X-ray photoemission spectroscopy of nitrogen-doped UNCD/a-C:H films prepared by pulsed laser deposition

Nitrogen-doped ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) films were deposited by pulsed laser deposition (PLD). Nitrogen contents in the films were controlled by varying a ratio in the inflow amount between nitrogen and hydrogen gases. The film doped with a nitrogen content of 7.9 at.% possessed n-type conduction with an electrical conductivity of 18 Ω^? 1 cm^? 1 at 300 K. X-ray photoemission spectra, which were measured using synchrotron radiation, were decomposed into four component spectra due to sp², sp³ hybridized carbons, C=N and C–N. A full-width at half-maximum of the sp³ peak was 0.91 eV. This small value is specific to UNCD/a-C:H films. The sp²/(sp³ + sp²) value was enhanced from 32 to 40% with an increase in the nitrogen content from 0 to 7.9 at.%. This increment probably originates from the nitrogen incorporation into an a-C:H matrix and grain boundaries of UNCD crystallites. Since an electrical conductivity of a-C:H does not dramatically enhance for this doping amount according to previous reports, we believe that the electrical conductivity enhancement is predominantly due to the nitrogen incorporation into grain boundaries.     

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.     

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.     

Temperature effect on bonding structures of amorphous carbon containing more than 30at.% silicon

Bonding evolution of amorphous carbon incorporated with Si or a-C(Si) in a thermal process has not been studied. Unhydrogenated a-C(Si) films were deposited by magnetron sputtering to undergo two different thermal processes: i) sputter deposition at substrate temperatures from 100 to 500 °C; ii) room temperature deposition followed by annealing at 200 to 1000 °C. The hardness of the films deposited at high temperature exhibits a monotonic decrease whereas the films deposited at room temperature maintained their hardness until 600 °C. X-ray photoelectron spectroscopy and Raman spectroscopy were used to analyze the composition and bonding structures. It was established that the change in the mechanical property is closely related to the atomic bonding structures, their relative fractions and the evolution (conversion from C–C sp³ → CC sp² or CC sp² → C–Si sp³) as well as clustering of sp² structures.     

Effect of substrate temperature on microstructure and optical properties of nanocrystalline alumina thin films

Aluminum oxide (Al₂O₃) thin films were deposited on silicon (100) and quartz substrates by pulsed laser deposition (PLD) at an optimized oxygen partial pressure of 3.0×10^?3 mbar in the substrate temperatures range 300–973 K. The films were characterized by X-ray diffraction, transmission electron microscopy, atomic force microscopy, spectroscopic ellipsometry, UV–visible spectroscopy and nanoindentation. The X-ray diffraction studies showed that the films deposited at low substrate temperatures (300–673 K) were amorphous Al₂O₃, whereas those deposited at higher temperatures (≥773 K) were polycrystalline cubic γ-Al₂O₃. The transmission electron microscopy studies of the film prepared at 673 K, showed diffuse ring pattern indicating the amorphous nature of Al₂O₃. The surface morphology of the films was examined by atomic force microscopy showing dense and uniform nanostructures with increased surface roughness from 0.3 to 2.3 nm with increasing substrate temperature. The optical studies were carried out by ellipsometry in the energy range 1.5–5.5 eV and revealed that the refractive index increased from 1.69 to 1.75 (λ=632.8 nm) with increasing substrate temperature. The UV–visible spectroscopy analysis indicated higher transmittance (>80%) for all the films. Nanoindentation studies revealed the hardness values of 20.8 and 24.7 GPa for the films prepared at 300 K and 973 K respectively.     

Dependence of the composition and bonding structure of carbon nitride films deposited by direct current plasma assisted pulsed laser ablation on the deposition temperature

Carbon nitride films were deposited by direct current plasma assisted pulsed laser ablation of a graphite target under nitrogen atmosphere. Atomic force microscopy (AFM), Fourier transform infrared (FTIR), Raman, and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface morphology, bonding structure, and composition of the deposited films. The influence of deposition temperature in the range 25–400 °C on the composition and bonding structure of carbon nitride films was systematically studied. AFM images show that surface roughness and cluster size increase monotonically with deposition temperature. XPS, FTIR, and Raman spectra indicate directly the existence of CN, CN, and CN bonds in the deposited films. The increase of deposition temperature results in a drastic decrease in the N/C ratio, the content of CN bond and N atoms bonded to sp³ C atoms, in addition to the increase in the content of disorder sp² C atoms and N atoms bonded to sp² C atoms in the deposited films. Raman spectra show that the intensity ratio of D peak over G peak increases with increasing deposition temperature to 200 °C, then decreases with the further increase of deposition temperature, which results from the continuous growth of sp² cluster in the films.     

Improved surface coverage of an optical fibre with nanocrystalline diamond by the application of dip-coating seeding

Growth processes of diamond thin films on the fused silica optical fibres (10 cm in length) were investigated at various temperatures. Fused silica pre-treatment by dip-coating in a dispersion consisting of detonation nanodiamond (DND) in dimethyl sulfoxide (DMSO) with polyvinyl alcohol (PVA) was applied. Nanocrystalline diamond (NCD) films were deposited on the fibres using the microwave plasma assisted chemical vapour deposition (MW PA CVD) method. The longitudinal variation of NCD morphology, structure and optical parameters were specifically investigated. The evolution of the film morphology and film thickness along the fibre length was studied using scanning electron microscopy (SEM). The chemical composition of the NCD film was examined with micro-Raman Spectroscopy. The sp³/sp² band ratio was calculated using the Raman spectra deconvolution method. An approximately 5 cm-long homogeneous diamond film has been obtained on the surface of the fibre sample. Thickness, roughness and optical properties of NCD films in the VIS–NIR range were investigated on the reference quartz slides using spectroscopic ellipsometry. The samples exhibited relatively low deviations of refractive index (2.3 ± 0.25) and extinction coefficient (0.05 ± 0.02) along the length of 5 cm, as estimated at a wavelength of 550 nm. In order to show the effectiveness of deposition process on optical fibres, diamond films were also grown on the fibre with induced long-period grating (LPG). The results of transmission measurements demonstrated that an LPG with diamond overlay exhibits the appropriate dependency on the optical properties of external medium. Thus, the deposition process has a negligible effect on the fibre transmission properties.     

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.     

Microstructure and optical band gap control of DLC film deposited by pulsed discharge plasma CVD

DLC films were deposited on silicon and quartz glass substrates by pulsed discharge plasma chemical vapor deposition (CVD), where the plasma was generated by pulsed DC discharge in H₂–CH₄ gas mixture at about 90 Torr in pressure, and the substrates were located near the plasma. The repetition frequency and duty ratio of the pulse were 800 Hz and 20%, respectively. When CH₄ / (CH₄ + H₂) ratio, i.e. methane concentration (Cm), increased from 3 to 40%, C₂ species in the plasma was increased, and corresponding to the increase of C₂, deposition rate of the film was increased from about 0.2 to 2.4 μm/h. The absorption peaks of sp³C–H and sp²C–H structures were observed in the FT-IR spectra, and the peak of sp²C–H structure was increased with increasing Cm, showing that sp² to sp³ bonding ratio was increased when Cm was increased. Corresponding to these structural changes due to the increase of Cm, optical band gap (Eg) was decreased from 3 to 0.5 eV continuously when Cm was increased from 3 to 40%.     

Deposition of hard amorphous hydrogenated carbon films by radiofrequency parallel-plate hollow-cathode plasmas

Hard amorphous hydrogenated carbon (a-C:H) films were deposited by plasma decomposition of CH₄ gas in a RF parallel-plate hollow-cathode system. The deposition system was built by placing a metallic plate in parallel to and in electrical contact with an usual RF-PECVD planar cathode. Self-bias versus RF power curves were used to make an initial characterization of plasma discharges in nitrogen gas atmospheres, for pressures between 10 and 100 mTorr. The strongly increased power consumption to obtain the same self-bias in the hollow-cathode system evidenced an increase in plasma density. The a-C:H films were deposited onto Si single crystalline substrates, in the − 50 to − 500 V self-bias range, at 5, 10 and 50 mTorr deposition pressures. The film deposition rate was found to be about four times than that usually observed for single-cathode RF-PECVD-deposited films, under methane atmosphere, at similar pressure and self-bias conditions. Characterization of film structure was carried out by Raman spectroscopy on films deposited at 10 and 50 mTorr pressures. Gaussian deconvolution of the Raman spectra in its D and G bands shows a continuous increase in the I_D/I_G integrated band intensity ratio upon self-bias increase, obeying the expected increasing behavior of the sp² carbon atom fraction. The peak position of the G band was found to increase up to − 300 V self-bias, showing a nearly constant behavior for higher self-bias absolute values. On the other hand, the G band width showed a nearly constant behavior within the entire self-bias range. Nanohardness measurements have shown that films deposited with self-bias greater than 300 V are as hard as films obtained by the usual PECVD techniques, showing a maximum hardness of about 18 GPa. Films were also found to develop high internal compressive stress. The stress dependence on self-bias showed a strong maximum at about − 200 V self-bias, with a maximum stress value of about 5 GPa.     

Hydrogen plasma etching of diamond films deposited on graphite

Poly- and nanocrystalline diamond films have been deposited using microwave plasma enhanced CVD with gas mixtures of x%CH₄/15%H₂/Ar (x = 0.5, 1, 3, and 5). After deposition the resulting films were exposed to a hydrogen plasma etching for 30 min. The hydrogen plasma produced preferential etching of non-diamond carbon on the surface of the samples and the development of steps and pits. Raman spectroscopy and X-ray photoelectron spectroscopy analyses on the etched films showed increased sp³/sp² ratio and decreased surface oxygen. The etch mechanism proposed is regression of pre-existing steps and step flow.     

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.     

The role of substrate temperature on the properties of nanocrystalline Mo doped ZnO thin films by spray pyrolysis

Transparent conducting molybdenum (2 at.%) doped zinc oxide (MZO) films were prepared with various substrate temperatures by spray pyrolysis technique on glass substrates. The effect of substrate temperature on the structural, surface morphological, electrical, optical and photoluminescence properties of these films were studied. The X-ray diffraction analysis revealed that the films are polycrystalline in nature having a wurtzite structure with a preferred grain orientation in the (0 0 2) direction. The average crystallite size of the films increases from 17 nm to 28 nm with the increase of substrate temperature from 573 K to 623 K, thereafter it slightly decreases with further increase of substrate temperature to 723 K. Analysis of structural parameters indicates minimum strain and stress values for films deposited at a substrate temperature of 673 K. From atomic force microscopy (AFM) analysis, it is found that rms roughness of the films deposited at 623 K is a minimum, indicating better optical quality. The scanning electron microscopy (SEM) measurements showed that the surface morphology of the films changes with substrate temperature. Optical parameters such as optical transmittance, reflectance, refractive index, extinction coefficient, dielectric constant and optical band gap have been studied and discussed with respect to substrate temperature. Room temperature photoluminescence (PL) spectra show the deep-level emission in the MZO thin films. The films exhibit a low electrical resistivity of 6.22 × 10^?2 Ω cm with an optical transmittance of 75% in the visible region at a substrate temperature of 623 K.     

Thermal release of hydrogen retained in multilayer graphene films prepared by mist-chemical vapor deposition

In this study, we investigated the absorption and thermal desorption processes of H and H₂O and the thickness of multilayer graphene films deposited on Cu foils using a mist-chemical vapor deposition method. Ion beam analysis techniques such as nuclear reaction analysis (NRA), elastic recoil detection (ERD), and Rutherford backscattering spectrometry (RBS) were employed. The RBS measurements revealed that the thickness of the multilayer graphene films was approximately 8 ± 3 nm (24 ± 9 layers). The depth distribution of H was analyzed using NRA and ERD. Based on these measurements, the residual H/C ratio for multilayer graphene was estimated to be approximately 0.03 in the bulk and 0.88 on the top-most surface. Additionally, the thermal desorption temperature for H from the multilayer graphene film was less than 373 K, which was much lower than that from isotropic graphite bulk (approximately 673 K). These results suggest that the thermal release of H did not occur because of desorption from sp²- and sp³-hybridized C atoms, such as intercalation and defect sites. Instead, it occurred owing to the desorption of H₂O adsorbed near the surface.     

Very hard ZrC thin films grown by pulsed laser deposition

Thin ZrC films were grown on (1 0 0) Si substrates at temperatures from 30 to 500 °C by the pulsed laser deposition technique. Auger electron spectroscopy investigations found that films contained oxygen concentration below 2.0 at%, while X-ray photoelectron spectroscopy investigations showed that oxygen is bonded in an oxy-carbide type of compound. The films’ mass densities, estimated from X-ray reflectivity curve simulations, and crystallinity improved with the increase of the substrate temperature. Williamson–Hall plots and residual-stress measurements using the modified sin² ψ method for grazing incidence X-ray diffraction showed that the deposited films are nanostructured, with crystallite sizes from 6 to 20 nm, under high micro-stress and compressive residual stress. Nanoindentation investigations found hardness values above 40 GPa for the ZrC films deposited at substrate temperatures higher than 300 °C. The high density of the deposited films and the nm-size crystallites are the key factors for achieving such high hardness values.     

Hydrogenated amorphous carbon films deposited in an electron cyclotron resonance–chemical vapor deposition discharge reactor using acetylene

Hydrogenated amorphous carbon (a-C:H) films have been deposited from acetylene gas in a microwave electron cyclotron resonance (ECR) plasma reactor. The films were deposited at a pressure of 0.2 mTorr and at radio frequency (r.f.) induced substrate biases from 80–300 V. Selected film properties, including optical bandgap and bonded hydrogen content, were measured. At r.f. induced biases from 150 to 300 V, corresponding to ion energies for C₂H₂⁺ of approximately 150–300 eV, the hydrogen content remains constant and the optical bandgap peaks at a bias of 200 V, or approximately 100 eV per carbon in the C₂H₂⁺ ions. This ECR system result is in agreement with those observed by other researchers using different deposition methods where an optical bandgap maximum and an sp³ maximum occurs at ion energies of 90–100 eV per carbon atom. The discharge properties measured include a partial pressure analysis of the residual exit gas and the substrate current density.     

Deposition of aromatic polyimide thin films in supercritical carbon dioxide

The deposition of aromatic polyimide (API) thin films was carried out in supercritical carbon dioxide (scCO₂) with 20 mol% of N,N-dimethylformamide (DMF) as a cosolvent, and using 4,4′-diaminodiphenyl ether (ODA) and pyromellitic dianhydride (PMDA) as monomers. A new apparatus based on a flow method that consisted of a cold-wall type reactor and two supply lines for each of the API monomers was used. The effect on the morphology of the films was investigated at feeding monomer concentrations and deposition temperatures ranging from 5 × 10⁻⁴ to 5 × 10⁻⁶ on a mole fraction basis and from 423 to 523 K, respectively. The results showed that increasing the monomer concentration and decreasing the deposition temperature increased the thickness of the films, and a smooth surface of the film was obtained at 423 K. Additionally, FT-IR study and thermogravimetric (TG) analysis of the film deposited at monomer mole fractions of 5 × 10⁻⁵ and at a deposition temperature of 473 K were also carried out. The FT-IR spectrum of the deposited film in scCO₂ with DMF represented imide structures although there was a small peak of amide carbonyl stretching that originated from the polyamic acid and DMF. The TG curve indicated the temperature of 5% weight loss was more than 800 K under an air atmosphere after complete imidization.     

Electron-assisted deposition of cubic boron nitride by r.f. magnetron sputtering

Cubic boron nitride (cBN) has been deposited on silicon (100) substrates by means of radio frequency (r.f.) magnetron sputtering in nitrogen using a hexagonal boron nitride target with the assistance of a simultaneous electron bombardment of the growing surface. Unlike most thin-film deposition processes for cBN, intentional bombardment of the growing surface by ion beams within specific ranges in energy and flux is not required for this process to achieve high-purity cBN films. Fourier transform infra-red (FTIR) spectra of cBN films show a strong absorption band around 1070 cm⁻¹. With electrons bombarding the growing surface at a current density of 140 mA cm⁻² or higher, pure (according to FTIR spectra) cBN films are deposited on silicon substrates at temperatures above 750°C. The effects of electron current density and nitrogen gas pressure on the synthesis of cBN films will be discussed.     

Enhanced cycling stability of Ni-MH battery by depositing amorphous carbon film on the Ti1.4V0.6Ni negative electrode

Amorphous carbon (a-C) films with various thicknesses depending on the reaction time are deposited on the surface of Ti_1.4V_0.6Ni alloy electrodes for Ni-MH (nickel-metal hydride) battery by radio frequency plasma enhanced chemical vapor deposition (RF-PECVD). With the increasing deposition time, the Raman spectra show a gradually disordered sp²-bonding change of the films and the changing trend of sp²/sp³ is obtained by X-ray photoelectron spectroscopy. The a-C film of depositing for 30 min with the thickness of 400 nm shows a favorable stability in alkaline electrolyte, the capacity is enhanced by 36.2% after 50 cycles than the bare electrode, and the charge voltage is 80 mV lower than the bare one. The a-C film with high sp²-bonded carbon content effectively reduces the charge transfer resistance, and as a coating layer, the dissolution of V of the alloy is also inhibited. In particular, to get a proper discharge voltage and a stable capacity simultaneously, covering completely and an appropriate thickness of the a-C film are crucial for an expected performance.     

Substrate temperature effects on the microhardness and adhesion of diamond-like thin films

Diamond-like films were deposited on silicon substrates by r.f. plasma-enhanced chemical vapor deposition from gas methane. In this study, the substrate temperature, T_S, was varied in a wide range from 20 to 370°C while maintaining fixed other important process parameters such as r.f. power (70 W) or pressure (2.5 Pa). The increase of T_S causes an increase of the sp²/(sp²+sp³) bonded carbon ratio and a decrease of the hydrogen content. These changes produce a great modification of the mechanical properties: microhardness, friction coefficient and adhesion. The variations of mechanical properties with T_S correlate well with the sp²/(sp²+sp³) bonded carbon ratio and the hydrogen content in the films showing a gradual transformation of the diamond-like structure into a more sp²-rich one.