Electrochemical behavior of diamond-like-carbon coatings deposited on AlTiC (Al2O3 + TiC) ceramic composite substrate in HCl solution

The electrochemical characterization/corrosion behavior of diamond-like carbon thin films is worthwhile to study and needed in the field (as there has been limited comprehensive evaluation of this across all types of DLC in the literature). In this paper, newly developed tetrahedral amorphous carbon (ta-C) and hydrogenated amorphous carbon (a-C:H) films, prepared by filtered cathodic arc deposition (FCVA) and plasma enhanced chemical vapor deposition (PECVD) respectively were deposited over AlTiC (Al₂O₃ + TiC) ceramic composite substrate. Electrochemical impedance spectroscopy (EIS) and polarization measurements have been used to evaluate the coating performance in 2 M HCl solution. This ceramic substrate is used widely for the hard disk drives and read and write heads in computer. The memory of the hard disks can be increased by improving the surface quality and decreasing the pinholes. The DLC coatings were modified under different preparation conditions by changing the nitrogen-doping ratios as an attempt for improving the surface distribution and minimizing the surface coating defects.     

Improved adhesion and tribological properties of fast-deposited hard graphite-like hydrogenated amorphous carbon films

Graphite-like hard hydrogenated amorphous carbon (a-C:H) was deposited using an Ar-C₂H₂ expanding thermal plasma chemical vapour deposition (ETP-CVD) process. The relatively high hardness of the fast deposited a-C:H material leads to high compressive stress resulting in poor adhesion between the carbon films and common substrates like silicon, glass and steel. A widespread solution to this problem is the use of an adhesion interlayer. Here we report on the changes in adhesion between the graphite-like a-C:H films and M2 steel substrates when different types of interlayers are used. Insignificant to very small improvements in adhesion were observed when using amorphous silicon oxide (a-SiO_x), amorphous organosilicon (a-SiC_xO_y:H_z) and amorphous hydrogenated silicon carbide (a-SiC_x:H_y) as adhesion layers. However, when sputtered Ti was used as an interlayer, the adhesion increased significantly. The dependence of the adhesive properties on the deposition temperature and interlayer thickness, as well as on the thickness of the a-C:H layer is presented and discussed. The low wear rates measured for the a-C:H/Ti/M2 stack suggest that these films are ideal for tribological applications.     

Characterization of the mechanical properties of diamond-like carbon films

A recently suggested method to measure the elastic modulus of diamond-like carbon (DLC) films was reviewed. This method used a DLC bridge or free overhang which is free from the mechanical constraint of the substrate. Because of the high residual compressive stress of the DLC film, the bridge or the overhang exhibited a sinusoidal displacement on removing the mechanical constraint. Measuring the amplitude and wavelength of the sinusoidal displacement made it possible to measure the strain of the film which occurred by stress relaxation. Combined with independent stress measurement using the laser reflection method, this method allowed the calculation of the biaxial elastic modulus of the DLC film. This method was successfully applied to obtain the elastic properties of various DLC films from polymeric hydrogenated amorphous carbon (a-C:H) to hard tetrahedral amorphous carbon (ta-C) films. Since the substrate is completely removed from the measurement system, this method is insensitive to the mechanical properties of substrate. The mechanical properties of very thin DLC films could be thus measured and then can reveal the structural evolution of a-C:H films during the initial stages of deposition.     

The Effects of Accelerated Aging and Contact with Food Simulants on the Adhesion of Amorphous Hydrogenated Carbon Films Deposited on Clarified Polypropylene

This work focuses mainly on the influence of time, temperature, and contact with food simulants on the adhesion of amorphous hydrogenated carbon (a-C:H) films obtained by plasma-enhanced chemical vapor deposition (PECVD) in clarified polypropylene (cPP). Two types of films prepared by PECVD were studied: diamond-like carbon (DLC) and polymer-like carbon (PLC) films that can both act as a functional barrier. The adhesion between the film and polymer substrates is critical in relation to the barrier effectiveness during the packaging shelf life. Therefore, the adhesion was analyzed by a tape test and scanning electron microscopy (SEM). The films were exposed to Food and Drug Administration (FDA) listed food simulants and were submitted to an accelerated aging test to evaluate the long-term adhesion performance of a-C:H films. The chemical alterations on the surface related to the accelerated aging test and the liquid simulants were analyzed by a contact angle test. It showed that the polarity of a-C:H films increased after immersion in liquid simulants, indicating a change on the surface. Before the accelerated aging test, the SEM micrographs and the tape test indicated that the PLC film has a structure with lower surface tension and, therefore, regions with fewer detachment points in relation to the DLC film. The results obtained in this study showed that the adhesion behavior and preservation of the a-C:H structure (DLC or PLC) are related to intrinsic factors such as the type of film structure (flexible or rigid) and the polymeric substrate.     

Diamond-like carbon films: electron spin resonance (ESR) and Raman spectroscopy

Tetrahedral diamond-like carbon (ta-C) films and hydrogenated a-C:H films were deposited onto Si substrates using filtered cathodic vacuum arc (FCVA) process and direct ion beam deposition from CH₄/C₂H₄ plasma, respectively. Stress of deposited films was varied in the range 2.8–8.5 GPa depending on deposition conditions. Stationary and pulse electron spin resonance (ESR), and Raman spectroscopy techniques were used to analyze sp² related defects in pseudo-gap of undoped as deposited and annealed 20–100 nm thick films.¹ High density of ESR active paramagnetic centers (PC) N_s=(1.0–4.5)×10²¹ cm⁻³ at g=2.0025 was observed in the films. The dependence of ESR line width and line shape vs. deposition conditions and internal film stress were investigated. The several actual mechanisms for ESR line width broadening were considered: spin–spin dipole–dipole and exchange interactions, super-hyperfine interaction (SHFI) with ¹H (for a-C:H), averaging of SHFI due to electron jumps between PC positions with different SHFI values, and broadening due to Mott's electron hopping process. Three types of samples were revealed depending on relative contribution of these mechanisms. Effects of annealing on mechanical and paramagnetic properties of films were studied. An electrical resistance anisotropy at room temperature for ta-C films and g-value anisotropy at low temperature (T<77 K) for both ta-C and a-C:H films were found for the first time. Nature and distribution details of paramagnetic defects in DLC films, anisotropy effects and Raman spectroscopy data are discussed.     

Carbon spheres generated in ‘dusty plasmas’

The formation of spherical hydrogenated amorphous carbon (a-C:H) particulates generated in a radio frequency plasma enhanced chemical vapour deposition (rf-PECVD) system is reported. These particulates appear as a white powder—no other contaminants appear to be present. electron energy loss spectroscopy (EELS) shows characteristics typical of a-C:H with a reduced plasmon energy due to hydrogen incorporation. Raman spectroscopy however revealed a 1456 cm⁻¹ line which was previously not reported on a-C:H films deposited using similar processes. Infrared (IR) spectroscopy shows that these spheres are mainly partially oxidised, methyl-rich, aliphatic hydrocarbons.     

Nanotribological study of PECVD DLC and reactively sputtered Ti containing carbon films

Amorphous carbon film, also known as DLC film, is a promising material for tribological application. It is noted that properties relevant to tribological application change significantly depending on the method of preparation of these films. These properties are also altered by the compositions of these films. DLC films are well known for their self-lubricating properties, as well. In view of this, the objective of the present work is to compare the tribological properties of diamond like carbon (DLC) film obtained by plasma enhanced chemical vapour deposition (PECVD) with the Ti containing nanocrystalline carbon (Ti/a-C:H) film obtained by unbalanced magnetron sputter deposition (UMSD) in nN load range. Towards that purpose, DLC and Ti/a-C:H films are deposited on silicon substrate by PECVD and UMSD processes respectively. The microstructural features and the mechanical properties of these films are determined by scanning electron microscope (SEM), transmission electron microscope (TEM) and nano indenter. The surface topographies and the friction force surfaces of these films are evaluated by means of an atomic force microscope (AFM). The results show that although PECVD DLC film has higher elastic modulus and higher hardness than UMSD Ti/a-C:H film, the surface roughness and the friction coefficient of PECVD film is significantly higher than that of UMSD Ti/a-C:H film.     

Comparative study on the structural make-up and mechanical behavior of silicon and silver doped amorphous carbon films

Silicon - Silicon (Si) and silver (Ag) doped amorphous carbon (a-C) thin film were deposited on chrome nitrided 316 LVM stainless steel using filtered cathodic vacuum arc (FCVA) deposition...     

Properties of a-C:H films grown in inert gas ambient with camphoric carbon precursor of pulsed laser deposition

The influence of the ambient argon gas (Ar) pressure on the properties of the hydrogenated amorphous carbon (a-C:H) films deposited by pulsed laser deposition (PLD) using camphoric carbon (CC) target have been studied. The a-C:H films are deposited with varying Ar pressure range from 0.01 to 0.23 Torr. SEM and AFM show that the particle size of films is decreases, while the roughness increases with higher Ar pressure. The FTIR measurement revealed the presence of hydrogen in the a-C:H films. We found the surface morphology, structural and physical properties structure of a-C:H films are influenced by the presence of inert gas and the ratio of sp² trigonal component to sp³ tetrahedral component is strongly dependent on the inert gas pressure. We suggest that these phenomena are due to the effect of the optimum concentration of the Ar atoms in the C lattice. Improvement of the structural properties of the a-C:H films deposited in inert gas environment using CC target reveals different behaviour than reported earlier.     

Amorphous hydrogenated carbon films as barrier for gas permeation through polymer films

The influence of amorphous hydrogenated carbon (a-C:H) coatings on the gas permeation through polymer films was investigated. a-C:H films were deposited from a 13.56-MHz RF glow discharge in methane or acetylene atmosphere. Thin poly(ethylene terephthalate) and polyimide foils were used as substrates. The permeation of the gases H₂, N₂, O₂ and CO₂ was measured and the reduction of the permeability coefficient was correlated to composition and density of the a-C:H films. The stoichiometry of the layers was analyzed using ion-beam techniques on films deposited onto silicon samples. The a-C:H/PET surfaces were analyzed using optical microscopy and atomic force microscopy (AFM). Multilayer structures comprising different types of a-C:H films were also investigated. A reduction of the permeability coefficient by 80% for hard, dense and 94% for soft, polymer-like layers was found. Surprisingly, the barrier efficacy of the coating decreases with increasing a-C:H film density. This unexpected result is attributed to the appearance of a network of deep cracks spread out over the whole coating.     

Surface and interface morphology and structure of amorphous carbon thin and multilayer films

We review the implementation of X-ray reflection (reflectivity and scattering) techniques for the study of amorphous Carbon (a-C, a-C:H, ta-C) thin and multilayer films and in particular in the determination of the film density and surface and interface morphology, which are intrinsically significant for ultra-thin films. We present studies of various a-C and a-C:H films, which include in particular: i) the morphology of a-C/Si interface, ii) the surface morphology and density evolution during sputter growth of a-C, iii) the morphology of the sp²-rich a-C/sp³-rich a-C interfaces in multilayer a-C films, iv) the universal correlation between the film density and the refractive index of a-C and a-C:H films. We also compare and validate the experimental results with relative results from Monte-Carlo simulations within an empirical potential scheme. The computational results shed light on the atomistic mechanisms determining the structure and morphology of the a-C interfaces between individual sp²- and sp³-rich a-C layers and between a-C and Si substrates.     

Nanoindentation-induced deformation behaviour of tetrahedral amorphous carbon coating deposited by filtered cathodic vacuum arc

The nanoindentation-induced deformation behaviour of a ta-C (tetrahedral amorphous carbon) coating deposited on to a silicon substrate by a filtered vacuum cathodic vapour arc technique was investigated. The 0.17-μm-thick ta-C coating was subjected to nanoindentation with a spherical indenter and the residual indents were examined by cross-sectional transmission electron microscopy. The hard (~ 30 GPa) ta-C coatings exhibited very little localized plastic compression, unlike the softer amorphous carbon coatings deposited by plasma-assisted chemical vapour deposition. However, neither through-thickness cracks nor delamination was observed in the coating for the loads studied. Rather, the silicon substrate exhibited plastic deformation for indentation loads as low as 10 mN and at higher loads it showed evidence of both phase transformation and cracking. These microstructural features were correlated to the observed discontinuities in the load-displacement curves. Further, it was observed that even a very thin coating can modify the primary deformation mechanism from phase transformation in uncoated Si to predominantly plastic deformation in the underlying substrate.     

Ion beam deposition of amorphous hydrogenated carbon films on amorphous silicon interlayer: Experiment and simulation

A thick layer of amorphous silicon (a-Si) was deposited on industrial grade crystalline n-Si < 111 > substrate by means of electron beam evaporation. On top of a-Si layer, amorphous hydrogenated carbon (a-C:H) film was grown by direct ion beam deposition from acetylene precursor gas. In order to study on atomic level the a-C:H film growth on amorphous silicon, a theoretical model was developed in a form of reaction rate (kinetic) equations. Numerical simulation using this model has revealed that the ratio of sp³/sp² content in the film is heavily influenced by relaxation rate of the carbon atoms in a sub-surface region of the film that were activated by ion irradiation. The final structure of a-C:H film does not depend much on elemental composition and structure of amorphous Si coating, provided that deposition procedure is not terminated at its initial stage but continues for more than 60 s. It became evident, therefore, that the use of a-Si interlayer with a-C:H films could be particularly beneficial when a need arises to minimize or eliminate the effect of the substrate. As one of such cases, a poor adhesion of amorphous carbon on steel and other ferrous alloys could be mentioned.     

Photoconductivity and recombination in diamond-like carbon

The steady-state photoconductivity of tetrahedral amorphous carbon (ta-C) and hydrogenated ta-C (ta-C:H) has been studied as a function of temperature, light intensity, and photon energy, in order to understand the transport and recombination process in diamond-like carbon. It is found that the levels demarking the recombination states can span only part of the gap, so that the recombination centres can vary from every defect, to some defects, to some tail states, according to conditions.     

Diamond like carbon used as antireflective coating on crystalline silicon solar cells

Amorphous carbon with different structures was used as antireflective coating on crystalline silicon solar cells. Polymeric-like carbon (PLC) and diamond-like carbon (DLC) were deposited by the PECVD technique on the anode and cathode electrode, respectively. Tetrahedral-like carbon (ta-C) was deposited by the filtered cathodic vacuum arc (FCVA). An increase in the short circuit current comparable to that obtained by conventional antireflective coating (SnO₂) was obtained using PLC antireflective coating. The effect on the short circuit current of the other structures (DLC and ta-C) is reduced mainly due to the band gap and/or a mismatch on the index of refraction of the film and the crystalline silicon substrate.     

Investigation on the change in structure of tetrahedral amorphous carbon by a large amount of nitrogen incorporation

The change of the structure of carbon films after nitrogen incorporation is a topic of extensive discussion. Concerning this topic, tetrahedral amorphous carbon (ta-C) prepared by filtered cathodic arc deposition was chosen for the present investigations with up to 29 at.% nitrogen incorporated into the films. Studies on the film microstructure in a high-resolution transmission electron microscope (TEM) showed nanocrystalline structures of nitrogenated carbon from the films with a high nitrogen concentration. The variation of the microstructure of the films was thoroughly emphasized from carbon and nitrogen K-edges using electron energy loss spectroscopy (EELS) as well as near-edge X-ray absorption fine structure (NEXAFS), spectroscopy. In addition, NEXAFS spectra were used to find out the most probable molecular structure of the CN system and have been shown to be consistent with results obtained from EELS.     

Superhydrophobic carbon nanotube/amorphous carbon nanosphere hybrid film

Fabrication of superhydrophobic surfaces has been widely investigated due to their wide range of applications. Here, synthesis of self-assembled aligned carbon nanotubes (ACNT)/amorphous carbon (a-C) nanosphere hybrid film is reported. Carbon plasma produced by FCVA was used to deposit a-C nanospheres on the ACNT films fabricated by PECVD. The superhydrophobic properties of the surface was investigated by static contact angle (CA) measurement. It is found that the surface morphology of the film which depends on the size of the a-C nanospheres, has a great influence on the hydrophobic properties of the surface. The hydrodynamic properties of the surface is discussed in terms of both Cassie and Wenzel mechanisms. The microstructure of the films is also investigated by XPS and HRTEM. It is shown that the bombardment of the CNTs with high energy carbon ions will damage the crystalline structure of the CNT walls as well.     

Properties and tool performance of ta-C films deposited by double-bend filtered cathodic vacuum arc for micro drilling applications

This paper describes the results of the application of ta-C films to micro drilling operation for deep and small machining boreholes. Tetrahedral amorphous carbon (ta-C) films were successfully deposited on WC-Co substrates by a double-bend filtered cathodic vacuum arc (FCVA) system. The structure, mechanical and tribological properties of both pure ta-C and ta-C incorporated argon gas (ta-C:Ar-flow) films were systematically investigated. And then, high-speed through-hole drilling tests were performed on the PCB (printed circuit board) workpiece to investigate the machining performance of ta-C coated micro drills. The experimental results show that the ta-C:Ar-flow (2 sccm) coated micro drill has excellent microstructure, microhardness, and friction coefficient properties and represents the optimal coatings for micro drilling applications.     

Techniques for filtering graphite macroparticles in the cathodic vacuum arc deposition of tetrahedral amorphous carbon films

Filtered cathodic vacuum arc (FCVA) deposition has been found to be a reliable technique for the production of high quality tetrahedral amorphous carbon films (ta-C). These coatings can be used as protective coatings for different applications ranging from cutting tools to human hip joint prosthesis. The FCVA technique is widely used in different laboratories around the world with somewhat different technical implementations. A serious disadvantage in the FCVA technique is the graphite particles that are emitted from the solid graphite cathode during the arc-discharge. A variety of different techniques exist to diminish their production and transport. However, some of the magnetic filtering designs that are used to reduce the macroparticle transport into the substrate do not work well with high melting point cathode materials such as graphite. Although the influence of graphite particles for the ta-C coating performance in some applications is controversial, many applications demand that the produced ta-C film is practically particle-free. This is especially important in corrosion resistance, electrical and optical applications. In this paper an introduction to different FCVA devices is presented. Different magnetic filtering designs together with control techniques for macroparticle generation have been reviewed and their advantages and disadvantages in the plasma transport and particle filtering efficiency have been discussed.     

Probing the tribochemical degradation of hydrogenated amorphous carbon using mechanically stimulated gas emission spectroscopy

Mechanically Stimulated Gas Emission (MSGE) spectroscopy was used for investigation into tribochemical reactions and gas emission for four types of amorphous hydrogenated carbon (a-C:H) coatings, which were obtained by either ion beam deposition (IBD) or plasma enhanced chemical vapour deposition (PECVD). The results of statistical analysis, which was employed to identify the components of the emitted gases from the mass-spectrometry data, argue against the hypothesis that considerable amount of CH₃ could be present in the emitted gases. For the IBD coatings the main components of the emitted gases were methane and/or argon, whereas for the PECVD coatings they were mainly methane and hydrogen. Noticeable emission of ethane, propane, carbon mono- and dioxides was also detected under sliding of PECVD coatings deposited with the lowest ion energy. While frictional heating has been definitely ruled out as the driving mechanism for MSGE, there are experimental evidences that MSGE has to be associated with structural degradation of the coating.