Preparation of boron carbon nitride thin films by radio frequency magnetron sputtering

Boron carbon nitride films were deposited by radio frequency magnetron sputtering using a composite target consisting of h-BN and graphite in an Ar-N₂ gas mixture. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The results suggest that the films are atomic-level hybrids composed of B, C and N atoms. The boron carbon nitride films prepared in the present experiment have a disordered structure. The sputtering power varied from 80 W to 130 W. This sputtering power was shown to have regular effect on the composition of boron carbon nitride films. The samples deposited at 80 W and 130 W are close to the stoichiometry of BC₃N. The sample deposited at 110 W is close to the stoichiometry of BCN. The samples deposited at 100 W and 120 W approach to BC₂N. It is very significant for us to synthesize boron carbon nitride compound with controllable composition by changing the sputtering power.     

Influence of assisted ion energy on surface roughness and mechanical properties of boron carbon nitride films synthesized by DIBSD

The BCN thin films were produced by dual ion beam sputtering deposition (DIBSD). The influence of assisted ion energy on surface roughness and mechanical properties of BCN films were investigated. The surface roughness was determined by atomic force microscopy (AFM) and the mechanical properties of BCN firms were evaluated by nano-indentation in N₂ gas. The composition, structure and chemical bonding of the BCN thin films were analyzed by using energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), laser Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR). These films appeared as amorphous structure. As a result, the BCN films with the smoothest surface (R_a = 0.35 nm and R_p-v = 4.4 nm) and the highest nano-hardness of 30.1 GPa and elastic modulus of 232.6 GPa were obtained at 200 eV and 12 mA with N₂:Ar = 1:1, and the chemical composition of this BCN film was 81 at.% B, 14 at.% C and 5 at.% N. Moreover, several bonding states such as B-N, B-C and C-N were observed in BCN thin films.     

Electron transport in semiconducting nanoparticle and nanocluster carbon-polymer composites

The electron transport properties of two types of carbon-polyimide (C-PI) nanocomposite thin films have been evaluated. Conductive nanocomposites formed by incorporation of 30 nm carbon particles prior to polymer cross linking (ex situ formation) has been compared to high energy ion beam irradiation in situ formation of nanoscale carbon clusters within the polymer composite. Addition of carbon nanoparticles were able to reduce the resistivity by 13 orders of magnitude for 8 vol% carbon content. The irradiated in situ formed film showed a comparable resistivity to this 8% C-PI film. All the films exhibited negative temperature coefficient of resistance (NTCR) behaviour. While in the ex situ films the NTCR decreased progressively with increasing temperature above 350 K, the in situ film exhibited a constant NTCR value at ambient as well as elevated temperatures indicating that films formed by ion beam irradiation eliminate possible clustering of nanoparticles prior to crosslinking seen in the ex situ films. The optimum hop energies for the ex situ films ranged from 23.1 to 8.05 meV when carbon content increased from 1 to 8 vol% and the corresponding value for the in situ formed film was 34.94 meV. These films had appreciable NTCR values, and were evaluated for their thermistor behaviour as a class of material with potential for temperature sensing devices.     

Characterization of BCN films synthesized by radiofrequency plasma enhanced chemical vapor deposition

Boron carbonitride (BCN) films have been synthesized on Si(1 0 0) substrate by radio frequency plasma enhanced chemical vapor deposition using tris-(dimethylamino)borane (TDMAB) as a precursor. The deposition was performed at the different RF powers of 400-800 W, at the working pressure of 2×10⁻¹ Torr. The formation of the sp²-bonded BCN phase was confirmed by Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy measurements showed that B atoms were bonded to C and N atoms to form the BCN atomic hybrid configurations with the chemical compositions of B₅₂C₁₂N₃₆ (sample 1; prepared at the RF power of 400 W), B₅₂C₁₀N₃₈ (sample 2; at 500 W) and B₄₆C₁₈N₃₆ (sample 3; at 800 W), respectively. Near-edge X-ray absorption fine structure (NEXAFS) measurements indicated that B atoms were bonded not only to N atoms but also to C atoms to form various configurations of sp²-BCN atomic hybrids. The polarization dependence of NEXAFS suggested that the predominant hybrid configuration of sp²-BCN films oriented in the direction perpendicular to the Si substrate.     

Preparation and hydrogen storage of activated rayon-based carbon fibers with high specific surface area

Activated carbon fibers were prepared from rayon-based carbon fibers by two step activations with steam and KOH treatments. Hydrogen storage properties of the activated rayon-based carbon fibers with high specific surface area and micropore volume have been investigated. SEM, XRD and Brunauer-Emmett-Teller (BET) were used to characterize the samples. The adsorption performance and porous structure were investigated by nitrogen adsorption isotherm at 77 K on the base of BET and density functional theory (DFT). The BET specific surface area and micropore volume of the activated rayon-based carbon fibers were 3144 m²/g and 0.744 m³/g, respectively. Hydrogen storage properties of the samples were measured at 77 and 298 K with pressure-composition isotherm (PCT) measuring system based on the volumetric method. The capacities of hydrogen storage of the activated rayon-based carbon fibers were 7.01 and 1.46 wt% at 77 and 298 K at 4 MPa, respectively. Possible mechanisms for hydrogen storage in the activated rayon-based carbon fibers are discussed.     

Dielectric properties of anodic films on sputter-deposited Ti-Si porous columnar films

For electrolytic capacitor application of the single-phase Ti alloys containing supersaturated silicon, which form anodic oxide films with superior dielectric properties, porous Ti-7 at% Si columnar films, as well as Ti columnar films, have been prepared by oblique angle magnetron sputtering on to aluminum substrate with a concave cell structure to enhance the surface area and hence capacitance. The deposited films of both Ti and Ti-7 at% Si have isolated columnar morphology with each column revealing nanogranular texture. The distances between columns are ∼500 nm, corresponding to the cell size of the textured substrate and the gaps between columns are 100-200 nm. When the porous Ti-7 at% Si film is anodized at a constant current density in ammonium pentaborate electrolyte, the growth of a uniform amorphous oxide film continues to ∼35 V, while it is limited to less than 6 V on the porous Ti film. The maximum voltage of the growth of uniform amorphous oxide films on the Ti-7 at% Si films is similar for both the flat and porous columnar films, suggesting little influence of surface roughness on the amorphous-to-crystalline transition of growing anodic oxide under the high electric field. Due to the suppression of crystallization to sufficiently high voltages, the anodic oxide films formed on the porous Ti-7 at% Si film shows markedly improved dielectric properties, in comparison with those on the porous Ti film.     

Efficient field emission from coiled carbon nano/microfiber on copper substrate by dc-PECVD

Crystalline coiled carbon nano/micro fibers in thin film form have been synthesized via direct current plasma enhanced chemical vapor deposition (PECVD) on copper substrates with acetylene as a carbon precursor at 10 mbar pressure and 750 °C substrate temperature. The as-prepared samples were characterized by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). XRD pattern as well as selected area electron diffraction (SAED) pattern showed that the samples were crystalline in nature. SEM and HRTEM studies showed that as synthesized coiled carbon fibers are having average diameter ∼100 nm and are several micrometers in length. The as-prepared samples showed moderately good electron field emission properties with a turn-on field as low as 1.96 V/μm for an inter-electrode distance 220 μm. The variation of field emission properties with inter-electrode distance has been studied in detail. The field emission properties of the coiled carbon fibrous thin films are compared with that of crystalline multiwalled carbon nanotubes and other carbon nanostructures.     

Blue-cathodoluminescent layers synthesis by high-dose N, C and B SiO2 implantation

Thermal silicon oxide layers have been implanted at 600 °C with N⁺+C⁺, N⁺+B⁺ and N⁺+C⁺+B⁺ ions. Two different implantation doses have been chosen in order to introduce peak concentrations at the projected range comparable to the SiO₂ density. Some pieces of the samples have been annealed in conventional furnace at 1200 °C for 3 h. After annealing, cathodoluminescence measurements show in all cases a main broad band centered at 460 nm (2.7 eV). High doses of C implantation give rise to an intensity attenuation. Phases formed in the oxides have been investigated by Fourier transform infrared spectroscopy before and after annealing. The spectra suggest that N incorporates as BN and probably as a ternary BCN phase in the triply implanted samples, while C seems to bond mainly with B. Boron is also bonded to O in B-O-Si configuration. Depth structure and quantitative composition of the films were deduced from fittings of the spectroscopic ellipsometry measurements.     

Improved electrical properties of silicon-incorporated anodic niobium oxide formed on porous Nb-Si substrate

In the present study, porous Nb-Si alloy films with isolated nano-column morphology have been successfully developed by oblique angle magnetron sputtering on to aluminum substrate with concave cell structure. The deposited films are amorphous with the 15 at% silicon supersaturated into niobium. The porous Nb-15 at% Si films, as well as niobium films with similar morphology, are anodized at several voltages up to 50 V in 0.1 mol dm⁻³ ammonium pentaborate electrolyte. Due to the presence of sufficient gaps between neighboring columns, the gaps are not filled with anodic oxide, despite the large Pilling-Bedworth ratio (for instance, 2.6 for Nb/Nb₂O₅) and hence, a linear correlation between the reciprocal of capacitance and formation voltage is obtained for the Nb-15 at% Si. From the comparison with the anodic films formed on porous niobium films, it has been found that silicon addition improves the thermal stability of anodic niobium oxide; the change in capacitance and increase in leakage current become small for the Nb-Si. The findings indicate the potential of oblique angle deposition to tailor porous non-equilibrium niobium alloy films for high performance niobium-base capacitor.     

The electrochemical preparation and microwave absorption properties of magnetic carbon fibers coated with Fe3O4 films

Electrodeposition was employed to fabricate magnetite (Fe₃O₄) coated carbon fibers (MCCFs). Temperature and fiber surface pretreatment had a significant influence on the composition and morphology of Fe₃O₄ films. Uniform and compact Fe₃O₄ films were fabricated at 75 °C on both nitric acid treated and untreated carbon fibers, while the films prepared at 60 °C were continuous and rough. Microwave measurements of MCCF/paraffin composites (50 wt.% of MCCFs, pretreated carbon fibers as deposition substrates) were carried out in the 2-18 GHz frequency range. MCCFs prepared at 60 °C obtained a much higher loss factor than that prepared at 75 °C. However, the calculation results of reflection loss were very abnormal that MCCFs prepared at 60 °C almost had no absorption property. While MCCFs prepared at 75 °C exhibited a good absorption property and obtained −10 dB and −20 dB refection loss in wide matching thickness ranges (1.0-6.0 mm and 1.7-6.0 mm range, respectively). A secondary attenuation peak could also be observed when the thickness of MCCF/paraffin composite exceeded 4.0 mm. The minimum reflection loss was lower.     

Investigation of heat-treatment and pre-treatment on microstructure and electrochemical properties of cerium nano-oxide films on AA7020-T6 by sol-gel methods

In this paper cerium nano-oxide films were applied on AA7020-T6 alloy by sol-gel method. Potentiodynamic polarization and EIS studies have been used to study the corrosion behavior of cerium oxide nano films in 3.5% NaCl. Microstructural and phase properties of cerium oxide were investigated by SEM and XRD. The results showed that heat-treatment temperature and pre-treatment have an important effect on microstructure and electrochemical properties of cerium nano-oxide films. It can be seen from the results that with increasing heat-treatment temperature from 150 to 300 °C, the corrosion resistance of the films increased. It is related to increase the condensation of the films with adding temperature. Also, it can be seen that with adding temperature from 300 to 400 °C, the corrosion resistance of the films decrease. This is an important case related to crystallization of the cerium oxide films between 300 and 400 °C which showed that crystallized ceria films illustrate less corrosion resistance with respect to an amorphous film. Although with applying cerium oxide films the corrosion resistance of the films increased but still the passive region of the ceria films was tiny. So that in this research especially pre-treatment (etching in NaOH solution for 1 min, washing with deionized water for 5 min, etching with acid solution which contained several acids (H₂SO₄, HF, HCl, H₃PO₄), washing with deionized water for 5 min and after that following the samples in boiling deionized water for 1 h) was applied on samples before ceria treatment. The results showed that after applying this pre-treatment the passive region of the films increased extremely. It is related to formation of the thick and porous alumina films after applying pre-treatment which are similar to millepore.     

Structure evolution from nanocolumns to nanoporous of nitrogen doped amorphous carbon films deposited by magnetron sputtering

Different nitrogen doped amorphous carbon (CNx) films were obtained by magnetron sputtering of carbon target in argon and nitrogen atmosphere at the increasing negative bias voltages from 0 to 150 V. The films structures have experienced great change, from the novel column to nanoporous structure at the bias voltage of 0 V to the porous structure at 150 V. The proposed growth process was that the CNx nuclei grew at 0 V acted as the “seeds” for the growth of the nanocolumns, and ion etching effects at 150 V induced the formation of nanoporous structures. Furthermore, a comparison study showed that the field emission properties of the CNx films were related with the introduction of the nitrogen atoms, the size and concentration of sp² C clusters and the surface roughness. The films with rougher surface have lower threshold field.     

Preparation of vertically aligned carbon nanotube arrays grown onto carbon fiber fabric and evaluating its wettability on effect of composite

Vertically aligned carbon nanotube (CNT) arrays have been grown onto the carbon fiber fabric using a catalytic chemical vapor deposition (CCVD) method. The as-synthesized CNT arrays are about 20 μm in height, and the nanotube has a mean inner and outer diameter of 2.6 nm, 5.5 nm, respectively. The CNT-grafted carbon fabric shows a hydrophobic property with a contact angle over 145°, and the single CNT-grafted carbon fiber shows a sharp increase of dynamic contact angle in de-ionized water from original 71.70° to about 103°, but a little increase does in diiodomethane or E-51 epoxy resin. However, the total surface energy of carbon nanotube-grafted carbon fiber is almost as same as that of as-received carbon fiber. After CNTs growth, single fiber tensile tests indicated a slight tensile strength degradation within 10% for all different lengths of fibers, while the fiber modulus has not been significantly damaged. Compared with the as-received carbon fibers, a nearly 110% increase of interfacial shear strength (IFSS) from 65 to 135 MPa has been identified by single fiber pull-out tests for the micro-droplet composite, which is reinforced by as-received carbon fiber or CNT-grafted carbon fiber.     

Characterization of boron carbon nitride film modified by excimer laser annealing

Boron carbon nitride (BCN) shows promise as a field emitter material because of its mechanical hardness, chemical inertness, and low electron affinity. This study investigated the modification of a BCN film with an amorphous area using KrF excimer laser (wavelength: 248 nm, photon energy: 5.0 eV) annealing without substrate heating. This achieved significant variation in characteristics, such as an increase in bandgap energy and decrease in electron affinity. Laser annealing reduced electron affinity from 0.7 to 0.3 eV. The results indicate that the modification of the BCN film by KrF excimer laser annealing achieves characteristics similar to hexagonal BN (h-BN) film without losing the desirable properties of the BCN film, such as physical stability.     

The study of magnetic properties and microstructures of nano-size FePt islands on amorphous carbon film

This work focuses on the formation mechanisms of nano-island FePt film on commercial copper grids covered with an amorphous carbon film. FePt films of different thickness (1-7.5 nm) were deposited on amorphous carbon film and then post-annealed at 700 °C for 30 min. The configuration of the film was changed during the annealing process due to the surface energy difference between the amorphous carbon films and FePt alloy. We have prepared nanometer-size island-shaped FePt films on the amorphous carbon films and investigated their magnetic properties and microstructures. A discontinuous nano-size island magnetic film can reduce the exchange coupling of the media and increase the recording density.     

Characterization of ZnO-SnO2 thin film composites prepared by pulsed laser deposition

Thin films of ZnO-SnO₂ composites have been deposited on Si(1 0 0) and glass substrates at 500 °C by pulsed laser ablation using different composite targets with ZnO amount varying between 1 and 50 wt%. The effect of increasing ZnO-content on electrical, optical and structural properties of the ZnO-SnO₂ films has been investigated. X-ray diffraction analysis indicates that the as-deposited ZnO-SnO₂ films can be both crystalline (for ZnO <1 wt%) and amorphous (for ZnO ≥ 10 wt%) in nature. Atomic force microscopy studies of the as-prepared composite films indicate that the surfaces are fairly smooth with rms roughness varying between 3.07 and 2.04 nm. The average optical transmittance of the as-deposited films in the visible range (400-800 nm), decreases from 90% to 72% for increasing ZnO concentration in the film. The band gap energy (E_g) seems to depend on the amount of ZnO addition, with the maximum obtained at 1 wt% ZnO. Assuming that the interband electron transition is direct, the optical band gap has been found to be in the range 3.24-3.69 eV for as-deposited composite films. The lowest electrical resistivity of 7.6 × 10⁻³ Ω cm has been achieved with the 25 wt% ZnO composite film deposited at 500 °C. The photoluminescence spectrum of the composite films shows a decrease in PL intensity with increasing ZnO concentration.     

Low dielectric loss Ba0.6Sr0.4TiO3/MgTiO3 composite thin films prepared by a sol–gel process

The dielectric properties of Ba_0.6Sr_0.4TiO₃ (BST)/MgTiO₃ (MT) composite thin films deposited on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by the sol–gel method were investigated. The X-ray pattern analysis indicates that the thin films exhibit good crystalline quality with perovskite phase and that insertion of MT layer does not obviously affect the phase structure of BST thin films. The characterization of dielectric properties demonstrates that configuration of BST/MT/BST thin films is an effective approach to obtain low dielectric loss and dielectric tunability of BST thin films. At room temperature, the tunability of pure BST60 films and BST/MT (15 nm)/BST composite thin films is 47% and 36%, respectively, at the frequency of 1 MHz with an applied electric field of 400 kV/cm. For BST/MT/BST composite thin films, considerable reduction in the dielectric loss values is observed, which renders them attractive for tunable microwave device applications.     

Study of porous carbon thin films produced by pulsed laser deposition

Amorphous carbon is an interesting material and its properties can be varied by tuning its diamond-like (sp³) fractions. The diamond-like fractions in an amorphous carbon films depends on the kinetic energy of the deposited carbon ions. Porous amorphous carbon thin films were deposited onto silicon substrates at room temperature in a vacuum chamber by Glancing Angle Pulsed Laser Deposition (GAPLD). Krypton fluoride (248 nm) laser pulses with duration of 15 ns and intensities of 1-20 GW/cm² were used. In GAPLD, the angles between the substrate normal and the trajectory of the incident deposition flux are set to be almost 90°. Porous thin films consisting of carbon nanowires with diameters less than 100 nm were formed due to a self-shadowing effect. The kinetic energies of the deposited ions, the deposition rate of the films and the size of the nanowires were investigated. The sp³ fraction of the porous carbon films produced at intensity around 20 GW/cm² were estimated from their Raman spectra.     

Structure and mechanical properties of titanium nitride/carbon nitride multilayers

The structure and mechanical properties of the multilayers consisting of 5-73 nm thick titanium nitride (TiN) and 4.6 nm thick carbon nitride (CN) have been investigated. It has been found that the CN layers are amorphous and the TiN layers thinner than 17 nm are amorphous. The TiN layers become crystallized as the thickness is increased to 30 nm or thicker. The hardness from the composite response of the multilayered films and their substrates determined using continuous stiff measurement is smaller than the film-only hardness (without substrate effects) calculated using Bhattacharya-Nix empirical equation. The hardness increases with raising the thickness of TiN layers. With the crystallization of the TiN layer, the multilayers become even harder than that calculated based on the rule of mixtures. However, no enhancement in hardness has been observed when the TiN layers are amorphous.     

Study on structural properties of epitaxial silicon films on annealed double layer porous silicon

In this paper, epitaxial silicon films were grown on annealed double layer porous silicon by LPCVD. The evolvement of the double layer porous silicon before and after thermal annealing was investigated by scanning electron microscope. X-ray diffraction and Raman spectroscopy were used to investigate the structural properties of the epitaxial silicon thin films grown at different temperature and different pressure. The results show that the surface of the low-porosity layer becomes smooth and there are just few silicon-bridges connecting the porous layer and the substrate wafer. The qualities of the epitaxial silicon thin films become better along with increasing deposition temperature. All of the Raman peaks of silicon films with different deposition pressure are situated at 521 cm⁻¹ under the deposition temperature of 1100 °C, and the Raman intensity of the silicon film deposited at 100 Pa is much closer to that of the monocrystalline silicon wafer. The epitaxial silicon films are all (4 0 0)-oriented and (4 0 0) peak of silicon film deposited at 100 Pa is more symmetric.