Bonding defects and optical band gaps of DLC films deposited by microwave surface-wave plasma CVD

The effects of CH₄ / C₂H₄ flow ratio and annealing temperature on the defect states and optical properties of diamond-like carbon (DLC) films deposited by novel microwave surface-wave plasma chemical vapour deposition (MW SWP CVD) are studied through UV/VIS/NIR measurements, atomic force microscopy, Raman spectroscopy and electron spin resonance analysis. The optical band gap of DLC has been tailored between a relatively narrow range, 2.65–2.5 eV by manipulating CH₄ / C₂H₄ flow ratio and a wide range, 2.5–0.95 by thermal annealing. The ESR spin density varied between 10¹⁹ to 10¹⁷ spins/cm³ depending on the CH₄ / C₂H₄ flow ratio (1 : 3 to 3 : 1). The defect density increased with increasing annealing temperature. Also, there is a strong dependence of spin density on the optical band gap of the annealed-DLC films, and this dependency has been qualitatively understood from Raman spectra of the films as a result of structural changes due to sp³/sp² carbon bonding network. The surfaces of the films are found to be very smooth and uniform (RMS roughness < 0.5 nm).     

Properties of DLC films deposited by an oxyacetylene flame

Diamond-like carbon (DLC) films were obtained by spinning a tungsten carbide substrate at a high speed using an oxyacetylene flame. The films deposited at a typical experimental condition of substrate temperature of 810°C, rotation of 600 rpm and 3 h deposition time, exhibited an uniform, very smooth, hard and glassy surface covering the entire exposed face of the substrate. These films were identified as DLC by their characteristic broad Raman spectra centered at 1554 cm⁻¹ and micro-Vicker's hardness >3400 kg mm⁻². For substrate temperatures <800°C the film started losing the uniform glassy surface and the hardness deteriorated. For temperatures >950°C the film was still hard and shiny, but black in color. DLC films were also obtained in a wide range of speeds of rotation (300–750 rpm), as long as the temperature remained close to 850°C.     

Sulphur doped DLC films deposited by DC magnetron sputtering

Diamond‐like carbon (DLC) and sulphur doped diamond‐like carbon (S‐DLC) films were synthesised at different sulphur molar percentage of 0%, 2%, 5%, 8% and 10% by direct current (DC) magnetron sputtering process using novel compressed sulphur‐graphite targets at relatively low power density. Films were characterised for their morphologies, structural, electrical and optical properties. Scanning electron microscope images reveal changes in the quality of the obtained films shown by the denser packing of DLC grains at different sulphur percentage. The conductivities of S‐DLC films were found to be in the range of 6.0 × 10^?3–0.6/Ω cm. The optical band gap energies were found to be in the range of ～1.4–2.0 eV. Both electrical and optical measurements exhibit nonlinear responses with optimum at around 5% sulphur molar percentage (minimum for conductivity and maximum for optical band gap energy). These trends of change in both conductivity and optical band gap energy are consistent with the variation in bond characters of the films indicated by Raman spectroscopy. © 2011 Canadian Society for Chemical Engineering     

Photoconductivity of DLC film deposited by pulsed discharge plasma CVD

DLC films were deposited by a new pulsed DC discharge plasma chemical vapour deposition (CVD) using hydrogen and methane gas mixture. When methane concentration (Cm) i.e. CH₄/(H₂ + CH₄) was increased from 3 to 40%, the graphitization of the carbon film increases as evident from Raman study. When Cm was increased to 30%, DLC film shows photoconducting property. The white light photoconductivity (S = I_l/I_d, where I_l is light current and I_d is dark current) measured with solar simulator under AM 1.5 condition was approximately 20 at room temperature. The photoconductivity was not clear when Cm was lower than 20%. ESR measurements also show that the electron spin density was slightly decreased with decreasing concentration of methane. Thus we can conclude here that at higher concentrations of methane at 30%, Sp² content of the film increases and the DLC film becomes photoconducting.     

Mechanical properties of DLC films prepared inside of micro-holes by pulse plasma CVD

Diamond-like carbon (DLC) films are metastable amorphous carbon materials with superior tribological characteristics. In order to improve wear resistance of micro-extrusion dies with numerous imperceptible holes, DLC films were deposited on the inner wall surface of model dies with holes of 2 and 0.9 mm in diameter, and 20 mm in depth by using pulse plasma CVD method. This paper will discuss how argon gas, deposition pressure and time affect the characteristics of films deposited on the inner wall surface of dies. This micro-coating method can be applied widely for inner wall surface treatment of components with thin holes.     

Tribological properties of DLC films deposited on steel substrate with various surface roughness

Tribological properties of diamond-like carbon (DLC) films in water were investigated concerning with the influence of surface roughness and various mating materials. The DLC films were deposited by pulsed-bias CVD method on AISI630 stainless steel. The substrate roughness (R_a) is in the range of 1.4–740 nm. AISI 440C, AISI 304 stainless steel and brass balls were used as a mating ball. The friction coefficients of DLC films against with AISI 440C stainless steel ball indicated under 0.1 irrespective of the roughness. The film having smooth surface (R_a=1.4 nm) had severe damage at a load of 9.4 N. However, the film having rough surface (R_a=263 nm) had no damage at the same load. The specific wear rate of the steel ball increased with increase of roughness of the surface. In the case of AISI 304 stainless steel ball, the specific wear rate of the ball showed similar tendency. The friction with brass ball showed relatively high friction coefficient in the range of 0.12–0.25. However, the damage on the films could not be observed after friction test. It is considered that the roughness of the surface is important factor for the rupture of the film in water environment.     

Influence of plasma nitriding treatment on the adhesion of DLC films deposited on AISI 4140 steel by PVD magnetron sputtering

Duplex surface treatments composed of diamond like carbon (DLC) coating followed by plasma nitriding have drawn attention for a while. In this study, AISI 4140 steel substrates were plasma nitrided at different treatment temperatures and times. Then, DLC films were deposited on both untreated and plasma nitrided samples using PVD magnetron sputtering. The effect of different plasma nitriding temperatures and times on the structural, mechanical and adhesion properties of DLC coatings was investigated by XRD, SEM, microhardness tester and scratch tester, respectively. It was found that surface hardness, intrinsic stresses, layer thickness values and phase distribution in modified layers and DLC coating were the main factors on adhesion properties of duplex coating system. The surface hardness and residual stress values of AISI 4140 steel substrates significantly increased with both DLC coating and duplex surface treatment (plasma nitriding + DLC coating). Increasing plasma nitriding temperature and time also increased the diffusion depth and the thickness of modified layers. Hard surface layers led to a significant improvement on load bearing capacity of the substrate material. However, it was also determined that the process parameters, which provided lower intrinsic stresses, improved the adhesion properties of the duplex coating system.     

Stress and structural properties of diamond-like carbon films deposited by electron beam excited plasma CVD

Diamond-like carbon (DLC) films prepared using CH₄ or C₆H₆ with varying deposition parameters by an electron beam excited plasma CVD system were investigated for the internal stress, dynamic hardness and structural properties such as the film density, total, bonded and unbound hydrogen contents, sp³ ratio and graphite crystallite. From the correlations between internal stress and structural properties, the following conclusions were derived. The fraction of unbound hydrogen to total hydrogen content was the most influential factor for the compressive stress of the DLC films deposited from CH₄. It is suggested that unbound hydrogen may be trapped into the disordered microstructure of graphite crystallites embedded in the network of film. For the DLC films deposited from C₆H₆, it was shown that the compressive stress was correlated with not only the fraction of unbound hydrogen content but also the degree of cross-linking between graphite crystallites in the film.     

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%.     

DLC films by plasma assisted chemical vapor deposition near room temperature

This work concentrates on the preparation of diamond-like amorphous carbon films using a d.c. glow discharge with and without coupling to a microwave source. Films were deposited on single crystal silicon, glass and several plastics at temperatures between room temperature and 150°C. A variety of carbon containing feed gases have been used at pressures ranging from few milliTorrs to 1 Torr with an applied electric field up to 3300 V in⁻¹. The films obtained range from transparent to semi-transparent and can be very hard as observed by an ASTM scratch tester. The visible, IR and Raman spectra of the films have been obtained, and these are related to their structure and hardness. The DLC films grown on plastics were found to suffer from deformations due to the flexibility of the underlying material, and hence their performance was judged to be less than ideal despite the hardness of the overlying material. The results are discussed in terms of chemical composition and growth kinetics of the films.     

Electronic properties of hydrogenated amorphous carbon films deposited using ECR-RF plasma method

A combination of junction capacitance, electron spin resonance and electrical conductivity measurements are used to investigate the electronic properties of two different types of a-C:H films grown in a dual ECR-RF glow discharge system at substrate bias equal to −30 and −600 V, respectively. The analysis of the steady state admittance (both capacitance C and conductance G) as a function of frequency (ω=5 Hz–1 kHz) and temperature (20–350 K) allows an estimate of the density of states at the Fermi level of approximately 7×10¹⁵ and 9.7×10¹⁶ eV⁻¹ cm⁻³ for the −30 and −600 V deposited samples, respectively, values well below those deduced for the density of spins from the electron spin resonance experiments, of approximately 10¹⁹–10²⁰ cm⁻³. Concerning the conductance results, two transport processes operating, respectively, below and above 290 K are shown. The high temperature process is associated with an activation energy of 0.5 and 0.41 eV for the −30 and −600 V samples, respectively, in good agreement with the values obtained in the high temperature range (>300 K) for the activation energy of the electrical conductivity. Regarding the effect of the frequency and temperature on the conductance, we show that for temperatures below 290 K, a Variable Range Hopping mechanism is possible by facing our data to the Mott's model. Annealing at high temperature induces structural changes accompanied by an increase in the spin density in both types of samples with however, a different behaviour from one type to another.     

Stoichiometric cBN films deposited by electron-cyclotron-wave-resonance plasma sputtering of hBN

Electron-cyclotron-wave-resonance (ECWR) plasma of pure nitrogen was employed to deposit cBN thin films onto Si(100) substrates by hBN target sputtering. The ion current density and ion energy can be varied fairly independently. Deposition was achieved with ion energies between 70 and 230 eV. The cBN phase was identified with both Fourier transform-infrared spectroscopy (FT-IR) and high-resolution transmission electron microscopy (TEM). Thicker films with nearly 100% cBN phase in the upper layer appeared bright gray or transparent. A maximum thickness of 350 nm for the cBN layer was measured. The film growth follows the aBN→hBN→cBN sequence, with nanoarches being located at the hBN–cBN interface. Energy-dispersive X-ray (EDX) analysis verified the perfect stoichiometry of the deposits. Depending on the processing parameters the films displayed varied morphology. In particular, the surface of the film deposited at 74 eV exhibited large islands with diffuse boundaries on a compact base plane, suggesting the reduction of compressive stress at low ion energy.     

Structural and mechanical properties of DLC films prepared by bipolar PBII&D

In the present study, diamond-like carbon (DLC) films were prepared by bipolar plasma based ion implantation and deposition (PBII&D), and the structural and mechanical properties of the DLC films deposited on Si substrates were evaluated by Raman spectroscopy. In the PBII&D processing, the positive and negative pulse voltages were varied from 1 to 3 kV and from ? 1 to ? 15 kV, respectively. With an increase in the pulse voltages, the Raman G-peak position and I(D) / I(G) ratio increased, and the G-peak full width at half maximum (FWHM(G)) decreased, indicating graphitization of the DLC films. In the low wavenumber regime, the FWHM(G) increases when the G-peak shifts to higher wavenumbers, reaching a maximum value at around 1540 cm^? 1, and then decreases. This behavior was due to the structural changes occurring in the DLC films with an increase in the wavenumber. DLC to polymer-like carbon (PLC) transition occurred in the low wavenumber regime, and DLC to graphite-like carbon (GLC) transition occurred in the high wavenumber regime. Further, two different trends were observed in the relationship between the mechanical properties (hardness, elastic modulus, and internal stress) of the DLC films and the FWHM(G), originating from the structural change from DLC to GLC and PLC.     

Microstructure and mechanical properties of Mo/DLC nanocomposite films

Mo-doped diamond-like carbon (Mo/DLC) films were deposited on stainless steel and Si wafer substrates via unbalanced magnetron sputtering of molybdenum combined with inductively coupled radio frequency (RF) plasma chemical vapor deposition of CH₄/Ar. The effects of Mo doping and sputtering current on the microstructure and mechanical properties of the as-deposited films were investigated by means of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, atomic force microscopy (AFM), and nano-indentation. It was found that Mo doping led to increase in the content of sp² carbon, and hence decreased the hardness and elastic modulus of Mo/DLC films as compared with that of DLC films. The content of Mo in the films increased with the increasing sputtering current, and most of Mo reacted with C atoms to form MoC nanocrystallites at a higher sputtering current. Moreover, the Mo-doped DLC films had greatly decreased internal stress and increased adhesion to the substrate than the DLC film, which could be closely related to the unique nanocomposite structure of the Mo-doped films. Namely, the Mo/DLC film was composed of MoC nanoparticles embedded in the cross-linked amorphous carbon matrix, and such a kind of nanostructure was beneficial to retaining the loss of hardness and elastic modulus.     

Thermal stability of the optical properties of plasma deposited diamond-like carbon thin films

In present paper we studied the optical constants of the diamond-like carbon (DLC) films and their changes with annealing. The multisample modification of combined variable angle spectroscopic ellipsometry and near normal spectroscopic reflectometry was used. The optical constants of the DLC films were simulated by our recently published six-parameter dispersion model employing a parameterization of the density of electronic states (DOS). Based on the dispersion model parameters the density of π and σ electrons were evaluated. We showed that from our model and the independently determined hydrogen atomic fraction of the films before and after annealing the ratio between momentum matrix elements of π → π* and σ → σ* transitions and the correct sp³-to-sp² carbon bonding configuration ratio can be calculated. It is worth to notice that the first quantity is usually assumed to be equal to unity but we showed that this assumption may cause a significant error in the determination of the sp³-to-sp² ratio. Therefore, our suggested method represents a novelty in this field.     

Characterization of thick and soft DLC coatings deposited on plasma nitrided austenitic stainless steel

Thick and soft a-C:H:Si coatings containing more than 45% hydrogen (thickness: 25–27 μm, hardness: 6 GPa, Young's Modulus 38 GPa and low ratio of sp³ bonds) were deposited by PACVD with a DC pulsed discharge on nitrided (duplex sample) and non-nitrided austenitic stainless steel (coated sample). After deposition, the chemical, microstructural and tribological properties were studied. Finally, the adhesion and the atmospheric corrosion resistance of a-C:H:Si coatings were also investigated.In pin-on-disk tests, the friction coefficient using an alumina pin of 6 mm in diameter as counterpart, under 0.59 GPa Hertzian pressure was 0.05 for the coated samples and 0.076 for the duplex samples. These values were more than one order of magnitude smaller than the friction coefficient of the nitrided sample without coating, which was around 0.65. In the coated samples, the wear loss could not be measured. In ball-on-disk tests under dry sliding conditions, the coatings were tested under different Hertzian pressures (1.29, 1.44 and 1.57 GPa) using a steel ball with a diameter of 1.5 mm as counterpart. Using a normal load of 9 N, the a-C:H:Si coating of the coated samples was broken and detached thus leading to a coefficient of friction of around 0.429. However, in contrast to that, the friction coefficient of the duplex samples remained stable and reached as maximum a value of 0.208.In abrasive tests, mass loss was undetectable in both duplex and coated samples. Furthermore it could be seen that the a-C:H:Si film showed only some smaller grooves and no severe damage or deformation. On the contrary, severe damage was observed in the only nitrided sample. With respect to adhesion, the critical load to break the coating was higher in the duplex sample (27 N) than in the only coated sample (16.3 N). By chemical analysis using the salt spray fog test, the duplex sample remained clean, but the coated sample failed and presented film delamination as well as general corrosion.     

Characterization of amorphous carbon films deposited by surface wave plasma CVD

Many dangling bonds in hydrogenated amorphous carbon (a-C:H) films are usually generated by bombardments of high-energy ion precursors in typical chemical vapor deposition (CVD). To generate low dangling bonds, a-C:H films should be deposited from low-energy radical species. Surface wave plasma (SWP) generates low-energy and high-density radicals. We prepare a-C:H films using SWP and investigate the relationship between the plasma characteristics and structures of a-C:H films. The microwave of the TM01 mode was introduced through the dielectric window and SWP generate under the dielectric window. An Ar and C₂H₂ plasma mixture mainly consists of neutral radical species, and the electron temperature is as low as 1 eV. Electron density significantly decreases with increasing distance from the dielectric window. The a-C:H films are prepared from these hydrocarbon and carbon low-energy radicals as main precursors. The sp² bonded network cluster size in a-C:H films increase with electron density in SWP. This structure change is the influence of the termination structure of clusters changing to CH from CH₃ and CH₂.     

Antibacterial activity of DLC and Ag–DLC films produced by PECVD technique

Diamond-like carbon (DLC) films have been the focus of extensive research in recent years due to its potential application as surface coatings on biomedical devices. Doped carbon films are also useful as biomaterials. As silver (Ag) is known to be a potent antibacterial agent, Ag–DLC films have been suggested to be potentially useful in biomedical applications. In this paper, DLC films were growth on 316L stainless steel substrates by using Plasma Enhanced Chemical Vapour Deposition (PECVD) technique with a thin amorphous silicon interlayer. Silver colloidal solution was produced by eletrodeposition of silver electrodes in distilled water and during the deposition process it was sprayed among each 25 nm thickness layer DLC film. The antibacterial activity of DLC, Ag–DLC and silver colloidal solution were evaluated by bacterial eradication tests with Escherichia coli (E. coli) at different incubation times. With the increase of silver nanoparticle layers in Ag–DLC, the total compressive stress decreased significantly. Raman spectra showed the film structure did not suffer any substantial change due to the incorporation of silver. The only alteration suffered was a slightly reduction in hardness. DLC and Ag–DLC films demonstrated good results against E. coli, meaning that DLC and Ag–DLC can be useful to produce coatings with antibacterial properties for biomedical industry.     

Capacitance properties of electrochemically deposited polyazulene films

Polyazulene films formed by electrochemical oxidation of azulene have been studied as active components in electrochemical capacitors. The film shows reversible electrochemical behavior in the positive potential range and exhibits p-doping properties. The influence of film formation conditions on the films electrochemical properties has been investigated. A strong effect of solvent on the polyazulene deposition has been observed. The highest yield of film deposition was found for dichloromethane. Polyazulene films also exhibit stable voltammetric properties in aprotic solvents. The voltammetric response of the film is affected by the size of the anion of the supporting electrolyte. In solutions containing tetra(alkyl)ammonium perchlorates, tetrafluoroborates or hexafluorophosphates, reversible oxidation of polyazulene is obtained. In the presence of large tetra(phenyl)borate anions, polyazulene is irreversibly oxidized upon electrochemical oxidation. The capacitance properties of these materials have been investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The polyazulene film displays a relatively high specific capacitance close to 400 F g⁻¹. Such high value of C_s locates this material among very good polymeric redox pseudo-capacitors.     

Etching of DLC films using a low intensity oxygen plasma jet

This article describes the characteristics of the etching process of diamond-like carbon (DLC) films using a new plasma system based on an oxygen plasma jet which comprises charged particles and activated neutral species in a range of energies and fluxes suitable for the etching process. This plasma source was used to etch DLC films which were grown on silicon substrates by magnetron sputtering technique. Prior to etching these films were characterized by different methods, namely Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), current×voltage curves and atomic force microscopy (AFM). Etch rates in the range 7.0–25 nm/min were measured for substrates placed at different positions along the axis of the plasma jet. An attractive feature observed in this work was the influence of an axial magnetic field applied to improve the confinement of the plasma stream. An increase by a factor of 3.4 in the etch rate was verified when the magnetic field increased from 2.5 to 6.0 mT. Raman spectra features (line shapes, frequencies and line width) of the etched films were compared with those obtained before etching. The results show that this plasma jet etching is a reliable technique for DLC film processing.