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.     

Effect of nitrogen incorporation into diamond-like carbon films by ECR-CVD

Diamond-like carbon (DLC) and nitrogenated DLC (a-C:N) films were prepared on Si and glass substrates using an electron cyclotron resonance-assisted microwave plasma chemical vapour deposition (ECR-MPCVD) system with radio frequency substrate bias. The hardness and optical bandgap of the resulting films were investigated and correlated to the elemental and phase composition. The a-C:N films, deposited under conditions identical to those for the DLC films except for the introduction of a nitrogen flow, contain nitrogen which partly substitutes for hydrogen and forms carbon–nitrogen triple bonds. These bonds obstruct the formation of carbon–carbon cross-linking, resulting in softer films. These changes can be interpreted with reference to various changes of active vibronic states determined by Raman spectroscopy.     

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.     

The effect of annealing on mechanical and tribological properties of diamond-like carbon multilayer films

The diamond-like carbon (DLC) multilayer films have been deposited by plasma CVD deposition onSi wafer substrate. The deposited films have then been post-annealed in vacuum at 250 °C for 2 h. Changes in internal stress, hardness, critical load, friction coefficient and wear have been investigated toassess the influence of annealing on mechanical and tribological properties of DLC multilayer films. At the same time, DLC single layerfilms are also deposited and annealed in the same method for a comparison.The results show that there is 28–33% decrease in internal stress and 10–13% decrease in hardness of theDLC single layer films after the anneal treatment. However, for the DLC multilayer films, there is 41–43% decreasein internal stress and less than 2% decrease in hardness. In addition, the annealed DLC multilayer filmhas the same friction and wear properties as that un-annealed film. This result indicates that the anneal treatment isan effective method for the DLC multilayer films to reduce the internal stress and to increase the critical load.The by-effect of the annealing, decrease of hardness and wear resistance of the multilayer film, can be restrictedby the multilayer structure.     

Study on the diamond-like carbon multilayer films for tribological application

In this paper, DLC multilayer films consisting of alternating layers of soft and hard carbon films were deposited on Si wafer by a plasma CVD deposition system. Different DLC multilayer films were prepared by varying the sub-layer thickness (from 1000 to 25 nm) and the ratio of hard to soft sub-layer (H/S) thickness (from 1:1 to 4:1). By using a ball-on-disk tribo-tester, the friction and wear properties of the DLC multilayer films were measured in vacuum, O₂ and dry-air environments respectively. By comparing with single-layer DLC film, the change of the multilayer structure has little influence on friction coefficient of the multilayer films. However, the wear rate of the DLC multilayer films is restricted effectively by constructed the multilayer structure in the film. The wear rate of the multilayer films is lower than that of the single film in reactive (O₂ and dry-air) environments. An DLC multilayer film with excellent wear resistance, approximately in the level of 10⁻⁸ mm³/Nm in different environments (dry-air, O₂ and vacuum), is obtained as the DLC multilayer film at a certain sub-layer thickness and ratio.     

液相沉积类金刚石膜的沉积机理研究

根据电化学的相关理论,提出了钛合金表面液相沉积DLC膜的反应机理,给出了可能电极过程,认为膜是通过甲基阳离子的亲电取代反应而不断生长。讨论了氢原子对金刚石结构的稳定作用,并解释了实验条件对膜结构和性能的影响。     

Effects of hydrogen on the properties of Si-incorporated diamond-like carbon films prepared by pulsed laser deposition

We have deposited unhydrogenated and hydrogenated Si-incorporated DLC (Si-DLC) films by pulsed laser deposition using KrF excimer laser, and systematically examined the structure and the mechanical and tribological properties of the films. Hydrogenated Si-DLC films were prepared by atomic-hydrogen irradiation during deposition. The Si/(Si+C) ratio in DLC films increased by atomic-hydrogen irradiation during deposition, indicating that the hydrogen etching is more effective for C atoms compared with Si atoms. The formation of Si–C bonds in the films and silicon oxides only at the surfaces was confirmed by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. It was found that the atomic-hydrogen irradiation led to the formation of Si–H bonds to prevent the surface oxidation of the Si-DLC films. The scratch tests revealed that the critical loads of the films deposited with hydrogen were higher than those of the films deposited without hydrogen. We found that the moderately hydrogen-irradiated Si-DLC films tended to have higher wear resistance than the unhydrogenated Si-DLC films.     

The properties of fluorine-containing diamond-like carbon films prepared by pulsed DC plasma-activated chemical vapour deposition

Diamond-like carbon films containing up to 23.1 at. % of fluorine (F-DLC), were deposited onto silicon substrates by low-frequency, pulsed DC, plasma-activated, chemical vapour deposition (PACVD). The influence of fluorine on plasma current density, deposition rate, composition, bonding structure, surface energy, hardness, stress and biocompatibility was investigated and correlated with the fluorine content. X-ray photoelectron spectroscopy (XPS) analysis revealed the presence C–C, C–CF and C–F for F-DLC films with a low fluorine concentration (1.5–12.1 at. %), however for films with a higher fluorine content (23.0 at. %) an additional peak due to CF₂ bonding was detected. The addition of fluorine into the DLC film resulted in lower stress and hardness values. The reduction in these values was attributed to the substitution of strong C=C by weaker C–F bonds which induces a decrease in hardness. Ion scattering spectrometery (ISS) measurements revealed the presence of fluorine atoms in the outmost layer of the F-DLC films and there was no evidence of surface oxygen contamination. The water contact angle was found to increase with increasing fluorine content and has been attributed to the change of the bonding nature in the films, in particularly increasing CF and CF₂ bonds. Biocompatibility tests performed using MG-63 osteoblast-like cell cultures indicated homogeneous and optimal tissue integration for both the DLC and the F-DLC surfaces. This pulsed-PACVD technique has been shown to produce biocompatible DLC and F-DLC coatings with a potential for large area applications.     

Structure and mechanical properties of W incorporated diamond-like carbon films prepared by a hybrid ion beam deposition technique

W incorporated diamond-like carbon films were prepared on silicon(1 0 0) wafers using a hybrid deposition system composed of an end-Hall-type hydrocarbon ion gun and a tungsten DC magnetron sputter source. The W concentration in the films was controlled by changing the fraction of Ar in the Ar and C₆H₆ reaction gas. The chemical composition, atomic bond structure, and mechanical properties were investigated for W concentrations ranging from 0 to 8.6 at.%. When the W concentration was <2.8 at.%, the W atoms were dissolved in the amorphous carbon matrix without forming a WC_1−x phase. Amorphous and crystalline WC_1−x nano-particles appeared when the W concentration was >2.8 and >3.6 at.%, respectively. It was found that the hardness and elastic modulus were not sensitive to the W concentration in this concentration range. On the other hand, the residual compressive stress was strongly dependent on the chemical state of the incorporated W atoms. The change in mechanical properties is discussed in terms of the microstructural changes induced by W incorporation.     

Electrically conductive properties of tungsten-containing diamond-like carbon films

Tungsten-containing diamond-like carbon films with different metal concentrations were investigated. The films of several hundred nanometers in thickness were deposited on the silicon wafer using RF-PECVD (radio frequency plasma enhanced chemical vapor deposition) method. During deposition, metal component was co-sputtered using DC magnetron of tungsten target. The six samples with the concentration of 3.8, 6.1, 8.0, 16.3, 24.3 and 41.4 at.% of tungsten were made. The structural analyses were performed by TEM (transmission electron microscope) and Raman spectroscopy. These results indicated that tungsten clusters were well dispersed in amorphous carbon host matrix in the case of tungsten concentration from 3.8 to 24.2 at.%. However, no such a structure can be observed in the sample with 41.4 at.%. The AC electrical resistance was measured in the temperature range of 2–300 K using four-probe method in vacuum condition. The observed temperature dependence of electrical conductivity can be expressed by σ=σ₀exp−2(C₀/kT)^1/2 and tungsten concentration from 3.8 at.% to 24.2 at.%. In addition, the sample with 41.4 at.% showed the resistive superconducting transition at T_c of around  5.5 K.     

Mechanical properties of alternating high-low sp3 content thick non-hydrogenated diamond-like amorphous carbon films

Thick non-hydrogenated DLC films (∼ 1μm), consisting of alternating sub-layers of high/low sp³ content, were deposited onto n++ Si substrates using the filtered cathodic vacuum arc method. These films were systematically studied to determine how the changes in composition of the sub-layers would affect the mechanical properties such as intrinsic stress, hardness, friction coefficient, wear rate and surface roughness. Variations of both the ratio of hard to soft layers (from 1:3 to 3:1) and thickness of individual layers (from 12.5nm to 75nm) were studied in detail. The stress of the film was sufficiently lowered (7.8GPa–2.4GPa) by the multilayer approach. The results indicated that although hardness has some correlations with the internal composition of the film, the reduced Young's modulus is largely not affected. Wear and frictional characterizations also showed that the multilayer was a good candidate for many mechanical applications.     

Microstructure and adhesion characteristics of diamond-like carbon films deposited on steel substrates

For tribological applications, the low friction coefficient and high microhardness of diamond-like carbon (DLC) films give significant advantages in cutting and forming non-ferrous materials. The inherently large residual stress of DLC films, however, prevents the depositing of thicker films. This study designed and implemented a compound interface, comprising a series of metal, metal nitride, and metal carbonitride interlayers deposited in a graded structure, between the DLC (a metal-doped a-C:H) film and M2 steel substrates. The tribological performance of the interface was evaluated using a scratch tester and ball-on-disk tribometer. Meanwhile, the failure mechanism of DLC deposited on M2 steel substrates was examined using SEM/EDS and TEM microscopy. Experimental results demonstrate an improved DLC hard coating with superior adhesion strength on the steel substrates.     

Characterization of the mechanical properties of diamond-like carbon films

A recently suggested method to measure the elastic modulus of diamond-like carbon (DLC) films was reviewed. This method used a DLC bridge or free overhang which is free from the mechanical constraint of the substrate. Because of the high residual compressive stress of the DLC film, the bridge or the overhang exhibited a sinusoidal displacement on removing the mechanical constraint. Measuring the amplitude and wavelength of the sinusoidal displacement made it possible to measure the strain of the film which occurred by stress relaxation. Combined with independent stress measurement using the laser reflection method, this method allowed the calculation of the biaxial elastic modulus of the DLC film. This method was successfully applied to obtain the elastic properties of various DLC films from polymeric hydrogenated amorphous carbon (a-C:H) to hard tetrahedral amorphous carbon (ta-C) films. Since the substrate is completely removed from the measurement system, this method is insensitive to the mechanical properties of substrate. The mechanical properties of very thin DLC films could be thus measured and then can reveal the structural evolution of a-C:H films during the initial stages of deposition.     

Synthesis and mechanical properties of carbon nanotube/diamond-like carbon composite films

Diamond-like carbon (DLC) coatings were successfully deposited on carbon nanotube (CNT) films with CNT densities of 1 × 10⁹/cm², 3 × 10⁹/cm², and 7 × 10⁹/cm² by a radio frequency plasma-enhanced chemical vapor deposition (CVD). The new composite films consisting of CNT/DLC were synthesized to improve the mechanical properties of DLC coatings especially for toughness. To compare those of the CNT/DLC composite films, the deposition of a DLC coating on a silicon oxide substrate was also carried out. A dynamic ultra micro hardness tester and a ball-on-disk type friction tester were used to investigate the mechanical properties of the CNT/DLC composite films. A scanning electron microscopic (SEM) image of the indentation region of the CNT/DLC composite film showed a triangle shape of the indenter, however, chippings of the DLC coating were observed in the indentation region. This result suggests the improvement of the toughness of the CNT/DLC composite films. The elastic modulus and dynamic hardness of the CNT/DLC composite films decreased linearly with the increase of their CNT density. Friction coefficients of all the CNT/DLC composite films were close to that of the DLC coating.     

Effect of structure of carbon films on their tribological properties

A comparative study of the tribological properties of a library of different carbon forms is presented. The library includes hydrogen free and hydrogenated carbon films with different bonding (CC, CH, different sp³ fractions) and structure configurations (amorphous, graphitic) leading to a wide range of densities and hardness. Reference samples (Si substrates, thermally evaporated amorphous carbon, graphitic foil) were studied as well. The tribological properties were measured using a reciprocal sliding tribometer under humid (50% RH) and dry (5% RH) air conditions. Friction coefficients were measured versus the number of sliding cycles and the wear was studied using optical profilometry and imaging as well as SEM.The friction and wear performance of the carbon films were found to depend on both the structure and the ambient conditions. Hydrogen free films have friction coefficients < 0.1 for 80% sp³ bonded films and > 0.1 for 100% sp² bonded films. The wear resistance of the hydrogen free films (much larger for sp³ bonded films) significantly decreases under dry conditions. In contrast, hydrogenated films show reduction in friction with decreasing humidity (from 0.2 under 50% RH to < 0.1 under 5% RH). The wear resistance of hydrogenated films is larger for dry and smaller for humid conditions.     

Optical and microstructural properties of diamond-like carbon films grown by pulsed laser deposition

Diamond-like carbon films have been fabricated using 308 nm excimer laser ablation in vacuum followed by deposition at temperatures between 77 K and 573 K. Optical band gap energies are obtained from UV/optical spectroscopy. Raman spectra and X-ray photoelectron spectra (XPS) show that the sp³/(sp² + sp³) ratio in these films is in excess of 0.7 in films deposited at 77 K and 300 K. This ratio decreases to 0.2 in films deposited at 573 K. It is found that films deposited at cryogenic temperatures consist of a matrix structure assembled from embedded nanometer clusters, while films deposited at 300 K or higher temperature are amorphous and atomically flat. Microstructural features in cryogenic films are discussed in relation to the mechanism of deposition and possible phase transitions during assembly of these films.     

Electrical and optical properties of diamond-like carbon films deposited by pulsed laser ablation

Pulsed laser ablation of a graphite target was carried out by ArF excimer laser deposition at a laser wavelength of 193 nm and fluences of 10 and 20 J/cm² to produce diamond-like carbon (DLC) films. DLC films were deposited on silicon and quartz substrates under 1 × 10^? 6 Torr pressure at different temperatures from room temperature to 250 °C. The effect of temperature on the electrical and optical properties of the DLC films was studied. Laser Raman Spectroscopy (LRS) showed that the DLC band showed a slight increase to higher frequency with increasing film deposition temperature. Spectroscopic ellipsometry (SE) and ultraviolet–visible absorption spectroscopy showed that the optical band gap of the DLC films was 0.8–2 eV and decreased with increasing substrate temperature. These results were consistent with the electrical resistivity results, which gave values for the films in the range 1.0 × 10⁴–2.8 × 10⁵ Ω cm and which also decreased with deposition temperature. We conclude that at higher substrate deposition temperatures, DLC films show increasing graphitic characteristics yielding lower electrical resistivity and a smaller optical band gap.     

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.     

Microstructure and mechanical properties of CeO2 doped diamond-like carbon films

A kind of rare earth oxide, CeO₂, was doped into the diamond-like carbon (DLC) films with thickness of 180–200 nm, using unbalanced magnetron sputtering. All the adhesion strength of CeO₂ doped DLC films is increased, while the residual compressive stress is obviously decreased compared to pure DLC film. Specially, the residual compressive stress of the deposited films are reduced by 90%, when the CeO₂ content is in the range of 5–7%, from a value of about 4.1 GPa to 0.5 GPa. When the CeO₂ content is increased to 10%, the deposited films possess the highest adhesion strength of 85 mN, 37% higher than that of pure DLC film. The nanohardness and elastic modulus exist a transition point at 8% of CeO₂ content within the DLC film. Before this value, nanohardness and elastic modulus of CeO₂ doped DLC films are lower than those of pure DLC film, and after this value, they are higher or adjacent to those of pure DLC film. Auger electron spectroscopy shows a more widened interface of 6% CeO₂ doped DLC film compared to pure DLC film. The enhancement of adhesion strength is mainly attributed to the widening of the film-substrate interface, as well as the decrease of residual compressive stress.     

Structure and mechanical properties of oxygen doped diamond-like carbon thin films

In this study, structure and mechanical properties of doped diamond-like carbon (DLC) films with oxygen were investigated. A mixture of methane (CH₄), argon (Ar) and oxygen (O₂) was used as feeding gas, and the RF-PECVD technique was used as a deposition method. The thin films were characterized by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy (RS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and a combination of elastic recoil detection analysis and Rutherford backscattering (ERDA-RBS). Nano-indentation tests were performed to measure hardness. Also, the residual stress of the films was calculated by Stoney equation. The XPS and ERDA-RBS results indicated that by increasing the oxygen in the feeding gas up to 5.6 vol.%, the incorporation of oxygen into the films' structure was increased. The ratio of sp² to sp³ sites was changed by the variation of oxygen content in the film structure. The sp²/sp³ ratios are 0.43 and 1.04 for un-doped and doped DLC films with 5.6 vol.% oxygen in the feeding gas, respectively. The Raman spectroscopy (RS) results showed that by increasing the oxygen content in doped DLC films, the amount of sp² CC aromatic bonds was raised and the hydrogen content reduced in the structure. The attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) confirmed the decrease of hydrogen content and the increase the ratio of CC aromatic to olefinic bonds. Hardness and residual stress of the films were raised by increasing the oxygen content within the films' structure. The maximum hardness (19.6 GPa) and residual stress (0.29 GPa) were obtained for doped DLC films, which had the maximum content of oxygen in structure, while the minimum hardness (7.1 GPa) and residual stress (0.16 GPa) were obtained for un-doped DLC films. The increase of sp³ CC bonds between clusters and the decrease of the hydrogen content, with a simultaneous increase of oxygen in the films' structure is the reason for increase of hardness and residual stress.