The microstructure and properties of energetically deposited carbon nitride films

The intrinsic stress, film density and nitrogen content of carbon nitride (CN_x) films deposited from a filtered cathodic vacuum arc were determined as a function of substrate bias, substrate temperature and nitrogen process pressure. Contour plots of the measurements show the deposition conditions required to produce the main structural forms of CN_x including N-doped tetrahedral amorphous carbon (ta-C:N) and a variety of nitrogen containing graphitic carbons. The film with maximum nitrogen content (~ 30%) was deposited at room temperature with 1.0 mTorr N₂ pressure and using an intermediate bias of − 400 V. Higher nitrogen pressure, higher bias and/or higher temperature promoted layering with substitutional nitrogen bonded into graphite-like sheets. As the deposition temperature exceeded 500 °C, the nitrogen content diminished regardless of nitrogen pressure, showing the meta-stability of the carbon–nitrogen bonding in the films. Hardness and ductility measurements revealed a diverse range of mechanical properties in the films, varying from hard ta-C:N (~ 50 GPa) to softer and highly ductile CN_x which contained tangled graphite-like sheets. Through-film current–voltage characteristics showed that the conductance of the carbon nitride films increased with nitrogen content and substrate bias, consistent with the transition to more graphite-like films.     

Oxygen to carbon atoms ratio effect on the size,morphology and purity of functionalized carbon nanoshells by using alcohol mixtures as carbon source

The effect of the ratio of oxygen to carbon atoms (O/C) on the morphology of carbon nanostructures has been studied by varying the methanol and ethanol ratio in the reaction mixtures. Notable morphological differences in the synthesized carbon nanostructures are observed as a function of the O/C ratio. At a high O/C ratio, i.e., using methanol (O/C = 1), the synthesized carbon nanoshells (CNS) are faceted. Moreover, other faceted nanostructures, such as triangular and hexagonal, are observed in this strong oxidative environment. Decreasing the O/C ratio in the mixture by adding ethanol induces changes in the CNSs morphology; they are less faceted and favor only the growth of single-walled carbon nanotubes mixed with the CNSs. The importance of the O/C ratio is corroborated by replacing ethanol (O/C = 0.5) with polyethylene glycol (O/C = 0.5) in the methanol:ethanol reaction mixture. Finally, at very low O/C ratios, i.e., methanol:octanol mixtures, CNS are obtained and no faceted nanostructures or SWCNT are found. Thus, adjusting the O/C ratio is a method for obtaining high purity samples of CNS. Moreover, the use of the alcohols during the synthetic process is a simple and green method of functionalizing CNS.     

Lanthanum nickelate thin films deposited by spray pyrolysis: Crystallization,microstructure and electrochemical properties

Thin films from the La_n+1Ni_nO_3n+1 system exhibit favorable dielectric and electrochemical properties that may prove useful for a variety of devices ranging from ferroelectrics to low-temperature solid oxide fuel cells. The present work covers the compositional, microstructural and electrochemical characterization of thin lanthanum nickelate films deposited by spray pyrolysis. In accordance with the phase diagram, LaNiO_3?δ or La₄Ni₃O_10?δ films were obtained during annealing of spray deposited films at temperatures between 540 °C and 1100 °C. Whereas LaNiO_3?δ films exhibited a high metallic conductivity, La₄Ni₃O_10?δ films were semiconducting. Electrochemical impedance spectroscopy indicated an increase of the area specific oxygen reduction resistance with the annealing temperature. The study highlights how the phase and microstructure of thin films from the La_n+1Ni_nO_3n+1 system can be tailored by annealing of initially amorphous films. LaNiO_3?δ films have a high potential for application in electrochemical devices operating at low temperatures where high electrical conductivity is required.     

Stress and structural properties of diamond-like carbon films deposited by electron beam excited plasma CVD

Diamond-like carbon (DLC) films prepared using CH₄ or C₆H₆ with varying deposition parameters by an electron beam excited plasma CVD system were investigated for the internal stress, dynamic hardness and structural properties such as the film density, total, bonded and unbound hydrogen contents, sp³ ratio and graphite crystallite. From the correlations between internal stress and structural properties, the following conclusions were derived. The fraction of unbound hydrogen to total hydrogen content was the most influential factor for the compressive stress of the DLC films deposited from CH₄. It is suggested that unbound hydrogen may be trapped into the disordered microstructure of graphite crystallites embedded in the network of film. For the DLC films deposited from C₆H₆, it was shown that the compressive stress was correlated with not only the fraction of unbound hydrogen content but also the degree of cross-linking between graphite crystallites in the film.     

Effect of substrate bias voltage on the properties of diamond-like carbon thin films deposited by microwave surface wave plasma CVD

Diamond-like carbon (DLC) thin films were deposited on silicon and ITO substrates with applying different negative bias voltage by microwave surface wave plasma chemical vapor deposition (MW SWP-CVD) system. The influence of negative bias voltage on optical and structural properties of the DLC film were investigated using X-ray photoelectron spectroscopy, UV/VIS/NIR spectroscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. Optical band gap of the films decreased from 2.4 to 1.7 with increasing negative bias voltage (0 to − 200 V). The absorption peaks of sp³ CH and sp² CH bonding structure were observed in FT-IR spectra, showing that the sp²/sp³ ration increases with increasing negative bias voltage. The analysis of Raman spectra corresponds that the films were DLC in nature.     

Effects of iodine doping on optoelectronic properties of diamond-like carbon thin films deposited by microwave surface wave plasma CVD

We report the effects of iodine (I) doping on the electrical and optical properties of diamond-like carbon (DLC) thin films grown on silicon and quartz substrates by microwave surface wave plasma chemical vapor deposition at low temperature (<100 °C). For film deposition, we used argon gas with methane or camphor dissolved with ethyl alcohol composition as plasma source. The optical gap and photoconductivity measurements of the samples were carried out before and after the iodine doping. The results show that optical gap dropped from 3.4 to 0.9 eV corresponding to nondoping to iodine-doping conditions, respectively. The photovoltaic measurements show that the open-circuit voltage (V_oc) and short-circuit current density (J_sc) of I-doped DLC film deposited on n-type silicon substrate under light illumination (AM1.5, 100 mW/cm²) were approximately 177 mV and 1.15 μA, respectively, and the fill factor was found to be 0.217.     

Substrate effect on the optical properties and thickness of diamond-like carbon films deposited by the RF PACVD method

The paper presents analyses of the optical properties and thickness of diamond-like carbon (DLC) films deposited on oxidized silicon wafers and silicon wafers with various resistivity and different crystallographic orientations. The influence of the parameters of the radio frequency plasma-assisted chemical vapor deposition (RF PACVD) process, notably the duration of the deposition process and the negative self-bias voltage of RF-powered electrode, on the optical properties and thickness of the DLC film were investigated. These properties were determined by spectroscopic ellipsometry. To the best of our knowledge, this is the first comparative analysis of these properties for various silicon and oxidized silicon substrates. Our results show that the substrate has a significant influence on both the optical properties and the thickness of the DLC film. The differences observed are highly dependent on the discussed process parameters.     

Synthetic diamond electrodes: The effect of surface microroughnesson the electrochemical properties of CVD diamond thin films on titanium

The electrochemical behavior of B-doped diamond films on Ti substrates subjected to different pretreatment procedures (annealing, sand-blasting, and etching in HCl) is evaluated as a function of surface microroughness. Generally, the differential capacitance follows the true surface area of the electrodes. The width of the potential window also increases, but slightly, with the roughness. The electrode reversibility in the [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻ redox system increases with increasing surface roughness. The apparent increase in the reversibility of the reaction may be also explained by the decrease in the true current density. Although the variations in the electrochemical parameters are not strongly pronounced, the tendencies observed can be used to optimise the electrode properties.     

Effect of deposition voltage on the microstructure of electrochemically deposited hydrogenated amorphous carbon films

Hydrogenated amorphous carbon (a-C:H) films were deposited on Si substrates by electrolysis in a methanol solution at ambient pressure and a low temperature (50 °C), using various deposition voltages. The influence of deposition voltage on the microstructure of the resulting films was analyzed by visible Raman spectroscopy at 514.5 nm and X-ray photoelectron spectroscopy (XPS). The contents of sp³ bonded carbon in the various films were obtained by the curve fitting technique to the C1s peak in the XPS spectra. The hardness and Young’s modulus of the a-C:H films were determined using a nanoindenter. The Raman characteristics suggest an increase of the ratio of sp³/sp² bonded carbon with increasing deposition voltage. The percentage of sp³-bonded carbon is determined as 33–55% obtained from XPS. Corresponding to the increase of sp³/sp², the hardness and Young’s modulus of the films both increase as the deposition voltage increases from 800 V to 1600 V.     

Preparation and electrochemical properties of LiMn2O4 by the microwave-assisted rheological phase method

Pure-phase and well-crystallized spinel LiMn₂O₄ powders as cathode materials for lithium-ion batteries were successfully synthesized by a new simple microwave-assisted rheological phase method, which was a timesaving and efficient method. The physical properties of the as-synthesized samples compared with the pristine LiMn₂O₄ obtained from the rheological phase method were investigated by thermogravimetry analysis (TGA), X-ray diffraction (XRD) and scanning electronic microscope (SEM). The as-prepared powders were used as positive materials for lithium-ion battery, whose charge/discharge properties and cycle performance were examined in detail. The powders resulting from the microwave-assisted rheological phase method were pure, spinel structure LiMn₂O₄ particles of regular shapes with distribution uniformly, and exhibited promising electrochemical properties for battery. Furthermore, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to characterize the reactions of Li-ion insertion into and extraction from LiMn₂O₄ electrode.     

Structure,electrochemical properties and functionalization of amorphous CN films deposited by femtosecond pulsed laser ablation

Amorphous carbon nitride (a-C:N) material has attracted much attention in research and development. Recently, it has become a more promising electrode material than conventional carbon based electrodes in electrochemical and biosensor applications. Nitrogen containing amorphous carbon (a-C:N) thin films have been synthesized by femtosecond pulsed laser deposition (fs-PLD) coupled with plasma assistance through Direct Current (DC) bias power supply. During the deposition process, various nitrogen pressures (0 to 10 Pa) and DC bias (0 to − 350 V) were used in order to explore a wide range of nitrogen content into the films. The structure and chemical composition of the films have been studied by using Raman spectroscopy, electron energy-loss spectroscopy (EELS) and high-resolution transmission electron microscopy (HRTEM). Increasing the nitrogen pressure or adding a DC bias induced an increase of the N content, up to 21 at.%. Nitrogen content increase induces a higher sp² character of the film. However DC bias has been found to increase the film structural disorder, which was detrimental to the electrochemical properties. Indeed the electrochemical measurements, investigated by cyclic voltammetry (CV), demonstrated that a-C:N film with moderate nitrogen content (10 at.%) exhibited the best behavior, in terms of reversibility and electron transfer kinetics. Electrochemical grafting from diazonium salts was successfully achieved on this film, with a surface coverage of covalently bonded molecules close to the dense packed monolayer of ferrocene molecules. Such a film may be a promising electrode material in electrochemical detection of electroactive pollutants on bare film, and of biopathogen molecules after surface grafting of the specific affinity receptor.     

Investigation into the effect of substrate material on microstructure and optical properties of thin films deposited via magnetron sputtering technique

This study aims at investigating the effect of the substrate material on growth mechanism and also microstructure of Ta₂O₅ thin films. For this purpose, atomic force microscopy, scanning electron microscopy, and interferometry analyses were implemented to reveal the influence of silicon wafer and amorphous BK7 glass substrates on the nucleation and growth mechanisms of Ta₂O₅ thin films deposited via the radio frequency magnetron sputtering technique. Results indicated that those films with finer morphologies had relatively higher nucleation densities. Compared with BK7 glass substrate, crystals formed on the silicon wafer were shown to be finer and had lower mean areas in more nucleation sites. Moreover, optical properties and morphological characteristics of the films on the silicon substrates had much more endurance after the annealing treatment. It was observed that shift in the transmission spectra of the deposited films after the treatment was insignificant, implying high packing density of the films. However, a 6-nm shift in the transmission spectra indicated low density and high porosity of the films. Finally, atomic force microscopy analysis along with the light scattering measurements confirmed the formation of a low-roughness film on the silicon wafer substrates.     

The effect of electrolytic oxidation on the electrochemical properties of multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWNTs) were electrochemically oxidized by a constant-potential electrolysis method and then investigated in detail using scanning electron microscope, transmission electron microscope, FT-IR, electrical impedance spectroscopy, and cyclic voltammetry. The FT-IR spectra showed that the amount of hydroxyl generated on the surface of MWNTs increased with increasing the electrochemical oxidation time of MWNTs. The CV results, being conducted in nitrobenzene solution, showed that the nitrobenzene reduction current increased with the increase in oxidation time of the MWNTs within the first 60 min of electrolysis. An electrical equivalent circuit model for electrical impedance spectroscopy was further established to analyze the surface capacitance and resistance of the MWNTs, and the model results showed that the capacitance of the oxidized MWNTs increased greatly while the charge transfer resistance decreased, suggesting electrochemical oxidized MWNTs modified pyrolytic carbon electrode being an effective electrochemical sensor for nitrobenzene determination.     

Effect of nitrogen pressure on the microstructure,mechanical and electrochemical properties of CrAlN coatings deposited by filter cathode vacuum arc

CrAlN coatings were prepared on Al–Si alloys using filter cathode vacuum arc deposition technique with nitrogen as the reactive gas and Cr₂₅Al₇₅ alloy target as the arc source. The effect of nitrogen pressure on the microstructure, mechanical properties and electrochemical properties of the coatings had been systematically studied. The results showed that the composition, structure and performance of the CrAlN coating depended on the nitrogen pressure. As the nitrogen pressure increased, the Al and Cr content decreased while the N content increased slowly in the coating. Meanwhile, the phase structure gradually changed from AlN phase to CrN phase. The hardness of the CrAlN coating increased significantly with the increase of nitrogen pressure from 0.04 to 0.06 Pa due to the formation of CrN phase and grain refinement. However, further increasing the nitrogen pressure to 0.07 Pa, the hardness was reduced owing to the deterioration of the surface quality caused by target poisoning. Moreover, the adhesion strength of the coating gradually decreases, and the corrosion resistance of the CrAlN coating first increased and then decreased with increasing the nitrogen pressure. The CrAlN coating deposited at a nitrogen pressure of 0.05 Pa had the best corrosion resistance, with the highest polarization resistance, charge transfer resistance and pore resistance, which was related to the combined effect of great compactness and AlN-dominant phase structure in the coating.     

Effects of modulation ratio on the microstructure,mechanical and tribological properties of WB2/Cr multilayer films deposited by magnetron sputtering

WB₂/Cr multilayer films with different modulation ratios (λ = 1, 3, 5, 7, 12, and 20) were deposited by a combination of direct-current and pulse direct-current magnetron sputtering, and the number of bilayers was fixed at ten. The effect of the modulation ratio on the microstructure, mechanical and tribological properties of the multilayer films was investigated in detail. X-ray diffraction demonstrates that a preferred orientation of WB₂ (101) and Cr (110) exists, and WB₂ (101) dominates the film's growth with increasing of modulation ratio. The TEM results show that the multilayer films consist of nanograins dispersed in an amorphous matrix in WB₂ layers and polycrystalline grains in Cr layers. The hardness increases with the increasing modulation ratio, and the maximum hardness (31.1 GPa) is obtained at λ = 20. The indentation toughness presents an opposite changing trend, and the maximum indentation toughness (1.264 MPa m^1/2) is obtained in S1 at λ = 1 which conforms to the rule of mixture due to the relatively thick bilayer thickness (Λ = 160–192 nm). The wear mechanism is investigated, and the results suggest that the multilayer film with λ = 7 possesses the best wear resistance (2.06 × 10^?7 mm³/Nm), benefiting from the balance of hardness and indentation toughness.     

Influence of phase composition on microstructure and thermal properties of ytterbium silicate coatings deposited by atmospheric plasma spray

In this study, ytterbium silicate coatings with different compositions were designed by controlling the Yb₂O₃/ SiO₂ ratio and fabricated by atmospheric plasma spray. The microstructure and thermal properties of these coatings were characterized. Results showed that the Yb₂O₃-rich coatings contained Yb₂O₃ and Yb₂SiO₅ phases, which were characterized by Yb₂O₃ columnar grains, obvious interfaces between splats and many microcracks. The SiO₂-rich coatings were composed of Yb₂SiO₅ and Yb₂Si₂O₇ phases, which were composed of well bonded splats with many spherical pores. The Yb₂O₃-rich coatings had higher coefficient of thermal expansion values and lower thermal conductivities than the SiO₂-rich coatings. The SiO₂-rich coatings presented much better thermal cycling resistance than the Yb₂O₃-rich coatings. The relationship among phase composition, microstructure and thermal properties of ytterbium silicate coatings was analyzed. The results of this study may provide some clues for designs and applications of rare-earth silicates as environmental barrier coatings.     

The production of carbon nanofibers and thin films on palladium catalysts from ethylene-oxygen mixtures

The characteristics of carbonaceous materials deposited in fuel rich ethylene-oxygen mixtures on three types of palladium: foil, sputtered film, and nanopowder, are reported. It was found that the form of palladium has a dramatic influence on the morphology of the deposited carbon. In particular, on sputtered film and powder, tight ‘weaves’ of sub-micron filaments formed quickly. In contrast, on foils under identical conditions, the dominant morphology is carbon thin films with basal planes oriented parallel to the substrate surface. Temperature, gas flow rate, reactant flow ratio (C₂H₄:O₂), and residence time (position) were found to influence both growth rate and type for all three forms of Pd. X-ray diffraction, high resolution transmission electron microscopy, temperature-programmed oxidation, and Raman spectroscopy were used to assess the crystallinity of the as-deposited carbon, and it was determined that transmission electron microscopy and X-ray diffraction were the most reliable methods for determining crystallinity. The dependence of growth on reactor position, and the fact that no growth was observed in the absence of oxygen support the postulate that the carbon deposition proceeds by combustion generated radical species.