Diamond-like carbon (DLC) films as electrochemical electrodes

Amorphous carbon can be any mixture of carbon bonds of sp³, sp², and even sp¹, with the possible presence of hydrogen. The group of mixture, of which there is a high fraction of diamond-like (sp³) bonds, is named diamond-like carbon (DLC). Unlike the crystalline carbon materials: diamond, graphite, carbon nanotube, fullerene and graphene, DLC can be deposited at room temperature without catalyst or surface pretreatment. Furthermore, its properties can be tuned by changing the sp³ content, the organization of sp² sites and hydrogen content, and also by doping. This paper firstly reviewed the electrochemical properties of DLC films and their applications.     

Properties of diamond-like carbon films on crystalline quartz and lithium niobate

One-micron thick DLC films are deposited on Y-X cut quartz and Y-cut lithium niobate substrates using a plasma-enhanced CVD technique. From the Raman spectra, we find that the films have a small intensity ratio of ‘D’ to ‘G’ peak, indicating a high carbon sp³/sp² ratio and high hardness characteristic. The effect of accelerating a surface acoustic wave by the DLC films has been confirmed by comparing two delayed signals from two near-by delay lines. One was coated with the DLC, while the other was kept as the free quartz or lithium niobate surfaces. It is observed that the one-micron thick DLC films are able to speed up SAW by 2.4% (at 198 MHz) for DLC/quartz and 2.5% (at 430 MHz) for DLC/lithium niobate samples, respectively.     

The effect of CNT content on the surface and mechanical properties of CNTs doped diamond like carbon films

The carbon nanotubes (CNTs) doped diamond like carbon films were carried out by spinning coating multi-walled carbon nanotubes (CNTs) on silicon covered with diamond like carbon films via PECVD with C₂H₂ and H₂. The results show that the I_D/I_G and sp²/sp³ ratios are proportional to the CNT contents. For wettability and hydrogen content, the increase of CNT content results in more hydrophobic and less hydrogen for CNT doped DLC films. As for mechanical properties, the hardness and elastic modulus increases linearly with increasing CNT content. The residual stress is reduced for increasing CNT content. As for the surface property, the friction coefficient is reduced for higher CNT content. For CNT doped DLC films, the inclusion of horizontal CNT into DLC films increases the hardness, elastic modulus and reduces the hydrogen content, friction coefficient and residual stress. Like the light element and metal doping, the CNT doping has effects on the surface and mechanical properties on DLC which might be useful to specific application.     

Influence of bias voltage on diamond like carbon (DLC) film deposited on polyethylene terephthalate (PET) film surfaces using PECVD and its blood compatibility

In this paper, diamond like carbon (DLC) films were coated on polyethylene terephthalate (PET) film substrate as a function of biasing voltage using plasma enhanced chemical vapour deposition. The surface morphology of the DLC films was analyzed by scanning electron microscopy and atomic force microscopy. The chemical state and structure of the films were analyzed by X-ray photoelectrons spectroscopy and Raman spectroscopy. The micro hardness of the DLC films was also studied. The surface energy of interfacial tension between the DLC and blood protein was investigated using contact angle measurements. In addition, the blood compatibility of the films was examined by in vitro tests. For a higher fraction of sp³ content, maximum hardness and surface smoothness of the DLC films were obtained at an optimized biasing potential of ? 300 V. The in vitro results showed that the blood compatibility of the DLC coated PET film surfaces got enhanced significantly.     

Electrochemical characterization of diamond like carbon thin films

Diamond-like carbon (DLC) thin films were deposited from pure graphite target by DC magnetron sputtering method. Experimental parameters, i.e., substrate temperature and negative bias voltage, have been changed to finely tune the chemical bonding property (sp²/sp³) of the as-deposited DLC films. The as-deposited DLC films were characterized as anode materials for Li–ion batteries and special attentions were paid to the effects of sp²/sp³ ratio on the electrochemical properties of the DLC films. The results indicated that a high fraction of sp² bonding in the DLC films is preferred for high lithium storage capacity, flat and low charge voltage plateau, and long cycling retention.     

Electrochemical properties of N-doped hydrogenated amorphous carbon films fabricated by plasma-enhanced chemical vapor deposition methods

Nitrogen-doped hydrogenated amorphous carbon thin films (a-C:N:H, N-doped DLC) were synthesized with microwave-assisted plasma-enhanced chemical vapor deposition widely used for DLC coating such as the inner surface of PET bottles. The electrochemical properties of N-doped DLC surfaces that can be useful in the application as an electrochemical sensor were investigated. N-doped DLC was easily fabricated using the vapor of nitrogen contained hydrocarbon as carbon and nitrogen source. A N/C ratio of resulting N-doped DLC films was 0.08 and atomic ratio of sp³/sp²-bonded carbons was 25/75. The electrical resistivity and optical gap were 0.695 Ω cm and 0.38 eV, respectively. N-doped DLC thin film was found to be an ideal polarizable electrode material with physical stability and chemical inertness. The film has a wide working potential range over 3 V, low double-layer capacitance, and high resistance to electrochemically induced corrosion in strong acid media, which were the same level as those for boron-doped diamond (BDD). The charge transfer rates for the inorganic redox species, Fe^2+/3+ and Fe(CN)₆^4−/3− at N-doped DLC were sufficiently high. The redox reaction of Ce^2+/3+ with standard potential higher than H₂O/O₂ were observed due to the wider potential window. At N-doped DLC, the change of the kinetics of Fe(CN)₆^3−/4− by surface oxidation is different from that at BDD. The rate of Fe(CN)₆^3−/4− was not varied before and after oxidative treatment on N-doped DLC includes sp² carbons, which indicates high durability of the electrochemical activity against surface oxidation.     

Structural characterization and properties enhancement of diamond-like carbon films synthesized under low energy Ne bombardment

Diamond-like carbon (DLC) films were synthesized by Ar⁺ sputtering graphite with concurrent Ne⁺ bombardment. Transmission electron microscopy diffraction revealed that some diamond crystals were distributed in the amorphous matrix of DLC films synthesized under Ne⁺ bombardment at an energy of 200 eV and ion current density of 0.19 mA cm⁻². X-ray photo electron spectra showed that the valence band of the DLC films was similar to that of diamond, and the binding energy of electrons was 284.9 eV. The DLC films possessed a high hardness of 42.14 GPa and excellent wear resistance. It was confirmed that the wide atomic intermixed film-substrate interface meant that the DLC films would improve greatly the wear-resistant properties of AISI 52100 steel if the DLC films were coated on its surface.     

Piezoresistive properties of diamond like carbon films containing copper

In the present study diamond like carbon films containing copper (DLC:Cu) were deposited by reactive magnetron sputtering. Direct current (DC) sputtering and high power pulsed magnetron sputtering (HIPIMS) were used. The influence of the composition and structure on piezoresistive properties of DLC:Cu films was investigated. Structure of DLC:Cu films was investigated by Raman scattering spectroscopy and transmission electron microscopy (TEM). Chemical composition of the films was studied by using energy-dispersive X-ray spectrometry (EDS) and X-ray photoelectron spectroscopy (XPS). Particularly analysis of XPS O1s spectra revealed oxidation of Cu nanoparticles. Piezoresistive gauge factor of DLC:Cu films was in 3–6 range and decreased with the increase of copper atomic concentration. Tendency of the decrease of the gauge factor of DLC:Cu films with the increased D/G peak area ratio (decreased sp³/sp² carbon bond ratio) was observed. It was found that resistance (R) of DLC:Cu films decreased with the increase of Cu atomic concentration by logarithmic law. It is shown that a quasilinear increase of piezoresistive gauge factor with log(R) is in good accordance with percolation theory. Temperature coefficient of resistance (TCR) of DLC:Cu films was negative and decreased with copper amount in Cu atomic concentrations ranging up to ~ 40%. Very low TCR values (zero TCR) were observed only for DLC:Cu films with low gauge factor that was close to the gauge factor of the metallic strain gauges. Role of some possible mechanisms: copper amount as well as Cu cluster size on the value of gauge factor is discussed.     

Effect of nitrogen concentrations on optical,structural and mechanical properties of self organized a-C:N films

Low friction and surface hardness has become an important aspect to study and understand surface engineering of diamond like coating. Investigation of structural and mechanical properties of nitrogenated amorphous Diamond Like Carbon coating has been done. The cross-sectional microstructures, elemental compositions and various phase constituent of the coated layers under different processing conditions have been characterized. Films are deposited in presence of 5%–20% with the increasing rate of 5% and 40% of N₂ partial pressure along with Ar gas. 20% N₂ pressure shows a critical behavior in Raman spectroscopy and XPS. In this condition the film shows more uniform coating with vertical growth structures as well as brittle behavior. The micro-structural changes on the surface due to migration of N₂ and its related surface properties have been examined. AFM studies clearly show that the percentage change in average roughness decreases to 17% as the film thickness increases at 20% N₂ incorporation. The positive changes in its mechanical properties have been observed by Nano-indentation techniques. Significance of DLC coating in this condition is clearly seen with the increasing sp³compositions by XPS analysis. All results have been correlated and hence critical range of nitrogen partial pressure has been observed between 20%-23% to give similar sp³ fraction and hence properties that of pure DLC films.     

Structure of the silver containing diamond like carbon films: Study by multiwavelength Raman spectroscopy and XRD

In the present study structure of silver containing diamond like carbon (DLC:Ag) films deposited by reactive magnetron sputtering was investigated by X-ray diffractometry (XRD) and multiwavelength Raman spectroscopy. In the case of the DLC:Ag films containing low amount of silver, crystalline silver oxide prevails over silver. While at higher Ag atomic concentrations formation of the silver crystallites of the different orientations was observed. Surface enhanced Raman scattering (SERS) effect was detected for high Ag content in the films. For UV excited Raman spectra sp³ bonded carbon related Raman scattering T peak at ~ 1060 cm^− 1 was detected only for the films with the highest amount of silver (34.3 at.%). The dependence of the Raman scattering spectra parameters such as position of the G peak, G peak full width at half maximum (FWHM(G)), D/G peak area ratio on Ag atomic concentration in DLC:Ag film as well as Raman scattering spectra excitation wavelength were studied. The dependence on Ag amount in film was more pronounced in the case of the Raman scattering spectra excited by higher wavelength laser beam, while in the case of the spectra excited by 325 nm and 442 nm laser beams only weak dependence (or no dependence) was observed. Overall tendency of the decrease of the dispersion of the G peak with the increase of Ag atomic concentration was found. Thus sp³/sp² bond ratio in DLC:Ag film decreased with the increase of Ag atomic concentration in the films.     

Piezoresistive,optical and electrical properties of diamond like carbon and carbon nitride films

In the present study diamond like carbon (DLC) and carbon nitride (a-CN_x:H) films were deposited by closed drift ion source from the acetylene and nitrogen gas mixture. The piezoresistive, electrical and optical properties of ion beam synthesized DLC films were investigated. Piezoresistive properties of the diamond like carbon and carbon nitride films were evaluated by four point bending test. The piezoresistors were fabricated on crystalline alumina substrates using Al-based interdigitated finger type electrodes. Effects of the nitrogen concentration on the piezoresistive gauge factor were investigated. The dependence of the resistance of the metal/a-CN_x:H/metal structures on temperature has been studied. Current–voltage (I–V) and capacitance–voltage characteristics were measured for a-CN_x:H/Si heterostructures. The main current transport mechanisms were analyzed. Optical parameters of the synthesized films such as optical bandgap and B parameter (slope of the linear part of the Tauc plot) were investigated to study possible correlation with the piezoresistive properties.     

Substrate bias effect on structure of tetrahedral amorphous carbon films by Raman spectroscopy

Diamond-like carbon (DLC) films form a critical protective layer on magnetic hard disks and their reading heads. Now tetrahedral amorphous carbon films (ta–C) thickness of 2 nm are becoming the preferred means due to the highly sp³ content. In this paper, Raman spectra at visible and ultraviolet excitation of ta–C films have been studied as a function of substrate bias voltage. The spectra show that the sp³ content of 70 nm thick DLC films increases with higher substrate bias, while sp³ content of 2 nm ultra-thin films falls almost linearly with bias increment. And this is also consistent with the hardness measurement of 70 nm thick films. We proposed that substrate bias enhances mixing between the carbon films and either the Si films or Al₂O₃TiC substrate such that thin films contain less sp³ fraction. These mixing bonds are longer than C–C bonds, which inducing the hardness decreasing of ultra-thin DLC films with bias. But for 70 nm DLC, the effect of mixing layer can be negligible by compared to bias effect with higher carbon ion energy. So sp³ content will increase for thick films with substrate bias.     

Electrochemical insertion of lithium into a doped diamond film grown on carbon felt substrates

This paper summarizes the preliminary results obtained from lithium electrochemical intercalation into boron-doped diamond films grown on carbon felt (BDD/CF electrode). BDD films have been grown by Hot Filaments Chemical Vapor Deposition (HFCVD) and have been characterized by Scanning Electron Microscopy (SEM) and Raman Scattering spectroscopy. BDD/CF composite electrodes, which contain a diamond layer, lead to higher conductivity and smaller grain sizes. In turn, they are richer in boundary or sp² sites, and present a reversible specific capacity that is much larger than that of the substrate alone, indicating that the diamond layer effectively participates in lithium storage. Diamond layers displaying boron doping levels of 10¹⁹ and 10²¹ part cm^− 3 provide a specific capacity of 160 and 370 mA h g^− 1, respectively, which is associated with lithium storage.     

Characteristics of carbon films prepared by plasma-based ion implantation

A series of carbon films have been prepared by plasma-based ion implantation (PBII) with C on pure Al and Si. Emphasis has been placed on the effect of implanting voltage on the characteristics of these films. The structures of the films were analyzed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The morphologies were observed by atomic force microscope (AFM). Surface hardness and electrical resistivity were also measured. The results indicate that the characteristics of these films are strongly dependent on the implanting voltage. An implanting voltage threshold value ranging from 3 to 5 kV starts to form a C-substrate transition layer owing to C⁺ ions implanted into the substrate. The transition layer exhibits a gradual change in composition and structure and effectively connects the carbon film and the substrate. Also, an implanting voltage threshold value ranging from 5 to 10 kV starts to form diamond-like carbon (DLC) films. An increasing voltage causes the resultant DLC films to be smoother and more compact. Moreover, Raman spectrum, chemical state of C1s, surface hardness and electrical resistivity all prove an optimum voltage of approximately 30 kV corresponding to the lowest ratio of sp²/sp³.     

Characteristics and surface energy of silicon-doped diamond-like carbon films fabricated by plasma immersion ion implantation and deposition

Diamond-like carbon (DLC) films doped with different silicon contents up to 11.48 at.% were fabricated by plasma immersion ion implantation and deposition (PIII-D) using a silicon cathodic arc plasma source. The surface chemical compositions and bonding configurations were determined by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results reveal that the sp³ configuration including Si–C bonds increases with higher silicon content, and oxygen incorporates more readily into the silicon and carbon interlinks on the surface of the more heavily silicon-doped DLC films. Contact angle measurements and calculations show that the Si-DLC films with higher silicon contents tend to be more hydrophilic and possess higher surface energy. The surface states obtained by silicon alloying and oxygen incorporation indicate increased silicon oxycarbide bonding states and sp³ bonding states on the surface, and it can be accounted for by the increased surface energy particularly the polar contribution.     

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.     

Multifunctional three-dimensional nanodiamond-nanoporous alumina nanoarchitectures

Hybrid composite nanomaterials provide an attractive and versatile material platform for numerous emerging nano- and biomedical applications by offering the possibility to combine diverse properties which are impossible to obtain within a single material. In this work, we present the fabrication of novel hybrid diamond and amorphous diamond-like carbon (DLC) coated nanoporous alumina materials that exhibit multiple functionalities, such as high surface area, quasi-ordered nanopore structure, tunable surface chemistry and electrical conductivity, excellent biological, chemical and corrosion resistance. These multifunctional nanohybrid materials are fabricated using the plasma-induced carbonization method that effectively modifies the surface and the inside of the nanopores of anodic alumina, producing a homogenous ultrathin DLC protecting layer over the whole external and internal surfaces of the membranes. We demonstrate that the interplay between internal and external carbon supply is a critical factor for the formation of the ultrathin sp³-bonded carbon layer in the nanopores. This study brings new insights in the DLC growth mechanisms in confined nanospaces and opens new avenues to fabricate hybrid, chemically resistant and biocompatible carbon-coated nanoarchitectures on other inorganic supports.     

Transmission electron microscopy study of diamond nucleation and growth on smooth silicon surfaces coated with a thin amorphous carbon film

Amorphous carbon (a-C) films with high contents of tetrahedral carbon bonding (sp³) were synthesized on smooth Si(100) surfaces by cathodic arc deposition. Before diamond growth, the a-C films were pretreated with a low-temperature methane-rich hydrogen plasma in a microwave plasma-enhanced chemical vapor deposition system. The evolution of the morphology and microstructure of the a-C films during the pretreatment and subsequent diamond nucleation and initial growth stages was investigated by high-resolution transmission electron microscopy (TEM). Carbon-rich clusters with a density of ∼10¹⁰ cm⁻² were found on pretreated a-C film surfaces. The clusters comprised an a-C phase rich in sp³ carbon bonds with a high density of randomly oriented nanocrystallites and exhibited a high etching resistance to hydrogen plasma. Selected area diffraction patterns and associated dark-field TEM images of the residual clusters revealed diamond fingerprints in the nanocrystallites, which played the role of diamond nucleation sites. The presence of non-diamond fingerprints indicated the formation of Si–C-rich species at C/Si interfaces. The predominantly spherulitic growth of the clusters without apparent changes in density yielded numerous high surface free energy diamond nucleation sites. The rapid evolution of crystallographic facets in the clusters observed under diamond growth conditions suggested that the enhancement of diamond nucleation and growth resulted from the existing nanocrystallites and the crystallization of the a-C phase caused by the stabilization of sp³ carbon bonds by atomic hydrogen. The significant increase of the diamond nucleation density and growth is interpreted in terms of a simple three-step process which is in accord with the experimental observations.     

Biased enhanced growth of nanocrystalline diamond films by microwave plasma chemical vapor deposition

Smooth nanocrystalline diamond thin films with rms surface roughness of ∼17 nm were grown on silicon substrates at 600°C using biased enhanced growth (BEG) in microwave plasma chemical vapor deposition (MPCVD). The evidence of nanocrystallinity, smoothness and purity was obtained by characterizing the samples with a combination of Raman spectroscopy, X-ray diffraction (XRD), atomic force microscopy and Auger electron spectroscopy. The Raman spectra of the films exhibit an intense band near 1150 cm⁻¹ along with graphitic bands. The former Raman band indicates the presence of nanocrystalline diamond. XRD patterns of the films show broad peaks corresponding to inter-planar spacing of (111) and (220) planes of cubic diamond supporting the Raman results. Auger line shapes closely match with the line shape of diamond suggesting high concentration of sp³ carbon on the surfaces of the films. The growth of dominantly sp³ carbon by BEG in the MPCVD system at the conditions used in the present work can be explained by the subsurface implantation mechanism while considering some additional effects from the high concentration of atomic hydrogen in the system.     

Field emission from nano-cluster carbon films

Field emission has been reported to occur at much lower fields in carbon based thin film systems than from any other material systems. The emission has been shown to depend on the various material parameters, but whichever carbon based system is used, it is found that emission occurs at localised sites rather than uniformly over the entire surface. Carbon films with mixed sp³/sp² bonding, like nanocrystalline diamond and nanocluster graphitic films emit at lower fields with a higher emission site density than single-phase films. The sp² cluster size in any carbon film can be altered during deposition, but it is easier to control nanocluster size by post-deposition annealing. Annealing increases the sp² cluster size embedded in a sp³ matrix until the sp³ matrix disappears completely and the film transforms into nanocrystalline graphite. To distinguish the effects of the sp² cluster size from other material parameters, a series of different carbon films were annealed post-deposition and the sp² cluster size was measured using visible Raman. Field emission was then measured at a vacuum of 10⁻⁸ mbar on all films using a parallel plate configuration. It was found that the field emission for all films tested depended upon the clustering of the sp² phase and this effect dominates the effects of the other parameters, such as chemical composition, surface termination, sp³ content or conductivity. The optimum size of the sp² was of the order of 1 nm for all systems tested. We believe that field emission occurs form the localised conducting, predominantly sp² bonded regions, which provideds the large field enhancement required for effective emission.