Effects of thermal annealing and Si incorporation on bonding structure and fracture properties of diamond-like carbon films

The effects of thermal annealing and Si incorporation on the structure and properties of diamond-like carbon (DLC) films were investigated. As-deposited DLC film (DLC) and Si incorporated DLC film (Si-DLC), both with and without thermal annealing, were analyzed for bonding structure, residual stress, film thickness, elastic modulus and fracture properties using Raman spectroscopy, wafer curvature, nanoindentation, four-point bend fracture testing, and X-ray photoelectron spectroscopy (XPS). Raman spectroscopy clearly showed that thermal annealing of DLC films promotes more sp² bonding character, whereas Si incorporation into the films promotes more sp³ bonding character. Interfacial fracture energies, film hardness and elastic modulus, and residual film stress were all found to vary strongly with the degree of sp³ bonding in the DLC film. These changes in mechanical properties are rationalized in terms of the degree of three dimensional inter-links within the atomic bond network.     

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.     

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.     

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.     

Electrochemical characteristics of lithium metal anodes with diamond like carbon film coating layer

To overcome the poor electrochemical characteristics of lithium metal anodes due to the dendrite formations, diamond like carbon (DLC) films were deposited onto the surface of lithium metal by radio frequency-plasma enhanced chemical vapor deposition (CVD) technique using acetylene gas as carbon precursor. The substrate temperature was selected as the main experimental parameter to control the bonding characteristic (sp²/sp³ ratio) of the films. The presence of diamond like structures was confirmed by Raman and Fourier transform infra red spectroscopy. The DLC coated lithium metal was then characterized as an anode material for lithium secondary batteries. The results showed that the DLC coated lithium metal anodes exhibited better electrochemical characteristics in terms of higher specific capacity and smaller interfacial impedance. These improved characteristics were attributed to the presence of DLC film coating which might suppress the dendrite's formation by protecting the lithium metal surface from the direct contact with the electrolyte.     

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.     

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.     

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.     

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.     

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.     

The carbon nitride films prepared at various substrate temperatures by vacuum cathodic arc method

Carbon nitride films have been grown by vacuum cathodic arc method in the substrate temperature range of 100–500 °C. The bonding structure of the films was investigated by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and infrared (IR) spectroscopy. With increasing substrate temperature, the films indicate various characteristics. At 100 °C, it can be described as a network similar to DLC in which aromatic sp²C phase is cross-linked by sp³C phase. Between 200 and 400 °C, with increasing substrate temperature the films become graphitized and the sp²CN phase increases, meanwhile the non-aromatic sp²CN phase appears at the edges of aromatic clusters in planar position as well as in out-of-planar regions. While at 500 °C the non-aromatic sp²CN phase almost comes to the same level as the aromatic sp²CN phase. So in the network of the film the aromatic sp²C phase is cross-linked by the non-aromatic sp²C phase. Based on the variation of the microstructure of the films, a comprehensive assignment pattern for the XPS C1s and N1s at different substrate temperature is proposed. In addition, the interpretation of p electron band in valence band spectra at various substrate temperatures is also discussed.     

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.     

Microstructure,mechanical property and thermal stability of diamond-like carbon coatings with Al,Cr and Si multi-doping

In this paper, AlCrSi atoms were co-doped into DLC coatings by using a high power impulse magnetron sputtering combining with an anode-layer linear ion beam. The doped AlCrSi contents were controlled via adjusting the Ar fraction in the sputtering gas mixture of Ar and C₂H₂. The influences of the AlCrSi multi-doping on the composition, microstructure, residual stress, mechanical property and tribological behavior of the as-deposited DLC coatings were studied systemically by using EDS, XPS, TEM, stress-tester, nanoindentation and ball-on-plate tribometer as a function of the Ar fraction. The thermal stability of the coatings was also researched by a vacuum heat treatment with various temperatures. The results show that the carbide former Cr preferred to form hard carbide components which were conducive to the hardness of the coatings, while the weak carbide former Al dissolved in the DLC matrix as metallic state, which can effectively released the stress of the DLC coatings. The doped Si would bond with sp²-C to form sp³ CSi, and thus maintained the sp³-C structure stability and improved the thermal stability of the coatings. Accordingly, the DLC coatings with AlCrSi multi-doping not only exhibited relatively low residual stress and high hardness, but also showed a high thermal stability over 500 °C. It was believed that the AlCrSi multi-doping may be a good way for improving the comprehensive properties of the DLC coatings.     

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.     

Diamond nucleation and growth on zeolites

In this work, we report the use of zeolites as substrates for the deposition of porous diamond films. Films were deposited in a hot-filament chemical vapor deposition (HFCVD) apparatus. The HFCVD system was fed with a mixture of methane (0.8%) with the balance being hydrogen. A series of depositions were done in the pressure range 20–120 Torr and at substrate temperature 880 °C. The morphologies of the as-deposited films were analyzed by scanning electron microscopy and show isolated diamond grains in the initial nucleation stages, which develop into a microporous film in the next stage and form a continuous film after long time deposition. Raman spectroscopy was used to investigate the crystal morphology, structure and non-diamond impurities in the films deposited at various growth conditions. The nature of the hydrogen bonding with sp³ and sp² network and the quantitative analysis were done by Fourier transform infrared spectroscopy.     

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.     

The origin of conductivity in ion-irradiated diamond-like carbon – Phase transformation and atomic ordering

Focused ion irradiation of insulating diamond-like carbon (DLC) films is a well-recognized approach to write defined nanostructures with drastically changed properties compared to the unexposed matrix. In particular, the electrical conductivity of the film areas that are irradiated increases by several orders of magnitude. Furthermore it is known that the conductivity increase is directly related to the irradiation-induced sp³–sp² rehybridization. This experimental work shows in detail that ion-induced microstructural ordering of the carbon atom arrangement far beyond the sp³–sp² conversion saturation is an important microscopic mechanism for the alteration of physical properties, including an increase in the conductivity. The atomic ordering correlates with the local energy density deposited during the ion impact. Thus the ion-induced phase transformation of DLC is proposed to comprise a rehybridization stage, caused by nuclear collisions, and a rearrangement stage (graphite-like ordering) that is thermally driven by the ion impact. These conclusions are based on in-depth investigations of amorphous DLC films that were locally irradiated by a number of ion species employing several temperature regimes. The ion irradiation experiments cover a wide range of fluences. X-ray photoelectron spectroscopy, μ-Raman spectroscopy, transmission electron microscopy, and low temperature transport measurements have been applied to characterize the films.     

Effects of post-deposition annealing on different DLC films

Amorphous hydrogenated carbon films have been deposited by plasma-enhanced chemical vapour deposition at different process pressures and substrate temperatures, resulting in film properties ranging from polymer-like to diamond-like. The deposition parameter combinations were chosen by experimental design to enable the determination of both deposition pressure and deposition temperature effects on the annealing behaviour. The deposited films have then been annealed in vacuum at successively higher temperatures. Changes in optical band gap, internal stress, film thickness and infrared (IR) absorption spectra have been recorded to assess the influence of deposition parameters on the thermal stability of diamond-like carbon (DLC) and to identify temperature-induced modifications in the bonding structure. The results show a large variation in thermal stability between the different DLC films; samples deposited at low pressure display the greatest stability. The internal stress of the films starts decreasing at very low annealing temperature (<100 °C for the majority of samples), in most cases long before any decrease in the optical band gap can be detected. This is explained by a movement of hydrogen from sp² to sp³ sites as detected by IR measurements.     

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.     

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).