the deposited fluorocarbon films. The hardness and elastic modulus of the films are strongly dependent on the R.F. power and deposition pressure. The film hardness is in the range from 0.8 GPa to 1.3 GPa while the film elastic modulus is in the range from 8 GPa to 18 GPa. Harder films exhibit higher scratch resistance. Differences in nanoindentation behavior between the deposited fluorocarbon films, diamond-like carbon (DLC) films and PTFE were discussed. The fluorocarbon films should find more applications in the magnetic storage and micro/nanoelectromechanical systems.     

直流溅射ITO薄膜光电性能研究

采用直流溅射法制备了高性能的ITO薄膜。结果表明,氧气分压比和衬底温度对薄膜的方阻、可见光透射率具有重要的影响。其最佳值分别为0.5/50和350℃;同时,随着膜厚的增加,薄膜的晶粒增大,导电率也相应降低。     

Structural effects of nanocomposite films of amorphous carbon and metal deposited by pulsed-DC reactive magnetron sputtering

The relationship between metal-induced (W, Mo, Nb and Ti) structures and the surface properties of Me–DLC thin films is discussed. Nanocomposite films were deposited on c–Si wafers by pulsed-DC reactive magnetron sputtering controlling the gas ratio CH₄/Ar. The sputtering process of metals such as Ti, Nb and Mo (unlike the tungsten) in the presence of methane shows a low reactivity at low methane concentration. The deposition rate and the spatial distribution of sputtered material depend of Z-ratio of each metal. The surface contamination of metal targets by carbon, owing to methane dilution, limits the incorporation of metals into DLC films according to an exponential decay. Results of electron probe microanalysis and X-ray photoelectron spectroscopy indicate a C rich Me/C composition ratio for low relative methane flows. According to the depth profile by secondary ion mass spectrometry, the films are systematically homogeneous in depth, whereas at high carbon contents they exhibit a metal-rich interfacial layer on the substrate. Moreover, high resolution transmission electron microscopy has evidenced important structural modifications with respect to DLC standard films, with marked differences for each Me/C combination, providing nanodendritic, nanocrystallized or multilayered structures. These particular nanostructures favour the stress decrease and induce significant changes in the tribological characteristics of the films. This study shows the possibilities of controlling the amorphous carbon films structure and surface properties by introducing metal in the DLC matrix.     

Study of the thermal stability of carbon nitride thin films prepared by reactive magnetron sputtering

CN_x amorphous films have been prepared by reactive magnetron sputtering in a pure N₂ discharge. The films grown on NaCl have been characterised by Fourier transform infrared spectroscopy (IR), transmission electron microscopy (TEM), and electron energy loss spectroscopy (EELS). C/N atomic ratios have been determined by EELS with values in the range 2.0–1.2 for samples grown under different conditions. The thermal stability of the films upon heating in vacuum was followed ‘in situ’ at the transmission electron microscope by EELS. This study has been completed by a thermogravimetric and mass spectrometer analysis of evolved gases upon heating in nitrogen flow and vacuum, respectively. Under these conditions the films are stable up to 1023 K. Above this temperature the films decompose by elimination of nitrogen remaining a carbonaceous residue. The thermal stability of the films upon annealing in air was studied by following the evolution of the X-ray photoelectron spectroscopy (XPS) peaks during heating in air of films grown on steel. Deconvolution analysis of the XPS spectra allows to determine the evolution of the different type of bonds. In particular pure carbon in the films appears more reactive to oxygen than CN and C–N bonds.     

Sulphur doped DLC films deposited by DC magnetron sputtering

Diamond‐like carbon (DLC) and sulphur doped diamond‐like carbon (S‐DLC) films were synthesised at different sulphur molar percentage of 0%, 2%, 5%, 8% and 10% by direct current (DC) magnetron sputtering process using novel compressed sulphur‐graphite targets at relatively low power density. Films were characterised for their morphologies, structural, electrical and optical properties. Scanning electron microscope images reveal changes in the quality of the obtained films shown by the denser packing of DLC grains at different sulphur percentage. The conductivities of S‐DLC films were found to be in the range of 6.0 × 10^?3–0.6/Ω cm. The optical band gap energies were found to be in the range of ～1.4–2.0 eV. Both electrical and optical measurements exhibit nonlinear responses with optimum at around 5% sulphur molar percentage (minimum for conductivity and maximum for optical band gap energy). These trends of change in both conductivity and optical band gap energy are consistent with the variation in bond characters of the films indicated by Raman spectroscopy. © 2011 Canadian Society for Chemical Engineering     

Mechanical and tribological properties of boron,nitrogen-coincorporated diamond-like carbon films prepared by reactive radio-frequency magnetron sputtering

We have deposited boron- and/or nitrogen-incorporated DLC films by radio-frequency magnetron sputtering, and systematically investigated the structure and the mechanical and tribological properties. The N content in DLC films increased with increasing N₂ flow ratio [N₂/(Ar + N₂)], and it tended to be saturated at higher N₂ flow ratios. The N content further increased with an increase in the B content of the targets. The B/C ratios of the films were almost the same as those of the B-containing targets regardless of the N content. Scratch tests revealed that the adhesion strength of N-incorporated DLC films decreased with increasing N₂ flow ratio and the critical loads of B-incorporated films were lower than that of an unincorporated film. It was found that for B, N-coincorporated films there was an optimum N₂ flow ratio at which the critical load became a maximum value, which was higher than that of the unincorporated film. The optimum N₂ flow ratio increased with an increase in the B composition of the targets. The N-incorporated films peeled off during ball-on-plate friction tests. On the other hand, the B, N-coincorporated films showed good wear-resistant properties that the specific wear rates were lower than those of the unincorporated and B-incorporated films.     

Structure, elemental composition, and mechanical properties of films prepared by radio-frequency magnetron sputtering of hydroxyapatite

The phase composition, substructure, and surface morphology of 0.1-to 5.0-μm-thick films grown on different substrates by radio-frequency magnetron sputtering of a hydroxyapatite ceramic target are investigated using transmission electron microscopy (TEM), high-energy electron diffraction, X-ray diffraction, IR spectroscopy, Auger electron spectroscopy, ultrasoft X-ray emission spectroscopy, Rutherford backscattering spectroscopy, scanning electron microscopy (SEM), and atomic-force microscopy (AFM). The hardness and adhesion strength of these films are studied using the nanoindentation and scratching methods. It is revealed that the structure of the films depends on the spatial inhomogeneity of the plasma discharge. Single-phase dense nanocrystalline hydroxyapatite films are formed when the substrate is located above the erosion zone. According to the X-ray diffraction, high-energy electron diffraction, and IR spectroscopic data, the structure of the films corresponds to the hydroxyapatite structure. As follows from the Auger electron, ultrasoft X-ray emission, and Rutherford backscattering spectroscopic data, the elemental composition of the films is similar to the stoichiometric composition of hydroxyapatite. The analysis of the X-ray diffraction and AFM data demonstrates that the films have a dense structure. The results of the mechanical tests show that the hardness of the coatings is higher than 10 GPa and that the maximum adhesion strength (L _C = 12.8 N) is observed for the hydroxyapatite coatings on the titanium substrate modified by the TiC-TaC-Ca₃(PO₄)₂ composite layer.     

The structural and mechanical characterization of TiC and TiC/Ti thin films grown by DC magnetron sputtering

The formation of TiC and Ti phases and their influence on their mechanical properties was studied in this work. Thin layers were deposited by DC magnetron sputtering at room temperature in ultrahigh vacuum from Ti and C targets.Cubic TiC phase (c-TiC) was formed from 58 to 86?at.% Ti content. First formation of hexagonal Ti (h-Ti) occurred from 86?at.% Ti content. The c-TiC disappears from 90?at.% Ti content. Films with 86?at.% Ti content the c-TiC structure can transform to h-Ti by sequential stacking faults. Dominance of c-TiC(111) texture with increasing Ti content was observed.The hardness of thin films agree with structural observations. The highest hardness value (～26?GPa) showed the c-TiC thin film with 67?at% Ti content. The nanohardness values showed decreasing character with increasing Ti content over 70?at.%. The lowest values of nanohardness (～10?GPa) was observed for thin films with only h-Ti phase.     

A correlation between the microstructure and optical properties of hydrogenated amorphous carbon films prepared by RF magnetron sputtering

Comparative and systematic studies of the effect of the radiofrequency (RF) bias on the microstructure and the optical properties of hydrogenated amorphous carbon (a-C:H) have been carried out on films deposited by RF magnetron sputtering under different RF power varying from 10 to 250 W applied to the graphite target, leading to a negative bias voltage at the target in the range of −60 to −600 V.A combination of infrared (IR) absorption experiments, which give information about the local microstructure (i.e. C–C and C–H bonding), and optical transmission measurements in the UV-visible and near IR, from which we determined the optical gap E₀₄ and the refractive index n, are applied to fully characterize the samples in their as-deposited state. The results show first that the films deposited at low RF power (i.e. low negative bias) exhibit a more open microstructure (polymeric character) with a lower density than those deposited at high RF power (i.e. high negative bias). They also indicate that the total bonded H content as well as the sp³/sp² ratio of carbon atoms bonded to H decrease with increasing RF power leading to the formation of higher proportions of C-sp² sites. The same tendency is observed for the optical gap E₀₄. On the contrary, the refractive index increases with increasing RF power, suggesting the densification of the films in going to a higher RF power.     

ZAO薄膜使用射频溅射法生长之参数的研究

以氧化铝锌陶瓷为溅射靶材,在氩气环境下,使用射频溅射法在玻璃基片上制备氧化铝锌(ZAO)薄膜。通过调节气体压强、基片温度、溅射功率制膜,得到以C轴(002)为选择取向的氧化锌薄膜。由XRD、原子力显微镜(AFM)等对薄膜进行分析。结果表明,制备薄膜的最佳条件为:溅射压强0.4 Pa,溅射功率200 W,基片温度300℃。     

Structural and mechanical properties of CNx thin films prepared by magnetron sputtering

In an attempt to define the role of nitrogen in CN chemical bonding and in the formation of CN_x thin films, several coatings with a variable concentration of N₂ were grown onto (100) Si substrates using magnetron sputtering in N₂/Ar discharge. The chemical composition of the as-deposited films was investigated by means of Rutherford backscattering spectroscopy (RBS) and showed an [N]/[C] ratio up to 0.7. Raman and Fourier transform infrared (FTIR) spectroscopy were carried out to measure the optical vibration properties for studying the bonding state of nitrogen.By means of grazing incidence X-ray diffraction (XRD) and transmission electron microscopy (TEM) electron diffraction the structure of the deposited films was proven to be mainly amorphous containing small crystallites of CN_x compounds. Scanning tunneling microscopy (STM) shows the clusterlike surface of the films where the cluster size is characterized by scaling behaviour. The mechanical properties of the CN_x thin films adhering their substrates were investigated using the nanoindentation technique. From the load–displacement curve the hardness H and the Young's modulus E of the films were calculated.The relationships between deposition parameters and properties of CN_x films are shown and discussed. In particular, the influence of the applied r.f. power and the role of the N₂ partial pressure are demonstrated.     

Hardness of nanocomposite a-C:Si films deposited by magnetron sputtering

Hydrogen-free a-C:Si films with Si concentration from 3 to 70 at.% were prepared by magnetron co-sputtering of pure graphite and silicon at room temperature. Mechanical properties (hardness, intrinsic stress), film composition (EPMA and XPS) and film structure (electron diffraction, Raman spectra) were investigated in dependence on Si concentration, substrate bias and deposition temperature. The film hardness was maximal for ∼ 45 at.% of Si and deposition temperatures 600 and 800 °C. Reflection electron diffraction indicated an amorphous structure of all the films. Raman spectra showed that the films in the range of 35–70 at.% of Si always contain three bands corresponding to the Si, SiC and C clusters. Photoelectron spectra showed dependency of Si–C bond formation on preparation conditions. In the films close to the stoichiometric SiC composition, the surface and sub-surface carbon atoms exhibited dominantly sp³ bonds. Thus, the maximal hardness was observed in nanocomposite a-C:Si films with a small excess of carbon atoms.     

Diamond-like a-C:H(:F) films obtained by d.c. magnetron sputtering

Diamond-like a-C:H and a-C:H:F films were obtained by reactive d.c. magnetron sputtering from a glassy carbon target in an argon-hydrogen atmosphere. For the deposition of a-C:H:F layers, hexafluoroethane (C₂F₆) was added to the sputtering atmosphere. The a-C:H(:F) films are transparent and mechanically hard. The films can be used as protective and antireflective coatings on a-Si:H photoreceptors. Electrical, optical and structural properties of the a-C:H(:F) films are examined. Fluorinated films are found to have a more compact structure and exhibit a higher stability to ambient temperatures than unfluorinated material.     

Zinc oxide films deposited by radio frequency plasma magnetron sputtering technique

Zinc oxide (ZnO) is a wide band gap transparent conductive oxide (TCO) material with a lot of potential applications including transparent thin-film sensors, transistors (TFTs), solar cells, and window insulation systems. In this work, ZnO films were deposited on glass substrates by the radio frequency (RF) plasma magnetron sputtering deposition technique. The effects of the RF power on the properties of the ZnO films were elucidated. The influences of the RF power on the surface morphology, structural, and optical properties of the ZnO films were investigated by Mahr surface profilometer, Atomic Force Microscopy (AFM), X-ray diffractometer (XRD), and ultraviolet–visible (UV–VIS) spectrophotometer. To allow for accurate comparison of the power effects, ZnO films with similar thickness deposited at different RF powers were examined. The RF power effects on the properties of the ZnO films are revealed and discussed in this paper.