Pyrolysis behavior of poly[(n-propylamino/methylamino)borazine]

A processable poly[(n-propylamino/methylamino)borazine] (PPAB) has been pyrolyzed in Ar to study its thermal decomposition behavior. The structural evolution and chemical composition change during pyrolysis were characterized by chemical analysis, thermal gravimetry–mass spectrometry (TG–MS), Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results indicated that the polymer-to-ceramic transition of PPAB involved two steps. Below 400 °C, the gas species were mainly methane and methylamine, while from 400 to 900 °C those were methane and n-propylamine. The PPAB displayed a ceramic yield of 52 wt% at 1000 °C and the pyrolyzed product was amorphous boron nitride (BN) with a small quantity of carbon impurity, in presence as CC and CN bonds. Moreover, for the pyrolyzed product, further heat treatment resulted in the occurrence of a transformation from amorphous to turbostratic.     

Correlation between microstructure and electrical resistivity of hexagonal boron nitride ceramics

Hexagonal boron nitride is a material with a unique combination of mechanical, chemical and electrical properties and therefore of considerable technical and commercial interest. Nevertheless, there exists only very limited knowledge concerning the microstructure and electrical properties of such materials. In this work different materials produced by SPS from ‘turbostratic’ and well-crystallised powders are compared with commercial materials in terms of densification, microstructure and electrical properties. The turbostratic powders could be densified at temperatures as low as 1500–1600 °C, but recrystallisation of the grains took place at much higher temperatures (1800–1900 °C). The electrical resistivity of the investigated materials reached values of up to 10¹⁵ Ω cm and strongly depended on the microstructure. The main factor influencing the resistivity was the amount and nature of the grain boundary phase.     

Low temperature growth mechanisms of vertically aligned carbon nanofibers and nanotubes by radio frequency-plasma enhanced chemical vapor deposition

Using radio frequency-plasma enhanced chemical vapor deposition (RF-PECVD), carbon nanofibers (CNFs) and carbon nanotubes (CNTs) were synthesized at low temperature. Base growth vertical turbostratic CNFs were grown using a sputtered 8 nm Ni thin film catalyst on Si substrates at 140 °C. Tip growth vertical platelet nanofibers were grown using a Ni nanocatalyst in 8 nm Ni films on TiN/Si at 180 °C. Using a Ni catalyst on glass substrate at 180 °C a transformation of the structure from CNFs to CNTs was observed. By adding hydrogen, tip growth vertical multi-walled carbon nanotubes were produced at 180 °C using FeNi nanocatalyst in 8 nm FeNi films on glass substrates. Compared to the most widely used thermal CVD method, in which the synthesis temperature was 400–850 °C, RF-PECVD had a huge advantage in low temperature growth and control of other deposition parameters. Despite significant progress in CNT synthesis by PECVD, the low temperature growth mechanisms are not clearly understood. Here, low temperature growth mechanisms of CNFs and CNTs in RF-PECVD are discussed based on plasma physics and chemistry, catalyst, substrate characteristics, temperature, and type of gas.     

The influence of ion beam assisted deposition parameters on the properties of boron nitride thin films

We studied ion beam assisted deposition of cubic boron nitride thin films on silicon (100) and high speed steel. The boron nitride films were grown by the electron beam evaporation of pure boron (99.4%) and the simultaneous ion bombardment of a mixture of nitrogen and argon ions from a Kaufman ion source. At a constant boron evaporation rate, the ion energy, ion current density, substrate temperature and process gas mixture was varied. The thickness of the films was kept between 200 and 300 nm. Boron nitride films with >80% of the cubic phase (determined by Fourier transform infrared spectroscopy) were obtained with nitrogen/argon mixtures of 50/50 at ion energies of 450 eV and substrate temperatures of 400°C. The current density amounted to 0.45 mA cm⁻² at a nominal boron rate of 200 pm s⁻¹. Cubic boron nitride films were deposited on high speed steel by introducing a titanium interlayer for adhesion improvement.     

Thermal behaviour of a series of poly[B-(methylamino)borazine] for the preparation of boron nitride fibers

The thermal behaviour of a series of poly[B-(methylamino)borazine] prepared at various temperatures ranging from 140 to 200 °C is studied in the present paper as potential BN fiber precursors. It was shown that the softening capability of poly[B-(methylamino)borazine] can be tailored by controlling the temperature at which polymers were prepared to achieve melt-spinning and produce high quality green fibers. Thus as-spun fibers could be next converted into boron nitride fibers using ammonia (25–1000 °C) and nitrogen (25–1800 °C) atmospheres. The quality of boron nitride fibers was shown to depend on the first part of the pyrolysis step (25 and 1000 °C; ammonia atmosphere) in which the great majority of the weight loss necessary for boron nitride production occurs. Ideal poly[B-(methylamino)borazine] as BN fiber precursors are those prepared between 170 and 180 °C. They display appropriate melt-spinnability and ceramic conversion capability.     

Microstructure and deposition mechanism of CVD amorphous boron carbide coatings deposited on SiC substrates at low temperature

Amorphous boron carbide (α-B₄C) coatings were prepared on SiC substrates by chemical vapor deposition (CVD) from CH₄/BCl₃/H₂/Ar mixtures at low temperature (900–1050 °C) and reduced pressure (10 kPa). The deposited coatings were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), micro-Raman spectroscopy, energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The results showed that two kinds of α-B₄C coatings were deposited with different microstructures and phase compositions, and the effect of deposition temperature was significant. When deposited at 1000 °C and 1050 °C, the coatings exhibited a nodular morphology and had a relatively low content of boron. The free carbon was distributed in them inhomogeneously; in contrast, when deposited at 900 °C and 950 °C, the coatings presented a comparatively flat morphology and had a uniform internal structure and high boron content. They did not contain free carbon. At the last of this paper, the pertinent mechanisms resulting in differences in microstructure and phase composition were discussed.     

Thermal stability of mesoporous boron nitride templated with a cationic surfactant

The preparation of mesoporous boron nitride by using tris(monomethylamino)borazine (MAB) as boron nitride source and cetyl-trimethylammonium bromide (CTAB) as structurating agent is reported. The X-ray diffraction, TEM and pore size analysis show that highly porous boron nitride (specific surface area of 800 m²/g and mesoporous volume of 0.5 cm³/g) is synthesized with mesopores of 6 nm in diameter. Moreover, the mesoporosity is conserved up to 1600 °C under an inert atmosphere.     

Fabrication and electrical properties of SrTiO3/diamond junctions

Strontium titanate (STO) films were directly deposited on Ib (100) single crystal diamond by r.f. magnetron sputtering. The as-deposited STO film was in amorphous state. On the other hand, the crystalline STO film was obtained under the optimized condition of a deposition temperature of 250 °C and a post-annealing temperature of 650 °C. STO/diamond junctions were fabricated on boron-doped homoepitaxial layers grown on p⁺-type single crystal diamond substrates. Electrical properties of the STO/diamond junction were investigated by changing the surface terminations of diamond with hydrogen or oxygen and the crystallinity of the STO film. It was found that the amorphous STO acted like a semi-insulator on H-diamond surface and that the amorphous STO/O-diamond junction behaved like a Schottky diode. The crystalline STO/O-diamond showed a complex rectifying behavior. The crystalline STO film possessed a higher dielectric constant as compared to that of the amorphous one.     

Optical reflectivity studies of GaN and AlN chemical beam epitaxy on GaAs(100)

The deposition of gallium nitride and aluminium nitride thin films on GaAs(100) substrates by chemical beam epitaxy is reported. In-situ dynamic optical reflectivity has been used to compare growth rates of the nitride layers as a function of substrate temperature with their arsenide analogues. The relative growth efficiency of gallium nitride/gallium arsenide from triethyl gallium was found to be in the range 75–85%. The growth temperature for gallium nitride extends to higher temperatures, compared with gallium arsenide, probably due to lower evaporation rates of Ga bound to the nitride surface. At the same beam equivalent pressure, the growth rate of aluminium nitride from ethyldimethyl aluminium alane is approximately one-third of that for gallium nitride from triethyl gallium. Atomic force microscopy reveals that the gallium nitride surface formed at 500 °C is facetted, whereas an aluminium nitride surface deposited at 400 °C exhibits a rounded columnar type growth habit. Reflection anisotropy spectra indicate that atomic nitrogen readily reacts with the GaAs(100)-c(4×4) As stabilized surface at temperatures as low as 400 °C but without the gross facetting that has been observed at higher temperatures.     

Superior high-temperature oxidation resistance of magnetron sputtered Hf–B–Si–C–N film

A hard and optically transparent amorphous Hf₇B₂₃Si₁₇C₄N₄₅ film with a contamination level less than 4 at%, prepared by reactive pulsed dc magnetron sputtering, was subjected to systematic investigation of high-temperature oxidation behavior in air up to 1700 °C. We focus on thermogravimetric analysis of the film in air and on the evolution of the film structure, microstructure and elemental composition with an annealing temperature ranging from 1100 °C to 1700 °C. The film exhibits a superior oxidation resistance up to 1600 °C due to a formation of a nanocomposite protective oxide layer on the surface above 1000 °C. The layer consists of monoclinic and tetragonal (or orthorhombic) HfO₂ nanocrystallites surrounded by a SiO₂-based amorphous matrix, most probably containing boron. The HfO₂ nanocrystallites exhibit a gradient in size with a dense population of small (a couple of nm) crystallites next to the interface and larger but dispersed crystallites close to the surface.     

Formation of cBN nanocrystals by He+ implantation into hBN

The structural modifications of polycrystalline hexagonal boron nitride implanted with He⁺ beams at energies between 200 keV and 1.2 MeV to fluences of 1.0 × 10¹⁷ ions cm^? 2 were investigated using micro-Raman spectroscopy. The measured Raman spectra show evidence of implantation-induced structural transformations from the hexagonal phase to nanocrystalline cubic boron nitride, rhombohedral boron nitride and amorphous boron nitride phases. The first-order Longitudinal-Optical cubic boron nitride phonon was observed to be downshifted and asymmetrically broadened and this was explained using the spatial correlation model coupled with the high ion implantation-induced defect density.     

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.     

Reactive sintering cBN-Ti-Al composites by spark plasma sintering

When synthesizing polycrystalline cubic boron nitride (PcBN) at normal pressure, cBN had a trend of hexagonal transformation, which reduces the hardness and strength of PcBN. The cBN-Ti-Al composite was prepared by spark plasma sintering with introducing Ti and Al to absorb hexagonal boron nitride (hBN) transformed from cBN. By the results of X-ray diffraction (XRD), Ti and Al reacted with BN and forming TiN, TiB₂, and AlN, which combined cBN as the binder by chemical bonding. The mechanical properties of the prepared composite increased as the increment of sintering temperature. The threshold temperature for preparing composite without hBN phase was at 1400 °C. The composite with optimal mechanical properties was prepared at 1400 °C, and the relative density, the bending strength, hardness, and fracture toughness were 98.9 ± 0.1%, 390.7 ± 4.4 MPa, 14.1 ± 0.5 GPa, and 7.6 ± 0.1 MPa·m^0.5, respectively.     

Atomic structures of bamboo-type boron nitride nanotubes with cup-stacked structures

Bamboo-type boron nitride (BN) nanotubes with cup-stacked structures were produced by annealing of Fe₄N and boron particles at 1000 °C for 5 h in nitrogen atmosphere. The iron nitride particles were reduced to α-Fe. Atomic structure models and the formation mechanism were proposed from the results of high-resolution electron microscopy (HREM), image simulations and molecular mechanics calculations. The nanotube structures would be stabilized by stacking of BN cup-layers.     

Application of as-synthesized Co–Al layered double hydroxides for the preparation of the electroactive composites containing N-doped carbon nanotubes

A set of electrically conductive, porous and electrocatalytically active composites was prepared by catalytic chemical vapor deposition using Co–Al layered double hydroxides and acetonitrile. The effect of synthesis temperature, i.e. 600, 700 and 800 °C on their composition, structure and morphology was examined by means of X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, nitrogen sorption and scanning electron microscopy. Electrochemical properties of the composites were evaluated by cyclic voltammetry (CV) in alkaline solution in the presence and absence of oxygen. The composites were composed of metallic cobalt, metal oxides and turbostratic/graphitic carbon. Graphite-like carbon was doped with nitrogen (according to XPS analysis N concentration is 2 at.%) and occurred as multi-walled carbon nanotubes with diameters ranging from 10 up to 55 nm. The composites were a mixture of compounds showing strongly temperature-dependent crystallinity therefore they showed various specific surface areas (125, 114 and 53 m² g^− 1) and different specific capacitances (9, 7 and 3 F g^− 1). The oxygen reduction peak in the CVs recorded in 0.1 M KOH was observed at − 0.26, − 0.28 and − 0.31 V versus Ag/AgCl/KCl_sat electrode for the samples prepared at 600, 700 and 800 °C, respectively.     

Synthesis and characterization of nanocrystaline hexagonal boron nitride powders: XRD and luminescence properties

Nanocrystalline hexagonal boron nitride powders (h-BN) were synthesized from urea and boric acid followed by pirolysis and subsequent heat treatment in nitrogen atmosphere. Materials have been analyzed by means of X-ray diffraction, Photoluminescence and Field emission electron microscopy methods. Obtained results show that starting h-BN powder, synthesized at 750 °C, is composed of ~11 layer crystallites with average crystallite thickness and crystallite lateral size of 3.94 and 10.4 nm, respectively. A broad emission and intense luminescence intensity were observed due to the large atomic disorder. Higher annealing temperature increases crystallite size and turbostratic h-BN transforms to well crystallized h-BN at 1500 °C.     

Influence of organics on ZnO coatings prepared by chemical solution deposition

Highly c-axis-oriented ZnO thin films were prepared on soda–lime–silica glass substrates by chemical solution deposition process using a zinc-naphthenate precursor as a starting material. In order to investigate the effect of pyrolysis temperature on properties of the films such as crystallinity, surface morphology and transmittance in visible spectra region, the precursor films were pyrolyzed at 300 °C or 500 °C, followed by final heat treatment at 600 °C. Highly transparent films in visible spectra region were obtained. The relationship between residual organics and properties of the annealed films was discussed.     

Synthesis of boron nitride nanotubes by catalytic pyrolysis of organic-inorganic hybrid precursor

Large quantities of hexagonal boron nitride (h-BN) nanotubes (BNNTs) with high purity have been successfully synthesized under ammonia gas flow at 1200 °C via catalytic pyrolysis of organic-inorganic hybrid precursor which was pre-prepared through a wet chemistry method at 95 °C. Several characterizations, such as SEM, TEM, XRD, FTIR, EDS, XPS and SAED measurements, were used to confirm the morphology, composition and crystalline structure of the as-synthesized powders. It was observed that the obtained product was a kind of nanotubes (NTs) in hexagonal BN phase with a curved shape and smooth surface. The diameter of BNNTs was distributed in a range of 60–200 nm while its length was about tens of microns. The possible growth mechanism of BNNTs was also proposed in this paper.     

Reversed texture in nanometric carbon/boron nitride multilayers

A structure-controlled series of carbon/boron nitride multilayers, with bilayer thicknesses from 1.25 to 160 nm has been grown by sequential evaporation of carbon and boron assisted with nitrogen ions. The minimum bilayer thickness for a stable stack is 2.9 nm. A turbostratic texture of the carbon and BN phases is evidenced even for small periods of the bilayers. Interestingly, BN and C basal planes of adjacent sub-layers exhibit perpendicular alignment between them: along the growth direction for h-BN rich layers, and parallel to the surface for the C rich ones.     

Feasibility study on cubic boron nitride coated glass press molds

We report the feasibility of glass press molds using high-quality, thick cubic boron nitride (cBN) films prepared in a plasma jet by chemical vapor deposition. A press test using a cBN film for an optical glass is carried out at a high temperature (≥ 650 °C), above the glass transition temperature. Surface morphology, chemical composition, and optical transparency of the glass after a press test are examined by atomic force microscopy, X-ray photoelectron spectroscopy, energy dispersion X-ray spectroscopy, and ultraviolet-visible-near-infrared (UV-VIS-near-IR) and IR spectroscopy. The B and N concentrations at the top several nanometers of the glass increase by several at.% after a press test. This is attributed to diffusion of B and N from the film into the glass. The UV-VIS-near-IR transparency of the glass in a short wavelength range (≤ 900 nm) decreases by several % due to light scattering at the roughened glass surface. In contrast, the IR transparency of the glass remains constant despite an increase in the surface roughness.