Synthesis of BCN thin films by nitrogen ion beam assisted pulsed laser deposition from a B4C target

Using sintered B₄C as target material, ternary BCN thin films were synthesized on Si(100) substrates by means of reactive pulsed laser deposition assisted by nitrogen ion beam. The composition, bonding configuration and crystalline structure of the synthesized films were characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and transmission electron microscopy. The prepared films contain several bonds including B–C, N–C, B–N with B–C–N atomic hybridization. The ablation of the B₄C target results in the deposition of a film with B:C ratio about 3:1, deficient in boron compared with the target material. Nitrogen provided by the ion beam is incorporated in the film and bonded to boron and carbon. Heating of the substrate enhances the incorporation of nitrogen and influences the bonding configuration and crystalline structure of the film as well.     

Structural and chemical analysis of amorphous B–N–C thin films deposited by RF sputtering

Ternary Boron–Nitrogen–Carbon (B–N–C) thin films were deposited, onto silicon substrates, by reactive radio frequency (RF) sputtering from a boron carbide (B₄C) target in a gas mixture of nitrogen and argon. The influence of the RF power (P_RF) on the structure and the chemical composition of these films are studied by Fourier transform Infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) measurements. The two techniques reveal the presence of B, C and N atoms in the deposited films. The presence of nitrogen in the atmosphere of the deposition chamber produces ternary B–N–C films composed mainly with a mixture of B–N and CN bonds as revealed by these techniques. The boron content increases while carbon and nitrogen contents decrease with P_RF. The higher proportion of boron atoms produced a strong contribution of the boron nitride in the final compound B–N–C films.     

Cathodoluminescence and electron field emission of boron-doped a-C:N films

The optical and electrical properties of so-called carbon nitride films (a-C:N) and boron doped so-called carbon nitride films (a-C:N:B) are studied with cathodoluminescence (CL) spectroscopy and electron field emission measurement. The a-C:N films were first deposited on Si by a filtered cathodic arc plasma system, and then boron ions (∼1 × 10¹⁶ cm⁻²) were implanted into the a-C:N films to form a-C:N:B films by a medium current implanter. The structural and morphological properties of a-C:N and a-C:N:B films were then analyzed using secondary ion mass spectrometer, X-ray photoelectron spectroscopy, FT-IR spectra, Raman spectroscopy and atomic force microscopy. The a-C:N film exhibits luminescence of blue light (∼2.67 eV) and red light (∼1.91 eV), and the a-C:N:B film displays luminescence of blue light (∼2.67 eV) in CL spectra measured at 300 K. Furthermore, the incorporated boron atoms change the electron field emission property, which shows a higher turn on field for the a-C:N:B film (3.6 V/μm) than that for the a-C:N film (2.8 V/μm).     

Influence of the methyl group on the dielectric constant of boron carbon nitride films containing it

LSI interconnect insulators made using low dielectric constant (low-k) materials are required for high performance devices with a small RC delay. We investigated a boron carbon nitride film containing the methyl group (Me–BCN) using tris-di-methyl-amino-boron (TMAB: B[N(CH₃)₂]₃) gas as a low-k material. In addition, we studied the influence of the methyl group on the dielectric constant (k-value) and the properties of the Me–BCN films. It was found that the k-value of the Me–BCN films decreases with increasing number of C–H bonds due to the methyl group (CH₃). The number of O–H bonds due to water incorporation is suppressed by increasing the number of C–H bonds. Consequently, we suggested that a lower k-value can be realized by the suppression of water invasion by a hydrophobic surface due to methyl bonds. Thus, the control of the methyl group is important to achieve a low-k material using Me–BCN films.     

纳米六方氮化硼负载离子液体润滑添加剂的摩擦学特性

制备了超声剥离的六方氮化硼负载油酸咪唑离子液体(OL-IL/h-BN)润滑添加剂,利用SEM、TEM、FTIR、TG及XRD等对其结构和形貌进行了表征。利用Zeta电位测试方法表征了其在聚乙二醇400中的分散性能,结果发现分散稳定性得到大幅提升。利用四球摩擦磨损试验机测试了摩擦学性能,结果显示减摩抗磨性能都优于h-BN。利用SEM和XPS对其磨斑表面形貌和成分进行了分析,XPS分析结果显示表面膜中含有化学吸附膜以及Fe₂O₃和B₂O₃等化学反应膜,这些膜的形成对减摩抗磨性能起到至关重要的作用。     

Wear-corrosion behavior of ultra-thin diamond-like carbon nitride films on aluminum alloy

Diamond-like carbon films exhibit high hardness, high wear resistance and a low friction coefficient. They are extensively utilized in the mechanical, electronic and biomedical industries. This work evaluates the effect of the thickness of ultra-thin diamond-like carbon nitride films on their corrosion properties and their wear-corrosion resistance in a mixed 1 M NaCl + 1 M H₂SO₄ solution using electrochemical methods. The corrosion current density and weight loss of all films during and after wear-corrosion test are also recorded. This work employs ion beam-assisted deposition (IBAD) to deposit DLC nitride films of various thicknesses (1.5, 2.0, 2.5 and 3.0 nm), containing 60% nitrogen gas in the form of a gaseous mixture of C₂H₂ + 60%N₂. The thickness of the films was measured using a transmission electron microscope (TEM). The atomic bonding structures of these DLC nitride films are analyzed using a Raman spectrometer and by electron spectroscopy for chemical analysis (ESCA). A scanning electron microscope (SEM) was adopted to elucidate the surface morphologies of the specimens after corrosion and wear-corrosion. The results indicated that all of the nitrogen-containing DLC films excellently protected the 5088 Al–Mg alloy substrate with an electroless plated Ni–P interlayer against corrosion, and that the degree of protection increases with the thickness of the film. In the wear-corrosion tests various potentials were applied during wear in the particular corrosive solution. The results further demonstrated that the wear-corrosion resistance of all the nitrogen-containing DLC films was as effective as corrosion protection, and that the wear-corrosion loss decreased as the film thickness increased.     

Investigating the microstructures and properties of Mg-Al LDH film-coated Mg-Li alloy: Effect of hydrothermal temperature

Magnesia-alumina layered double hydroxide (Mg-Al LDH) films grown in situ on LA43M magnesium-lithium (Mg-Li) alloy were synthesized utilizing the hydrothermal method. Scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), and X-ray diffraction (XRD) were used to characterize the surface morphologies, composition, and phase of the Mg-Al films. The corrosion resistance of the Mg-Al films was estimated via immersion experiment and hydrogen evolution test, and the tribological properties were investigated using tribological wear tests. The results showed that the thickness of the Mg-Al LDH film enhanced, and the size of the LDH sheets increased as the hydrothermal temperature raised, resulting in the improvement of the corrosion and wear resistance. When the hydrothermal temperature reached 110°C, interlayer anions were loaded the most, and the film achieved the optimal thickness. The Mg-Al LDH film had the optimum corrosion resistance and tribological properties. At this point, the weight loss of the film was 1.3560 mg·cm^–2, and the average friction coefficient was .149. It demonstrated that synthesizing Mg-Al LDH at a hydrothermal temperature of 110°C was an effective approach to improve the corrosion resistance of LA43M.     

Thermal properties and formation mechanism of h‐BN nanoneedles synthesized via carbothermic reduction reaction

Hexagonal boron nitride (BN) was synthesized through the carbothermic reduction reaction (CRR) of boric acid using lactose as a carbon source under the nitrogen atmosphere at 1500^°C for 3 hours. The boron/carbon (B/C) molar ratio was controlled during the CRR, and the produced samples were investigated by XRD diffraction pattern, FTIR analysis, and Raman spectra. Boron carbide (B₄C) was formed in samples that have a higher carbon content, in addition to boron nitride. While boron nitride pure sample was produced from lower carbon content samples. Formation of B₄C was found to depend on the B/C molar ratio. The morphology of the produced powder was also investigated by SEM and TEM, which revealed that the samples consist of nanoneedles of BN and hexagonal particles of B₄C. The vapor‐solid (VS) reaction mechanism was processed greatly with increasing boron amount, producing boron nitride nanoneedles, which compete with the liquid‐solid (LS) reaction mechanism. The physicochemical properties of the produced samples were studied by DTA, UV, PL, and AC impedance measurements, and revealed that the samples are promising to many proper applications.     

Corrosion and tribological properties of ultra-thin DLC films with different nitrogen contents in magnetic recording media

The corrosion spot density and contact–start–stop tribological properties that correlate to mechanical properties, electrical resistivity and lubricant bonded ratio of DLC overcoats on different disks of various surface roughness were investigated. DLC overcoats of hydrogenated carbon (CH) and nitrogenated carbon (CN) films were deposited by ion beam deposition (IBD) and sputter, respectively. Results show that the intensity ratio I(D)/I(G) increases with decreasing IBD-CH film thickness and increasing N₂ concentration of sputtered-CN layer, which implies that the films prepared at higher N₂ concentration contain a relatively lower sp³ bonded carbon. The composite hardness and Young's modulus of DLC films decrease with decreasing IBD-CH thickness and increasing N₂ concentration of sputtered-CN layers. Compared to disk overcoats deposited with only IBD-CH of comparable thickness, the lubricant bonded ratio is dramatically increased from 12 to 30% when the 0.5 nm CN is deposited on IBD-CH film. By increasing the N₂ concentration in the CN layer from 10 to 50 at.%, the electrical resistivity decreased from 3.6 to 0.8 kΩ and the lubricant bonded ratio increased from 30 to 46%. The corrosion spots density of sputtered-CN film surface decreases with increasing N₂ concentration. It is concluded that the dual layer of 1.5 nm IBD-CH/0.5 nm sputtered-CN with 30% N₂ deposition has the best integrated performance of corrosion resistance and CSS tribological properties.     

Effect of BN or B4C content on physical and tribological properties of copper-clad laminates reinforced with carbon fiber and epoxy resin

Plasma treatment was used to improve the surface roughness of copper foil. The copper-clad laminates reinforced with carbon fiber, boron nitride (BN), or boron carbide (B₄C), and epoxy resin were prepared by hot pressing. The effect of BN or B₄C content on the physical properties and tribological properties of copper-clad laminates reinforced with carbon fiber and epoxy resin were studied. The resulting copper-clad laminate exhibited desirable properties, such as dielectric constant, peel strength, oxygen index, and arc resistance, which were influenced by the concentration of BN or B₄C particles. Additionally, the wear and friction properties of the laminate were evaluated, revealing the effects of load, sliding speed, and particle content on weight loss, specific wear rate, and coefficient of friction. SEM analysis of worn surfaces provided insight into the stages of wear, highlighting the importance of an oxide layer in reducing wear and protecting the copper surface.     

High density carbon fiber/boron nitride matrix composites: Fabrication of composites with exceptional wear resistance

This paper describes the fabrication of high density (ρ ∼ 1.75 g/cc) composites containing a hybrid (carbon and boron nitride), or complete boron nitride matrix. The composites were reinforced with either chopped or 3D needled carbon fibers. The boron nitride was introduced via liquid infiltration of a borazine oligomer that can exhibit liquid crystallinity. The processing scheme was developed for the chopped carbon fiber/boron nitride matrix composites (C/BN) and later applied to the 3D carbon fiber reinforced/boron nitride matrix composites (3D C/BN). The hybrid matrix composites were produced by infiltrating the borazine oligomer into a low density 3D needled C/C composite to yield 3D C/C-BN. In addition to achieving high densities, the processing scheme yielded d₀₀₂ spacings of 3.35 Å, which afforded boron nitride with excellent hydrolytic stability. The friction and wear properties of the composites were explored over the entire energy spectrum for aircraft braking using an inertial brake dynamometer. The C/BN composites outperformed both the previously reported C/C-BN and chopped fiber reinforced C/C. The high density 3D C/BN performed as well as both the 3D C/C and the C/BN. The 3D C/C-BN provided outstanding wear resistance, incurring nearly zero wear across the entire testing spectrum. The coefficient of friction was relatively stable with respect to energy level, varying from 0.2 to 0.3.     

Effects of silicon incorporation on composition,structure and electric conductivity of cubic boron nitride thin films

We have achieved in-situ Si incorporation into cubic boron nitride (c-BN) thin films during ion beam assisted deposition. The effects of silicon incorporation on the composition, structure and electric conductivity of c-BN thin films were investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and electrical measurements. The results suggest that the content of the cubic phase remains stable on the whole with the incorporation of Si up to a concentration of 3.3 at.%, and the higher Si concentrations lead to a gradual change from c-BN to hexagonal boron nitride. It is found that the introduced Si atoms only replace B atoms and combine with N atoms to form Si–N bonds, and no evidence of the existence of Si–B bonds is observed. The resistance of the Si-doped c-BN films gradually decreases with increasing Si concentration, and the resistivity of the c-BN film with 3.3 at.% Si is lowered by two orders of magnitude as compared to undoped samples.     

Microstructure and tribological properties of ternary BCN thin films with different carbon contents

Boron carbon nitrogen (BCN) thin films with different carbon contents are deposited on high-speed steel substrates by reactive magnetron sputtering (RMS) and their microstructure and tribological properties are studied. The BCN films with carbon contents from 26.9 wt.% to 61.3 wt.% have an amorphous structure with variable amounts of carbon bonds (sp²C–C, sp²C–N and sp³C–N bonds). A higher carbon content enhances the film hardness but reduces the friction coefficient against GCr15 steel balls in air. BCN films with higher hardness, lower friction coefficient, and better wear resistance can be obtained by increasing the carbon content.     

Low‐Temperature Deposition of Hexagonal Boron Nitride via Sequential Injection of Triethylboron and N2/H2 Plasma

Hexagonal boron nitride (hBN) thin films were deposited on silicon and quartz substrates using sequential exposures of triethylboron and N₂/H₂ plasma in a hollow‐cathode plasma‐assisted atomic layer deposition reactor at low temperatures (≤450°C). A non‐saturating film deposition rate was observed for substrate temperatures above 250°C. BN films were characterized for their chemical composition, crystallinity, surface morphology, and optical properties. X‐ray photoelectron spectroscopy (XPS) depicted the peaks of boron, nitrogen, carbon, and oxygen at the film surface. B 1s and N 1s high‐resolution XPS spectra confirmed the presence of BN with peaks located at 190.8 and 398.3 eV, respectively. As deposited films were polycrystalline, single‐phase hBN irrespective of the deposition temperature. Absorption spectra exhibited an optical band edge at ~5.25 eV and an optical transmittance greater than 90% in the visible region of the spectrum. Refractive index of the hBN film deposited at 450°C was 1.60 at 550 nm, which increased to 1.64 after postdeposition annealing at 800°C for 30 min. These results represent the first demonstration of hBN deposition using low‐temperature hollow‐cathode plasma‐assisted sequential deposition technique.     

Ion implantation induced phase transformation in carbon and boron nitride thin films

The mechanism behind energetic ion impact induced stress reduction in highly stressed tetrahedral amorphous carbon and cubic boron nitride thin films is investigated by real time in situ spectroscopic ellipsometry and ex situ electron microscopy. Highly stressed carbon and boron nitride films were grown by filtered cathodic vacuum arc and RF magnetron sputtering, respectively. The films were then implanted by 5–10 keV argon ions and the film optical properties and thickness monitored in situ by spectroscopic ellipsometry. In both cases the films were observed to expand due to a reduction in the density of the ion-modified layer. Cross-sectional transmission electron microscopy and electron energy loss spectroscopy of the carbon films showed that this reduction in density is associated with a conversion of diamond-like bonding to graphite-like bonding. In situ stress measurements performed on the boron nitride films revealed a simultaneous reduction in stress with expansion of the material.     

Solvothermal synthesis of hexagonal B–C–N compound at low temperature conditions

Hexagonal B–C–N crystals have been successfully synthesized by a solvothermal method from carbon tetrachloride and calcium boron nitride at 400 °C. The characterization of synthesized product was carried out using X-ray diffraction, scanning electron microscopy and transmission electron microscopy equipped with electronic energy loss spectrometer. The composition of the hexagonal B–C–N single crystal is detected by electronic energy loss spectrometer as B_0.52C_0.11N_0.37.     

Study of CNx films on 316L stainless steel for orthodontic application

In order to improve the friction property and corrosion resistance of 316L stainless steel (316LSS) in orthodontic application, carbon nitride (CNx) films were synthesized by using IBAD technique at a set of assisted N ion beam currents. X-ray photoelectron spectroscopy and Raman spectroscopy were used to characterize the bonding state and the microstructure of the CNx films. Results of tribological tests indicated that the 316LSS coated by CNx films exhibited lower friction coefficients than the uncoated one both in air and in artificial saliva. The electrochemical tests in artificial saliva confirmed that the corrosion resistance of 316LSS was evidently improved after coated with CNx films.     

Micromechanical and microtribological properties of BCN thin films near the B4C composition deposited by r.f. magnetron sputtering

Ternary materials with compositions in the B–C–N system offer properties of great interest. In particular, mechanical and tribological properties are expected to be excellent, as they can combine some of the specific properties of BN, B₄C and C₃N₄. In this paper, BCN thin films deposited by r.f. magnetron sputtering are characterized by their micromechanical and microtribological behavior. BCN coatings with different composition were obtained by varying the N₂/Ar proportion in the sputtering gas. Hardness and elastic modulus of the coatings were measured by nanoindentation. The adhesion and friction coefficient against diamond have been evaluated by microscratch and the coatings have been characterized in their wear behavior at the nanometric scale. These mechanical and tribological properties have been related to film composition and structure, which have been studied in a previous work. It is found that the measured wear resistance at the nanometric scale is directly related to the coating microhardness rather than friction behavior or adhesion of the coating to the substrate, which are the determinant factors in the macroscopic scale wear behavior.     

Simultaneous enhancement of hardness and wear and corrosion resistance of high-entropy transition-metal nitride

Binary transition-metal nitrides (TMNs) are widely used as protective coating materials, and enhancing key performance characteristics are crucial to improving their robust and durable applications in harsh service environments. Compositional modulation via multiple elemental species offers an effective approach for optimizing physicochemical properties of TMNs, and establishing the composition–property relation is essential to the design of high-performance TMNs. In this work, we report on a comparative study of our synthesized NbN, NbMoN, and (NbMoTaW)N films and examined their microstructure, mechanical properties, and tribological and corrosion behaviors. The high-entropy (NbMoTaW)N film exhibits the highest hardness of 23.5 ± 1.35 GPa, which is ascribed to its high structural stability, increased elastic constant, and elastic modulus compared to the NbN and NbMoN films. The (NbMoTaW)N film also possesses the best wear resistance stemming from the highest H/E ratio and formation of self-lubricating MoO₃ and WO₃ species; moreover, this film shows the best corrosion resistance attributed to the sluggish diffusion of Cl⁻ due to lattice contraction and the structural stability caused by high-entropy effect. This work demonstrates simultaneously enhanced hardness and wear and corrosion resistance in a high-entropy TMN, opening a pathway for developing a new generation of advanced protective coating materials.     

Thermal diffusivity in diamond,SiCxNy and BCxNy

Thermal diffusivity (α) of free standing diamond, amorphous silicon carbon nitride (a-SiC_xN_y) and boron carbon nitride (a-BC_xN_y) thin films on crystalline silicon, has been studied using the travelling wave technique. Thermal diffusivity in all of them was found to depend on the microstructure. For a-SiC_xN_y and a-BC_xN_y thin films two distinct regimes of high and low carbon contents were observed in which the microstructure changed considerably and that has a profound effect on the thermal diffusivity. The defective C(sp)N phase plays a key role in determining the film properties.