Evaluation of microstructures and mechanical properties of diamond like carbon films deposited by filtered cathodic arc plasma

Diamond-like carbon (DLC) films were deposited by a cathodic arc plasma evaporation (CAPD) process, using a mechanical shield filter combined with a magnetic filter with enhanced arc structure at substrate-bias voltage ranging from − 50 to − 300 V. The film characteristics were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and high-resolution transmission electron microscopy (HRTEM). The mechanical properties were investigated by using a nanoindentation tester, scratch test and ball on disc wear test. The Raman spectra of the films showed that the wavenumber ranging from 900 to 1800 cm^− 1 could be deconvoluted into 1140 cm^− 1, D band and G band. The bias caused a significant effect on the sp³ content which was increased with the decreasing of I_D/I_G ratio. The XPS spectra data of the films which were etched by H⁺ plasma indicated the sp³ content are higher than those of the as-deposited DLC films. This implied that there is a sp²-rich layer present on the surface of the as-deposited DLC films. The nanoindentation hardness increased as the maximum load increased. A 380 nm thick and well adhered DLC film was successfully deposited on WC-Co substrate above a Ti interlayer. The adhesion critical load of the DLC films was about 33 N. The results of the wear tests demonstrated that the friction coefficient of the DLC films was between 0.12 and 0.2.     

Analysis of plastic deformation in diamond like carbon films-steel substrate system with tribological tests

The influence of plastic deformation of the substrate on the tribological properties of diamond like carbon (DLC) films was investigated in DLC films-steel substrate system. The tribological properties of DLC films deposited on different hardness steel were evaluated by a ball on disk rotating-type friction tester at room temperature under different environments. In dry nitrogen, DLC films on soft steel exhibited excellent tribological properties, especially obvious under high load (such as 20 N and 50 N). However, DLC films on hard steel were worn out quickly at load of 20 N. Plastic deformation was observed on soft steel after tribological tests. The width and depth of plastic deformation track increased with increase of the experimental load. Super low friction and no measurable wear were kept in good condition even large plastic deformation under high load conditions in DLC films-soft steel system. In open air, DLC films on soft steel exhibited high coefficient of friction and DLC films on ball were worn out quickly. Plastic deformation was not observed on soft steel because the contact area increased and the thick hardened layer on contact surface were formed by DLC films and debris particles together on the steel substrate. The wear track on steel became deep and wide with increase of loads and DLC films were worn out. The experimental results showed that super low friction and high wear resistance of DLC films on soft steel can be attributed to the good adhesion and plastic deformation. Plastic deformation played an active role in the tribological properties of DLC films on soft steel in the present work.     

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.     

Microstructure of interface for high-adhesion DLC film on metal substrates by plasma-based ion implantation

The diamond-like carbon (DLC) film was prepared on various metal substrates with a plasma-based ion implantation and deposition using superimposed RF and negative high-voltage pulses. The adhesion strength of DLC film was enhanced above the epoxy resin strength by implantation of carbon ions or mixed ions of carbon and silicon to the substrate surface before DLC deposition. In order to clarify the mechanism for improvement in adhesive strength, the microstructure of an interface between DLC film and substrate was examined in detail by transmission electron microscopy (TEM) observations in combination with EDS analysis. As a result, the enhancement in adhesion strength of DLC film by C ion implantation resulted from the formation of amorphous-like phase in the ion-implanted region of substrate, the production of carbon-component graded interface, the destruction of the oxide layer on the top surface of substrate, and the reduction of residual stress in DLC film by ion implantation during the deposition. The production of stress-free DLC film allowed us to demonstrate a supra-thick DLC film of more than 400 μm in thickness.     

Wear behaviour and rolling contact fatigue life of Ti/TiN/DLC multilayer films fabricated on bearing steel by PIIID

In order to improve the friction and wear behaviours and rolling contact fatigue (RCF) life of bearing steel materials, Ti/TiN/DLC (diamond-like carbon) multilayer hard films were fabricated onto AISI52100 bearing steel surface by plasma immersion ion implantation and deposition (PIIID) technique. The micro-Raman spectroscopy analysis confirms that the surface film layer possess the characteristic of diamond-like carbon, and it is composed of a mixture of amorphous and crystalline phases, with a variable ratio of sp²/sp³ carbon bonds. Atomic force microscope (AFM) reveals that the multilayer films have extremely smooth area, excellent adhesion, high uniformity and efficiency of space filling over large areas. The nanohardness (H) and elastic modulus (E) measurement indicates that the H and E of DLC multilayer films is about 32 GPa and 410 GPa, increases by 190.9% and 86.4%. The friction and wear behaviours and RCF life of DLC multilayer films specimen have also been investigated by ball-on-disc and three-ball-rod fatigue testers. Results show that the friction coefficient against AISI52100 steel ball decreases from 0.92 to 0.25, the longest wear life increases nearly by 22 times. In addition, wear tracks of the PIIID samples as well as wear tracks of the sliding steel ball were analyzed with the help of optical microscopy and scanning electron microscopy (SEM). The L₁₀, L₅₀, L_a and mean RCF life L of treated bearing samples, in 90% confidence level, increases by 10.1, 4.2, 3.5 and 3.4 times, respectively. Compared with the bearing steel substrate, the RCF life scatter extent of Ti/TiN/DLC multilayer films sample is improved obviously.     

Investigation on preparation and properties of thick DLC film in medium-frequency dual-magnetron sputtering

Chromium-doped DLC film of about 6 μm in thickness was deposited using a medium-frequency dual-magnetron sputtering. The basic condition was Cr and C target powers in a range of 2-5 kW and substrate bias voltage held at −100 V in unipolar mode. Surface morphology, microstructure, hardness, adhesion, and friction property were investigated for the DLC film to be used as protective coating in industrial applications such as cutting tools, forming dies, etc. The thick DLC film with graded and multilayered structure exhibited some advisable properties: Vickers hardness was 1560 kg/mm² at 250 g; adhesion was 52 N (L_c), a majority of film maintained at the end stage of scratch test; friction coefficient was 0.09, maintained in a long sliding endurance.     

Diluting and annealing effects on electromigration and morphology of chemical vapor-deposited copper films

The crystallization and orientation of chemical vapor-deposited copper films were investigated by means of X-ray diffraction. The ratios of Cu (1 1 1) peak intensity to Cu (2 0 0) [I(1 1 1)/I(2 0 0)] of the film deposited at different temperatures were plotted as a function of temperature. Then it can be found that the ratio of I(1 1 1)/I(2 0 0) increased with the deposition temperature, and 400 °C is the best one for electromigration when the films are grown in diluting N₂, and/or annealing by N₂ or by H₂. In addition, the morphology of copper films was characterized by atomic force microscopy, and it was found that the smoothness of the films grown in diluting N₂ and/or annealing by N₂ are improved, while the films annealing by H₂ have no significant changes.     

Metallic contacts to nitrogen and boron doped diamond-like carbon films

Hydrogenated diamond-like carbon (DLC) was deposited using a radio-frequency plasma-enhanced chemical vapor deposition method. Electrical properties of Al, Au, Ti, and Zr contacts to nitrogen and boron doped DLC films have been studied, and mechanisms of the observed current-voltage (I-V) characteristics are investigated. Linear I-V characteristics were observed for Au, Ti, and Zr contacts to both nitrogen and boron doped DLC films. A band structure model for metal-DLC contact is proposed to explain the observed ohmic contacts. Fermi level shifting at the surface of DLC films produces an ohmic resistive layer instead of a Schottky barrier for metal-DLC contacts. Al contacts to both nitrogen and boron doped DLC films show nonlinear I-V characteristics, which are attributed to a dielectric layer of carbide (Al₄C₃) instead of a Schottky barrier suggested by other groups. Inert elements such as Au and Pt, and transition metals such as Ti, Zr and W, which form conductive carbides, are considered good contacting metals for electrical studies of DLC films.     

Structural and ferroelectric properties of La modified Sr0.8Bi2.2Ta2O9 thin films

La modified SBT (Sr_0.8La_0.1Bi_2.1Ta₂O₉) thin films of different thickness were fabricated on Pt/Ti/SiO₂/Si substrates by the metalorganic decomposition technique. All the films were annealed layer-by-layer at 800 °C using a rapid thermal annealing furnace. X-ray diffraction analysis indicated that the relative intensity of the (2 0 0) diffraction peak [I(2 0 0)/I(1 1 5)] increased with the increase of the film thickness. Eventually, an a-axis preferentially oriented SLBT film was obtained. These results are discussed with respect to the anisotropy of the grain growth. The a-axis preferentially oriented SLBT film, whose relative intensity of the (2 0 0) peak [I(2 0 0)/I(1 1 5)] was 1.05, had a remanent polarization (2P_r) value of 21 μC/cm² and a coercive field (2E_c) value of 70 kV/cm under the electric field of 200 kV/cm.     

XPS study of the a-C:H/Ti and a-C:H/a-Si interfaces

In this study ultrathin hydrogenated amorphous carbon (a-C:H) films have been grown onto the titanium and amorphous silicon (a-Si) overlayers by direct ion beam deposition using acetylene gas as a hydrocarbon source. X-ray photoelectron spectroscopy (XPS) was used for study of the DLC-Ti and DLC-Si interfaces. It was revealed that a-Si is a good interlayer for improvement of adhesion in the case of diamond-like carbon film deposition onto the steel substrate at room temperature. a-C:H film growth without substantial intermixing occurred on the a-Si. On the other hand, adhesion between the Ti interlayer and the diamond like carbon film was very sensitive to the deposition conditions (presence of the pump oil) as well as structure and stress level of the Ti film. It was explained by strong intermixing between the growing carbon film and Ti. Bad adhesion between the growing DLC film and Ti interlayer was observed despite formation of the TiC. At the same time, formation of the TiO_x was not an obstacle for good adhesion. It is shown that composition of the used hydrocarbon gas, structure of the Ti thin film and mechanical stress in it had greater influence on adhesion with a-C:H film than elemental composition of the Ti interlayer surface.     

Deposition of diamond-like carbon films on the inner surface of narrow stainless steel tubes

Diamond-like carbon (DLC) films were deposited on the inner surface of 304-type stainless steel tube with an inner diameter of 10 mm by DC glow discharge plasma. The influence of the deposition time, pressure and the ratios of CH₄ in CH₄/Ar gas mixture on the DLC film deposition were investigated. The images of Scanning Electron Microscopy (SEM) show that the DLC films are featureless and free of porosity. Fibre-like structure was recognized on the film surface by Atomic Force Microscopy (AFM). The film deposition rate decreases with increasing the deposition time. Relative higher deposition rate (40 nm/min) can be obtained at 20-30 Pa, higher and lower pressure will significantly decrease the deposition rate. Raman spectrum analysis shows that the films deposited in 30 min at 20-30 Pa have more sp³ content. The corrosion resistance of the films was measured by potentiodynamic polarization test. The DLC films deposited on the inner surface of the 304-type stainless steel tube significantly improve its corrosion resistance.     

Effects of duty cycle and water immersion on the composition and friction performance of diamond-like carbon films prepared by the pulsed-DC plasma technique

Diamond-like carbon (DLC) films were prepared in a pulsed-DC discharged CH₄/Ar plasma. Effects of duty cycle ([t_on/(t_on + t_off)] × 100%) on the composition and properties of DLC films were investigated. In general, the increased duty cycle led to an up-shift of the G peak position, an increase in the I_D/I_G and sp²/sp³ ratio, and a reduction of the number of C-H bonds and the film hardness, revealing a graphitization tendency with increasing duty cycle. Tribologically, ultralow and steady friction coefficients (0.005 and 0.008) in dry nitrogen atmosphere were obtained for the films prepared under a duty cycle of 50% and 65%. The unique mechanical property and chemical nature brought by the moderate sp²/sp³ ratio and the proper H content were considered to be responsible as the films deposited in this duty cycle range could simultaneously provide the high chemical inertness and the ultrasmooth sliding surfaces required for achieving ultralow friction. In addition, the structure was less vulnerable to water molecules in the case of stewing. The diamond-like nature and the ultralow friction performance were hardly affected even experiencing a 4-month immersion in water.     

Mechanical properties and thermal stability of nitrogen incorporated diamond-like carbon films

The nitrogen incorporated diamond-like carbon films were deposited on Si (100) substrates by arc ion plating (AIP) under different N₂ content in the gas mixture of Ar and N₂. The influence of N₂ content on the film microstructure and mechanical properties was studied by atomic force microscopy, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and nanoindentation. It was found that the hardness (H), elastic modulus (E), elastic recovery (R) and plastic resistance parameter (H/E) decrease with increasing the nitrogen content. The decrease of mechanical properties of DLC films resulted from nitrogen incorporation was associated with total sp³ carbon bond content and N-sp³C bond content. The structural modification as well as mechanical properties of the annealed nitrogen incorporated diamond-like carbon films was investigated as a function of annealing temperature. Raman spectra indicate that the I_D/I_G ratio starts to increase and G peak position shifts upward at the annealing temperature over 500 °C. The hardness and elastic modulus of thermally annealed nitrogen incorporated DLC films decreased slightly at lower annealing temperature and then significantly decreased at higher annealing temperature. The strong covalent bonding between C and N atoms is expected to be effective on their thermal stability enhancement.     

The influence of fluorine doping on the optical properties of diamond-like carbon thin films

Optical properties of fluorine doped diamond-like carbon (F:DLC) films deposited by the direct current plasma enhanced chemical vapor deposition (PECVD) technique were studied in detail. Surface morphologies of the F:DLC films were studied by an atomic force microscope, which indicated surface roughness increased with increase in at.% of F in the films. The chemical binding was investigated by X-ray photoelectron spectroscopic studies. Fourier transformed infrared spectroscopic studies depicted the presence of CF_x (x = 1,2,3) and CH_n (n = 1,2) bonding within the F:DLC films. Optical transparency and the optical band gap decreased with the fluorine incorporation in the DLC film. Optical band gap calculated from the transmittance spectra decreased from 2.60 to 1.95 eV with a variation of 0-14.8 at.% of F concentration in the diamond-like carbon films. Urbach parameter determined from the band tail of the transmittance spectra showed that it increased with the doping concentration.     

Preparation of various DLC films by T-shaped filtered arc deposition and the effect of heat treatment on film properties

Different types of diamond-like carbon (DLC) films (ta-C, a-C, ta-C:H and a-C:H) were prepared on super hard alloy (WC-Co) substrate using a T-shape filtered arc deposition (T-FAD) system. At first, the film properties, such as structure, hydrogen content, density, hardness, elastic modulus, were measured. Ta-C prepared with a DC bias of −100 V showed the highest density (3.1 g/cm³) and hardness (70-80 GPa), and the lowest hydrogen content (less than 0.1 at. %). It was found that the hardness of the DLC film is proportional to approximately the third power of film density. The DLC films were then heated for 60 min in an electric furnace at 550 °C in N₂. Only the ta-C film hardly change its structure, although other films were graphitized. The 200-nm thick ta-C film was then heated for 60 min through the temperature range from 400 to 800 °C in N₂ with 2 vol.% of O₂ and the film structure found to be stable up to 700 °C. The substrate was oxidized at 800 °C, indicating the ta-C film had a thermal barrier function up to that temperature.     

Properties of PEDOT:PEG/ZnO/p-Si heterojunction diode

The zinc oxide (ZnO) and poly(3,4-ethylenedioxythiophene) bis-poly(ethyleneglycol) (PEDOT:PEG) films were deposited on p-Si substrate by sputter and spin coating methods, respectively. An organic/inorganic heterojunction diode having PEDOT:PEG/ZnO on p-Si substrate was fabricated. The barrier height (BH) and the ideality factor values for the device were found to be 0.82 ± 0.01 eV and 1.9 ± 0.01, respectively. It has been seen that the value of BH is significantly larger than those of conventional Au/p-Si metal–semiconductor contacts. The PEDOT:PEG/ZnO/p-Si heterostructure exhibits a non-ideal I–V behavior with the ideality factor greater than unity that could be ascribed to the interfacial layer, interface states and series resistance. The modified Norde's function combined with conventional forward I–V method was used to extract the parameters including the barrier height and series resistance. At the same time, the physical properties of ZnO and PEDOT:PEG films deposited by sputter and spin coating technique, respectively, were investigated at room temperature. The obtained results indicate that the electrical parameters of the diode are affected by structural properties of ZnO film and PEDOT:PEG organic film.     

Stable p-type conductivity and enhanced photoconductivity from nitrogen-doped annealed ZnO thin film

We report on the growth of p-type ZnO thin films with improved stability on various substrates and study the photoconductive property of the p-type ZnO films. The nitrogen doped ZnO (N:ZnO) thin films were grown on Si, quartz and alumina substrates by radio frequency magnetron sputtering followed by thermal annealing. Structural studies show that the N:ZnO films possess high crystallinity with c-axis orientation. The as-grown films possess higher lattice constants compared to the undoped films. Besides the high crystallinity, the Raman spectra show clear evidence of nitrogen incorporation in the doped ZnO lattice. A strong UV photoluminescence emission at ~ 380 nm is observed from all the N:ZnO thin films. Prior to post-deposition annealing, p-type conductivity was found to be unstable at room temperature. Post-growth annealing of N:ZnO film on Si substrate shows a relatively stable p-type ZnO with room temperature resistivity of 0.2 Ω cm, Hall mobility of 58 cm²/V s and hole concentration of 1.95 × 10¹⁷ cm^− 3. A homo-junction p-n diode fabricated on the annealed p-type ZnO layer showed rectification behavior in the current-voltage characteristics demonstrating the p-type conduction of the doped layer. Doped ZnO films (annealed) show more than two orders of magnitude enhancement in the photoconductivity as compared to that of the undoped film. The transient photoconductivity measurement with UV light illumination on the doped ZnO film shows a slow photoresponse with bi-exponential growth and bi-exponential decay behaviors. Mechanism of improved photoconductivity and slow photoresponse is discussed based on high mobility of carriers and photodesorption of oxygen molecules in the N:ZnO film, respectively.     

Microstructural, mechanical and electrochemical corrosion properties of sputtered titanium-aluminum-nitride films for bio-implants

The effect of aluminum (Al) addition to titanium nitride (TiN) matrix on the structural, mechanical and corrosion resistance properties of titanium-aluminum-nitride was studied. Ti_1−xAl_xN where x = 0, 0.5 and 1 films were coated onto substrates like Si wafer, AISI 316L stainless steel and low carbon steel by a direct current magnetron sputtering process. The layers were sputtered in pure Argon with a substrate temperature maintained at 400 °C, power of 250 W and a sputtering time of 120 min. XRD, TEM-SAED pattern and XPS analyses were made to study the structural properties of these films. Laser Raman spectrum showed the characteristic peaks at 249 and 659 cm⁻¹ for the Ti_0.5Al_0.5N film. AFM analysis showed a relatively smooth surface for the ternary film. Corrosion performance analysis indicated that the Ti_0.5Al_0.5N coated specimen had superior corrosion resistance when compared to TiN and AlN coated substrates. Higher values of nanohardness and lower coefficient of friction were observed for the Ti _0.5Al_0.5N specimen. Blood platelet adhesion experiments were made to examine the interaction between human blood and the materials in vitro.     

Growth and structural investigations of epitaxial hexagonal YMnO3 thin films deposited on wurtzite GaN(001) substrates

Epitaxial hexagonal YMnO₃ (h-YMnO₃) films having sharp (00l) X-ray diffraction peaks were grown above 700 °C in 5 mTorr O₂ via pulsed laser deposition both on as-received wurtzite GaN/AlN/6H-SiC(001) (w-GaN) substrates as well as on w-GaN surfaces that were etched in 50% HF solution. High-resolution transmission electron microscopy revealed an interfacial layer between film and the unetched substrate; this layer was absent in those samples wherein an etched substrate was used. However, the substrate treatment did not affect the epitaxial arrangement between the h-YMnO₃ film and w-GaN substrate. The epitaxial relationships of the h-YMnO₃ films with the w-GaN(001) substrate was determined via X-ray diffraction to be (001)_YMnO3 ‖ (001)_GaN : [11¯0]_YMnO3 ‖ [110]_GaN; in other words, the basal planes of the film and the substrate are aligned parallel to one another, as are the most densely packed directions in planes of the film and the substrate. Interestingly, this arrangement has a larger lattice mismatch than if the principal axes of the unit cells were aligned.     

Vibrational and AFM studies of adsorption of glycine on DLC and silicon-doped DLC

A better understanding of protein adsorption onto surfaces of materials is required to control biocompatibility and bioactivity. Diamond-like carbon (DLC) is known to have excellent biocompatibility. Various samples of a-C:H and silicon-doped a-C:H thin films (Si-DLC) were deposited onto silicon substrates using plasma-enhanced chemical vapour deposition (PECVD). Subsequently, the adsorption of the simplest amino acid glycine onto the surfaces of the thin films was investigated to elucidate the mechanisms involved in protein adhesion. The physicochemical characteristics of the surfaces, before and after adsorption of glycine, were investigated using Raman spectroscopy and atomic force microscopy (AFM). The Raman study highlighted a slight decrease in the I _D/I _G ratio with increasing the silicon dopant levels. Following exposure to glycine solutions, the presence of bands at ~1735 and ~1200 cm⁻¹ indicates that the adsorption of glycine onto the surfaces has taken place. Glycine was bound to the surfaces via both deprotonated carboxyl and protonated amino groups whilst, as the silicon content in the DLC film increased the adsorption of glycine decreased. AFM analysis showed that the surface roughness increased following exposure to glycine. These results show that at low silicon doping the adsorption of the amino acid was enhanced whilst increased doping levels led to a reduced adsorption compared to undoped DLC. Therefore, doping of DLC may provide an approach to control the protein adsorption.