Doped Diamond-like Carbon Research Articles

Conductive Polymer Composites And Coated Metals As Alternative Bipolar Plate Materials For All-vanadium Redox-flow Batteries

In this study polypropylene (PP) based conductive composites and metal doped diamond like carbon (DLC) coated metallic substrates are studied as alternative bipolar materials for all-vanadium redox flow battery (VRFB). Graphite and carbon nanotube (CNT) filled PP based bipolar plates were produced via twin-screw co-rotating extruder and injection molding. Addition of 3 wt. % CNTs into highly filled graphite-PP matrix increased in-plane and through-plane electrical conductivities from 10 S/cm to 50 S/cm and from 2 S/cm to 10 S/cm respectively. PP composites with 78 wt. % graphite and 2 wt. % CNT filling ratio showed flexural strength value of 48,01 MPa. Produced bipolar plates were examined with galvanostatic charge- discharge test in a single-cell VRFB. Energy efficiency of 85,43 % at 25 mA/cm2 and discharge power density of 78,48 mW/cm2 at 75 mA/cm2 were achieved and those values were found to be comparable with commercial bipolar plates. Titanium, vanadium, chromoium and tungsten doped diamond-like coating (DLC) films were coated on metallic substrates (e.g. stainless steel 1.4301 and titanium alloy 3.7165) by a physical vapor deposition. The metallic dopant is necessary to achieve high conductivities in the order of ~100 S/cm. The values range from 0.5 to 35 S/cm for in-plane and from 10 to 110 S/cm for through-plane. The hydrogen evolution reaction (HER) and the anodic corrosions stability in 2 molar sulfuric acid constituted the main focus area for our investigations on metallic bipolar plates. An interesting material for coated metallic bipolar plate is the 10 µm Ti-DLC on 1.4301 which exhibits the highest hydrogen evolution overpotential of all investigated materials (710 mV µA/cm²). It also showed improved corrosion stability for anodic potentials. Copyright © 2014 VBRI press.

Enhanced field emission properties of PECVD synthesized chlorine doped diamond like carbon thin films

Chlorine doped diamond like carbon (DLC) has been deposited for the first time on both Si and glass substrate by plasma enhanced chemical vapor deposition using acetylene and carbon tetrachloride as the source for carbon and chlorine respectively. The Chlorine concentration is varied from 0% to 3.63% as confirmed by X-Ray Photoelectron Spectroscopy. The pure and doped samples were characterized by Atomic Force Microscopy, UV–vis–NIR spectroscopy and FTIR spectroscopy. The electron field emission properties of all the pure and doped samples have been studied in high vacuum field emission set up and it is seen that the field emission properties of the DLC sample have been considerably improved after chlorine was added to it. The doped sample shows good field emission stability with turn on field as low as 4.75V/μm for highest Chlorine concentration. The dependence of field electron emission on inter-electrode distances was studied for three different inter-electrode distances. The enhanced field emission characteristics have been explained in terms of dielectric inhomogeneity induced field enhancement in sp2–sp3 bonded mixed carbon network.

Gas Permeation, Mechanical Behavior and Cytocompatibility of Ultrathin Pure and Doped Diamond-Like Carbon and Silicon Oxide Films

Protective ultra-thin barrier films gather increasing economic interest for controlling permeation and diffusion from the biological surrounding in implanted sensor and electronic devices in future medicine. Thus, the aim of this work was a benchmarking of the mechanical oxygen permeation barrier, cytocompatibility, and microbiological properties of inorganic ~25 nm thin films, deposited by vacuum deposition techniques on 50 µm thin polyetheretherketone (PEEK) foils. Plasma-activated chemical vapor deposition (direct deposition from an ion source) was applied to deposit pure and nitrogen doped diamond-like carbon films, while physical vapor deposition (magnetron sputtering in pulsed DC mode) was used for the formation of silicon as well as titanium doped diamond-like carbon films. Silicon oxide films were deposited by radio frequency magnetron sputtering. The results indicate a strong influence of nanoporosity on the oxygen transmission rate for all coating types, while the low content of microporosity (particulates, etc.) is shown to be of lesser importance. Due to the low thickness of the foil substrates, being easily bent, the toughness as a measure of tendency to film fracture together with the elasticity index of the thin films influence the oxygen barrier. All investigated coatings are non-pyrogenic, cause no cytotoxic effects and do not influence bacterial growth.

Extreme Pressure Lubricant Additives Interacting on the Surface of Steel- and Tungsten Carbide–Doped Diamond-Like Carbon

Certain diamond-like carbon (DLC) coatings offer excellent tribological properties under both dry and oil-lubricated sliding conditions. However, the underlying mechanisms under lubricated conditions are generally not fully understood, especially when performance depends on strong tribochemical interactions with lubricant additives. The aim of the present work is to explore the friction and wear performance of steel and tungsten carbide (WC)-doped DLC (WC-DLC) surfaces in the presence of different types of extreme pressure (EP) and nitrogen–sulfur-based (NS) additives. Tribological tests were performed on a ball-on-disc test rig, and X-ray photoelectron spectroscopy (XPS) was used for physical and chemical characterization of the tribofilms. It was observed that EP and NS additives significantly reduced the wear of WC-DLC surfaces in comparison with tests conducted on steel surfaces. XPS indicated that the additive interactions on the WC-DLC surface formed a distinctive tribofilm that promoted better friction and wear performance. The higher concentration of carbon compounds and lower concentration of oxygen compounds in the tribofilm significantly improved friction and wear characteristics.

Fouling behaviour of milk and whey protein isolate solution on doped diamond-like carbon modified surfaces

Doped diamond-like carbon (DLC) coated stainless steel surfaces were studied for their fouling behaviour with milk and whey protein isolate (WPI) solution at both laboratory and pilot-scale. Stainless steel (316 SS 2B) surfaces were modified with three different doped DLC coatings (DLC-1, DLC-2 and DLC-3) using plasma assisted chemical vapour deposition. At the laboratory-scale, the DLC-1 coated surface showed a statistically significant reduction in the mass of milk fouling deposits. However, at the pilot-scale, none of the modified surfaces offered significant benefit in fouling mitigation over the control stainless steel surface. Subsequently, in the laboratory-scale trials with a whey protein isolate (WPI) solution, the mass of fouling deposits for all doped DLC modified surfaces were about 35–40% lower in comparison to their controls when fouled for 120min. However, these benefits were reduced to less than 15% with longer fouling duration. Thus, the results obtained in this study found no commercial benefit of modified surfaces in fouling mitigation when fouled for longer times with skim milk, whole milk or WPI solution.

Characterization of Cr Doped Diamond-Like Carbon Films and Research on Mechanical Properties

Diamond-like carbon (DLC) films have been extensively studied for more than a decade due to their unique combination of properties. The internal compressive stress affects their adhesion and preventing wide usage of these films. Metal-containing DLC films are expected to relax internal stress. The present work focused on the synthesis, chemical bond and mechanical property characterization of Cr-containing DLC films. The films thickness, internal stress and composition were characterized by scanning electron microscopy, optical interferometry and X-ray photoelectron spectroscopy respectively. Incorporation of Cr into DLC causes an initial internal stress reduction and subsequent stabilization around 0.5 GPa. The hardness behavior was found to depend on Cr content. Films with less than 7.36 at.% Cr (no formation of C-Cr bond) showed a dramatically hardness reduction compared to pure DLC films. Above 7.36 at.% Cr (C-Cr bond formed) the hardness increases above 12 GPa.

Antifog coating for bronchoscope lens

Current bronchoscopes suffer from fogging and the adhesion of mucus plugs to the lens. A doped diamond-like carbon film was developed as a possible solution to this problem. A silicon monoxide dopant was found to produce a film that was transparent, hydrophilic and stable in simulated body fluid (SBF) and therefore showed potential as an antifogging coating. The film was deposited by pulsed laser deposition and characterised by Raman spectroscopy, atomic force microscopy, spectrophotometry and contact angle measurements. Root mean square surface roughness was found to be <1 nm. The unique characteristics of these films include production without secondary processing, a lowest contact angle of 25° and stability in SBF for several months combined with transparency.

Doped diamond-like carbon coatings for surgical instruments reduce protein and prion-amyloid biofouling and improve subsequent cleaning

Doped diamond-like carbon (DLC) coatings offer potential antifouling surfaces against microbial and protein attachment. In particular, stainless steel surgical instruments are subject to tissue protein and resilient prion protein attachment, making decontamination methods used in sterile service departments ineffective, potentially increasing the risk of iatrogenic Creutzfeldt-Jakob disease during surgical procedures. This study examined the adsorption of proteins and prion-associated amyloid to doped DLC surfaces and the efficacy of commercial cleaning chemistries applied to these spiked surfaces, compared to titanium nitride coating and stainless steel. Surfaces inoculated with ME7-infected brain homogenate were visualised using SYPRO Ruby/Thioflavin T staining and modified epi-fluorescence microscopy before and after cleaning. Reduced protein and prion amyloid contamination was observed on the modified surfaces and subsequent decontamination efficacy improved. This highlights the potential for a new generation of coatings for surgical instruments to reduce the risk of iatrogenic CJD infection.

Resistive switching behavior in diamond-like carbon films grown by pulsed laser deposition for resistance switching random access memory application

In this paper, nonvolatile bipolar resistive memory effects were observed in nitrogen doped diamond-like carbon (DLC) thin films prepared by a pulsed laser deposition technique. It is observed that the fabricated Pt/Ti/DLC/Pt structure exhibits good memory performances with an ON/OFF ratio &amp;gt;10, data retention time &amp;gt;104 s, and low operation voltage (&amp;lt;1.5 V). The current mechanism is fitted by Ohmic and space charge limited conduction laws in low resistance state and high resistance state scenarios. The formation/rupture of metal filaments is due to the diffusion of the titanium ions.

Application of holographic sub-wavelength diffraction gratings for monitoring of kinetics of bioprocesses

In this work we present a refractive index (RI) sensor based on a sub-wavelength holographic diffraction grating. The sensor chip was fabricated by dry etching of the finely spaced (d=428nm) diffraction grating in SiOx doped diamond like carbon (DLC) film. It is shown that employing a fabricated sensor chip, and using the proposed method of analysis of data, one can inspect kinetics of processes in liquids occurring in the vicinity of the grating surface. The method is based on the spectral composition analysis of polarized polychromatic light reflected from the sub-wavelength diffraction grating. The RI measurement system was tested with different model liquid analytes including 25wt.%, 50wt.% sugar water solutions, 10°C, 50°C distilled water, also Gram-positive bacteria Bacillus subtilis interaction with ion-permeable channels forming antibiotic gramicidin D and a murolytic enzyme lysozyme. Analysis of the data set of specular reflection spectra enabled us to follow the kinetics of the RI changes in the analyte with millisecond resolution. Detectable changes in the effective RI were not worse than Δn=10−4.

A finite element study on the hardness of carbon nanotubes-doped diamond-like carbon film

Abstract

Improving the conductivity of diamond-like carbon films with zinc doping and its material properties

Zinc doped diamond-like carbon (DLC) nanocomposite thin films are fabricated by KrF pulsed laser deposition. Carbon targets containing 3.0, 5.0 and 10.0 atomic percentages of zinc are used as the source for the laser system. Investigation of electrical properties by the four-point probe shows that doping zinc into DLC can lower the electrical sheet resistivity. Microstructural analysis by Raman spectroscopy and XPS show a lower sp 3 content but a higher SiC content with an increasing amount of zinc incorporation. The increase of SiC leads to an increase in adhesion strength. Surface roughness of the films also increases while the coefficients of friction for the films do not change.

Effect of Sputtering Power on Structure, Adhesion Strength and Corrosion Resistance of Nitrogen Doped Diamond-Like Carbon Thin Films

Nitrogen doped diamond-like carbon (DLC:N) thin films were deposited on highly conductive p-Si substrates using a DC magnetron sputtering deposition system. The DLC:N films were characterized using X-ray photoelectron spectroscopy (XPS), micro-Raman spectroscopy, atomic force microscopy (AFM), contact angle measurement and micro-scratch test. The XPS and Raman results indicated that the sputtering power significantly influenced the properties of the films in terms of bonding configuration in the films. The corrosion performance of the DLC:N films was investigated in a 0.6 M NaCl solution by means of potentiodynamic polarization testing. It was found that the corrosion performance of the films could be enhanced by higher sputtering powers.

Effect of Working Pressure on Corrosion Behavior of Nitrogen Doped Diamond-Like Carbon Thin Films Deposited by DC Magnetron Sputtering

Nitrogen doped diamond-like carbon thin films were deposited on highly conductive p-silicon(100) substrates using a DC magnetron sputtering deposition system by varying working pressure in the deposition chamber. The bonding structure, adhesion strength, surface roughness and corrosion behavior of the films were investigated by using X-ray photoelectron spectroscopy, micro-Raman spectroscopy, micro-scratch test, atomic force microscopy and potentiodynamic polarization test. A 0.6 M NaCl electrolytic solution was used for the corrosion tests. The optimum corrosion resistance of the films was found at a working pressure of 7 mTorr at which a good balance between the kinetics of the sputtered ions and the surface mobility of the adatoms promoted a microstructure of the films with fewer porosities.

Characterization of coating probe with Ti-DLC for electrical scanning probe microscope

In electrical scanning probe microscope (ESPM) applications, the wear and conductivity of the probe are undoubtedly serious concerns since they affect the integrity of the measurements. This study investigates the characterization of Ti doped diamond-like-carbon (DLC) as coating material on a silicon cantilever for ESPM. We deposited a layer of Ti-DLC thin film on the surface of Si cantilever by magnetron sputtering. The morphology and composition of the Ti-DLC films were characterized by scanning electron microscopy and Raman spectroscopy, respectively. We also compared the wear resistance, electric conductivity and scanning image quality of the Ti-DLC-coated probes with those of commercially available conductive probes. The results showed that the electric conductivity and the scanning image quality of the Ti-DLC-coated probes were the same as the commercial conductive probes, while the wear resistance and service life was significantly better.

Microstructural, mechanical and tribological properties of tungsten-gradually doped diamond-like carbon films with functionally graded interlayers

A series of tungsten-gradually doped diamond-like carbon (DLC) films with functionally graded interlayer were prepared using a hybrid technique of vacuum cathodic arc/magnetron sputtering/ion beam deposition. With ‘compositionally graded coating’ concept, the deposition of wear-resistant carbon-based films with excellent adhesion to metallic substrate was realized. In the films, a functionally graded interlayer with layer sequence of Cr/CrN/CrNC/CrC/WC was first deposited onto the substrate, and then, a DLC layer doped with gradually decreasing content of W was coated on. The W concentration gradient along depth of the film was tailored by adjusting the W target current and deposition time. The characterized results indicate that the microstructural, mechanical and tribological properties of these films show a significant dependence on the W concentration gradient. A high fraction of W atom in carbon matrix can promote the formation of sp2 sites and WC1−x nanoparticles. Applying this coating concept, strongly adherent carbon films with critical load exceeding 100N in scratch test were obtained, and no fractures or delaminations were observed at the end of the scratched trace. The hardness was found to vary from 13.28 to 32.13GPa with increasing W concentration. These films also presented excellent tribological properties, especially significantly low wear rate under dry sliding condition against Si3N4 ball. The optimum wear performance with friction coefficient of 0.19 and wear rate of 8.36×10−7 mm3/Nm was achieved for the tungsten-gradually doped DLC film with a graded W concentration ranging from 52.5% to 17.8%. This compositionally graded coating system might be a potentially promising candidate for wear-resistant carbon-based films in the demanding tribological applications.

Anti-sticking behavior of DLC-coated silicon micro-molds

Pure carbon- (C), nitrogen- (N) and titanium- (Ti) doped diamond-like carbon (DLC) coatings were deposited on silicon (Si) micro-molds by dc magnetron sputtering deposition to improve the tribological performance of the micro-molds. The coated and uncoated Si molds were used in injection molding for the fabrication of secondary metal-molds, which were used for the replication of micro-fluidic devices. The bonding structure, surface roughness, surface energy, critical load and friction coefficient of the DLC coatings were characterized with micro-Raman spectroscopy, atomic force microscopy (AFM), contact angle, microscratch and ball-on-disc sliding wear tests, respectively. It was observed that the doping conditions had significant effects on Raman peak positions, mechanical and tribological properties of the coatings. The G peak shifted toward a lower position with N and Ti doping. The DLC coating deposited with 1 sccm N2 flow rate showed the lowest G peak position and the smoothest surface. The surface energies of the pure carbon and Ti-doped DLC coatings were lower than that of the N-doped DLC, which was more significant at a higher N2 flow rate. In terms of adhesion and friction coefficient, it was observed that the Ti-doped DLC coating had the best performance. Ti incorporated in the DLC coating decreased the residual stress of the coating, which improved the adhesive strength of the coating with the Si substrate.

Optical characterization of hydrogen-free CeO 2 doped DLC films deposited by unbalanced magnetron sputtering

A novel kind of hydrogen-free CeO 2 doped diamond-like carbon (DLC) films with thickness of 180–200 nm were deposited on silicon by unbalanced magnetron sputtering. Reduced reflectance and increased lifetime are expected with respect to pure DLC films, making these coatings good candidates as optical protective coatings for IR windows and solar cells. X-ray photoelectron spectroscopy confirms that CeO 2 is formed within the DLC films. Auger electron spectroscopy exhibits that the C, O, and Ce elements distribute uniformly across the film thickness, and C element diffuses into the Si substrate at the interface between the substrate and film. AFM shows that nanoparticles with diameter of around 50 nm are formed on the surface of deposited films, whose surface roughness is in the range of 1.3–2.3 nm. Raman spectra show the CeO 2 doped DLC films are amorphous DLC films, and both the G frequency and relative intensity ratio I D/ I G are higher than those of pure DLC films. The photoluminescence of CeO 2 doped DLC films is obviously more intense than that of a pure DLC film, which indicates a promising potential as optical protective films for solar cells and IR window.

Facile synthesis of CNTs-doped diamond-like carbon film by electrodeposition

A simple and effective process for synthesis of carbon nanotubes (CNTs)-doped diamond-like carbon (DLC) film via electrodeposition has been reported. Transmission electron microscope (TEM), Raman, X-ray photoelectron spectroscopy (XPS), and Fourier transformation infrared spectrometry (FTIR) were employed to investigate the microstructure, chemical composition, and various carbon phases of the films. The experimental results clearly showed that the CNTs were well dispersed in the carbon film and the D and G bands of the composite carbon film both downshifted comparing with those of the undoped carbon film. The hardness of the carbon film was improved with the incorporation of CNTs from 10.28 to 12.47 GPa, while the Young's modulus was decreased from 253.64 to 206.66 GPa. Simultaneously, the residual stress of the carbon film was greatly reduced from 1.2 to 0.83 GPa after the incorporation of CNTs.

Optical properties of La 2O 3 doped diamond-like carbon films

A novel kind of La 2O 3 doped diamond-like carbon (DLC) films with thickness of 100–120 nm were deposited by unbalanced magnetron sputtering. Raman spectra and photoluminescence properties were measured by Raman spectrometer operated by 325 nm He-Cd laser and 514 nm Ar + laser, respectively. The intensities of Raman spectra and photoluminescence are higher than those of pure DLC films. The La 2O 3 doped DLC films have the potential promising for the application of solar cell coatings.