Studies of diamond-like carbon films prepared by ion beam-assisted deposition

Ion beam-assisted deposition offers a novel and unique process to prepare diamond-like carbon (DLC) films at room temperature, with particularly good interface adhesion. This advantage was explored in this study to deposit highly wear-resistant coating on bearing 52100 steel. Both dual ion beam sputtering and ion beam deposition were employed. Various bombarding species and energy were investigated to optimize the process. Raman, X-ray photoelectron and Auger electron spectroscopy were used to characterize the bonding structure of DLC. Extensive experiments were carried out to examine the tribological behaviour of the DLC/52100 system. A metal intermediate layer can help tremendously in wear resistance. The results are optimistic and may lead to useful applications.     

Contact damage evolution in a diamond-like carbon (DLC) coating on a stainless steel substrate

A diamond-like carbon thin film was coated onto a stainless steel substrate using plasma assisted chemical vapour deposition (PACVD). Instrumented indentation and scratching were used, supported by focused ion beam (FIB) microscopy, to explore deformation and fracture behaviours of this coating system. The formation and growth of ring and radial cracks in the coating, as well as plastic flow in the ductile substrate, were observed to be the predominant deformation processes for this coating system. Lateral cracking occurred at the interface of the coating/substrate following indentation, but in the middle of the coating following scratching. No evidence of plastic flow within the coating was observed. Coating deformation is, therefore, controlled by its fracture energy. An indentation-energy-based model was applied to evaluate the fracture toughness of the coating.     

Nanoindentation-induced deformation behaviour of diamond-like carbon coatings on silicon substrates

The deformation behaviour of diamond-like carbon (DLC) coatings on silicon substrates induced by indentation has been investigated. DLC coatings, deposited by a plasma-assisted chemical vapour deposition technique, were subjected to nanoindentation over a range of maximum loads from 100 mN to 300 mN. The resulting load-displacement plots displayed pop-ins for maximum loads of 200 mN and above, with no distinct pop-out for any of the loads studied. Compressive deformation of the coating, up to a strain of ∼ 9%, was observed. The coating-substrate composite was devoid of cracks at lower loads, but at the maximum load of 300 mN, ring cracks in the coating and a median crack in the substrate were observed. Furthermore, cracking, {111} slip and localized phase transformations were observed in the silicon substrate. The onset of these structural changes was correlated to the mechanical behaviour during indentation.     

Effect of coating thickness on the deformation behaviour of diamond-like carbon-silicon system

The effect of coating thickness on the deformation behaviour of diamond-like carbon (DLC) coatings on silicon substrates was investigated. Following nanoindentation of a 0.6 µm thick DLC coating, the subsurface microstructures were characterized and the data was compared to prior studies on a similar, but thicker coating. Indentation resulted in localized plastic compression in the coating without any through-thickness cracking. It was shown that the discontinuities in the load-displacement curves appeared at lower loads for the thinner coating. Accordingly, the silicon substrate exhibited cracking, plastic deformation and phase transformation at significantly lower loads than in the case of the thicker coating. Further, the widths, parallel to the interface, over which slip and the phase transformation zone are spread out in the substrate, was found to increase with the thickness of the coating. The mechanism responsible for the first pop-in was found to change from phase transformation in uncoated silicon to dislocation nucleation in the presence of the coating.     

Oxygen plasma etching of silver-incorporated diamond-like carbon films

Diamond-like carbon (DLC) film as a solid lubricant coating represents an important area of investigation related to space devices. The environment for such devices involves high vacuum and high concentration of atomic oxygen. The purpose of this paper is to study the behavior of silver-incorporated DLC thin films against oxygen plasma etching. Silver nanoparticles were produced through an electrochemical process and incorporated into DLC bulk during the deposition process using plasma enhanced chemical vapor deposition technique. The presence of silver does not affect significantly DLC quality and reduces by more than 50% the oxygen plasma etching. Our results demonstrated that silver nanoparticles protect DLC films against etching process, which may increase their lifetime in low earth orbit environment.     

Structural and mechanical properties of diamond-like carbon films deposited by an anode layer source

An anode layer source is a special ion gun, which can be fed with carbon precursors like acetylene to deposit hard and highly defect-free hydrogenated diamond-like carbon films at room temperature. The present study focuses on the influence of the process parameters — discharge voltage, process pressure and acetylene flow — on structure and mechanical properties of the deposited films. Raman spectra show that an increased discharge voltage yields decreased structural disorder, i.e. a lower C-C sp³ hybridised fraction of carbon atoms in the films. By an elevation of the discharge voltage from 1 to 3 kV the full width at half maximum of the G-band decreases from 194 ± 0.2 cm^− 1 to 183 ± 0.7 cm^− 1. Films deposited at the lowest discharge voltage show in accordance to the spectroscopic data the highest nanohardness (36 ± 1 GPa), stress (− 2.34 ± 0.2 GPa) and reduced elastic modulus (180 ± 4 GPa).     

Investigation of the microstructure, mechanical properties and tribological behaviors of Ti-containing diamond-like carbon films fabricated by a hybrid ion beam method

Diamond-like carbon (DLC) films with various titanium contents were investigated using a hybrid ion beam system comprising an anode-layer linear ion beam source and a DC magnetron sputtering unit. The film composition and microstructure were characterized carefully by X-ray photoelectron spectroscopy, transmission electron microscopy and Raman spectroscopy, revealing that the doped Ti atoms had high solubility in the DLC films. The maximum solubility was found to lie between about 7 and 13 at.%. When the Ti content was lower than this solubility, the doped Ti atoms dissolved in the DLC matrix and the films exhibited the typical features of the amorphous DLC structure and displayed low compressive stresses, friction coefficients and wear rates. However, as the doped content exceeded the solubility, Ti atoms bonded with C atoms, resulting in the formation of carbide nano-particles embedded in the DLC matrix. Although the emergence of the carbide nano-particles promoted graphitizing due to a catalysis effect, the film hardness was enhanced to a great extent. On the other hand, the hard carbides particles caused abrasive wear behavior, inducing a high friction coefficient and wear rate.     

Investigation of diamond-like carbon/silicon heterojunctions deposited by pulsed Nd:YAG laser

Diamond-like carbon (DLC) films were deposited on p-type silicon (Si-100) substrates by using a pulsed Nd:YAG laser for the ablation of a pyrolytic graphite target at a background pressure of 10⁻⁶ Torr. For a fixed distance of 3 cm between the target and substrate, samples of DLC/Si heterojunction were prepared for two different laser wavelengths of 355 nm and 1064 nm. All DLC films showed typical D and G bands in their Raman spectra. DLC films were also deposited on glass substrates for resistivity measurement by four-point probe. The electrical properties for DLC/Si heterojunctions were analyzed current-voltage measurement at room temperature in the dark and also under illumination. The dependencies of the electrical characteristics on the depositing parameters were discussed.     

Electrochemical performance of diamond-like carbon thin films

Diamond-like carbon (DLC) thin films used in this study were intended for their electrochemical properties. The DLC films were deposited by a filtered cathodic vacuum arc (FCVA) process on p-type silicon (100) substrates biased at different pulse voltages (0-2000 V). The chemical bonding structures of the DLC films were characterized with micro-Raman spectroscopy and the electrochemical properties were evaluated by means of electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. The DLC films showed high impedance, high polarization resistance and high breakdown potential in a 0.5 M H₂SO₄ aqueous solution, which were attributed to the high sp³ content and uniformity of the films. The excellent chemical inertness of the DLC films made them promising corrosion resistant coating materials.     

Dependence of field-emission threshold in diamond-like carbon films grown by various techniques

In this paper, we report field-emission measurements from ∼0.5-μm-thick hydrogenated amorphous carbon (diamond-like carbon (DLC)) films. These films were grown by a variety of easily implementable plasma-enhanced chemical vapor deposition (PECVD) based techniques and also by a method that uses a saddle-field fast atom beam source. Field-emission behavior in these materials has been discussed in light of residual stress, hardness, optical band gap, and characteristic energy of band tails (Urbach energy). Onset emission-fields as low as ∼6 V/μm, together with low residual stress of 0.25 GPa, hardness of 17.5 GPa, optical band gap of 1.5 eV, and Urbach energy of 165 meV, have been obtained in DLC films grown by pulsed-PECVD at 13.56 MHz. DLC films of comparable quality could also be grown using a saddle-field fast atom beam source, which operates on modest dc power supply and with no heated filaments or magnets.     

A study on the bactericidal properties of Cu-coated carbon nanotubes

A Cu layer was coated on carbon nanotubes (CNTs) by ion beam-assisted deposition (IBAD). Standard agar dilution method was used to evaluate the bactericidal rate against E. coli and S. aureus bacteria. The structure and chemical states of the Cu-coated CNTs were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results show that the Cu-coated CNTs possess a very high bactericidal rate. In comparison with the Cu-coated pyrolytic carbon sample, the Cu-coated CNTs show much stronger bactericidal property.     

不同等离子源形成的DLC涂层对NiTi合金腐蚀行为的影响

采用等离子浸没离子注入和沉积(PIIID)法分别以C2H2和石墨为等离子源在NiTi合金表面形成DLC涂层来提高该合金的耐腐蚀性.利用Raman光谱和扫描电镜分析膜层结构.利用电化学测试和原子吸收光谱测试涂层前后基体的耐腐蚀性和Ni离子析出.结果表明:采用等离子浸没离子注入和沉积法以乙炔和石墨为等离子源在NiTi合金表面形成均匀致密、结合力良好的DLC涂层.两种涂层都明显地提高了NiTi合金的耐腐蚀性能和有效地抑制了Ni离子的溶出.     

Investigation of the properties of diamond-like carbon thin films deposited by single and dual-mode plasma enhanced chemical vapor deposition

In this study diamond-like carbon (DLC) films were deposited by a dual-mode (radio frequency/microwave) reactor. A mixture of hydrogen and methane was used for deposition of DLC films. The film structure, thickness, roughness, refractive index of the films and plasma elements were investigated as a function of the radio frequency (RF) and microwave (MW) power, gas ratio and substrate substance. It was shown that by increasing the H₂ content, the refractive index grows to 2.63, the growth rate decreases to 10 (nm/min) and the surface roughness drops to 0.824 nm. Taking into consideration the RF power it was found that, as the power increases, the growth rate increases to 11.6 (nm/min), the variations of the refractive index and the roughness were continuously increasing, up to a certain limit of RF power. The Raman G-band peak position was less dependent on RF power for the glass substrate than that of the Si substrate and a converse tendency exists with increasing the hydrogen content. Adding MW plasma to the RF discharge (dual-mode) leads to an increase of the thickness and roughness of the films, which is attributed to the density enhancement of ions and radicals. Also, optical emission spectroscopy is used to study the plasma elements.     

Buffered internal stresses in diamond-like carbon films reinforced with single-walled carbon nanotubes

Diamond-like carbon (DLC) films reinforced with single-walled carbon nanotubes (SWCNTs) were fabricated by sputter-deposition of DLC onto a few monolayers of spray-coated SWCNTs on glass substrates. The thickness-averaged internal stress was reduced by 1.5 GPa by incorporation of SWCNTs into 10-nm-thick DLC films. Stress analysis indicates that the internal stress is reduced by 1.8 GPa at the SWCNT-DLC nanocomposite layer and decreases exponentially as a function of film thickness. Microscopy reveals significant cracking and delamination in 150-nm-thick DLC films, while the SWCNT-reinforced films remain essentially intact. The results demonstrate that SWCNTs in DLC films influence the early stage of DLC film growth and act as an effective stress-buffering layer near the boundary between the film and substrate.     

Optical study of ion-deposited diamond-like carbon films using spectroscopic ellipsometry

Spectroscopic ellipsometry was used for the characterization of ion-deposited diamond-like carbon (DLC) films, including the determination of film thickness and optical properties of DLC. The measured spectra in the wavelength range from 300 to 850 nm were analyzed with an appropriate fitting model, which was constructed according to the nominal sample structure in which the optical properties of DLC were described by a Cauchy dispersion model. Reasonably good agreement was found between the measured and calculated spectra for all samples studied, indicating that the models used were appropriate and that the calculated results were reliable. The results of our analysis suggest that, under the same deposition conditions (i.e., same substrate temperature and same chamber pressure), the optical properties of ion-deposited DLC film did not change much even if the film was prepared with quite different gas flow ratios.     

Structure and mechanical properties of W-Se-C/diamond-like carbon and W-Se/diamond-like carbon bi-layer coatings prepared by pulsed laser deposition

Bi-layer W-Se-C/diamond-like carbon (DLC) and WSe_x/DLC coatings were obtained by standard and shadow-masked pulsed laser co-deposition from WSe₂ and graphite targets. W-Se-C coatings appeared as nanocomposites containing quasi-amorphous WSe₂, WC, spherical β-W nanocrystalline particles encapsulated in WSe₂ amorphous shell, and amorphous carbon phases. In WSe_x/DLC coatings, the formation of chemical bonds between W and C atoms was noticed at the interface. An increase of the C concentration over 40 at.% increases hardness and elasticity (up to 2 times at ~ 60 at.%C), and the Se/W ratio was always close to 1.4. The use of shadow-masked configuration avoids the deposition of micro- and nanoparticles. However, this method leads to a substantial increase of the Se content (Se/W ≥ 4), and the coatings became softer.     

Some electrical properties of diamond-like carbon thin films

Diamond-like carbon (DLC) belongs to very interesting materials used for a number of practical applications. It was noted that the electrical properties of DLC films obtained by RF PCVD discharge depend substantially on the deposition conditions. The results and discussion of the electrical properties of DLC films and DLC/Si heterostructures is presented. The electrical conductivity results are explained in terms of hopping mechanism. The relation between charge transport, structure of the energy gap and the deposition conditions is discussed.     

Deposition and microstructure of Ti-containing diamond-like carbon nanocomposite films

Ti-containing diamond-like carbon (DLC) films were deposited by plasma decomposition of CH₄/Ar gas mixtures with an introduction of tetrakis(dimethylamino)titanium (TDMAT, Ti[(CH₃)₂N]₄), which was used as a precursor of titanium. The films deposited were found to be nanocomposite coatings consisting of TiN nanocrystalline clusters and amorphous hydrocarbon (a-C:H), indicating that the nanocrystalline clusters were embedded in the DLC matrix. The crystallinity of TiN clusters, as well as the Ti atomic concentrations in the films, increased with an increase of substrate temperature. The substrate temperature applied to form a crystalline phase in the DLC matrix induced a graphitization of amorphous hydrocarbon matrix. The increase of volume fraction of TiN nanocrystalline clusters in the DLC matrix enhanced the mechanical properties of nanostructured coatings, although the graphite-like structural transition of DLC matrix happened due to the applied heating.     

The effects of plasma pre-treatment and post-treatment on diamond-like carbon films synthesized by RF plasma enhanced chemical vapor deposition

Diamond-like carbon (DLC) films were synthesized by RF plasma enhanced chemical vapor deposition and the effects of plasma pre-treatment and post-treatment on the DLC films were investigated. Experimental results show that the surface roughness of the substrate, ranging from 0.2 to 1.2 nm, created by the plasma pre-treatment, will affect the surface roughness of the DLC films deposited using methane as the carbon source. However, the film surface roughness (0.1-0.4 nm) is much smaller than that of the substrate. Raman analysis and hardness measurement by nanoindentation indicate that the structure and the hardness of the DLC films are relatively unchanged for the film surface roughness investigated. For the argon or hydrogen plasma post-treatment of the DLC films deposited using acetylene as the carbon source, it is found that surface roughness decreases with the post-treatment time. Although the hardness decreases after post-treatment, it remains relatively constant with increasing post-treatment time.     

Thickness of diamond-like carbon coatings quantified with Raman spectroscopy

A model is developed for quantifying the thickness of thin coatings and wear scars using Raman spectroscopy. The model, which assumes that both incident and Raman light obey Beer's law, was applied to Raman spectra from a diamond-like carbon (DLC) coating containing Si and O, known as DLN (diamond-like nanocomposite). The coatings ranged in thickness from 10 nm to 2 μm, according to stylus profilometry. Systematic variations in the Raman carbon (G band) and Si (1st order) peak intensities vs. thickness were found. Fits to the model gave an optical mean free path of λ250 nm for DLN. This value is in good agreement with optical absorption coefficient values of other DLC films. Thickness profiles of wear tracks in the coatings determined by the model compared well with depths determined by profilometry.