Identifying hexagonal boron nitride monolayers by transmission electron microscopy

Multislice simulations in the transmission electron microscope (TEM) were used to examine changes in annular-dark-field scanning TEM (ADF-STEM) images, conventional bright-field TEM (BF-CTEM) images, and selected-area electron diffraction (SAED) patterns as atomically thin hexagonal boron nitride (h-BN) samples are tilted up to 500 mrad off of the [0001] zone axis. For monolayer h-BN the contrast of ADF-STEM images and SAED patterns does not change with tilt in this range, while the contrast of BF-CTEM images does change; h-BN multilayer contrast varies strongly with tilt for ADF-STEM imaging, BF-CTEM imaging, and SAED. These results indicate that tilt series analysis in ADF-STEM image mode or SAED mode should permit identification of h-BN monolayers from raw TEM data as well as from quantitative post-processing.     

Scalable exfoliation for few-layered hexagonal boron nitride nanosheets (BNNSs) by microwave-assisted expansion and liquid nitrogen intercalation

The low cost and facile scalable exfoliation route for two-dimensional hexagonal boron nitride (h-BN) was still indispensable for potential applications. In this work, we presented a convenient and scalable exfoliation for few-layer BNNSs. Taking advantage of the advantages of swift heating of microwave and ultra low temperature vaporization of liquid nitrogen, bulk h-BN was high-efficiently exfoliated into few-layer BNNSs. The as-exfoliated BNNSs had a 2−6 nm thickness and approximately 7.91% yield, exhibiting scalable, facile and environment-friendly features. Furthermore, the as-exfoliated BNNSs were applied as additive in oil for reducing friction of oil. The COF of the BNNSs-based grease reduced by 20.10% compared to grease, and the antiwear performance decreased by 55.8% and 45.1% relative to grease and h-BN-based grease.     

Cleaning of pyrolytic hexagonal boron nitride surfaces

Hexagonal boron nitride (h‐BN) has recently garnered significant interest as a substrate and dielectric for two‐dimensional materials and devices based on graphene or transition metal dichalcogenides such as molybdenum disulfide (MoS₂). As substrate surface impurities and defects can negatively impact the structure and properties of two‐dimensional materials, h‐BN surface preparation and cleaning are a critical consideration. In this regard, we have utilized X‐ray photoelectron spectroscopy to investigate the influence of several ex situ wet chemical and in situ thermal desorption cleaning procedures on pyrolytic h‐BN surfaces. Of the various wet chemistries investigated, a 10 : 1 buffered HF solution was found to produce surfaces with the lowest amount of oxygen and carbon contamination. Ultraviolet/ozone oxidation was found to be the most effective ex situ treatment for reducing carbon contamination. Annealing at 1050 °C in vacuum or 10^?5 Torr NH₃ was found to further reduce oxygen and carbon contamination to the XPS detection limits. Copyright © 2015 John Wiley & Sons, Ltd.     

Neutron damage of hexagonal boron nitride: h-BN

Hexagonal boron nitride (h-BN) was neutron damaged at an integral flux of 2.40 × 10¹² n cm⁻² s⁻¹ for 1, 2, 3 and 4 h. The h-BN samples undergo a transition from sp² to sp³ hybridization as a consequence of the neutron induced damage with the formation of cubic boron nitride (c-BN) spots, as suggested both by FT–IR and Raman spectroscopy. In addition to c-BN, also a certain degree of amorphization is achieved by h-BN already at the lowest neutron fluence of 8.64 × 10¹⁵ n cm⁻² as clearly evidenced by Raman spectroscopy. The Wigner or stored energy to the radiation-damaged h-BN samples was studied by DSC and also in this case there was a clear evidence that the neutron damage was partly irreversible and insensitive to the thermal annealing up to 630 °C. Electron spin resonance (ESR) was employed to further study the structural defects induced by the neutron bombardment of h-BN. Two kinds of paramagnetic defective structures centered on ¹¹B atoms were identified.

     

氮化硼纳米片及其凝胶材料的研究进展

氮化硼纳米片具有高机械强度、良好的化学惰性和热稳定性等优点.除了这些性质,基于纳米氮化硼的凝胶材料还有高比表面积、大孔隙率等特点.因此它在催化、储氢、除污和气体吸附等领域具有潜在的应用前景.这篇综述主要介绍了氮化硼纳米片及其凝胶材料的制备,举例说明了氮化硼凝胶的关键应用并加以展望.     

Hydrothermal hot-pressing induced phase transition in hexagonal boron nitride

The phase transition of hBN nanocrystals induced by hydrothermal hot-pressing process has been investigated by XRD, FTIR, TEM and HRTEM. It was found that a phase transition of hBN → tBN → aBN occurred with increasing hot-pressing temperature, i.e., hBN transformed into tBN at above 270 °C, and followed by another transformation from tBN to aBN at 310 °C. In addition, FTIR spectra and HRTEM images indicate that a small amount of cBN formed directly from the amorphous BN matrix at 75 MPa and 310 °C. This phenomenon is similar to what happened in conventional high temperature and high pressure method, which is believed to promote the phase transition from hBN to cBN.     

A simple method to synthesize polyhedral hexagonal boron nitride nanofibers

Hexagonal boron nitride (h-BN) fibers with polyhedral morphology were synthesized with a simple-operational, large-scale and low-cost method. The sample obtained was studied by X-ray photoelectron spectrometer (XPS), electron energy lose spectroscopy (EELS), X-ray powder diffraction (XRD), Fourier transformation infrared spectroscopy (FT-IR), etc., which matched with h-BN. Environment scanning electron microscopy (ESEM) and transmission electron microscope (TEM) indicated that the BN fibers possess polyhedral morphology. The diameter of the BN fibers is mainly in the range of 100–500 nm.     

Surface study of hexagonal boron nitride powder by diffuse reflectance Fourier transform infrared spectroscopy

The surface chemistry of hexagonal boron nitride powder is examined. Surface functional groups are found to consist of a mixture of primary and secondary amine groups as well as hydroxyl groups. The surface has a net basic character indicating that the amine contribution to the overall surface chemistry is greater than that of the acidic hydroxyl contribution. A chemical surface treatment also is performed to modify the surface chemistry of hexagonal boron nitride powder. Copyright © 2005 John Wiley & Sons, Ltd.     

Fabrication and characterization of hexagonal boron nitride powder by spray drying and calcining-nitriding technology

Hexagonal boron nitride (hBN) powder was fabricated prepared by the spray drying and calcining-nitriding technology. The effects of nitrided temperature on the phases, morphology and particle size distribution of hBN powder, were investigated. The synthesized powders were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), Fourier transformed infrared spectrum, ultraviolet-visible (UV-vis) spectrum and photoluminescence (PL) spectrum. UV-vis spectrum revealed that the product had one obvious band gap (4.7 eV) and PL spectrum showed that it had a visible emission at 457 nm (λ_ex=230 nm). FESEM image indicated that the particle size of the synthesized hBN was mainly in the range of 0.5-1.5 μm in diameter, and 50-150 nm in thickness. The high-energy ball-milling process following 900 °C calcining process was very helpful to obtain fully crystallized hBN at lower temperature.     

Angle-resolved soft X-ray emission and absorption spectroscopy of hexagonal boron nitride

Angle-resolved soft X-ray emission and absorption spectra in the BK and NK regions of hexagonal BN were measured using polarized synchrotron radiation. The take-off/incident-angle-dependence on the spectral features in both X-ray emission and absorption is clearly observed. The configuration of the sigma and pi orbitals, which were calculated using discrete variational (DV)-Xalpha molecular orbital calculations, explains the angle-resolved soft X-ray emission and absorption spectra. The relative peak intensity of the 394-eV peak in the NK X-ray emission provides useful information about the BN layer ordering.     

Self-assembly of a hexagonal boron nitride nanomesh on Ru(0001)

Hexagonal boron nitride (h-BN) nanostructures were grown on Ru(0001), and are very similar to those previously reported on Rh(111). They show a highly regular 12 x 12 superstructure, comprising 2 nm wide apertures with a depth of about 0.1 nm. Valence band photoemission reveals two distinctly bonded h-BN species, and X-ray photoelectron spectroscopy indicates an h-BN monolayer film. The functionality of the h-BN/Ru(0001) nanomesh is demonstrated by using this structure for the assembly of gold nanoclusters.     

Oxidation of a two-dimensional hexagonal boron nitride monolayer: a first-principles study

Two-dimensional (2D) hexagonal boron-nitride oxide (h-BNO) is a structural analogue of graphene oxide. Motivated by recent experimental studies of graphene oxide, we have investigated the chemical oxidation of 2D h-BN sheet and the associated electronic properties of h-BNO. Particular emphasis has been placed on the most favorable site(s) for chemisorption of atomic oxygen, and on the migration barrier for an oxygen atom hopping to the top, bridge, or hollow site on the h-BN surface, as well as the most likely pathway for the dissociation of an oxygen molecule on the h-BN surface. We find that when an oxygen atom migrates on the h-BN surface, it is most likely to be over an N atom, but confined by three neighbor B atoms (forming a triangle ring). In general, chemisorption of an oxygen atom will stretch the B-N bond, and under certain conditions may even break the B-N bond. Depending on the initial location of the first chemisorbed O atom, subsequent oxidation tends to form an O domain or O chain on the h-BN sheet. The latter may lead to a synthetic strategy for the unzipping of the h-BN sheet along a zigzag direction. A better understanding of the oxidation of h-BN sheet has important implications for tailoring the properties of the h-BN sheet for applications.     

N,N-Dimethyl formamide facilitated formation of hexagonal boron nitride from boric acid

In this paper, we report on a promoting novel process for the formation of h-BN plates by using N,N-dimethyl formamide-treated boric acid (DMF-BA). Using this B source, the formation of h-BN can be indeed improved greatly compared to using pure boric acid (BA). This method effectively reduces the content of boric acid and amorphous boric oxide, enhancing the transformation rate of h-BN. For preparation of pure h-BN, it can obviously lower the resultant temperature without further purification process. Via graphitization index (G.I.) calculation and thermostability analysis, the pure h-BN plates obtained from the DMF-BA would be a promising candidate for raw material of c-BN and low-temperature applications in the air.     

Mechanochemistry of hexagonal boron nitride. 2. Reactivity upon interaction with water

Mechanical activation makes boron nitride chemically reactive with respect to water. The fact of the reaction proceeding, which is accompanied by a change in the structure of boron nitride, is confirmed by the data of IR spectroscopy, X-ray diffraction, transmission electron microscopy, differential thermal analysis, adsorption, and gravimetry. It is established that the most defective amorphous part of the material is primarily hydrolyzed. The reaction takes place at room temperature, with the conversion increasing to values of higher than 50% with the dose of mechanical energy supplied during the mechanical activation. In addition to ammonia, hydrolysis gives rise to the formation of ammonium pentaboride, NH₄B₅O₆(OH)₄ · 2H₂O. After the reaction products are removed, residual boron nitride, which is dried at T ≤ 100°C, crystallizes to form nanosized rods.     

Fluorinating hexagonal boron nitride into diamond-like nanofilms with tunable band gap and ferromagnetism

Cubic boron nitride (c-BN) possesses a number of extreme properties rivaling or surpassing those of diamond. Especially, owing to the high chemical stability, c-BN is desired for fabricating electronic devices that can stand up to harsh environments. However, realization of c-BN-based functional devices is still a challenging task due largely to the subtlety in the preparation of high-quality c-BN films with uniform thickness and controllable properties. Here, we present a simple synthetic strategy by surface fluorination of few-layered hexagonal boron nitride (h-BN) sheets to produce thermodynamically favorable F-terminated c-BN nanofilms with an embedded N-N bond layer and strong inbuilt electric polarization. Due to these specific features, the fluorinated c-BN nanofilms have controllable band gap by thickness or inbuilt and applied electric fields. Especially, the produced nanofilms can be tuned into substantial ferromagnetism through electron doping within a reasonable level. The electron-doping-induced deformation ratio of the c-BN nanofilms is found to be 1 order of magnitude higher than those of carbon nanotubes and graphene. At sufficient high doping levels, the nanofilm can be cleaved peculiarly along the N-N bond layer into diamond-like BN films. As the proposed synthesis strategy of the fluorinated c-BN nanofilms is well within the reach of current technologies, our results represent an extremely cost-effective approach for producing high-quality c-BN nanofilms with tunable electronic, magnetic, and electromechanical properties for versatile applications.