Humidity effect on friction behaviors of nano-undulated diamond-like carbon films

Humidity dependency of friction behavior of nano-undulated diamond-like carbon (DLC) films was investigated by a home-made ball-on-disk type tribometer under controlled relative humidity of 0, 50, and 90%. Nano-undulated DLC films with surface roughness ranging from 0.2 to 13.4 nm were prepared by deposition of DLC film on the Si substrate with Ni nanodots. Friction coefficient of the flat DLC surface increased with the relative humidity, while that of the nano-undulated surfaces revealed smaller dependence on the relative humidity. When the surface roughness increased to 13.4 nm, friction behavior was observed to be independent of the relative humidity. The analysis of chemical composition and atomic bond structure of the debris and the transfer layer revealed that the humidity dependence on the nano-undulated surface was minimized by suppressing the graphitization of the transfer layer even with high concentration of Fe in the debris.     

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.     

Iodine doping of amorphous diamond-like carbon films

Amorphous diamond-like carbon (a:DLC) films have been doped by incorporation of iodine during the films deposition. XPS and AES analysis shows the existence of iodine atoms with constant concentration of 0.9% along the iodine doped DLC film (a:I-DLC). The optical and electronic properties of the doped films were studied. Optical measurements in the visible light show that iodine affects the interband absorption of the a:DLC films. Iodine causes decreasing of the optical energy gap, from 1.07 to 0.78 eV and affects the density of states at the conducting band. Like the optical measurements, electrical measurements show that iodine also decreases the activation energy of the films from 0.34 to 0.22 eV. This shows that although both gaps decrease, the optical energy gap remains different from that of electrical gap, also after doping.     

Quantification of sliding-induced phase transformation in N3FC diamond-like carbon films

We investigate magnetron-sputtered “N3FC” diamond-like carbon films at the nanoscale using an in situ transmission electron microscopy sliding experiment. We measure the sliding-induced changes in sp³- and sp²-hybridized carbon using electron energy loss spectroscopy, taking into account the effect of the electron beam. The rate of the phase transformation from sp³ to sp² bonding is quantified as being between 0.009% and 0.018% volume transformed per sliding pass.     

Electrodeposition mechanism of hydrogen-free diamond-like carbon films from organic electrolytes

A brief introduction on the development of electrodeposition of diamond-like carbon (DLC) films was given, and our experiments were done, emphasizing on how to deposit hydrogen-free DLC films. Methanol, acetonitrile and N,N-dimethyl formamide (DMF) were chosen as electrolytes, while Si and conductive glass were used as substrates. The sample deposited on Si through methanol was the only one in this comparative research that produced hydrogen-free DLC film as it was indicated by the FTIR spectroscopy. Two explanations, based on reaction mechanism, were proposed to explain this fact. It was believed that the reaction rate and the effect of hydroxyl groups in the molecules of the electrolytes played important roles in the deposition of hydrogen-free DLC films.     

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.     

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.     

Local structure of composite Cr-containing diamond-like carbon thin films

Composite Cr-containing hydrogenated amorphous diamond-like carbon (Cr-DLC) films were synthesized by a hybrid PVD/CVD plasma-assisted deposition process. In a recent study, it was found that Cr-DLC films with <∼12 at.% Cr possess excellent tribological properties. However, the role of Cr in inducing these characteristics is not clear. In the present report, the local structure around the Cr atoms in the latter films was studied as a function of Cr content by X-ray absorption spectroscopy. The Cr K-edge X-ray absorption near edge structure spectra show that Cr in DLC has a chemical state similar to that of chromium carbide. Analysis of the extended X-ray absorption fine structure spectra shows that at low Cr content (<0.4 at.% Cr), Cr is dissolved in the amorphous DLC matrix forming an atomic-scale composite. Simulation studies suggest that in the latter films, Cr tends to be present as very small atomic clusters of 2-3 Cr atoms. At higher Cr contents (>1.5 at.%), Cr is present as nanoparticles (<10 nm) of a defected carbide structure forming a nanocomposite.     

In situ measurement of stresses in diamond-like carbon films

In situ determination of stresses in thin films can be used as an important tool to assist process development as well as to understand the thermodynamics of film formation. A simple technique for the measurement of stresses in growing films is described here. The technique consists of measuring the displacement of a laser beam reflected from the film surface. Displacement is induced by changes in the radius of the curvature of the substrate resulting from stresses in the film. The detector sensitivity at the used wavelength (635 nm) is approximately 12 mV μm⁻¹, for which our experimental set-up is equivalent to 4 mV μrad⁻¹. The actual data collected consist of the reflected beam displacement vs. time, and provides at any instant the value of the average stress. By knowing the deposition rate, time is directly correlated with film thickness, and the local stress can be determined. Examples of measurement of stresses in tetragonally bonded amorphous carbon films prepared by filtered cathodic arc are presented, as well as how this technique can be used to design the deposition process to virtually eliminate intrinsic stresses.     

Thermal gas effusion from diamond-like carbon films

Good-quality diamond-like carbon films (6 at.% H₂, 2400 kgf/mm² microhardness, 2.7 eV bandgap, higly insulating) have been obtained by the DC glow discharge decomposition of acetylene. Mass spectroscopic thermal effusion measurements were carried out on the films deposited under different deposition conditions. Analyses of hydrogen in conjunction with hydrocarbon effusing species yield information on the microstructure and nature of C---H bonding configurations. It is shown to be a useful analytical tool to study hydrogenated amorphous carbon films of different microstructures varying from polymer-like to diamond-like.     

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。     

Frictional properties of diamond-like carbon, glassy carbon and nitrides with femtosecond-laser-induced nanostructure

This paper reports macro and micro frictional properties of DLC, TiN, CrN films and GC substrate of which surfaces are nanostructured with femtosecond (fs) laser pulses. The friction coefficient μ of the nanostructured surface was measured at a usual load with a ball-on-disk friction test machine. The results have shown that carbon materials of DLC and GC provide lower values of μ than TiN and CrN, and μ of DLC and TiN measured with a hardened steel ball decreases with an increase of the laser pulse energy. On the other hand, μ of nanostructured surfaces of thin films monotonously increases with an increase in laser pulse energy, which was measured with a micro-scratch test at an ultralight load of 1.5 mN utilizing a diamond tip. The friction coefficient of the GC substrate irradiated at a low fluence around the ablation threshold has shown a lower value than that of the non-irradiated surface.     

液相沉积类金刚石膜的结构与性能研究

探讨了液相沉积法制备类金刚石的新工艺,并采用XPS,Raman光谱和SEM等对所得膜的结构进行表征,证实所得的是类金刚石膜。液相沉积得到的类金刚石膜与钛合金基材之间具有较强的结合强度,并具有较低的摩擦系数和一定的耐磨损能力。     

Characterization of diamond-like carbon films before and after heavy energetic ion implantations

Hydrogenated diamond-like carbon films were implanted by 110 keV Fe⁺ at doses ranging from 1 × 10¹³ to 5 × 10¹⁶ ions cm⁻². The film resistivities and the infra-red transmittances of the specimens were determined as functions of the implanted doses. Raman spectra and the infra-red transmittances of the film layers were used to characterize the structural changes of the implanted films. It was found that, when the implantation dose was higher than about 5 × 10¹⁴ or 1 × 10¹⁵ ions cm⁻², the film resistivity and the total infra-red transmittance of the specimens decreased significantly. However, when the dose was smaller than this value, the resistivity decreased firstly and then increased with dose and the measured values were higher than those of corresponding as-grown ones. The infra-red transmittance of the specimens was also improved to some extent under the lower dose range. By using structural characterization results, especially the infra-red transmittances of the film layers, we conclude that the electrical and optical property changes at doses higher than about 5 × 10¹⁴ or 1 × 10¹⁵ ions cm⁻² were due to the following changes, i.e., the decrease in the population of both sp² C-H and sp³ C-H bonds (compared with that of sp³ C-H bonds, the decrease in speed of sp² C-H bonds is smaller), the decrease of bond-angle disorder and the increased population of sp² C-C bonds. However, at doses between 1 × 10¹⁴ and 5 × 10¹⁴ or 1 × 10¹⁵ ions cm⁻², the implantation induced increase of C-H bonds was responsible for the observed property changes. Compared with the previous reports, the novelty of the present work is: the IR transmittance curves of the single film layers give us direct evidence for the changes of different C-H bonds with increasing ion dose and thus proved the transformation mechanism proposed previously.     

Evaluation of hardness, tribological behaviour and impact load of carbon-based hard composite coatings exposed to the influence of humidity

Diamond-like composite coatings were deposited by PACVD with an interface magnetron sputtered metallic layer prepared by d.c. unbalanced magnetron sputtering onto HSS substrates. The focus of the present work was on the study of the humidity effect on the tribological properties, hardness and impact resistance of the deposited coatings. The coatings were tested under both dry and humid conditions using several testing methods, like the pin-on-disc test equipped with linear reciprocating movement, impact test and depth sensing indentation test. It was found that the humidity may substantially influence not only the results of tribological tests, but surprisingly, also the results of the dynamic wear and hardness tests. By increasing the relative humidity, the value of dynamic impact resistance increased at an equivalent stress of 1.6 GPa more than three times. On the other hand, the wear rate of the coated part increased by more than four orders of magnitude. The results of the indentation test were influenced by humidity mainly at nanometre scales. The hardness measured at dry conditions was higher by 25% than the values obtained by the measurements under humid conditions.     

The effect of annealing of milled carbon fibers on the mechanical and tribological properties of solid-lubricant thermoplastic polyimide-based composites

The mechanical and tribological properties of polyimide (PI)-based composites loaded with polytetrafluoroethylene (PTFE) and milled carbon fibers (MCF) in the as received and annealed states were studied in order to increase adhesion to the polymer matrix. It has been shown that loading with micron-range MCF (200 μm) doubles elastic modulus of the composites while all other physical and mechanical properties remain at neat PI levels. The three-component composite loaded with annealed MCF and PTFE has possessed the highest wear resistance. In comparison with neat PI, its wear rate has decreased by ∼312 times for the metal-polymer tribological contact and by ∼286 times for the ceramic-polymer one. Based on the obtained experimental data, the most preferential conditions for their implementation (load-speed modes for the given types of the tribological contacts) have been determined using a developed computer algorithm. The designed solid-lubricant ''PI + 10 wt% PTFE + 10 wt% MCF_annealed'' composite has been recommended for both metal-polymer and ceramic-polymer tribological units.     

Vibratory response of diamond-like amorphous carbon cantilevers under different temperatures

Diamond-like amorphous carbon films were deposited using filtered cathodic vacuum arc (FCVA) with the plasma ion immersion implantation (PIII) system. A unique multilayer film, comprising of alternating high-sp³ content (90%), high-stress (9 GPa) films, low-sp³ content (50%), and low-stress films (<0.5 GPa), was fabricated. By alternating these layers, a 1.5-μm-thick film was subsequently deposited. Free-standing microcantilevers measuring 150×50 μm had been subsequently fabricated by using standard lithography and wet etching. The resonance frequency of the microcantilevers was measured by a vacuum laser vibrometer system to be 109.5 kHz. After gradual heating to 240 °C, the resonance frequency was observed to increase to a high of 111.5 kHz.     

Effects of iodine doping on optoelectronic properties of diamond-like carbon thin films deposited by microwave surface wave plasma CVD

We report the effects of iodine (I) doping on the electrical and optical properties of diamond-like carbon (DLC) thin films grown on silicon and quartz substrates by microwave surface wave plasma chemical vapor deposition at low temperature (<100 °C). For film deposition, we used argon gas with methane or camphor dissolved with ethyl alcohol composition as plasma source. The optical gap and photoconductivity measurements of the samples were carried out before and after the iodine doping. The results show that optical gap dropped from 3.4 to 0.9 eV corresponding to nondoping to iodine-doping conditions, respectively. The photovoltaic measurements show that the open-circuit voltage (V_oc) and short-circuit current density (J_sc) of I-doped DLC film deposited on n-type silicon substrate under light illumination (AM1.5, 100 mW/cm²) were approximately 177 mV and 1.15 μA, respectively, and the fill factor was found to be 0.217.     

Characteristics of nitrogen doped diamond-like carbon thin films grown by microwave surface-wave plasma CVD

Nitrogen doped diamond-like carbon (DLC:N) thin films were deposited on p-type silicon (p-Si) and quartz substrates by microwave (MW) surface-wave plasma (SWP) chemical vapor deposition (CVD) at low temperature (< 100 °C). For films deposition, argon (Ar: 200 sccm), acetylene (C₂H₂:10 sccm) and nitrogen (N: 5 sccm) were used as carrier, source and doping gases respectively. DLC:N thin films were deposited at 1000 W microwave power where as gas composition pressures were ranged from 110 Pa to 50 Pa. Analytical methods such as X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy, FTIR and Raman spectroscopy were employed to investigate the chemical, optical and structural properties of the DLC:N films respectively. The lowest optical gap of the film was found to be 1.6 eV at 50 Pa gas composition pressure.     

Sputtered DLC-TiB2 multilayer films for tribological applications

This study focuses upon the deposition of diamond-like carbon thin films for tribological applications. Carbon consists of mainly sp² bonds, having a low Hardness and low coefficient of friction. By depositing carbon in a methane (CH₄)-rich atmosphere, the energetics of the process favours the formation of diamond-like bonds, namely sp³. To improve the tribological properties of a multilayer system, a refractory metal ceramic TiB₂, has been multilayered with carbon and deposited on titanium (Ti) substrates to a total thickness of 3 μm. A multilayer stack of 10 bi-layers has been deposited, and the volume fraction of carbon in the coating has been varied by changing the thickness of the individual layers. This study employs pulsed-dc sputtering combined with Ar 7.5% CH₄ to deposit both carbon and TiB₂.The Raman spectroscopy data shows that the carbon deposited was amorphous in nature with an I_D / I_G ratio of 1.25. TiB₂ sputtered in Ar 7.5% CH₄ formed Ti-B-C, containing both a hard TiB₂ phase and a lubricating diamond-like carbon phase.Three volume fractions of carbon have been investigated: 25%, 50% and 75%. From nanoindentation studies, the Hardness varies from 5 to 3 GPa for the 75% and 25% carbon-containing coatings, respectively, measured at a penetration depth of approximately one-third of the coating. This increase in Hardness as a function of percentage of carbon has been attributed to the coatings forming load-bearing properties.From wear studies, friction coefficients of around 0.3 have been measured. Thus, these multi-layered TiB₂/C coatings are both load bearing and lubricious.