Chemical and morphological difference between TiN/DLC and a-C:H/DLC grown by pulsed vacuum arc techniques

In order to improve the adherence of DLC films, interlayers of amorphous hydrogenated carbon (a-C:H) and titanium nitride (TiN) were deposited by means of the pulsed vacuum arc technique. Bilayers were obtained by using a carbon target of 99.98% of purity in mixtures of (Ar + CH₄) and (Ar + H₂) for producing a-C and DLC, respectively and a target of titanium of 99.999% in a mixture of (Ar + N₂) for growing TiN. After the deposition, chemical and morphological differences between TiN/DLC and a-C:H/DLC bilayers grown on silicon and stainless steel 304 were studied using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and scanning probe microscopy (SPM) techniques. XPS analysis showed a difference in sp³/(sp²+sp³) bonds ratio for each bilayer, being 0.67 for TiN/DLC and 0.45 for a-C:H/DLC bilayers. sp³ and sp² bonds were also observed by the FTIR technique. SPM images, in atomic force microscopy (AFM) and lateral force microscopy (LFM) modes were carried out for illustrating the comparison between TiN/DLC and a-C/DLC morphologic characteristics. Roughness and grain size were studied as a function of the H₂ concentration for both bilayers.     

Evaluation of phase,composition, microstructure and properties in TiC/a-C:H thin films deposited by magnetron sputtering

Titanium carbide/amorphous-carbon (TiC/a-C:H) nanocomposite coatings deposited by pulsed unbalanced reactive magnetron sputtering have been investigated in terms of structure, chemical and phase composition by AFM, TEM, XPS and XRD analyses. Subject to total carbon content, metallic titanium, titanium carbide and amorphous-carbon phases were found in the deposited coatings, which contributed to the observed microstructures and morphologies. The specific resistivity of nanocomposite coatings scales up with increasing amount of matrix-forming carbon. Hardness profiles of the different compositions revealed that nearly stoichiometric TiC films with average crystallite size of 70 nm exhibit the maximum hardness, whereas the lowest friction coefficient (μ<0.1) was found in films rich in amorphous-carbon and containing smaller TiC nanocrystallites (〈d〉 ∼ 10 nm).     

Intrinsic mechanical properties of ultra-thin amorphous carbon layers

In this work, we extracted the film's hardness (H_F) of ultra-thin diamond-like carbon layers by simultaneously taking into account the tip blunting and the substrate effect. As compared to previous approaches, which did not consider tip blunting, this resulted in marked differences (30-100%) for the H_F value of the thinner carbon coatings. We find that the nature of the substrate influences this intrinsic film parameter and hence the growth mechanisms. Moreover, the H_F values generally increase with film thickness. The 10 nm and 50 nm thick hydrogenated amorphous carbon (a-C:H) films deposited onto Si have H_F values of, respectively, ∼26 GPa and ∼31 GPa whereas the 10 nm and 50 nm thick tetrahedral amorphous carbon (t-aC) films deposited onto Si have H_F values of, respectively, ∼29 GPa and ∼38 GPa. Both the a-C:H and t-aC materials also show higher density and refractive index values for the thicker coatings, as measured, respectively by X-ray reflectometry and optical profilometry analysis. However, the Raman analysis of the a-C:H samples show bonding characteristics which are independent of the film thickness. This indicates that in these ultra-thin hydrogenated carbon films, the arrangement of sp² clusters does not relate directly to the hardness of the film.     

The study of ion mixed amorphous carbon films on single crystal silicon by C ion implantation

Amorphous-carbon (a-C) films were deposited on a single-crystal silicon substrate by vacuum vapor deposition system and these amorphous carbon films were implanted with 110 keV C⁺ at fluences of 1 × 10¹⁷ ions/cm². The effect of ion mixing on the surface morphology, friction behavior and adhesion strengths of amorphous carbon films was examined making use of atomic force microscopy (AFM), ball-on-disk reciprocating friction tester, nano-indentation system and scanning electron microscope (SEM). The changes in chemical composition and structure were investigated by using X-ray photoelectron spectroscopy (XPS). The results show that the anti-wear life and adhesion of amorphous carbon films on the Si substrates were significantly increased by C ion implantation. The SiC chemical bonding across the interface plays a key role in the increase of adhesion strength and the anti-wear life of amorphous carbon film. The friction and wear mechanisms of amorphous carbon film under dry friction condition were also discussed.     

Adsorption of bovine serum albumin on amorphous carbon surfaces studied with dip pen nanolithography

This article reports the use of dip pen nanolithography (DPN) for the study of adsorption of bovine serum albumin (BSA) proteins on amorphous carbon surfaces; tetrahedral amorphous carbon (t-aC) and silicon doped hydrogenated amorphous carbon (a-C:H:Si). Contact angle study shows that the BSA proteins reduce the contact angle on both carbon materials. We also noticed that the drop volume dependence is consistent with a negative line tension, i.e. due to an attractive protein/surface interaction. The DPN technique was used to write short-spaced (100 nm) BSA line patterns on both samples. We found a line merging effect, stronger in the case of the a-C:H:Si material. We discuss possible contributions from tip blunting, scratching, cross-talk between lever torsion and bending and nano-shaving of the patterns. We conclude that the observed effect is caused in large measure by the diffusion of BSA proteins on the amorphous carbon surfaces. This interpretation of the result is consistent with the contact angle data and AFM force curve analysis indicating larger tip/surface adhesion and spreading for the a-C:H:Si material. We conclude by discussing the advantages and limitations of DPN lithography to study biomolecular adsorption in nanoscale wetting environments.     

Hybrid ICP/sputter deposition of TiC/CaO nanocomposite films for biomedical application

TiC/a-C nanocomposite films doped with CaO have been deposited by means of a hybrid PVD/PACVD technique, which combines dc magnetron sputtering of a TiC_0.5+10% CaO target, with a subsequent high density inductively coupled plasma (ICP) in order to excite and ionize the sputtered species to a high degree. The films were characterized according to their morphology, structure and thickness by scanning electron microscopy, their composition and bonding structure by X-ray photoelectron spectroscopy, and their crystalline properties by X-ray diffraction. The films consist of fcc titanium carbide nanocrystallites with grain sizes of 5–15 nm and an amorphous carbon phase. The average composition is Ti_0.43C_0.35Ca_0.02O_0.15N_0.05. The influence of the ICP plasma power and the bias voltage applied to the substrate on the major film properties has been investigated. A number of such TiC/a-C/CaO nanocomposite films on silicon substrates have been subjected to a 60 day cell test with human osteoblastic cells in order to investigate their suitability for the coating of prostetic implants. The results of these cell tests, some of which turned out to be rather promising, are discussed in terms of film properties such as surface roughness and biaxial stress. PACS 68.55.-a; 81.07.-b; 87.68.+z     

Structural and tribological properties of nitrogen doped amorphous carbon thin films synthesized by CFUBM sputtering method for protective coatings

Nitrogen doped amorphous carbon (a-C:N) films are a material that may successfully compete with DLC coatings, which have high hardness, high wear resistance, and a low friction coefficient. The a-C:N films were prepared on silicon substrate by a closed-field unbalanced magnetron sputtering method with a graphite target and using the Ar/N₂ mixture gases. And, we investigated the effects of various DC bias voltages from 0 to −300 V on the structural and tribological properties of the a-C:N films. This study was focused on improving physical properties of the a-C:N film by controlling process parameters like negative substrate DC bias voltage. The maximum hardness of the a-C:N film was 23 GPa, the friction coefficient was 0.08, and the critical load was 25 N on a Si wafer. Consequently, the structural and tribological properties of the a-C:N film showed a clear dependence on the energy of ions bombardment and the density of the sputtering and the reaction gases during film growth.     

Microstructure and tribological performance of self-lubricating diamond/tetrahedral amorphous carbon composite film

In order to smooth the rough surface and further improve the wear-resistance of coarse chemical vapor deposition diamond films, diamond/tetrahedral amorphous carbon composite films were synthesized by a two-step preparation technique including hot-filament chemical vapor deposition for polycrystalline diamond (PCD) and subsequent filtered cathodic vacuum arc growth for tetrahedral amorphous carbon (ta-C). The microstructure and tribological performance of the composite films were investigated by means of various characterization techniques. The results indicated that the composite films consisted of a thick well-grained diamond base layer with a thickness up to 150 μm and a thin covering ta-C layer with a thickness of about 0.3 μm, and sp³-C fraction up to 73.93%. Deposition of a smooth ta-C film on coarse polycrystalline diamond films was proved to be an effective tool to lower the surface roughness of the polycrystalline diamond film. The wear-resistance of the diamond film was also enhanced by the self-lubricating effect of the covering ta-C film due to graphitic phase transformation. Under dry pin-on-disk wear test against Si₃N₄ ball, the friction coefficients of the composite films were much lower than that of the single PCD film. An extremely low friction coefficient (∼0.05) was achieved for the PCD/ta-C composite film. Moreover, the addition of Ti interlayer between the ta-C and the PCD layers can further reduce the surface roughness of the composite film. The main wear mechanism of the composite films was abrasive wear.     

Nanocomposite TiC/a-C：H film prepared on titanium aluminium alloy substrates by PSII assistant MW-ECRCVD

Thin films of titanium carbide and amorphous hydrogenated carbon have been synthesized on titanium aluminium alloy substrates by PSII assisted MW-ECRCVD with a mirror field. The microstructure, chemical composition and mechanical property were investigated. Using XPS and TEM, the films were identified to be a-C：H film containing TiC nanometre grains （namely, the so-called nanocomposite structure）. The size of TiC grains of nanocomposite TiC/DLC film is about 5 nm. The nanocomposite structure has obvious improvement in the mechanical properties of DLC film. The hardness of a-C：H film with Ti is enhanced to 34 G Pa~ while that of a-C：H film without Ti is about 12 G Pa, and the coherent strength is also obviously enhanced at the critical load of about 35N.     

AFM investigation on surface evolution of amorphous carbon during ion-beam-assisted deposition

Hydrogen-free amorphous carbons (a-C) have been prepared on mirror-polished Si(1 1 1) wafers through thermally evaporated C₆₀ with simultaneous bombardments of Ne⁺ ions. The time evolution of film surfaces has been characterized by atomic force microscopy (AFM) at two temperatures of 400 and 700 °C, respectively. Based on the topography images and the root-mean-square (rms) roughness analysis, it is found that the a-C surfaces present roughening growth at the initial stage. With increasing growth time, the cooperative nucleation of the islands and pits appears on the surfaces, suggesting three-dimensional growth, and then they continue to evolve to irregular mounds at 400 °C, and elongated mounds at 700 °C. At the steady growth stage, these surfaces further develop to the structures of bamboo joints and ripples corresponding to these two temperatures, respectively. It is believed that besides ion sputtering effect, the chemical bonding configurations in the amorphous carbon films should be taken into considerations for elucidating the surface evolutions.     

Nanomechanical characterization of amorphous hydrogenated carbon thin films

Amorphous hydrogenated carbon (a-C:H) thin films deposited on a silicon substrate under various mixtures of methane-hydrogen gas by electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MPCVD) was investigated. Microstructure, surface morphology and mechanical characterizations of the a-C:H films were analyzed using Raman spectroscopy, atomic force microscopy (AFM) and nanoindentation technique, respectively. The results indicated there was an increase of the hydrogen content, the ratio of the D-peak to the G-peak (I_D/I_G) increased but the surface roughness of the films was reduced. Both hardness and Young's modulus increased as the hydrogen content was increased. In addition, the contact stress-strain analysis is reported. The results confirmed that the mechanical properties of the amorphous hydrogenated carbon thin films improved using a higher H₂ content in the source gas.     

X-ray photoelectron spectroscopic study of nitrogen incorporated amorphous carbon films embedded with nanoparticles

The effect of substrate bias on X-ray photoelectron spectroscopy (XPS) study of nitrogen incorporated amorphous carbon (a-C:N) films embedded with nanoparticles deposited by filtered cathodic jet carbon arc technique is discussed. High resolution transmission electron microscope exhibited initially the amorphous structure but on closer examination the film was constituted of amorphous phase with the nanoparticle embedded in the amorphous matrix. X-ray diffraction study reveals dominantly an amorphous nature of the film. A straight forward method of deconvolution of XPS spectra has been used to evaluate the sp³ and sp² contents present in these a-C:N films. The carbon (C 1s) peaks have been deconvoluted into four different peaks and nitrogen (N 1s) peaks have been deconvoluted into three different peaks which attribute to different bonding state between C, N and O. The full width at half maxima (FWHM) of C 1s peak, sp³ content and sp³/sp² ratio of a-C:N films increase up to −150 V substrate bias and beyond −150 V substrate bias these parameters are found to decrease. Thus, the parameters evaluated are found to be dependent on the substrate bias which peaks at −150 V substrate bias.     

Transport and optical properties of amorphous carbon and hydrogenated amorphous carbon films

In this paper we report on the electrical and optical properties of amorphous carbon (a-C) and hydrogenated amorphous carbon (a-C:H) films. Resistivity of both types of films decreases with increase in temperature. At lower temperatures (60-250 K) the electron transport is due to variable range hopping for the a-C films. At higher temperatures (300-430 K) it is thermally activated for both types of films. Analysis of the heterojunction between diamond-like carbon (DLC) and bulk silicon (Si) leads to the conclusion that our a-C films are of n-type and our a-C:H films are of p-type. The optical measurements with DLC revealed a Tauc bandgap of 0.6 eV for the a-C films and 1-1.2 eV for the a-C:H films. An Urbach energy around 170 meV could be determined for the a-C:H films. Strain versus resistance plots were measured resulting in piezoresistive gauge factors around 50 for the a-C films and in between 100 and 1200 for the a-C:H films.     

Characterization of bilayer coatings of TiN/ZrN grown using pulsed arc PAPVD

Nitride coatings have been used to increase hardness and to improve the wear and corrosion resistance of structural materials. Coatings of TiN/ZrN were grown on stainless steel substrates using a physical vapour deposition system assisted by pulsed arc plasma (PAPVD). The coatings have been characterized by X-ray diffraction (XRD) in order to identify the present phases of the films, microstrain level generated, crystallite size and the variation of the lattice parameter. The results showed plane orientations (1 1 1) and (2 0 0) in both TiN and ZrN films. Morphology surface analysis of the samples were performed using a scanning probe microscope to characterize the grain size and roughness in the mode of the atomic force microscopy (AFM) hence it was observed that the root-mean-squared (rms) roughness for ZrN is smaller than for TiN. Besides elastic and friction properties of the films were characterized qualitatively, and then, they were compared with those of the substrates by using force modulation microscopy (FMM) and lateral force microscopy (LFM) modes. In addition, an elemental analysis of the samples was realized by means of energy dispersive spectroscopy (EDS). Both, XRD and AFM results are given as a function of the number of shots. Chemical states of the TiN and ZrN films were determined by X-ray photoelectron spectroscopy (XPS).     

Characterization of Cu additive FePt-C granular films

FePt-C granular films doped with different Cu atomic fractions (x_Cu) were fabricated using facing-target sputtering at room temperature and subsequently annealed at 650 °C. Structural analyses reveal that the as-deposited films are in amorphous state. Appropriate Cu addition (x_Cu = 14) can improve the ordering of L1₀ FePt phase, and excessive Cu doping destroys the formation of ordered L1₀ phase with the appearance of Fe₃C and CuPt phases. Besides, preferential graphitization of amorphous carbon (a-C) occurs near large metal particles upon annealing. Annealing turns the as-deposited superparamagnetic films into ferromagnetic associated with coercivity peaks at x_Cu = 14, drops from ∼11.2 kOe at 5 K to ∼7.2 kOe at 300 K in a 50 kOe field.     

Effects of flow ratios on surface morphology and structure of hydrogenated amorphous carbon films prepared by microwave plasma chemical vapor deposition

A series of hydrogenated amorphous carbon (a-C:H) films were deposited on silicon substrates by microwave plasma chemical vapor deposition technique with a mixture of hydrogen and acetylene. The effects of flow ratio of hydrogen to acetylene on surface morphology and structure of a-C:H films were investigated using surface-enhanced Raman spectroscopy and scanning probe microscope (SPM) in the tapping AFM mode. Raman data imply a transition from graphite-like phase to diamond-like bonding configurations when the flow ratio increases. AFM measurements show that the increase in hydrogen content, to some extent, can smoothen the surface morphology and decrease the RMS roughness. Excessive hydrogen is found to cause the formation of polymeric hydrocarbon clusters in the films and reduce deposition rate.     

AFM lateral force imagining of modified polychloroprene: A study based on roughness analysis

Films of a binary polymer blends comprising polychloroprene (PCP) and piperylene-styrene copolymer (PSC) have been prepared by solution casting. The dependence of the surface morphology of the free blend films on PSC content was studied with both roughness and correlation analysis of lateral force microscopy (LFM) images. Significant changes in roughness and lateral parameter values of different blend film sides have been observed depending on the blend composition. It was shown that up to 15 wt.% PSC is distributed continuously in PCP bulk. The increase of roughness and lateral parameter values at the air/film surface shows the enrichment of PCP in the blends containing 25 wt.% or more PSC. The enrichment of PCP on the air/film surface favours the increase of PSC concentration at the backing/film surface. The films underside morphology becomes similar to that of PSC, when its content reaches 40 wt.%.     

Effect of Chromium on Structure and Tribological Properties of Hydrogenated Cr/a-C:H Films Prepared via a Reactive Magnetron Sputtering System

Hydrogenated Cr-incorporated carbon films(Cr/a-C:H) are deposited successfully by using a dc reactive magnetron sputtering system.The structure and mechanical properties of the as-deposited Cr/a-C:H films are characterized systematically by field-emission scanning electron microscope,x-ray diffraction,Raman spectra,nanoindentation and scratch.It is shown that optimal Cr metal forms nanocrystalline carbide to improve the hardness,toughness and adhesion strength in the amorphous carbon matrix,which possesses relatively higher nano-hardness of 15.7GPa,elastic modulus of 126.8 GPa and best adhesion strength with critical load(L_c) of36 N for the Cr/a-C:H film deposited at CH_4 flow rate of 20 sccm.The friction and wear behaviors of as-deposited Cr/a-C:H films are evaluated under both the ambient air and deionized water conditions.The results reveal that it can achieve superior low friction and anti-wear performance for the Cr/a-C:H film deposited at CH_4 flow rate of 20 sccm under the ambient air condition,and the friction coefficient and wear rate tested in deionized water condition are relatively lower compared with those tested under the ambient air condition for each film.Superior combination of mechanical and tribological properties for the Cr/a-C:H film should be a good candidate for engineering applications.     

The electrochemical and mechanical properties of Ti incorporated amorphous carbon films in Hanks’ solution

Ti incorporated amorphous carbon (a-C) films with variant Ti contents were prepared by the unbalanced magnetron sputtering process. Scanning electron microscopy, ultraviolet Raman spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy were used to characterize the microstructure of a-C films. The hardness and lubricated tribological properties were assessed using nanoindentation and ball-on-disk tribometer. As the Ti content in a-C films increases from 0 to 15.2 at.%, the sp³ volume fraction, the internal stress and the hardness of the films decreases gradually, while the disorder of sp² bond increases. The electrochemical tests reveal that the a-C films with lower than 1.5 at.% Ti possess good corrosion resistance in Hanks’ solution, while the a-C film with 15.2 at.% Ti is susceptible to crevice corrosion. The reduced friction of the a-C films is due to the sp² bonded film surface and boundary lubrication of the Hanks’ solution. The a-C film with 3.1 at.% Ti exhibits the best wear resistance in Hanks’ solution among the studied films.     

Amorphous hydrogenated carbon films on semiconductors

The adhesion quality of amorphous hydrogenated carbon films (a-C:H) on semiconductor substrates depends to a large degree on the properties of the interface. The present work complements the photoemission results of the preceding paper with a detailed investigation of the atomic structure of the a-C:H/Si and a-C:H/GaAs interfaces. We show that the method of substrate cleaning and the deposition parameters affect the thickness of the interfacial layer and the interface roughness. The carbide compounds that form in the interfacial layer are found to be amorphous and we present evidence for the precipitation of metallic Ga at the a-C:H/GaAs interface. Finally, we have determined the extent of atomic intermixing in the interfacial region and compare our results with different mechanisms of adhesion.