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.

     

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.     

Covalently functionalized hexagonal boron nitride nanosheets by nitrene addition

The covalent functionalization of exfoliated hexagonal boron nitride (h-BN) nanosheets by nitrene addition is described. Integration of functionalized h-BN nanosheets within a polycarbonate matrix is demonstrated and was found to afford significant increases in mechanical properties. This integration methodology was further extended by the covalent modification of the h-BN nanosheets with polymer chains of a polycarbonate analogue, and the integration of the polymer modified h-BN within the polymer matrix.     

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.     

Design of thermal hybrid composites based on liquid crystal polymer and hexagonal boron nitride fiber network in polylactide matrix

Development of high thermally conductive and electrically insulative composites is of interest for electronic packaging industry. Advancements in smaller and more compact electronic devices required improvements in packing materials, including their weight, thermal conductivity, and electrical resistivity. In addition, with the increasing environmental awareness, the usage of green (bio‐based) alternatives was equally important. In the present study a hybrid based on fibers of highly concentrated hexagonal boron nitride (hBN) in liquid crystal polymer (LCP) matrix were fabricated. These hybrids were formed by arranging hBN platelets into LCP fiber form to reach high filler concentration and then randomly mix it in polylactide (PLA) matrix. With appropriate filler interaction within the hybrid, thermal conductivity similar to that of pure fiber could be achieved. Filler interaction may be tailored by optimizing the fibers aspect ratio. This study demonstrated the effect of random fillers in fibers shape in increasing the overall thermal conductivity of PLA polymeric hybrid using hBN and LCP fibers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 457–464     

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.     

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.     

Effect of low-energy ion impact on the structure of hexagonal boron nitride films studied in surface-wave plasma

A high-density surface-wave plasma source is used to deposit hexagonal boron nitride (hBN) films in a gas mixture of He, H₂, N₂, Ar, and BF₃ under a high ion flux condition using low-energy ion irradiation. The ion energy is controlled between around zero and 100 eV by applying a negative or positive bias voltage to a substrate, while the ion flux is increased by locating a substrate upstream in the diffusive plasma. For ion energies above ∼37 eV, the structure of the films depends upon ion energy more than substrate temperature, typical of subplantation processes. As a result, the structural order and crystallinity of sp²-bonded phase in the films characterized by Fourier transform infrared spectroscopy and X-ray diffraction are increased with decreasing ion energy, while the mass density of the films characterized by X-ray reflectivity is retained relatively high with a slight dependence upon ion energy.     

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.     

Structural study on poly(ether ether ketone ketone)-poly(ether biphenyl ether ketone ketone) copolymers

Structures of poly(ether ether ketone ketone)-poly(ether biphenyl ether ketone ketone) copolymers were studied by using small angle X-ray scattering and the one-dimensional electron density correlation function method. The results revealed that structures of the aggregated state of the copolymers depend closely on the biphenyl content (n_b). When n_b = 0.35, invariant Q, long period L, average thickness of crystal lamellae d̄, electron density difference η_c − η_a and degree of crystallinity W_{c, x} assume minimum values.     

含联苯结构聚醚醚酮酮共聚物和共混物的制备及性能研究

聚醚醚酮（PEEK）是八十年代初投入市场的全芳香结构热塑性耐高温特种工程塑料，它的7’。一143“C，Tm一334C“‘，最大结晶度为48％，典型制品结晶度为20％～30％［”．PEEK可用通常的设备成型，其制件、纤维、涂料及复合材料在电子电器、机械设备、交通运输、宇航、原子能工程、军事等领域有广泛的用途［’j．聚醚醚酮酮（PEEKK）是继PEEK之后，由德国Hoechst公司开发出来的又一种全芳香结构热塑性耐高温特种工程塑料［‘j．为了研究该类聚合物的结构和性能的关系，我们在实验室中合成了PEEKK和含联苯结构聚醚醚酮酮（PE－＊…     

Covalent attachment of polymeric monolith to polyether ether ketone (PEEK) tubing

A new method of reproducible preparation of vinylic polymeric monolithic columns with a key step of covalently anchoring the monolith to PEEK surface is described. In order to chemically attach the polymer monolith to the tube wall, methacrylate functional groups were introduced onto PEEK surface by a three-step procedure, including surface etching, surface reduction and surface methacryloylation. The chemical state of the modified tubing surface was characterized by attenuated total reflectance infrared (ATR-IR) spectroscopy. It was found that the etching step is the key to successfully modifying the PEEK tubing surface. Poly(styrene-co-divinylbenzene) monoliths were in situ synthesized by thermally initiated free radical copolymerization within the confines of surface-vinylized PEEK tubings of dimensions close to ones conventionally used in HPLC and UHPLC (1.6 mm internal diameter, 10.0–12.5 cm length). Adhesion test was done by measuring the operating pressure drop, which the prepared stationary phases can withstand. Good pressure resistance, up to 140 bar/10 cm (flow rate 0.5 mL min⁻¹, acetonitrile as a mobile phase), indicates strong bonding of monolith to the tubing wall. The monolithic material was proven to have a permeability of 1.7 × 10 ⁻¹⁴ m², applying acetonitrile–water 70:30 (v/v) as a mobile phase.     

聚醚醚酮酮和含联苯聚醚醚酮酮共聚物的熔融热

根据Ｆｌｏｒｙ热力学统计理论和比容－熔融热作国法，由ＤＳＣ结果得到了不同联苯含量的聚醚醚酮酮－含联苯聚醚醚酮酮（ＰＥＥＫＫ－ＰＥＢＥＫＫ）共聚物的熔融热，两种方法获得的结果吻合。在此基础上给出了ＰＥＥＫＫ－ＰＥＢＥＫＫ共聚物不同联苯含量的熔点计算表达式。结果还表明，随着联苯含量ｎＢ，的变化，明显改变；当ｎＢ＝０．３５时，ＰＥＥＫＫＰＥＢＥＫＫ共聚物的值最小。     

Effect of hexagonal boron nitride on poly(vinyl phosphonic acid) composite polymer electrolytes for fuel cells

In this work, hexagonal boron nitride nanoparticles were used as inorganic fillers, which increase the mechanical and thermal stabilities as well as the proton conductivity of the proton conducting composite membranes prepared by blending of poly(vinyl phosphonic acid) and hexagonal boron nitride. Thermo gravimetric analysis showed that the polymer electrolyte membranes are thermally stable up to 200°C. Scanning electron microscopy analysis indicated the homogeneous distribution of boron nitride nanoparticles in the polymer matrix. The crystallinity of the membranes was characterized by using X-ray Diffraction. X-ray patterns support semi-crystalline nature of the composite materials.