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.     

Effect of oxygen plasma treatment on non-thrombogenicity of diamond-like carbon films

The non-thrombogenicity of oxygen-plasma-treated DLC films was investigated as surface coatings for medical devices. DLC films were deposited on polycarbonate substrates by a radio frequency plasma enhanced chemical vapor deposition method using acetylene gas. The deposited DLC films were then treated with plasma of oxygen gas at powers of 15 W, 50 W, and 200 W. Wettability was evaluated by water contact angle measurements and the changes in surface chemistry and roughness were examined by X-ray photoelectron spectroscopy and atomic force microscope analysis, respectively. Each oxygen-plasma-treated DLC film exhibited a hydrophilic nature with water contact angles of 11.1°, 17.7° and 36.8°. The non-thrombogenicity of the samples was evaluated through the incubation with platelet-rich plasma isolated from human whole blood. Non-thrombogenic properties dramatically improved for both 15 W- and 50 W-oxygen-plasma-treated DLC films. These results demonstrate that the oxygen plasma treatment at lower powers promotes the non-thrombogenicity of DLC films with highly hydrophilic surfaces.     

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

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

Preparation of diamond like carbon thin films above room temperature and their properties

Diamond like carbon (DLC) thin films were deposited on p-type silicon (p-Si), quartz and ITO substrates by microwave (MW) surface-wave plasma (SWP) chemical vapor deposition (CVD) at different substrate temperatures (RT ∼ 300 °C). Argon (Ar: 200 sccm) was used as carrier gas while acetylene (C₂H₂: 20 sccm) and nitrogen (N: 5 sccm) were used as plasma source. Analytical methods such as X-ray photoelectron spectroscopy (XPS), FT-IR and UV–visible spectroscopy were employed to investigate the structural and optical properties of the DLC thin films respectively. FT-IR spectra show the structural modification of the DLC thin films with substrate temperatures showing the distinct peak around 3350 cm^− 1 wave number; which may corresponds to the sp² C–H bond. Tauc optical gap and film thickness both decreased with increasing substrate temperature. The peaks of XPS core level C 1 s spectra of the DLC thin films shifted towards lower binding energy with substrate temperature. We also got the small photoconductivity action of the film deposited at 300 °C on ITO substrate.     

The properties of fluorine-containing diamond-like carbon films prepared by pulsed DC plasma-activated chemical vapour deposition

Diamond-like carbon films containing up to 23.1 at. % of fluorine (F-DLC), were deposited onto silicon substrates by low-frequency, pulsed DC, plasma-activated, chemical vapour deposition (PACVD). The influence of fluorine on plasma current density, deposition rate, composition, bonding structure, surface energy, hardness, stress and biocompatibility was investigated and correlated with the fluorine content. X-ray photoelectron spectroscopy (XPS) analysis revealed the presence C–C, C–CF and C–F for F-DLC films with a low fluorine concentration (1.5–12.1 at. %), however for films with a higher fluorine content (23.0 at. %) an additional peak due to CF₂ bonding was detected. The addition of fluorine into the DLC film resulted in lower stress and hardness values. The reduction in these values was attributed to the substitution of strong C=C by weaker C–F bonds which induces a decrease in hardness. Ion scattering spectrometery (ISS) measurements revealed the presence of fluorine atoms in the outmost layer of the F-DLC films and there was no evidence of surface oxygen contamination. The water contact angle was found to increase with increasing fluorine content and has been attributed to the change of the bonding nature in the films, in particularly increasing CF and CF₂ bonds. Biocompatibility tests performed using MG-63 osteoblast-like cell cultures indicated homogeneous and optimal tissue integration for both the DLC and the F-DLC surfaces. This pulsed-PACVD technique has been shown to produce biocompatible DLC and F-DLC coatings with a potential for large area applications.     

Properties of DLC films deposited by an oxyacetylene flame

Diamond-like carbon (DLC) films were obtained by spinning a tungsten carbide substrate at a high speed using an oxyacetylene flame. The films deposited at a typical experimental condition of substrate temperature of 810°C, rotation of 600 rpm and 3 h deposition time, exhibited an uniform, very smooth, hard and glassy surface covering the entire exposed face of the substrate. These films were identified as DLC by their characteristic broad Raman spectra centered at 1554 cm⁻¹ and micro-Vicker's hardness >3400 kg mm⁻². For substrate temperatures <800°C the film started losing the uniform glassy surface and the hardness deteriorated. For temperatures >950°C the film was still hard and shiny, but black in color. DLC films were also obtained in a wide range of speeds of rotation (300–750 rpm), as long as the temperature remained close to 850°C.     

Room temperature synthesis of boron nitride thin films by dual-ion beam sputtering deposition

Boron nitride (BN) films are prepared by dual-ion beam sputtering deposition at room temperature (~25 °C). An assisting argon/nitrogen ion beam (ion energy E_i=0–300 eV) directly bombards the substrate surface to modify the properties of the BN films. The effects of assisting ion beam energy on the characteristics of BN films were investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, Raman spectra, atomic force microscopy, and optical transmittance. The density of the B–N bond in the film increased with the increase in assisting ion beam energy. The highest transmittance of more than 95% in the visible region was obtained under the assisting ion beam energy of 300 eV. The band gap of BN films increased from 5.54 eV to 6.13 eV when the assisted ion-beam energy increased from 0 eV to 300 eV.     

Nitridation of silicon powder studied by XRD, 29Si MAS NMR and surface analysis techniques

The nitridation of elemental silicon powder at 900–1475 °C was studied by X-ray photoelectron spectroscopy (XPS), X-ray excited Auger electron spectroscopy (XAES), XRD, thermal analysis and ²⁹Si MAS NMR. An initial mass gain of about 12% at 1250–1300 °C corresponds to the formation of a product layer about 0·2 μm thick (assuming spherical particles). XPS and XAES show that in this temperature range, the surface atomic ratio of N/Si increases and the ratio O/Si decreases as the surface layer is converted to Si₂N₂O. XRD shows that above 1300 °C the Si is rapidly converted to a mixture of α- and β-Si₃N₄, the latter predominating >1400 °C. In this temperature range there are only slight changes in the composition of the surface material, which at the higher temperatures regains a small amount of an oxidised surface layer. By contrast, in the interval 1400–1475 °C, the ²⁹Si MAS NMR chemical shift of the elemental Si changes progressively from about −80 ppm to −70 ppm, in tandem with the growth of the Si₃N₄ resonance at about −48 ppm. Possible reasons for this previously unreported change in the Si chemical shift are discussed. ©     

Corrosion-resistance,robust and wear-durable highly amphiphobic polymer based composite coating via a simple spraying approach

This study successfully developed a simple spray approach to fabricate a robust highly amphiphobic poly(phenylene sulfide) (PPS)/fluorinated ethylene propylene (FEP)/poly(dimethylsiloxane) (PDMS) composite coating with high-performance in corrosion-resistance, wear-durable through designing the nano/micro two-tier roughness and fluorinating with materials of the low surface free energy. The highly amphiphobic and tribological properties of the coatings were measured by the contact angle meter and the pin-on-disc tribometer, respectively. It was interested to observe that the composite coating showed superhydrophobic and highly oleophobic simultaneously, with the highest contact angles of water, glycerine and ethylene glycol up to 173 ± 2.1°, 142 ± 2.2° and 139 ± 2.1°, respectively. Moreover, the surfaces of the PPS/FEP composite coatings were investigated by means of Fourier transform infrared spectroscopy (FT-IR), X-ray diffractometry (XRD) and energy-dispersive X-ray spectroscopic (EDS). The robust highly amphiphobic coating also showed remarkable durability against strong acid and strong alkali in the pH range from 1 to 14. After 47 h sliding wear test, no failure sign on the PPS/45%FEP/PDMS composite coating was observed. Such unique characteristics were attributed to the synergistic effect of the nano/micro two-tier roughness and fluorinating with low surface free energy groups (–CF₂–, –CF₃–).     

Electrochemical and microstructural characteristics of nanoperovskite oxides Ba0.2Sr0.8Co0.8Fe0.2O3−δ (BSCF) for solid oxide fuel cells

Nanoperovskite oxides, Ba_0.2Sr_0.8Co_0.8Fe_0.2O_3?δ (BSCF), were synthesized via the co-precipitation method using Ba, Sr, Co, and Fe nitrates as precursors. Next, half cells were fabricated by painting BSCF thin film on Sm_0.2Ce_0.8O_x (samarium doped ceria, SDC) electrolyte pellets. X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical impedance spectroscopy (EIS) measurements were carried out on the BSCF powders and pellets obtained after sintering at 900 °C. Investigations revealed that single-phase perovskites with cubic structure was obtained in this study. The impedance spectra for BSCF/SDC/BSCF cells were measured to obtain the interfacial area specific resistances (ASR) at several operating temperatures. The lowest values of ASR were found to be 0.19 Ω cm², 0.14 Ω cm² 0.10 cm², 0.09 Ω cm² and 0.07 Ω cm² at operating temperatures of 600 °C, 650 °C, 700 °C, 750 °C and 800 °C, respectively. The highest conductivity was found for cells sintered at 900 °C with an electrical conductivity of 153 S cm^?1 in air at operating temperature of 700 °C.     

Homoepitaxial diamond film with an atomically flat surface over a large area

Homoepitaxial diamond films with atomically flat surface were grown using the microwave plasma chemical vapor deposition method at a low CH₄ concentration of less than 0.05% in a CH₄ and H₂ mixed gas system. In Ib (001) diamond substrates having misorientation angles of 0.5°, atomic force microscope image on the surface of film grown at 0.025% CH₄ concentration showed that the films had atomically flat surface with mean roughness of 0.04 nm in area as large as 4×4 mm² (the whole region of the substrate).     

Amorphous carbonated apatite formation on diamond-like carbon containing titanium oxide

Thin films of diamond-like carbon (DLC) containing titanium oxide (DLC-TiO_x, x ≤ 2) were synthesized using a pulsed DC metal–organic plasma activated chemical vapor deposition (MOCVD) technique. X-ray photoelectron spectroscopy (XPS) results confirmed the presence of TiO₂ on the surface of the films. The compressive stress, elastic modulus and hardness of the films decreased with increasing Ti content. The water contact angle reduced from 62° for DLC to 45° for DLC-TiO_x films containing 13.3 at.% of Ti. The biomimetic growth of amorphous carbonated apatite on the DLC-TiO_x in simulated body fluid (SBF) was found and dependent on the Ti content of the film. UV light exposure prior to immersion in SBF increased the growth rate of apatite formation significantly as a result of increased hydrophilicity of the surface.     

Coating of nano-sized ionically conductive Sr and Ca doped LaMnO3 films by sol–gel route

In this study, Sr and Ca doped LaMnO₃ thin ceramic films were coated on Al₂O₃ substrates by using a sol–gel route as the cathode material for SOFC. Nitrate precursors were used for the preparation of the thin film coating solution, and methanol and acetyl acetone were also used as the solvent and chelating agent, respectively. After the solution was prepared, an Al₂O₃ single crystal substrate was dipped into the solution. Then it was fired at 500 °C and annealed at 1025 °C for the crystallization. Coated films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), focused ion beam (FIB) and atomic force microscopy (AFM). Conductivity of the coated films was measured by the four probe Van der Pauw method. XRD, SEM, AFM and FIB characterizations of the coated film showed that the LaMnO₃ phase was formed, surface of the films was uniform and had homogenously distributed pores sized about 10 nm, mean grain size was about 60–80 nm and the film thickness was about 180 nm. The specific resistivity of the film was calculated to be 0.524 Ω m.     

Electron field emission from filtered arc deposited diamond-like carbon films using Au and Ti layers

In this work, tetrahedral diamond-like carbon (DLC) films are deposited on Si, Ti/Si and Au/Si substrates by a new plasma deposition technique — filtered arc deposition (FAD). Their electron field emission characteristics and fluorescent displays of the films are tested using a diode structure. It is shown that the substrate can markedly influence the emission behavior of DLC films. An emission current of 0.1 μA is detected at electric field E_DLC/Si=5.6 V/μm, E_DLC/Au/Si=14.3 V/μm, and E_DLC/Ti/Si=5.2 V/μm, respectively. At 14.3 V/μm, an emission current density J_DLC/Si=15.2 μA/cm², J_DLC/Au/Si=0.4 μA/cm², and J_DLC/Ti/Si=175 μA/cm² is achieved, respectively. It is believed that a thin TiC transition layer exists in the interface between the DLC film and Ti/Si substrate.     

Thin-film nanocomposites of diamond-like carbon and titanium oxide; Osteoblast adhesion and surface properties

Thin films of a novel, nanocomposite material consisting of diamond-like carbon and polycrystalline/amorphous TiO_x (DLC-TiO_x, x ≤ 2) were prepared using pulsed direct-current plasma enhanced chemical vapour deposition (PECVD). Results from Raman spectroscopy indicate that the DLC and TiO_x deposit primarily as segregated phases. Amorphous TiO₂ is found to be present on the surface region of the film and there is evidence for the presence of crystalline TiO in the bulk of the film. The hydrophilicity of the DLC-TiO_x films increased with increasing titanium content. Culture studies with human osteoblasts revealed that the differences in three-day cell adhesion properties (count, morphology and area) between DLC and DLC-TiO_x films containing up to 13 at.% Ti were not statistically significant. However, the cell count was significantly greater for the films containing 3 at.% of Ti in comparison to those containing 13 at.% of Ti. A post-plasma treatment with Ar/O₂ was used to reduce the water contact angle, θ, by nearly 40° on the DLC-TiO_x films containing 3 at.% of Ti. A cell culture study found that the osteoblast count and morphology after three days on these more hydrophilic films did not differ significantly from those of the original DLC-TiO_x films. We compare these results with those for SiO_x-incorporated DLC films and evaluate the long-term osteoblast-like cell viability and proliferation on modified DLC surfaces with water contact angles ranging from 22° to 95°.     

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.     

A superhard diamond-like carbon film

A superhard hydrogen-free amorphous diamond-like carbon (DLC) film was deposited by pulsed arc discharge using a carbon source accelerator in a vacuum of 2×10⁻⁴ Pa. The growth rate was about 15 nm/min and the optimum ion-plasma energy was about 70 eV. The impact of doping elements (Cu, Zr, Ti, Al, F(Cl), N) on the characteristics of DLC films deposited on metal and silicon substrates was studied aiming at the choice of the optimum coating for low friction couples. The microhardness of thick (≥20 μm) DLC films was studied by Knoop and Vickers indentations, medium thick DLC films (1–3 μm) were investigated using a ‘Fischerscope’, and Young's module of thin films (20–70 nm) was studied by laser induced surface acoustic waves. The bonds in DLC films were investigated by electron energy loss spectroscopy (EELS), X-ray excited Auger electron spectroscopy (XAES), and X-ray photoelectron spectroscopy (XPS). The adhesion of DLC films was defined by the scratch test and Rockwell indentation. The coefficient of friction of the Patinor DLC film was measured by a rubbing cylinders test and by a pin-on-disk test in laboratory air at about 20% humidity and room temperature. The microhardness of the Patinor DLC film was up to 100 GPa and the density of the film was 3.43–3.65 g/cm³. The specific wear rate of the Patinor DLC film is comparable to that of other carbon films.     

Reaction of palladium thin films with an Si-rich 6H-SiC(0001)(3×3) surface

The reaction of Pd thin films evaporated in ultrahigh vacuum on a clean and Si-rich 6H-SiC(0001)(3×3) surface has been investigated in situ by low-energy electron diffraction (LEED) and photoelectron spectroscopy (UPS and XPS), and ex situ by atomic force microscopy (AFM) and glancing-incidence X-ray diffraction (GIXRD). For studying the interface formation, submonolayer amounts of Pd were sequentially deposited up to ∼20 Å on the substrate maintained at room temperature. This deposit was subsequently annealed to 600–800 °C. At room temperature, Pd starts to react with SiC when the thickness attains ∼2.5 Å, giving an interface Pd₂Si silicide. Under annealing the film is transformed into Pd₂Si islands standing on the SiC (1×1) surface. No extra-structure of C 1s is observed in the two cases; only an energy shift of about 0.25 eV is detected during the metal deposition, which is attributed to a change in the band bending. Further deposition of ∼100 Å of Pd on this annealed surface gives an epitaxial Pd(111) film, despite a lattice mismatch of more than 10% between the metal and the semiconductor. The film is disrupted after annealing at 600–800 °C. The combination of XPS, AFM and GIXRD analyses indicates that the film annealed at 800 °C is discontinuous and formed of sharp epitaxial Pd₂Si islands and graphite which probably surrounds the islands.     

The effects of the post-annealing time on the growth mechanism of Bi2Sr2Ca1Cu2O8+∂ thin films produced on MgO (100) single crystal substrates by pulsed laser deposition (PLD)

Bi₂Sr₂Ca₁Cu₂O_8+∂ thin films were deposited on MgO (100) substrates by pulsed laser deposition (PLD). The effects of post-annealing time on the phase formation, the structural and superconducting properties of the films have been investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature dependent resistivity (R–T), atomic force microscopy (AFM), and DC magnetization measurements. The films deposited at 600 °C were post-annealed in an atmosphere of a gas mixture of Ar (93%) and O₂ (7%), at 860 °C for 10, 30, and 60 min. All films have demonstrated a mainly single phase of 2212 with a high crystallinity (FWHM≈0.159°) and c-axis oriented. The critical temperature, T_C, of the films annealed for 10, 30, and 60 min were obtained as 77, 78, and 78 K, respectively. The highest critical current density, J_C, was calculated as 3.34×10⁷ A/cm² for the film annealed at 860 °C for 30 min at 10 K.     

Fabrication of highly efficient TiO2/Ag/TiO2 multilayer transparent conducting electrode with N ion implantation for optoelectronic applications

Fabrication of highly conductive and transparent TiO₂/Ag/TiO₂ (referred hereafter as TAT) multilayer films with nitrogen implantation is reported. In the present work, TAT films were fabricated with a total thickness of 100 nm by sputtering on glass substrates at room temperature. The as-deposited films were implanted with 40 keV N ions for different fluences (1×10¹⁴, 5×10¹⁴, 1×10¹⁵, 5×10¹⁵ and 1×10¹⁶ ions/cm²). The objective of this study was to investigate the effect of N⁺ implantation on the optical and electrical properties of TAT multilayer films. X-ray diffraction of TAT films shows an amorphous TiO₂ film with a crystalline peak assigned to Ag (111) diffraction plane. The surface morphology studied by atomic force microscopy (AFM) and field emission scanning electron microscope (FESEM) revealed smooth and uniform top layer of the sandwich structure. The surface roughness of pristine film was 1.7 nm which increases to 2.34 nm on implantation for 1×10¹⁴ ions/cm² fluence. Beyond this fluence, the roughness decreases. The oxide/metal/oxide structure exhibits an average transmittance ~80% for pristine and ~70% for the implanted film at fluence of 1×10¹⁶ ions/cm² in the visible region. The electrical resistivity of the pristine sample was obtained as 2.04×10⁻⁴ Ω cm which is minimized to 9.62×10⁻⁵ Ω cm at highest fluence. Sheet resistance of TAT films decreased from 20.4 to 9.62 Ω/□ with an increase in fluence. Electrical and optical parameters such as carrier concentration, carrier mobility, absorption coefficient, band gap, refractive index and extinction coefficient have been calculated for the pristine and implanted films to assess the performance of films. The TAT multilayer film with fluence of 1×10¹⁶ ions/cm² showed maximum Haacke figure of merit (FOM) of 5.7×10⁻³ Ω⁻¹. X-ray photoelectron spectroscopy (XPS) analysis of N 1s and Ti 2p spectra revealed that substitutional implantation of nitrogen into the TiO₂ lattice added new electronic states just above the valence band which is responsible for the narrowing of band gap resulting in the enhancement in electrical conductivity. This study reports that fabrication of multilayer transparent conducting electrode with nitrogen implantation that exhibits superior electrical and optical properties and hence can be an alternative to indium tin oxide (ITO) for futuristic TCE applications in optoelectronic devices.