Surface energy of metal containing amorphous carbon films deposited by filtered cathodic vacuum arc

Metal containing amorphous carbon (a-C:Me) films including a-C:Al, a-C:Ti, a-C:Ni, a-C:Si were prepared by the filtered cathodic vacuum arc (FCVA) technique with metal-carbon (5 at.% metal) composite targets. The substrate bias ranging from floating to 1000 V was applied. The wettability of the films was examined using the VCA Optima system from AST Products, Inc. Three types of liquid with different polarities were used to study the surface energy changes of the films. X-ray photoelectron spectroscopy (XPS) was used to analyze the composition and chemical state of the films. Atomic force microscopy (AFM) was employed to characterize the morphology and roughness of the films. The contact angle of the a-C:Me films remains relatively constant with different substrate bias. The Al containing films show the highest contact angle with water, which reaches as high as 101°. The Si containing films show the lowest contact angle approximately 64°. The contact angles of Ni and Ti containing films are approximately 80°, 97°, respectively. The harmonic-mean method was used to calculate the polar and depressive component of the surface energy. The absorption of oxygen on the surface plays an important role on the polar component of the a-C:Me films. The formation of AlO and TiO bonds is responsible for their lower polar component. The metal state Ni results in higher polar component. However, the SiO bond is contributed to the high polar component of a-C:Si films. As all films are atomic scale smooth, the RMS roughness is below 0.5 nm, the roughness does not have obvious effect on the surface energy.     

Carbon nanotubes grown on cobalt-containing amorphous carbon composite films

Carbon nanotubes (CNTs) have been produced on silicon wafer by filtered cathodic vacuum arc technique using cobalt-containing graphite targets followed by thermal chemical vapor deposition. The Co-containing amorphous carbon (a-C:Co) composite films have various contents of Co as a catalyst for CNTs growth. It is found that dense and random CNTs were grown on the a-C:Co composite film deposited using a 2 at.% Co-containing graphite target and nanoforest CNTs on the composite films using 5, 10 and 15 at.% Co-containing targets. The nanoforest CNTs using a 15 at.% Co-containing target have very good field emission properties with a low threshold field of 1.6 V/μm and a high and stable current density of 2.1 mA/cm² at 3 V/μm, which may result from the smaller diameter of CNTs. It is found that the field emission properties of the CNTs are significantly affected by the diameter of CNTs rather than its orientation.     

Water-repellency and surface free energy of a-C:H films prepared by heat-treatment of polymer precursor

Amorphous hydrogenated carbon (a-C:H) films with high water-repellency were prepared on Si substrates by a simple heat-treatment of the poly(phenylcarbyne) polymer at various temperature in Ar atmosphere. The contact-angle (CA) was measured by the sessile-drop technique. The use of CA for different liquid (water, ethylene glycol, and formamide) analysis for the evaluation of surface energy including the dispersion and polar components was described. The influences of surface roughness, chemical composition, and microstructure of carbon films on water CA and surface energy were investigated by atomic force microscopy (AFM), Fourier transforms infrared spectrometry (FTIR), and Raman spectroscopy, respectively. As the results, the a-C:H films exhibit good hydrophobicity and low surface free energy. The CA of a-C:H films slight increases and the surface free energy of a-C:H films reduces with the increase of the heat-treatment temperature. The a-C:H films are hydrophobic for not only pure water but also corrosive liquids, such as acidic and alkali solutions. The roughness of the films has no obvious effect on the CA and the reduction of surface energy with the increase of heat-treatment temperature is related to increase of sp² content in the film.     

Lu_2O_3:Tb薄膜的制备、结构和发光性能

采用Pechini溶胶-凝胶法结合旋涂技术在单晶硅衬底上制备出了均匀、无裂纹的掺Tb3+的Lu2O3(Lu2O3:Tb)薄膜。用热重-差示扫描量热法分析了前驱体干凝胶在室温至1000℃下发生的热分解现象。利用X射线衍射和Fourier红外光谱和原子力显微镜研究了热处理温度对Lu2O3:Tb薄膜的晶相、化学组成和表面形貌的影响。结果表明:在550～1000℃间热处理的Lu2O3:Tb薄膜为多晶氧化镥立方结构,晶粒尺寸随温度升高而逐渐长大至30nm左右。在220nm紫外光激发下,Lu2O3:Tb薄膜呈现出较强的绿光发射,主发射峰分别位于542nm和551nm处。随着热处理温度的提高,Lu2O3:Tb薄膜中缺陷减少,发光强度增强。     

Structural analysis of a-C:H and a-C:H:Si films under high-pressure and high-temperature by synchrotron X-ray diffraction

Amorphous carbon films have several outstanding tribology characteristics, including high hardness, surface smoothness, and low friction. Under tribological conditions, their surface is generally exposed to high-temperature and pressure. Although the structure of amorphous carbon films is likely changed by high temperature and pressure, there have been no reports on such structural changes of the films. To obtain information about their structural changes, synchrotron X-ray diffraction was used to analyze two kinds of amorphous carbon films, a-C:H and a-C:H:Si, under high-temperature and high-hydrostatic pressure conditions. Synchrotron X-ray diffraction was applied to films pressurized by a multi-anvil press installed in the PF-AR NE5C beamline at KEK at room temperature and at a high-temperature around 200 °C. The pair distribution functions derived by Fourier transformation of the obtained scattering intensity profiles showed that the sp²/sp³ ratios for both films decreased as the pressure increased and that the sp²/sp³ ratio for the a-C:H film increased as the temperature increased. This indicates that high-pressure creates sp³ stabilization in a-C:H and a-C:H:Si films while high-temperature creates sp² transition in a-C:H film. The sp²/sp³ ratio for the a-C:H:Si film did not change much even at high-temperature due to the high thermal-oxidative stability of a-C:H:Si.     

Sulfur doped nanocrystalline diamond films as field enhancement based thermionic emitters and their role in energy conversion

Sulfur doped nanocrystalline diamond films, like other nanostructured carbon films, exhibit electron emission characterized by a spatial non-uniformity of the field enhancement factor. While field emission effects are observed at room temperature, an increase in emitter temperature is accompanied by an amplified emission current with a simultaneous drop in the threshold field. At low extraction fields a fit of the emission current to the Richardson equation indicates a material work function of 2.5 eV. The Schottky formula describes thermionic emission at a moderate field and is utilized to determine the work function at an electric field of 0.8 V/μm with a value of 1.7 eV and a concurrently reduced Richardson constant. This significant difference in the work function of 2.5 and 1.7 eV for 0.5 and 0.8V/μm, respectively can be attributed to field enhancement effects.     

The effect of hydrogen plasma chemical annealing on electron field emission of amorphous carbon films

Layer-by-layer deposition method, in which nanometer-thick film deposition and hydrogen plasma annealing processes were alternatively repeated, was applied to fabricate hydrogenated amorphous carbon films in our present work. It was found that the hydrogen plasma treatment changed the sp²/sp³ ratio due to chemical etching. Consequently, a stable vacuum electron emission with a low threshold field was achieved compared with that from conventionally deposited a-C films. The threshold electric field is as low as 2 V/μm. The influence of the hydrogen plasma chemical annealing on the field emission behavior was systematically investigated. The improvement of field emission characteristics can be attributed to the large field enhancement effect due to the inhomogeneous distribution of nanometer scale sp² clusters.     

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.     

Characterization and biostability of HA/Ti6Al4V ACL anchor prepared by simple heat-treatment

Here, we report a simple heat-treatment process to prepare hydroxyapatite (HA)-coated Ti6Al4V anterior cruciate ligament (ACL) anchor that has good hard tissue compatibility and biostability. Heat treatment was carried out for 1.5 h at temperature range of 700–900 °C. Morphological characterization showed rougher surface and larger pore spaces as the heat treatment temperature was increased. The Ti6Al4V heat-treated at 800 °C had the highest diffused titanium phosphide formation, thus making it high in biocompatibility. For in vivo test, the most bone integration ability was obtained for heat-treatment at 800 and 900 °C. Furthermore, the HA/Ti6Al4V ACL anchor heat-treated at 800 °C had the highest amount of new bone formation. The present results suggest that an implant with complex shape like an ACL anchor could be prepared and used with an easy and low-cost technique by simple heat treatment surface modification method after dip-coating with HA.     

Enhanced room-temperature positive magnetoresistance of a-C:Fe film

Fe-doped amorphous carbon (a-C:Fe) film and pure amorphous carbon (a-C) film were synthesized on n-Si substrate using pulsed laser deposition. The a-C:Fe film has a positive magnetoresistance (15% at magnetic field B = 1 T) at room temperature, while it has a negative magnetoresistance below 260 K. The electrical conduction in a-C:Fe film is one order of magnitude higher than that in pure a-C film. It is found that a-C:Fe film has very different conduction mechanism from that of pure a-C film. The activation energy of electron conduction in a-C:Fe film could be tuned significantly by magnetic field. The magnetoresistance effect of the a-C:Fe film seems difficult to explain by known magnetoresistance mechanisms.     

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.     

Effects of titanium and aluminum incorporations on the structure of boron nitride thin films

Boron nitride (BN)-based composite thin films have been prepared by ion-beam-assisted deposition (IBAD) employing two electron-beam evaporators. Approximately 3–5 at.% of either Ti or Al was incorporated into the BN composite films. Fourier-transform infra-red (FTIR) spectroscopy was used for phase identification of the BN composite films. The influences of the Ti and Al additions on the cubic phase formation in the BN films are reported. It has been found that Al incorporation has a strong negative effect on cubic BN (cBN) formation. No cubic phase can be obtained under the presently chosen ion-bombardment parameters. However, the disturbance of 3∼5 at.% Ti addition, depending on the preparation conditions for the BN thin films, only shifts the threshold of the ion/atom ratio of the IBAD process, which is required for cBN formation to a higher value. In order to understand the different behaviors of the Ti and Al incorporations, the chemical states of the Ti and Al additions in the BN composite films were examined by X-ray photoelectron spectroscopy (XPS), indicating preferential formation of TiB₂ and AlN, respectively.     

Mechanical and tribological properties of TiC/amorphous hydrogenated carbon composite coatings fabricated by DC magnetron sputtering with and without sample bias

TiC/amorphous hydrogenated carbon (a-C:H) composite films were deposited by Ti DC magnetron sputtering using argon and acetylene as the carrier gas and precursor, respectively. The working pressure was maintained at 4 × 10^− 1 Pa and the composition of the films was modulated by controlling the partial pressure of acetylene. The composition and structure of the films were evaluated by X-ray photoelectron spectroscopy and glancing angle X-rays diffraction, whereas the hardness and elastic modulus values of the films fabricated using different sample biases were measured by nano-indentation. Ball-on-disk tribometry was used to measure the tribological properties, and secondary electron microscopy was used to analyze the wear tracks. The results show that the friction coefficients and wear rates do not vary significantly with the Ti concentrations when the Ti concentration is above 39.7 at.% or below 20 at.% but increase with increasing titanium concentrations between 20 at.% and 39.7 at.%. The wear mechanism depends on the relative amounts of TiC and a-C:H. At high Ti concentrations, the mechanism resembles that of TiC due to the thin a-C:H matrix surrounding the TiC grains. At low Ti concentrations, the mechanism is similar to that of DLC as the effects of the a-C:H matrix dominates over those of the TiC grains.     

Field emission from tetrahedral amorphous carbon films with various surface morphologies

Field emission properties of tetrahedral amorphous carbon films prepared by filtered cathodic vacuum arc technique have been compared with different surface morphologies. With fewer cycles of conditioning, field emission from relatively rough granular ta-C films on nickel-coated silicon substrates was routinely improved, due to a local field enhancement resulting from both a ‘protrusion-on-protrusion’ geometry and a relatively high sp² content in the film. A 2-MeV ion implantation machine was also employed to intentionally produce local graphitic channels in smooth ta-C films with a high fraction of sp³ content on bare silicon. A relatively low threshold field was obtained from the ta-C film implanted at a dose of 10¹² cm⁻², which still remained an extremely smooth surface. However, for the highly graphitic sample implanted with a higher dose of over 4×10¹³ cm⁻², no electron field emission was observed, even under a very high electric field of 40 V μm⁻¹. Therefore, a suitable sp² content in an sp³ matrix, resulting in graphitic conductive channels in amorphous carbon films to produce a local field enhancement, may be the main factor in obtaining low threshold fields. Furthermore, protrusive structures could further increase the field enhancement factor, due to a ‘protrusion-on-protrusion’ geometry.     

Low-temperature sintering and microstructure control of mullite–Mo composites

Dense mullite–Mo (45 vol%) composites with homogeneous microstructure have been obtained by plasma activated sintering of a mixture of Mo and mullite precursors at a relatively low temperature (1350 °C) and a pressure of 30 MPa. The mullite precursor was synthesized by a sol–gel process followed by a heat-treatment at 1000 °C. The influence of different mullite precursors on the densification behavior and the microstructure of mullite–Mo composites has been studied. The precursor powder heat-treated at 1000 °C with only Si–Al spinel but no mullite phase shows an excellent sintering activity. Following the sintering shrinkage curves, a two-stage sintering process is designed to enhance the composite densification for further reducing the sintering temperature. The study reveals that viscous flow sintering of amorphous SiO₂ at low temperatures effectively enhances the densification. Moreover, microstructure of these composites can be controlled by selecting different precursors and sintering temperatures.     

Cathodoluminescence and electron field emission of boron-doped a-C:N films

The optical and electrical properties of so-called carbon nitride films (a-C:N) and boron doped so-called carbon nitride films (a-C:N:B) are studied with cathodoluminescence (CL) spectroscopy and electron field emission measurement. The a-C:N films were first deposited on Si by a filtered cathodic arc plasma system, and then boron ions (∼1 × 10¹⁶ cm⁻²) were implanted into the a-C:N films to form a-C:N:B films by a medium current implanter. The structural and morphological properties of a-C:N and a-C:N:B films were then analyzed using secondary ion mass spectrometer, X-ray photoelectron spectroscopy, FT-IR spectra, Raman spectroscopy and atomic force microscopy. The a-C:N film exhibits luminescence of blue light (∼2.67 eV) and red light (∼1.91 eV), and the a-C:N:B film displays luminescence of blue light (∼2.67 eV) in CL spectra measured at 300 K. Furthermore, the incorporated boron atoms change the electron field emission property, which shows a higher turn on field for the a-C:N:B film (3.6 V/μm) than that for the a-C:N film (2.8 V/μm).     

Improved electron field emission from metal grafted graphene composites

Metal nanoparticle grafted graphene films (GFs) form a new composite for electron field emission devices. The GFs were deposited on Ni coated Si wafers by microwave plasma enhanced chemical vapour deposition. Graphene-based composites using Ti, Pd, Ag and Au were formed by thermal evaporation. The surface morphology and microstructure were probed by scanning and high resolution transmission electron microscopy. Improvement in the electron field emission and reduction in the turn on and threshold fields were observed in metal grafted GFs as compared to those from pristine films. It was found that among the grafted metals, Ti adsorption contributed more efficiently in enhancing the electron field emission properties by lowering its work function. The enhanced electron field emission characteristics were analyzed using the density functional theory calculations for metal grafted graphene ribbon. Our results indicate increased density of states near the Fermi level for metal grafted graphene ribbon which is responsible for the improvement in electron field emission. We suggest that grafting of metal nanoparticles on GFs could be exploited for the development of efficient field emitters.     

Electrochemical behavior of the Ti–6Al–4V alloy coated with a-C:H films

In this work diamond-like carbon films were deposited on the Ti–6Al–4V alloy, which has been used in aeronautics and biomedical fields, by electrical discharges using a magnetron cathode and a 99.999% graphite target in two different atmospheres, the first one constituted by argon and hydrogen and the second one by argon and methane. Films deposited using the argon/hydrogen mixture were called a-C:H, while films deposited using the argon/methane mixture were called DLC. Raman spectroscopy was used to study the structure of the films. The Raman spectra profile of the a-C:H films is quite different from that of the DLC films. The disorder degree of the graphite crystalline phase in a-C:H films is higher than in DLC films (a-C:H films present small values for the the I_D/I_G ratio). Potentiodynamic corrosion tests in 0.5 mol l⁻¹ NaCl aqueous solution, pH 5.8, at room temperature (≈25 °C) were carried out as for the a-C:H as for the DLC coated surfaces. Comparison between the corrosion parameters of a-C:H and DLC coated surfaces under similar deposition time, showed that DLC coated surfaces present bigger corrosion potential (E_corr) and polarization resistance than those coated with a-C:H films. Electrochemical impedance spectroscopy (EIS) was also used to study the electrochemical behavior of a-C:H and DLC coated surfaces exposed to 0.5 mol l⁻¹ aqueous solution. The EIS results were simulated with equivalent electrical circuit models for porous films. The results of these simulations showed similar tendency to the one observed in the potentiodynamic corrosion tests. The DLC film resistance and the charge transfer resistance (R_ct) for the DLC coated surface/electrolyte interface were bigger than the ones determined for the a-C:H coated surfaces.     

Cathodoluminescence of fluorine doped amorphous carbon nanoparticles deposited by a filtered cathodic arc plasma system

The fluorine doped amorphous carbon nanoparticles (a-C:F NPs) films with sizes 50-100 nm were deposited on polyethylene terephthalate in an atmosphere of CF₄ by a 90°-bend magnetic filtered cathodic arc plasma system. The surface morphology of a-C:F NPs films was observed by field emission scanning electron microscope and atomic force microscope. The microstructure and chemical bonding nature of the a-C:F NPs films were investigated by Raman, X-ray diffraction and X-ray photoelectron spectroscopy. This work presents cathodoluminescence (CL) spectra of a-C:F NPs films obtained at 1.9-2.4 eV and verifies luminescence from a-C:F NPs films in the visible region. The incorporation of fluorine into the carbon network results in orange emission (∼2.03 eV) due to the transitions between fluorine-related electron levels and σ* states, and the red emission (∼1.97 eV) results from the recombination of carriers in the valence π and conduction π* states. The peak at ∼2.10 eV may result from the defects of the structures in a-C:F NPs films.     

Optical and electrical properties of a-C:H deposited by magnetic confinement of r.f. PECVD plasma

Amorphous hydrogenated carbon (a-C:H) thin films have been deposited in an r.f. PECVD chamber using a magnetic multipole system to confine the plasma. The influence of magnetic field on both the plasma parameters and the film properties has been studied. The results are compared with those obtained under similar conditions using a standard PECVD system. Optical emission spectroscopy (OES) shows an increase in the intensity of the hydrogen and C–H lines in the plasma. EELS, optical, electrical and electron field emission measurements have been used to characterize the deposited films. The sp³/sp² ratio was increased using the magnetic field and the optical gap was also increased as compared to films grown using a standard process. The electron field emission was found to be improved (higher current density and smaller barrier height) for samples deposited in the presence of the magnetic field.