Influence of nitrogen ion energy on the Raman spectroscopy of carbon nitride films

Carbon nitride films were deposited by filtered cathode vacuum arc combined with radio frequency nitrogen ion beam source. Both visible Raman spectroscopy and UV Raman spectroscopy are used to study the bonding type and the change of bonding structure in carbon nitride films with nitrogen ion energy. Both C–N bonds and CN bonds can be directly observed from the deconvolution results of visible and UV Raman spectra for carbon nitride films. Visible Raman spectroscopy is more sensitive to the disorder and clustering of sp² carbon. The UV (244 nm) Raman spectra clearly reveal the presence of the sp³ C atoms in carbon nitride films. Nitrogen ion energy is an important factor that affects the structure of carbon nitride films. At low nitrogen ion energy (below 400 eV), the increase of nitrogen ion energy leads to the drastic increase of sp²/sp³ ratio, sp² cluster size and C---N bonds fraction. At higher nitrogen ion energy, increase leads to the slight increase of CN bonds fraction and sp² cluster size, slight decrease of C---N bonds fraction and sp²/sp³ ratio.     

Deposition of carbon nitride films by filtered cathodic vacuum arc combined with radio frequency ion beam source

Atomically smooth carbon nitride films were deposited by an off-plane double bend filtered cathodic vacuum arc (FCVA) technique. A radio frequency nitrogen ion source was used to supply active nitrogen species during the deposition of carbon nitride films. The films were characterized by atomic force microscopy (AFM), XPS and Raman spectroscopy. The internal stress was measured by the substrate bending method. The influence of nitrogen ion energy (0–1000 eV) on the composition, structure and properties of the carbon nitride films was studied. The nitrogen ion source greatly improves the incorporation of nitrogen in the films. The ratio of N/C atoms in the films increases to 0.40 with an increase in the ion beam energy to 100 eV. Further increase in the ion beam energy leads to a slight decrease in the N/C ratio. XPS results show that nitrogen atoms in the films are chemically bonded to carbon atoms as C---N, C=N, and CN bonds, but most of nitrogen atoms are bonded to sp² carbon. The increase in nitrogen ion energy leads to a decrease in the content of nitrogen atoms bonded to sp² carbon, and an increase in the content of nitrogen atoms bonded to sp³ and sp¹ carbon. Raman spectra indicate an increase in the sp² carbon phase in carbon nitride films with an increase in nitrogen ion energy. The increase in sp² carbon fraction is attributed to the decrease in internal stress with increasing nitrogen ion energy.     

Structural features of diamond layers photo-emitting at sub-band gap energies

The photoemission behaviour of a series of diamond-based polycrystalline films irradiated by the second (2.3 eV), third (3.5 eV) and fourth (4.7 eV) harmonics produced by a Q-switched-mode-locked Nd: Yag laser has been investigated and related to the structural and compositional characteristics of the layers. The materials were polycrystalline undoped diamond films as well as Nd- and N-containing diamond films grown by CVD techniques, diamond-like and amorphous carbon layers. The morphological and structural characteristics of the films were investigated by electron microscopy, Raman spectroscopy and electron diffraction. The analysis of the photoemission curves does not evidence any improvement of the emission efficiency in the case of Nd-containing films nor for the diamond films grown in the presence of N_2. The results evidence conversely a strong correlation between the characteristics of the photoemission process at sub-band gap energies and the presence of amorphous sp²-C patches located at the diamond film surfaces. The photoemitting properties of our samples are discussed and rationalized by considering charge emission occurring at the sp²-diamond-vacuum border and the emission process governed by the ratio of amorphous sp²-C to crystalline sp³-C. The rather high values of quantum efficiency measured in the course of the present research at 3.5 and 4.7 eV suggest that a proper distribution of amorphous carbon onto a good quality diamond surface is the key factor for the preparation of efficient and stable photocathode materials.     

The Evolutionary Process during Pyrolytic Transformation of Poly(N-methylsilazane) from a Preceramic Polymer into an Amorphous Silicon Nitride/Carbon Composite

The pyrolytic evolution of poly(N-methylsilazane), –[H₂SiN-Me] _x –, from preceramic polymer to ceramic product is followed by heating samples of the partially cross-linked polymer, in 200°C increments, from ambient temperature to 1400°C. The intermediate products are characterized by chemical analysis, diffuse reflectance Fourier transform IR spectroscopy (DRIFTS), Raman spectroscopy, and ²⁹Si and ¹³C magic-angle spinning (MAS) solid-state NMR. Spectro-scopic characterization indicates that the 1400°C pyrolysis products are amorphous silicon nitride mixed with amorphous and graphitic carbon (as determined by Raman spectroscopy), rather than silicon carbide nitride, as expected based on the presence of up to 20 mol% retained carbon. Efforts to crystallize the silicon nitride through heat treatments up to 1400°C do not lead to any crystalline phases, as established by transmission electron microscopy (TEM) and small-area electron diffraction (SAD). It appears that the presence of free carbon, along with the absence of oxygen, strongly inhibits crystallization of amorphous silicon nitride. These results contrast with the isostructural poly-(Si-methylsilazane), –[MeHSiNH] _x –, which is reported to form silicon carbide nitride on pyrolysis.     

Low-temperature deposition of optically transparent diamond using a low-pressure flat flame

The radial uniformity and scaleable nature of flat flames make them an attractive technique for diamond deposition. Due to the high temperatures involved in combustion synthesis, typically molybdenum and silicon have been used as substrates. Here we report low-temperature diamond deposition on glass substrates. Diamond deposition was achieved on ordinary sodium silicate glass at substrate temperatures of 500°C; however, film delamination occurred during cooling after deposition. Vycor™ and Pyrex™ are two glasses that have thermal expansion coefficients that are similar to diamond. Continuous, optically transparent films were successfully deposited on both glasses. The diamond films have been characterized by scanning electron microscopy, Raman spectroscopy and secondary ion mass spectroscopy (SIMS). The dependence of hydrogen and sp²-bonded carbon incorporation in the films on reactant composition was quantified. These films were optically transparent and showed good adhesion as measured by a simple tape test.     

Reaction and Formation of Crystalline Silicon Oxynitride in Si–O–N Systems under Solid High Pressure

Oxidized amorphous Si₃N₄ and SiO₂ powders were pressed alone or as a mixture under high pressure (1.0–5.0 GPa) at high temperatures (800–1700°C). Formation of crystalline silicon oxynitride (Si₂ON₂) was observed from amorphous silicon nitride (Si₃N₄) powders containing 5.8 wt% oxygen at 1.0 GPa and 1400°C. The Si₂ON₂ coexisted with β-Si₃N₄ with a weight fraction of 40 wt%, suggesting that all oxygen in the powders participated in the reaction to form Si₂ON₂. Pressing a mixture of amorphous Si₃N₄ of lower oxygen (1.5 wt%) and SiO₂ under 1.0–5.0 GPa between 1000° and 1350°C did not give Si₂ON₂ phase, but yielded a mixture of α,β-Si₃N₄, quartz, and coesite (a high-pressure form of SiO₂). The formation of Si₂ON₂ from oxidized amorphous Si₃N₄ seemed to be assisted by formation of a Si–O–N melt in the system that was enhanced under the high pressure.     

Pyrolysis of Preceramic Polymers in Ammonia: Preparation of Silicon Nitride Powders

The pyrolysis of cross-linked polycarbosilanes, polysilanes and polysilazanes in an ammonia atmosphere to 1473 K yields amorphous, low-carbon silicon nitride powders. The efficacy of carbon removal is independent of the polymer's structure or functionality but is partially dependent on the initial cross-linking temperature. The amorphous silicon nitride powders partially crystallize to α-Si₃N₄ by 1773 K.     

Evolution of the opto-electronic properties of amorphous carbon films as a function of nitrogen incorporation

The present work provides correlations between the optical, electronical and microstructural properties of amorphous carbon nitride films (a-CN_x) deposited by Direct Current (DC) magnetron sputtering technique versus the N₂/Ar + N₂ ratio. The microstructure of the films was characterized by Raman spectroscopy and optical transmission measurements. The evolution of both the density of states (DOS) located between the bandtail states and the density of states around the Fermi level N(E_f), have been investigated by electrical measurements versus temperature varying the N₂/Ar + N₂ ratio. The evolution of the microstructure versus N reveals a continuous structural ordering of the sp² phase, which is confirmed by the optical and the conductivity measurements. The conductivity variation was interpreted within the framework of the band structure model of the π electrons in a disordered carbon with the presence of localized states.     

Structure modelling of DLC-films formed by pulsed arc method

Reported here is the continuation of the structure characterization of carbon thin films produced by a pulsed vacuum arc plasma source. Hydrogen free carbon films with thickness up to 3 μm were prepared with average deposition rate of 5 μm/h onto various substrates. It was found that these carbon films are not quite amorphous and can be described by modelling the clustered structure with different sp³/sp²/sp bond ratios depending on deposition conditions. Results of the experimental investigations and numerical modelling of the films structure are presented.     

Near-edge X-ray absorption fine structure spectroscopy of arcjet-deposited cubic boron nitride

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy was employed to help determine the structure of boron nitride films grown by bias-enhanced chemical vapor deposition in a low-density supersonic arcjet flow. BN films containing 0.90% cubic boron nitride were analyzed by NEXAFS and compared with c-BN and h-BN reference spectra. The mainly cubic films have been shown previously to be nanocrystalline, which leads to the inability to obtain structural information from Raman scattering spectra. However, with NEXAFS, the nanocrystalline nature of the films does not strongly affect the structural interpretation. It is shown that films deposited with a bias of −75 V are primarily sp³ bonded. This high sp³ bonding character agrees with previous measrements based on infraredtransmission and reflectance spectroscopy, as well as X-ray photoelectron spectroscopy.     

Synthesis of a Polyborosilazane and Its Conversion into Inorganic Compounds

A novel polyborosilazane was synthesized by reacting per-hydropolysilazane with trimethyl borate. The chemical structure of this polymer was investigated by the techniques of infrared spectroscopy and nuclear magnetic resonance measurements. Amorphous silicon nitride was obtained by pyrolysis of this polymer in a stream of anhydrous ammonia to 1000°C with high ceramic yield. The pyrolysis product remained amorphous after additional heating to 1700°C under N₂. Crystallization to α-Si₃N₄ and β-Si₃N₄ proceeded with heat treatment at 1800°C under N₂. These results indicate that polyborosilazane is a good precursor for amorphous silicon nitride based materials.     

Observation of Hydrogenated Amorphous Carbon Films by Atomic Force Microscopy

Atomic force microscopy images were made of the surface of CVD hydrogenated amorphous carbon films. The films were deposited from toluene vapor with oxygen additions during deposition, producing very smooth surfaces. Average roughnesses of only 0.5 nm were measured for the films made with oxygen, whereas a surface roughness of 11 nm was obtained for the films deposited without oxygen. The results suggest that sp ²- and sp ³-bonded carbons were removed by oxygen rosion for CVD hydrogenated amorphous carbon films deposited in the presence of oxygen.     

Evaluation of diamond films by nuclear magnetic resonance and Raman spectroscopy

The quality of chemically vapor deposited diamond films was assessed in terms of sp²/sp³ content as determined by solid-state nuclear magnetic resonance (NMR) and Raman spectroscopy. While the results of the two techniques are in qualitative agreement, only the NMR spectra yield quantitative values for the sp²/sp³ ratio. Only sp³ carbon was observed in the NMR spectra of very high quality hot-filament, microwave plasma, and d.c. arc-jet chemically vapor deposited films. As expected, Raman spectroscopy is extremely sensitive to sp² bonded carbon, identifying small amounts below the detection limit of the NMR spectrometer. Comparison of the two techniques, however, indicates that Raman spectroscopy may be so sensitive to sp² bonded carbon that sp³ bonded carbon in films containing as much as 90% sp³ bonded material may remain undetected. NMR linewidths indicate that the sp³ carbon in such material shows more disorder than that found in high-quality polycrystalline films.     

On the low-temperature threshold for cubic boron nitride formation in energetic film deposition

The sharp threshold in substrate temperature below which cubic boron nitride (cBN) cannot be formed in energetic film-deposition processes was investigated. We found that cBN could be synthesized below the threshold temperature on top of cBN that had been previously formed above the threshold temperature. That the initial nucleation of cBN is more strongly dependent on temperature than its subsequent growth is suggested. How the structure of the sp²-bonded BN that accompanied cBN growth changed with temperature was also investigated. Lowering the substrate temperature decreased the local ordering within the graphitic planes, and below the threshold temperature the separation of the graphitic planes increased dramatically. How these structural changes may influence the nucleation of cBN is discussed.     

Crystallization of an amorphous silicon nitride powder produced in a radiofrequency thermal plasma

Crystallization behavior of an amorphous silicon nitride powder produced in an RF thermal plasma by the vapor-phase reaction of silicon tetrachloride and ammonia has been investigated. Effects of annealing conditions such as temperature and duration of heat treatment on the properties of powders were studied. Changes in the chemical and phase compositions, as well as in the morphology of powders were measured and interpreted. Annealing of the amorphous silicon nitride powder at 1450°C for 120 min resulted in a powder of about 80% crystalline phase content with an /β ratio of about 6.5. ©     

Synthesis and characterization of microporous carbon nitride

This research reports the preparation and characterization of amorphous microporous carbon nitride using HZSM-5 zeolite as template, and ethidene diamine and carbon tetrachloride as chemical precursors. Microporous amorphous carbon nitride is generated by removal of HZSM-5 zeolite in the obtained zeolite/carbon nitride composite using hydrofluoric acid after carbonization the precursor inside the channels of zeolite. The microporous carbon nitride was characterized by nitrogen sorption techniques, scanning electron microscopy, elemental analysis, X-ray diffraction, X-ray photoelectron spectroscopy, IR spectroscopy, Ultraviolet–visible spectroscopy, Raman spectroscopy, and thermo-gravimetric analysis. Amorphous microporous carbon nitride with high surface area and narrow pore size distribution is thermal stable under atmosphere conditions up to 700 K.     

Densification of nanosized amorphous and crystalline silicon nitride powders

The hot-pressing behavior of two amorphous and three crystalline silicon nitride powders, including both experimental and commercial samples has been investigated in the presence of MgO-Y₂O₃ sintering aid. The powders were characterized in terms of bulk and surface chemistry, phase composition and morphology. The sintering behavior was assessed on the basis of green and final densities, weight loss on densification and chemical and phase compositions of the dense material. ©     

Carbon content-dependent microstructures,surface characteristics and thermal stability of mechanical alloying derived SiBCN powders

Three types of SiBCN: carbon-lean, -moderate and -rich powders with the same Si/B/N mole ratio were subjected to high-energy ball milling to yield an amorphous structure. The effects of carbon content on microstructures, solid-state amorphization, surface characteristics and thermal stability of the as-milled powders were studied in detail. Results showed that the increases in carbon content can drive solid-state amorphization accompanied by strain-induced, crystallite refinement-induced and/or chemical composition-induced nucleation of nano-SiC from an amorphous body. The specific surface area increases as carbon content increases. The amorphous networks of Si–C, C–B/C–C, C–N, B–N and C–B–N bonds that compose the amorphous nature, but the species and contents of the chemical bonds are carbon content-dependent. Carbon-moderate powders possess satisfying thermal stability while carbon-rich ones perform the worst. Mechanical alloying derived SiBCN powders have outstanding oxidation resistance below 800 °C; however only carbon-moderate powders show desirable anti-oxidation ability at higher temperatures. Thus, mechanical alloying of SiBCN appears a suitable technique for developing amorphous matrix materials for practical applications.     

Microstructural Characterization of Sintered MoSi2/SiCP Composites

A MoSi₂/SiC_P composite was synthesized by in situ reactive sintering of a mixture of molybdenum, silicon, and carbon powders. Its microstructural features were studied by X-ray energy dispersive spectroscopy (EDS), conventional transmission electron microscopy (CTEM), and high-resolution transmission electron microscopy (HREM). It was determined that the composite was composed of α-MoSi₂ and β-SiC. There were no specific orientation relationships between the MoSi₂ matrix and SiC_P, because the MoSi₂ and SiC were formed at 1450°C by the reaction of solid Mo and C and liquid Si. The abrupt change occurring in the microstructure of the composite is explained by the presence of an interface between MoSi₂ and SiC_P, where no observable SiO₂ amorphous layer or particles were found. Microtwins and stacking faults were frequently observed in {111} planes of SiC_P.     

Synthesis of CoAl2O4 by double decomposition reaction between LiAlO2 and molten KCoCl3

Submicronic CoAl₂O₄ powders were prepared by double decomposition reaction between solid LiAlO₂ and molten KCoCl₃ at 500 °C for 24 h. The reaction mechanism involves the dissolution of LiAlO₂ shifted by the precipitation of CoAl₂O₄ until complete transformation and the reaction leads to powders with a very homogeneous chemical composition. The powders obtained were mainly characterized by XRD, FTIR, ICP, X.EDS, electron microscopy and diffraction and diffuse reflexion. The blue pigments obtained exhibit a high thermic stability allowing their use for the colouring of ceramic tiles.