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 and tribological properties of diamond-like carbon films prepared on steel by ECR-CVD process

Diamond-like carbon (DLC) films were prepared on AISI 440C steel substrates at room temperature by the electron cyclotron resonance chemical vapor deposition (ECR-CVD) process in C₂H₂/Ar plasma under different conditions. In order to prevent the inter-diffusion of carbon and improve the adhesion strength of DLC films, functionally gradient Ti/TiN/TiCN/TiC supporting underlayers were deposited on the steel substrates in advance. Using the designed interfacial transition layers, relatively thick DLC films (1–2 μm) were successfully prepared on the steel substrates without delamination. By optimizing the deposition parameters, DLC films with hardness up to 28 GPa and friction coefficients lower than 0.15 against the 100Cr6 steel ball were obtained. In addition, the specific wear rates of the films were found to be extremely low (∼10⁻¹⁷ m³/Nm). The friction-induced graphitization mechanism of DLC was confirmed by micro-Raman analysis.     

Microstructure,mechanical and tribological properties of TaCN composite films by reactive magnetron sputtering

In this paper, a series of TaCN composite films with different carbon content were deposited by the magnetron sputtering system and the microstructure, mechanical and tribological properties were investigated. The results showed that the deposited TaCN films exhibited a three-phase of face-centered cubic (fcc) Ta(C,N), hexagonal closed-packed (hcp) Ta(C,N) and amorphous CNx. With the increase of carbon content, the hardness of the TaCN films first increased and then decreased, after reaching a maximum of 33.1 GPa; the adhesion strength increased gradually; the coefficient of friction decreased monotonically and the wear property initially improved and then weakened at room temperature. The coefficient of friction of the TaCN film at 28.21 at.% carbon decreased first, then increased and then decreased again and its high-temperature wear rate first decreased slightly and then increased, as the temperature increased from room temperature (RT) to 600 °C. The TaCN film at 28.21 at.% carbon exhibited excellent an elevated-temperature tribological properties.     

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.     

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.     

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.     

Effects of nitrogen flow rate on the microstructure and mechanical and tribological properties of TiAlN films prepared via reactive magnetron sputtering

In this study, TiAlN ceramic films were fabricated via reactive magnetron sputtering on a Ti6Al4V titanium alloy substrate. The effects of N₂ flow rates on the microstructure and mechanical and tribological properties of the films were systematically studied. With increasing N₂ flow rate, the films underwent a morphological evolution from a fine columnar structure to a coarse structure with holes and microcracks. In addition, the preferred orientation of the films varied from TiAlN (220) to the (111) plane. However, a high N₂ flow rate (≥20sccm) resulted in target poisoning and reduced the deposition rate, which resulted in defects such as cavities and holes on the surface. Moreover, with increasing N₂ flow rate, the hardness and elastic modulus first increased and then reduced owing to grain refinement. The films deposited at a N₂ flow rate of 16 sccm exhibited the smallest wear width and the lowest wear rate. As the N₂ flow rate increased from 12 to 24 sccm, the wear mechanism of the films changed from abrasive and adhesion wear to abrasive wear caused by severe plastic deformation, which was directly related to the microstructural evolution and mechanical properties.     

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.     

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.     

Luminescence properties of terbium-doped SiCN thin films by rf magnetron reactive sputtering

Terbium-doped SiCN (SiCN:Tb) thin films were deposited by rf magnetron reactive sputtering at 800 °C. The as-prepared samples were characterized by XRD, FTIR, and XPS. The results showed that SiCN:Tb films mainly contained both SiC and Si₃N₄ nano-compositions with complicated chemical bond networks. Photoluminescence measurements indicated that the undoped SiCN films exhibited a blue-green light emission, while SiCN:Tb films emitted a strong green one. The SiC nanocrystallites formed in the undoped SiCN films might be responsible for the blue-green light emission, while the formed quaternary Si-C-Tb-O compositions in the doped samples could account for the strong green PL behaviors.     

Mechanical and tribological properties of diamond-like carbon coatings films deposited from an electron cyclotron resonance plasma

The friction coefficients have been investigated in amorphous diamond-like carbon (DLC) films deposited by a dual ECR–r.f. method, as a function of r.f. substrate bias in relation with the H content and bonding. Combined infrared absorption, elastic recoil detection analysis and tribological tests are used to characterize fully the films in their as-deposited state. Friction coefficients (μ) of the coatings against sapphire balls are determined in air at room temperature. The results indicate clearly that the samples exhibit high compressive stresses and the friction coefficients are found to be low and are affected by the magnitude of the biaxial stress and the microstructure of the films.     

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。     

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.     

Yttrium-doped TiO2 films prepared by means of DC reactive magnetron sputtering

Y₂O₃-doped TiO₂ films were prepared on glass substrates by means of pulsed DC reactive magnetron sputtering method using titanium and yttrium mixed target. XPS results showed that the films were composed of fully oxidation states of the two elements, Y₂O₃–TiO₂ composite oxides. The existence of yttrium inhibited the crystal growth of TiO₂ in the films and Y₂O₃ mainly presented in its amorphous state in the films. UV–vis transmittance of the films decreased whereas their reflectance increased slightly. Yttrium doping had detrimental effect on photocatalytic activity of the TiO₂ films. Photocatalytic degradation efficiency of methyl orange solution declined along with increasing yttrium concentration.     

Microstructural and optical properties of Ta-doped ZnO films prepared by radio frequency magnetron sputtering

Ta-doped ZnO films with different doping levels (0–5.02 at%) were prepared by radio frequency magnetron sputtering. The effects of the doping amount on the microstructure and the optical properties of the films were investigated. The grain size and surface roughness first significantly decrease and then slowly increase with the increase of Ta doping concentration. Both the grain size and the root mean square (RMS) roughness reach their minimum values at the doping content of 3.32 at%. X-ray Diffraction (XRD) patterns confirmed that the prepared Ta-doped ZnO films are polycrystalline with hexagonal wurtzite structure and a preferred orientation along the (002) plane. X-ray photoelectron spectroscopy (XPS) analysis reveals that Ta exists in the ZnO film in the Ta⁵⁺ and Ta⁴⁺ states. The average optical transmission values of the Ta-doped ZnO films are higher than those of the un-doped ZnO film in the visible region. The band gap energy extracted from the absorption edge of transmission spectra becomes large and the near band edge (NBE) emission energy obtained from PL spectra blueshifts to high energy when the Ta doping content grows from 0 at% to 5.02 at%, which can be explained by the Burstein–Moss shift.     

Influence of a hard transition layer on the microstructure and properties of diamond-like carbon/hydroxyapatite composite coating prepared by magnetron sputtering

The nanostructured diamond-like carbon/hydroxyapatite composite coating (DLC/HA) was deposited using magnetron sputtering technique with a densely packed columnar cross-sectional structure and a uniform granular surface morphology. After heat treatment, the amorphous structure of the coating was transformed into a crystal structure. Nanohardness and scratch tests results demonstrated the DLC transition layer significantly enhanced the nanohardness of Ti6Al4V substrates from 4.8 GPa to 10.4 GPa, and increased critical load from 16.6 N (pure HA layer) to 26.5 N (DLC layer) without obvious brittle fracture, flaking and delamination. Electrochemical and immersion tests results demonstrated that DLC/HA composite coatings with a dense gradient transition interlayer had better corrosion resistance and could prevent harmful metal ions being released into the SBF solution more effectively than single HA coatings. Furthermore, active Ca²⁺ ions can be rapidly released from the coating surface during initial immersion in the SBF solution, and facilitated the formation of bone-like apatite.     

Mechanical and tribological properties of TiC/amorphous hydrogenated carbon composite coatings fabricated by DC magnetron sputtering with and without sample bias

TiC/amorphous hydrogenated carbon (a-C:H) composite films were deposited by Ti DC magnetron sputtering using argon and acetylene as the carrier gas and precursor, respectively. The working pressure was maintained at 4 × 10^− 1 Pa and the composition of the films was modulated by controlling the partial pressure of acetylene. The composition and structure of the films were evaluated by X-ray photoelectron spectroscopy and glancing angle X-rays diffraction, whereas the hardness and elastic modulus values of the films fabricated using different sample biases were measured by nano-indentation. Ball-on-disk tribometry was used to measure the tribological properties, and secondary electron microscopy was used to analyze the wear tracks. The results show that the friction coefficients and wear rates do not vary significantly with the Ti concentrations when the Ti concentration is above 39.7 at.% or below 20 at.% but increase with increasing titanium concentrations between 20 at.% and 39.7 at.%. The wear mechanism depends on the relative amounts of TiC and a-C:H. At high Ti concentrations, the mechanism resembles that of TiC due to the thin a-C:H matrix surrounding the TiC grains. At low Ti concentrations, the mechanism is similar to that of DLC as the effects of the a-C:H matrix dominates over those of the TiC grains.     

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.