Preparation of tetrahedral amorphous carbon films by filtered cathodic vacuum arc deposition

Tetrahedrally bonded amorphous carbon (ta-C) and nitrogen doped (ta-C:N) films were obtained at room temperature in a filtered cathodic vacuum arc (FCVA) system incorporating an off-plane double bend (S-bend) magnetic filter. The influence of the negative bias voltage applied to substrates (from −20 to −350 V) and the nitrogen background pressure (up to 10⁻³ Torr) on film properties was studied by scanning electron microscopy (SEM), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-ray photoemission spectroscopy (XPS), secondary ion mass spectroscopy (SIMS) and X-ray reflectivity (XRR). The ta-C films showed sp³ fractions between 84% and 88%, and mass densities around 3.2 g/cm³ in the wide range of bias voltage studied. In contrast, the compressive stress showed a maximum value of 11 GPa for bias voltages around −90 V, whereas for lower and higher bias voltages the stress decreased to 6 GPa. As for the ta-C:N films grown at bias voltages below −200 V and with N contents up to 7%, it has been found that the N atoms were preferentially sp³ bonded to the carbon network with a reduction in stress below 8 GPa. Further increase in bias voltage or N content increased the sp² fraction, leading to a reduction in film density to 2.7 g/cm³.     

Changes in chemical bonding of diamond-like carbon films by atomic-hydrogen exposure

We have deposited unhydrogenated diamond-like carbon (DLC) films on Si substrate by pulsed laser deposition using KrF excimer laser, and investigated the effects of atomic-hydrogen exposure on the structure and chemical bonding of the DLC films by photoelectron spectroscopy (PES) using synchrotron radiation and Raman spectroscopy. The fraction of sp³ bonds at the film surface, as evaluated from C1s spectra, increased at a substrate temperature of 400 °C by atomic-hydrogen exposure, whereas the sp³ fraction decreased at 700 °C with increasing exposure time. It was found that the sp³ fraction was higher at the surfaces than the subsurfaces of the films exposed to atomic hydrogen at both the temperatures. The Raman spectrum of the film exposed to atomic hydrogen at 400 °C showed that the clustering of sp² carbon atoms progressed inside the film near the surface even at such a low temperature as 400 °C.     

Hydrogen plasma etching of diamond films deposited on graphite

Poly- and nanocrystalline diamond films have been deposited using microwave plasma enhanced CVD with gas mixtures of x%CH₄/15%H₂/Ar (x = 0.5, 1, 3, and 5). After deposition the resulting films were exposed to a hydrogen plasma etching for 30 min. The hydrogen plasma produced preferential etching of non-diamond carbon on the surface of the samples and the development of steps and pits. Raman spectroscopy and X-ray photoelectron spectroscopy analyses on the etched films showed increased sp³/sp² ratio and decreased surface oxygen. The etch mechanism proposed is regression of pre-existing steps and step flow.     

Microstructure and tribological properties of ternary BCN thin films with different carbon contents

Boron carbon nitrogen (BCN) thin films with different carbon contents are deposited on high-speed steel substrates by reactive magnetron sputtering (RMS) and their microstructure and tribological properties are studied. The BCN films with carbon contents from 26.9 wt.% to 61.3 wt.% have an amorphous structure with variable amounts of carbon bonds (sp²C–C, sp²C–N and sp³C–N bonds). A higher carbon content enhances the film hardness but reduces the friction coefficient against GCr15 steel balls in air. BCN films with higher hardness, lower friction coefficient, and better wear resistance can be obtained by increasing the carbon content.     

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.     

Mechanical measurements of ultra-thin amorphous carbon membranes using scanning atomic force microscopy

The elastic modulus of ultra-thin amorphous carbon films was investigated by integrating atomic force microscopy (AFM) imaging in contact mode with finite element analysis (FEA). Carbon films with thicknesses of ～10 nm and less were deposited on mica by electron beam evaporation and transferred onto perforated substrates for mechanical characterization. The deformation of these ultra-thin membranes was measured by recording topography images at different normal loads using contact mode AFM. The obtained force-distance relationship at the center of membranes was analyzed to evaluate both the Young’s modulus and pre-stress by FEA. From these measurements, Young’s moduli of 178.9 ± 32.3, 193.4 ± 20.0, and 211.1 ± 44.9 GPa were obtained for 3.7 ± 0.08, 6.8 ± 0.12, and 10.4 ± 0.17 nm thick membranes, respectively. Raman spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy were used for characterizing the chemical and structural properties of the films, including the content of sp² and sp³ hybridized carbon atoms.     

Sp3/sp2 character of the carbon and hydrogen configuration in micro- and nanocrystalline diamond

Hot filament and microwave plasma CVD micro- nanocrystalline diamond films are analysed by visible and ultra-violet excitation source Raman spectroscopy. The sample grain size varies from 20 nm to 2 μm. The hydrogen concentration in samples is measured by SIMS and compared to the grain size, and to the ratio of sp² carbon bonds determined by Raman spectroscopy from the 1332 cm^− 1 diamond peak and the sp² 1550 cm^− 1 G band. Hydrogen concentration appears to be proportional to the sp² bonds ratio. The 3000 cm^− 1 CH_x stretching mode band intensity observed on the Raman spectra is decreasing with the G band intensity. Thermal annealing modifies the sp² phase structure and concentration, as hydrogen outdiffuses.     

Thermal grafting of organic monolayers on amorphous carbon and silicon (111) surfaces: A comparative study

Thermally-assisted (160 °C) liquid phase grafting of linear alkene molecules has been performed simultaneously on amorphous carbon (a-C) and hydrogen passivated crystalline silicon Si(111):H surfaces. Atomically flat a-C films with a high sp³ average surface hybridization, sp³ / (sp² + sp³) = 0.62, were grown using pulsed laser deposition (PLD). Quantitative analysis of X-ray photoelectron spectroscopy, X-ray reflectometry and spectroscopic ellipsometry data show the immobilization of a densely packed (> 3 × 10¹⁴ cm^? 2) single layer of organic molecules. In contrast with crystalline Si(111):H and other forms of carbon films, no surface preparation is required for the thermal grafting of alkene molecules on PLD amorphous carbon. The molecular grafted a-C surface is stable against ambient oxidation, in contrast with the grafted crystalline silicon surface.     

X-ray photoemission spectroscopy of nitrogen-doped UNCD/a-C:H films prepared by pulsed laser deposition

Nitrogen-doped ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) films were deposited by pulsed laser deposition (PLD). Nitrogen contents in the films were controlled by varying a ratio in the inflow amount between nitrogen and hydrogen gases. The film doped with a nitrogen content of 7.9 at.% possessed n-type conduction with an electrical conductivity of 18 Ω^? 1 cm^? 1 at 300 K. X-ray photoemission spectra, which were measured using synchrotron radiation, were decomposed into four component spectra due to sp², sp³ hybridized carbons, C=N and C–N. A full-width at half-maximum of the sp³ peak was 0.91 eV. This small value is specific to UNCD/a-C:H films. The sp²/(sp³ + sp²) value was enhanced from 32 to 40% with an increase in the nitrogen content from 0 to 7.9 at.%. This increment probably originates from the nitrogen incorporation into an a-C:H matrix and grain boundaries of UNCD crystallites. Since an electrical conductivity of a-C:H does not dramatically enhance for this doping amount according to previous reports, we believe that the electrical conductivity enhancement is predominantly due to the nitrogen incorporation into grain boundaries.     

Structure and characteristics of amorphous (Ti,Si)–C:H films deposited by reactive magnetron sputtering

The hydrogenated amorphous carbon films doped with Ti and Si ((Ti,Si)–C:H) were deposited on silicon substrates using reactive magnetron sputtering Ti₈₀Si₂₀ composite target in an argon and methane gas mixture. The structures of the films were analyzed by X-ray photoelectron spectroscopy and Visible Raman spectroscopy. The morphologies were observed by atomic force microscope. The friction coefficients of the films were tested on the ball-on-disc tribometer. The results indicate that the sp³/sp² ratios in the films can be varied from 0.18 to 0.63 by changing Ti and Si contents at various CH₄ flow rates. The surface of the films becomes smoother and more compact as the CH₄ flow rate increases. The lowest friction coefficient is as low as 0.0139 for the film with Ti of 4.5 at.% and Si of 1.0 at.%. Especially, the film exhibits a superlow value (μ < 0.01) under ambient air with 40% relative humidity in friction process. The superlow friction coefficient in ambient air may be, attributable to synergistic effects of a combination of Ti and Si in the film.     

Iron-mediated growth of epitaxial graphene on SiC and diamond

Ordered graphene films have been fabricated on Fe-treated SiC and diamond surfaces using the catalytic conversion of sp³ to sp² carbon. In comparison with the bare SiC (0 0 0 1) surface, the graphitization temperature is reduced from over 1000 °C to 600 °C and for diamond (1 1 1), this new approach enables epitaxial graphene to be grown on this surface for the first time. For both substrates, a key development is the in situ monitoring of the entire fabrication process using real-time electron spectroscopy that provides the necessary precision for the production of films of controlled thickness. The quality of the graphene/graphite layers has been verified using angle-resolved photoelectron spectroscopy, scanning tunneling microscopy and low energy electron diffraction. Graphene is only formed on treated regions of the surface and so this offers a method for fabricating and patterning graphene structures on SiC and diamond in the solid-state at industrially realistic temperatures.     

Very high temperature annealing effect on amorphous carbon films grown on refractory oxide substrates by pulsed laser deposition

We have carried out very high temperature heat treatment at 1400–2700 °C of about 10 nm-thick amorphous carbon thin films deposited on refractory substrates MgO, Al₂O₃, and yttria-stabilized zirconia (YSZ) using pulsed laser deposition techniques. After the annealing, a few nanometer scale sp² crystallization of the films and a large corrugation with a height of more than 1 μm were observed by Raman spectroscopy analysis and optical/atomic force microscopes, respectively. The corrugation is probably caused by the formation of gases at the film/substrate interface during the heat treatment.     

Bias enhanced diamond nucleation onto 3C–SiC(100) surfaces studied by high resolution X-ray photoelectron and high resolution electron energy loss spectroscopies

The nature of hydrogen and carbon bonding configuration formed onto 3C–SiC(100) surfaces by the diamond bias enhanced nucleation process consisting of stabilization and biasing stages were investigated by high resolution electron energy loss spectroscopy and high resolution X-ray photoelectron spectroscopy. During the stabilization stage a sp³-CH_x bonded carbonaceous mono-layer is formed onto a hydrogenated 3C–SiC(100)–C–H terminated surfaces. After the biasing stage a hydrogenated nano-diamond film is formed. It was determined that hydrogen is strongly bonded to these nano-diamond surfaces and boundaries in sp³-C–H and sp²-C–H mono-hydride configuration. In addition, CH_x (x > 1) weakly bonded surface or sub-surface species were detected. Regions which are not fully covered by the nano-diamond film expose the SiC surface covered with a very thin carbonaceous layer.     

Hydrogen incorporation,bonding and stability in nanocrystalline diamond films

The hydrogen concentration in hot filament and microwave plasma CVD nanocrystalline diamond films is analysed by secondary ion mass spectrometry and compared to the film grain size. The surface and bulk film carbon bonds are analysed respectively by X-ray photoelectron spectroscopy (XPS) and ultra-violet Raman spectroscopy. XPS results show the presence of the hydrogenated p-type surface conductive layer. The respective intensities of the 1332 cm^− 1 diamond peak, of the G and D bands related to sp² phases, and of the 3000 cm^− 1 CH_x stretching mode band, are compared on Raman spectra. The samples are submitted to thermal annealing under ultra-high vacuum in order to get hydrogen out-diffusion. XPS analysis shows the surface desorption of hydrogen. Thermal annealing modifies the sp² phase structure as hydrogen out diffuses.     

Substrate temperature effects on the microhardness and adhesion of diamond-like thin films

Diamond-like films were deposited on silicon substrates by r.f. plasma-enhanced chemical vapor deposition from gas methane. In this study, the substrate temperature, T_S, was varied in a wide range from 20 to 370°C while maintaining fixed other important process parameters such as r.f. power (70 W) or pressure (2.5 Pa). The increase of T_S causes an increase of the sp²/(sp²+sp³) bonded carbon ratio and a decrease of the hydrogen content. These changes produce a great modification of the mechanical properties: microhardness, friction coefficient and adhesion. The variations of mechanical properties with T_S correlate well with the sp²/(sp²+sp³) bonded carbon ratio and the hydrogen content in the films showing a gradual transformation of the diamond-like structure into a more sp²-rich one.     

A superhard diamond-like carbon film

A superhard hydrogen-free amorphous diamond-like carbon (DLC) film was deposited by pulsed arc discharge using a carbon source accelerator in a vacuum of 2×10⁻⁴ Pa. The growth rate was about 15 nm/min and the optimum ion-plasma energy was about 70 eV. The impact of doping elements (Cu, Zr, Ti, Al, F(Cl), N) on the characteristics of DLC films deposited on metal and silicon substrates was studied aiming at the choice of the optimum coating for low friction couples. The microhardness of thick (≥20 μm) DLC films was studied by Knoop and Vickers indentations, medium thick DLC films (1–3 μm) were investigated using a ‘Fischerscope’, and Young's module of thin films (20–70 nm) was studied by laser induced surface acoustic waves. The bonds in DLC films were investigated by electron energy loss spectroscopy (EELS), X-ray excited Auger electron spectroscopy (XAES), and X-ray photoelectron spectroscopy (XPS). The adhesion of DLC films was defined by the scratch test and Rockwell indentation. The coefficient of friction of the Patinor DLC film was measured by a rubbing cylinders test and by a pin-on-disk test in laboratory air at about 20% humidity and room temperature. The microhardness of the Patinor DLC film was up to 100 GPa and the density of the film was 3.43–3.65 g/cm³. The specific wear rate of the Patinor DLC film is comparable to that of other carbon films.     

Microstructure and optical band gap control of DLC film deposited by pulsed discharge plasma CVD

DLC films were deposited on silicon and quartz glass substrates by pulsed discharge plasma chemical vapor deposition (CVD), where the plasma was generated by pulsed DC discharge in H₂–CH₄ gas mixture at about 90 Torr in pressure, and the substrates were located near the plasma. The repetition frequency and duty ratio of the pulse were 800 Hz and 20%, respectively. When CH₄ / (CH₄ + H₂) ratio, i.e. methane concentration (Cm), increased from 3 to 40%, C₂ species in the plasma was increased, and corresponding to the increase of C₂, deposition rate of the film was increased from about 0.2 to 2.4 μm/h. The absorption peaks of sp³C–H and sp²C–H structures were observed in the FT-IR spectra, and the peak of sp²C–H structure was increased with increasing Cm, showing that sp² to sp³ bonding ratio was increased when Cm was increased. Corresponding to these structural changes due to the increase of Cm, optical band gap (Eg) was decreased from 3 to 0.5 eV continuously when Cm was increased from 3 to 40%.     

Effects of plasma treatments on the nitrogen incorporated nanocrystalline diamond films

The nitrogen incorporated nanocrystalline diamond (NCD) films were grown on n-silicon (100) substrates by microwave plasma enhanced chemical vapor deposition (MPECVD) using CH₄/Ar/N₂ gas chemistry. The effect of surface passivation on the properties of NCD films was investigated by hydrogen and nitrogen-plasma treatments. The crystallinity of the NCD films reduced due to the damage induced by the plasma treatments. From the crystallographic data, it was observed that the intensity of (111) peak of the diamond lattice reduced after the films were exposed to the nitrogen plasma. From Raman spectra, it was observed that the relative intensity of the features associated with the transpolyacetylene (TPA) states decreased after hydrogen-plasma treatment, while such change was not observed after nitrogen-plasma treatment. The hydrogen-plasma treatment has reduced the sp²/sp³ ratio due to preferential etching of the graphitic carbon, while this ratio remained same in both as-grown and nitrogen-plasma treated films. The electrical contacts of the as-grown films changed from ohmic to near Schottky after the plasma treatment. The electrical conductivity reduced from ~ 84 ohm^– 1 cm^− 1 (as-grown) to ~ 10 ohm^– 1 cm^− 1 after hydrogen-plasma treatment, while the change in the conductivity was insignificant after nitrogen-plasma treatment.     

Characterization of physical and biomedical properties of nitrogenated diamond-like carbon films coated on polytetrafluoroethylene substrates

A technique to coat hydrogen-free diamond-like carbon (DLC) films on polytetrafluoroethylene (PTFE) substrates has been developed by sputtering of a negatively biased graphite target in a mixture of argon and nitrogen plasma. The coated films were characterized by various methods to investigate their chemical, electronic features, and particularly their biomedical properties. DLC films produced by this method have up to 20% sp³ carbon bonds depending on the nitrogen concentration in the plasma. Raman spectroscopy revealed that, bond-disorder increases with nitrogen doping. The average grain size of DLC decreases in the nitrogen doped samples by almost 30%. The roughness of the uncoated PTFE substrate surfaces decreased dramatically from 660 nm to 170 nm after DLC coating. However, the nitrogen contents in the plasma have little effects on the roughness, the cluster size, and shapes. Electronic band gap of the samples decreases with adding nitrogen from ~ 2 eV in nitrogen-free samples to ~ 1 eV in nitrogenated samples. Lower adhesion and aggregation of platelets on PTFE surfaces coated with DLC-10% nitrogen and DLC-20% nitrogen have been observed while there is greater adhesion of platelets on DLC-30% nitrogen and DLC-40% nitrogen.     

Optical properties and new carbon forms of sputtered amorphous carbon films

Amorphous carbon films were deposited by r.f. magnetron sputtering at various bias voltages V_b applied on Si substrate. We studied the optical properties of the films using in situ spectroscopic ellipsometry (SE) measurements in the energy region 1.5–5.5 eV. From the SE data analysis the dielectric function ε(ω) of the a-C films was obtained, providing information about the electronic structure and the bonding configuration of a-C films. Based on the SE data the films are classified in three categories. In Category I and II belong the films developed with V_b≥0 V (rich in sp² bonds) and −100≤V_b<0 V (rich in sp³ bonds), respectively. The dielectric function of the films belonging in these two categories can be described with two Lorentz oscillators located in the energy range 2.5–5 eV (π–π^*) and 9–12 eV (σ–σ^*). A correlation was found between the oscillator strength and the sp² and sp³ contents. The latter were calculated by analyzing the ε(ω) with the Bruggeman effective medium theory. In films deposited with V_b<−100 V (Category III), the formation of a new and dense carbon phase was detected which exhibits a semi-metallic optical behavior and the ε(ω) can be described with two oscillators located at ∼1.2 and ∼5.5 eV.