Diamond-like carbon films synthesized under atmospheric pressure synthesized on PET substrates

Diamond-like carbon films were synthesized under atmospheric pressure (AP-DLC) and their gas barrier properties and hardness were measured. The AP-DLC films were uniformly obtained by RF-plasma CVD method at room temperature with a size of 450 mm². The growth rate increased as a function of C₂H₂ concentration and the average growth rate was around 12 μm/min. The maximum deposition rate was ~ 1 μm/s, which is approximately 2000 times larger than that by low-pressure plasma CVD of 1–2 μm/h. The gas barrier properties of AP-DLC films, ~ 1 μm thick, were 5–10 times larger than those of uncoated PET substrates. The microhardness of AP-DLC films was around 3 GPa, measured by the nano-indentation method. The issue lies in the removal of macro-particles of the films to improve the microhardness and the surface roughness.In this paper, we report the physical properties of DLC films synthesized under atmospheric pressure by the radio-frequency CVD method. We also summarize a brief history of PET bottle coating by vacuum-DLC films, as well as that of the development of atmospheric pressure technology and related DLC films, focused on gas barrier properties and micro-hardness.     

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.     

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.     

Electron field emission from filtered arc deposited diamond-like carbon films using Au and Ti layers

In this work, tetrahedral diamond-like carbon (DLC) films are deposited on Si, Ti/Si and Au/Si substrates by a new plasma deposition technique — filtered arc deposition (FAD). Their electron field emission characteristics and fluorescent displays of the films are tested using a diode structure. It is shown that the substrate can markedly influence the emission behavior of DLC films. An emission current of 0.1 μA is detected at electric field E_DLC/Si=5.6 V/μm, E_DLC/Au/Si=14.3 V/μm, and E_DLC/Ti/Si=5.2 V/μm, respectively. At 14.3 V/μm, an emission current density J_DLC/Si=15.2 μA/cm², J_DLC/Au/Si=0.4 μA/cm², and J_DLC/Ti/Si=175 μA/cm² is achieved, respectively. It is believed that a thin TiC transition layer exists in the interface between the DLC film and Ti/Si substrate.     

Influence of UV-laser radiation on the synthesis of DLC films by ECR-plasma-CVD

Simultaneous UV-laser irradiation during the deposition of DLC films has been found to significantly influence the growth process and to favourably modify the film properties. The influence of the spectral and energetic parameters of laser radiation was investigated with respect to the optical, structural and mechanical properties of DLC films. Detailed investigations on the mechanism of laser-induced structural transformations in DLC films are presented, as studied by Raman spectroscopy. Further, the characteristic peak for the nanocrystalline diamond phase at 1140 cm⁻¹ was evident for irradiated films. Noteworthy is the increase in film microhardness with increasing energy of the deposited carbon ions with a simultaneous reduction in internal stresses, caused by photolytically induced modification of the film structure by UV-laser radiation. As a result, hard (up to 30 GPa) and thick (up to 3 μm) defect-free DLC films without cracks have been synthesized.     

Diamond-like carbon thin film with controlled zeta potential for medical material application

With the purpose of applying diamond-like carbon (DLC) thin films as a biocompatible material, we experimented with introducing functional groups such as amino and carboxyl groups to the surface of DLC thin films by plasma surface treatment. From the results, it was found that the contact angle values of the DLC thin films surface were decreased with increasing in the OCO bonded network on the surface. Measurement of the zeta potential when the amounts of the functional groups were varied showed that this successfully varied the zeta potential over the wide range of − 48 mV to + 12 mV. It was found that when carboxyl groups are introduced by O₂ plasma modification of the DLC thin films surface, the zeta potential was lower than that of untreated DLC thin films sample. It was also found that amino groups can be introduced to the DLC thin films surface by NH₃ plasma treatment, the zeta potential was higher than that of untreated DLC thin films sample. This means that zeta potential of the DLC thin films can also be controlled by controlling these two functional groups. Therefore, we have succeeded in developing a multifunctional DLC thin films that does not use polymers and is suitable as a biocompatible material.     

Preparation of diamond like carbon thin films above room temperature and their properties

Diamond like carbon (DLC) thin films were deposited on p-type silicon (p-Si), quartz and ITO substrates by microwave (MW) surface-wave plasma (SWP) chemical vapor deposition (CVD) at different substrate temperatures (RT ∼ 300 °C). Argon (Ar: 200 sccm) was used as carrier gas while acetylene (C₂H₂: 20 sccm) and nitrogen (N: 5 sccm) were used as plasma source. Analytical methods such as X-ray photoelectron spectroscopy (XPS), FT-IR and UV–visible spectroscopy were employed to investigate the structural and optical properties of the DLC thin films respectively. FT-IR spectra show the structural modification of the DLC thin films with substrate temperatures showing the distinct peak around 3350 cm^− 1 wave number; which may corresponds to the sp² C–H bond. Tauc optical gap and film thickness both decreased with increasing substrate temperature. The peaks of XPS core level C 1 s spectra of the DLC thin films shifted towards lower binding energy with substrate temperature. We also got the small photoconductivity action of the film deposited at 300 °C on ITO substrate.     

Monochromatic photoluminescence obtained from embedded ZnO nanodots in an ultrahard diamond-like carbon matrix

At room temperature, we observe the self assembly of nanoclusters in an amorphous matrix using a vacuum deposition technique. Self-assembled ZnO nanoclusters embedded in hard diamond-like amorphous carbon thin films, deposited by high vacuum Filtered Cathodic Vacuum Arc (FCVA) technique at room temperature without post-processing, have been observed. A selective self assembly of metal and oxygen ions in a 3-element plasma was observed. XPS distinctly showed presence of ZnO and DLC-mixture in 5, 7 and 10 at.% Zn (in target) films while maintaining high sp³ content. This in turn improved the Young's modulus value of the ZnO nanoclusters embedded in DLC film (~ 220 GPa) compared to bulk ZnO (~ 110 GPa). Films with ZnO detected were observed to exhibit absorption edge at 377 nm monochromatic UV light emissions. This corresponded to a band gap value of about 3.30 eV. The emission with greatest intensity (after normalization) was detected from 10 at.% Zn (in target) film where presence of ZnO nanoclusters (~ 40 nm) in DLC matrix were confirmed by TEM. This showed that well-defined crystalline ZnO nanoclusters contributed to strong PL signal. Strong monochromatic emissions detected hinted that no defect states were present.     

The effect of refractive index on the friction coefficient of DLC coated polymer substrates

This paper describes the enhanced mechanical performance that can be achieved by the application of diamond-like carbon (DLC) coatings to polymer substrates. The polymers coated are silicone and polyethylene, and the effect on the friction coefficient is studied. Film adhesion is found to depend on the DLC film refractive index (n), whereas the friction is largely independent of n in the range studied. Films were deposited from a He/C₂H₂ mixture at 20 Pa (0.15 Torr) on to the polymer substrates placed on a 10-cm-diameter electrode driven at 13.56 MHz. Film growth was monitored by in-situ ellipsometry (at 675 nm), which was performed on a glass slide placed near the polymer substrate. Friction measurements were obtained using a pin-on-disk tribometer, and measurements were carried out using a stainless-steel pin at a linear speed of 6 cm s⁻¹. Film adhesion was evaluated using a pull-adhesion tester. It was found that DLC coatings adhere well to the polymer substrates and can significantly reduce the friction coefficient of polymers such as silicone. Higher refractive index films (which are harder and have a higher mechanical strength) were found to have a poorer adhesion and provide a slightly increased friction on the polymer surface when compared to lower-index films. This study indicates that DLC may be used to enhance the tribological properties of polymers with potential applications in the biomaterials and light-engineering industries.     

Effect of oxygen plasma treatment on non-thrombogenicity of diamond-like carbon films

The non-thrombogenicity of oxygen-plasma-treated DLC films was investigated as surface coatings for medical devices. DLC films were deposited on polycarbonate substrates by a radio frequency plasma enhanced chemical vapor deposition method using acetylene gas. The deposited DLC films were then treated with plasma of oxygen gas at powers of 15 W, 50 W, and 200 W. Wettability was evaluated by water contact angle measurements and the changes in surface chemistry and roughness were examined by X-ray photoelectron spectroscopy and atomic force microscope analysis, respectively. Each oxygen-plasma-treated DLC film exhibited a hydrophilic nature with water contact angles of 11.1°, 17.7° and 36.8°. The non-thrombogenicity of the samples was evaluated through the incubation with platelet-rich plasma isolated from human whole blood. Non-thrombogenic properties dramatically improved for both 15 W- and 50 W-oxygen-plasma-treated DLC films. These results demonstrate that the oxygen plasma treatment at lower powers promotes the non-thrombogenicity of DLC films with highly hydrophilic surfaces.     

Effect of substrate bias voltage on the properties of diamond-like carbon thin films deposited by microwave surface wave plasma CVD

Diamond-like carbon (DLC) thin films were deposited on silicon and ITO substrates with applying different negative bias voltage by microwave surface wave plasma chemical vapor deposition (MW SWP-CVD) system. The influence of negative bias voltage on optical and structural properties of the DLC film were investigated using X-ray photoelectron spectroscopy, UV/VIS/NIR spectroscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. Optical band gap of the films decreased from 2.4 to 1.7 with increasing negative bias voltage (0 to − 200 V). The absorption peaks of sp³ CH and sp² CH bonding structure were observed in FT-IR spectra, showing that the sp²/sp³ ration increases with increasing negative bias voltage. The analysis of Raman spectra corresponds that the films were DLC in nature.     

Synthesis and mechanical properties of carbon nanotube/diamond-like carbon composite films

Diamond-like carbon (DLC) coatings were successfully deposited on carbon nanotube (CNT) films with CNT densities of 1 × 10⁹/cm², 3 × 10⁹/cm², and 7 × 10⁹/cm² by a radio frequency plasma-enhanced chemical vapor deposition (CVD). The new composite films consisting of CNT/DLC were synthesized to improve the mechanical properties of DLC coatings especially for toughness. To compare those of the CNT/DLC composite films, the deposition of a DLC coating on a silicon oxide substrate was also carried out. A dynamic ultra micro hardness tester and a ball-on-disk type friction tester were used to investigate the mechanical properties of the CNT/DLC composite films. A scanning electron microscopic (SEM) image of the indentation region of the CNT/DLC composite film showed a triangle shape of the indenter, however, chippings of the DLC coating were observed in the indentation region. This result suggests the improvement of the toughness of the CNT/DLC composite films. The elastic modulus and dynamic hardness of the CNT/DLC composite films decreased linearly with the increase of their CNT density. Friction coefficients of all the CNT/DLC composite films were close to that of the DLC coating.     

Experimental study on the stability of graphitic C3N4 under high pressure and high temperature

The stability and decomposition of graphitic C₃N₄ (g-C₃N₄) were studied in the pressure and temperature range of 10–25 GPa and up to 2000 °C by multi-anvil experiments and phase characterization of the quenched products. g-C₃N₄ was found to remain stable at relatively mild temperatures, but decomposes to graphite and nitrogen at temperatures above 600–700 °C and up to 15 GPa, while it decomposes directly to diamond (plus nitrogen) above 800–900 °C and between 22 and 25 GPa. The estimated decomposition curve for g-C₃N₄ has a positive slope (~ 0.05 GPa/K) up to ~ 22 GPa, but becomes inverted (negative) above this pressure. The diamond formed through decomposition is characterized by euhedral crystals which are not sintered to each other, but loosely aggregated, suggesting the crystallization in a liquid (nitrogen) medium. The nitrogen release from the graphitic CN framework may also play an important role in lowering the activation energy required for diamond formation and enhancing the grain growth rate. No phase transition of g-C₃N₄ was found in the studied P–T range.     

Influence of substrate bias voltage on structure and properties of hard Si–B–C–N films prepared by reactive magnetron sputtering

We systematically investigated the effect of the rf induced negative substrate bias voltage, U_b, on characteristics of novel quaternary Si–B–C–N films. The films were deposited on Si(100) or glass substrates by reactive dc magnetron co-sputtering of silicon, boron and carbon from a single C–Si–B or B₄C–Si target in nitrogen–argon gas mixtures at substrate temperatures of 180–350 °C. Elemental compositions of the films, their surface bonding structure, and mechanical and electrical properties were primarily controlled by the U_b values, varied from a floating potential (being between − 30 and − 40 V) to U_b = − 700 V. The energy and flux of ions bombarding the target and the growing films were evaluated on the basis of the measured discharge characteristics. The films were found to be amorphous with thickness up to 5 μm and density around 2.4 g/cm³. They exhibited hardness up to 44 GPa, modified Young's modulus between 170 and 280 GPa, elastic recovery up to 82% and good adhesion to substrates at a low compressive stress (0.6–1.8 GPa). The results of stress measurements were compared with predictions of the model developed by Davis and a beneficial role of silicon in reducing the compressive stress in the films was proved. Electrical conductivity of the semiconductive Si–B–C–N films with a high (approximately 40 at.%) carbon content was controlled by the nitrogen–argon gas mixture composition and the U_b values.     

Deposition of mechanically hard amorphous carbon nitride films with high [N] / ([N] + [C]) ratio

Mechanically hard amorphous carbon nitride films were prepared by a combination of negative radio frequency (RF) bias voltage (− V_RF) applied to a substrate and chemical vapor deposition using a decomposition reaction of BrCN with a microwave discharge flow of Ar. A pulsed operation of − V_RF was effective when − V_RF > 40 V to avoid excess sputtering of films. The [N] / ([N] + [C]) ratios of films were ≈ 0.5 irrespective of the application of − V_RF. The maximum hardness was 36 ± 10 GPa for the film obtained under the conditions of − V_RF = 100 V, a pulse period of 1000 s, and a pulse-on time of 800 s. According to the IR spectra, the intensity of the stretching vibration of the CN bond increased by the application of − V_RF. The Raman spectra showed increases in the relative intensity and width of the D-band. From these observations, the mechanism of film hardening was discussed.     

Temperature effect on bonding structures of amorphous carbon containing more than 30at.% silicon

Bonding evolution of amorphous carbon incorporated with Si or a-C(Si) in a thermal process has not been studied. Unhydrogenated a-C(Si) films were deposited by magnetron sputtering to undergo two different thermal processes: i) sputter deposition at substrate temperatures from 100 to 500 °C; ii) room temperature deposition followed by annealing at 200 to 1000 °C. The hardness of the films deposited at high temperature exhibits a monotonic decrease whereas the films deposited at room temperature maintained their hardness until 600 °C. X-ray photoelectron spectroscopy and Raman spectroscopy were used to analyze the composition and bonding structures. It was established that the change in the mechanical property is closely related to the atomic bonding structures, their relative fractions and the evolution (conversion from C–C sp³ → CC sp² or CC sp² → C–Si sp³) as well as clustering of sp² structures.     

Electrical and optical properties of diamond-like carbon films deposited by pulsed laser ablation

Pulsed laser ablation of a graphite target was carried out by ArF excimer laser deposition at a laser wavelength of 193 nm and fluences of 10 and 20 J/cm² to produce diamond-like carbon (DLC) films. DLC films were deposited on silicon and quartz substrates under 1 × 10^? 6 Torr pressure at different temperatures from room temperature to 250 °C. The effect of temperature on the electrical and optical properties of the DLC films was studied. Laser Raman Spectroscopy (LRS) showed that the DLC band showed a slight increase to higher frequency with increasing film deposition temperature. Spectroscopic ellipsometry (SE) and ultraviolet–visible absorption spectroscopy showed that the optical band gap of the DLC films was 0.8–2 eV and decreased with increasing substrate temperature. These results were consistent with the electrical resistivity results, which gave values for the films in the range 1.0 × 10⁴–2.8 × 10⁵ Ω cm and which also decreased with deposition temperature. We conclude that at higher substrate deposition temperatures, DLC films show increasing graphitic characteristics yielding lower electrical resistivity and a smaller optical band gap.     

Structural and mechanical properties of NbN and Nb-Si-N films: Experiment and molecular dynamics simulations

The structural and mechanical properties of NbN and Nb-Si-N films have been investigated both experimentally and theoretically, in their as-deposited and annealed states. The films were deposited using magnetron sputtering at substrate bias (U_B) between 0 and −70 V. While NbN films were found to crystallize in the cubic δ-NbN structure, Nb-Si-N films with Si content of 11–13 at% consisted of a two-phases nanocomposite structure where δ-NbN nanocrystals were embedded in SiN_x amorphous matrix. Films deposited at U_B=0 V were highly (001)-textured. Application of substrate bias potential led to a depletion of light atoms, and caused a grain size refinement concomitantly with the increase of (111) preferred orientations in both films. The maximum hardness was 28 GPa and 32 GPa for NbN and Nb-Si-N films, respectively. NbN and Nb-Si-N films deposited at U_B=−70 V exhibited compressive stress of −3 and −4 GPa, respectively. After vacuum annealing, a decrease in the stress-free lattice parameter was observed for both films, and attributed to alteration of film composition. To obtain insights on interface properties and related mechanical and thermal stability of Nb-Si-N nanocomposite films, first principles molecular dynamics simulations of NbN/SiN_x heterostructures with different structures (cubic and hexagonal) and atomic configurations were carried out. All the hexagonal heterostructures were found to be dynamically stable and weakly dependent on temperature. Calculation of the tensile strain-stress curves showed that the values of ideal tensile strength for the δ-NbN(111)- and ε-NbN(001)-based heterostructures with coherent interfaces and Si₃N₄–like Si₂N₃ interfaces were the highest with values in the range 36–65 GPa, but lower than corresponding values of bulk NbN compound. This suggests that hardness enhancement is likely due to inhibition of dislocation glide at the grain boundary rather than interfacial strengthening due to Si-N chemical bonding.     

Molecular structure of SiOx-incorporated diamond-like carbon films; evidence for phase segregation

Silicon-oxide incorporated amorphous hydrogenated diamond-like carbon films (SiO_x–DLC, 1 ≤ x ≤ 1.5) containing up to 24 at.% of Si (H is excluded from the atomic percentage calculations reported here) were prepared using pulsed direct current plasma-enhanced chemical vapour deposition (DC-PECVD). Molecular structure, optical properties and mechanical properties of these films were assessed as a function of Si concentration. The spectroscopic results indicated two structural regimes. First, for Si contents up to ~ 13 at.%, SiO_x–DLC is formed as a single phase with siloxane, O–Si–C₂, bonding networks. Second, for films with Si concentrations greater than 13 at.%, SiO_x–DLC with siloxane bonding and SiO_x deposit simultaneously as segregated phases. The variations in mechanical properties and optical properties as a function of Si content are consistent with the above changes in the film composition.     

Comparison of the wear particle size distribution of different a-C coatings deposited by vacuum arc

For biomedical application in the field of artificial hip joints diamond-like carbon (DLC) coatings have been widely studied due to their tribological properties. The wear particles as the main factor limiting the life expectancy of hip joints have attracted more and more interest, not only the number of them, but also the distribution of their size. In this study we have deposited DLC coatings on stainless steel (P2000) by a vacuum arc adjustable from anodic to cathodic operation mode, with the anode–cathode diameter ratio of d_a/d_c = 3/1 at a DC bias of − 250 V to − 1000 V. To improve the adhesion of the DLC coating on P2000, titanium as a metallic interlayer was deposited by cathodic vacuum arc evaporation. The internal structure of the coating was investigated by the visible Raman spectroscopy with the four-Gaussian curve fitting method. Comparing the results with the previous work (coatings deposited with d_a/d_c = 1/1), it was found that the anode–cathode diameter ratio has an effect on the structure (e.g. I_D/I_G) as well as the wear particle size distribution. It was shown that the maximum of the frequency distribution e.g. at − 1000 V bias can be shifted to below 1 μm with increasing d_a/d_c.