Microstructural development with crystallization of hexagonal boron nitride

Abstracts are not published in this journal This revised version was published online in November 2006 with corrections to the Cover Date.     

Oxygen-suppressed selective growth of monolayer hexagonal boron nitride on copper twin crystals

Controlled growth of hexagonal boron nitride (h-BN) with desired properties is essential for its wide range of applications.Here,we systematically carried out the chemical vapor deposition of monolayer h-BN on Cu twin crystals.It was found that h-BN nucleated and grew preferentially and simultaneously on the narrow twin crystal strips present in the Cu substrates.The density functional theory calculations revealed that the introduction of oxygen could efficiently tune the selectivity.This is because of the reduction in the dehydrogenation barrier of the precursor molecules by the introduction of oxygen.Our findings throw light on the direct growth of functional h-BN nanoribbons on nano-twinned crystal strips and switching of the growth behavior of h-BN films by oxygen.     

Synthesis of boron carbide powder from hexagonal boron nitride

We report the synthesis of boron carbide powder via the reaction of hexagonal boron nitride with carbon black. The reaction between hexagonal boron nitride and carbon black completed at 1900 °C for 5 h in vacuum. The particle sizes of the synthesized boron carbide powder were about 100 nm from transmission electron microscopy. The possible reaction mechanism was that hexagonal boron nitride decomposed into elemental boron and nitrogen even when there was no carbon at a relatively low rate, and introduction of carbon into hexagonal boron nitride powder facilitated the decomposition process; the boron from the decomposition of boron nitride reacted with carbon to form boron carbide.     

Oxidation kinetics of hexagonal boron nitride powder

The isothermal oxidation of hexagonal boron nitride powders was carried out at 900–1050°C in dry oxygen and air. The oxidation kinetics were found to obey linear rate law and were described by the surface chemical reaction-controlled shrinking cylindrical model. The apparent activation energies were found to be 298 and 330 kJ mol^–1in dry oxygen and air, respectively. The oxygen partial pressure dependence of the oxidation rate constant at 1000 °C is well represented by a Langmuir-type equation. Microscopic examination of the oxidized sample after removal of the oxide scale with water suggested that the rate of attack by oxygen was determined by an anisotropy due to the crystallographic direction, similar to oxidation in graphite. The volatilization of B₂O₃ was observed only in dry oxygen and obeyed a linear rate law, and was found not to affect the oxidation reaction.     

Electron microscopy of hexagonal boron nitride powder

The morphology and crystalline state of h-BN powder after one-stage or two-stage baking process were investigated extensively. The particles are scale-shaped and the flat surfaces have a (001) habit plane of hexagonal close-packed structure. The side shape of particles after one-stage baking is round, while that after two-stage baking is dodecan, a twelve-faced prism, with the side habit of (100), (110) or their variants. Lattice image observation shows that the side surface of a one-stage baked particle is wavy and thin, while that of a two-stage baked particle is straight and thick. Many particles after one-stage baking are composed of overlapped grains contacting with each other at (001) flat surfaces forming a twist boundary. These grains have relative rotation angles ranging from 5 ° to 26 ° around the common [001] axis and have a coincidence lattice relation with respect to (001) flat planes. X-ray photoelectron spectroscopy analysis shows that both C and O segregate onto the surface of one-stage baked particles, while only C segregates onto the surface of two-stage baked particles. Formation of coincidence lattice grain boundary and impurity segregation both restrict the growth of diameter and thickness in scale-shaped particles. It is concluded that two-stage baked particles, having side surface habits, are stable against various environments.     

Role of boron carbide in carbothermic formation of hexagonal boron nitride

Formation of hexagonal boron nitride by carbothermic reduction of boric oxide under nitrogen atmosphere at 1500 °C was investigated. Experiments were performed for durations in the range of 15 min to 3 h. Reaction products were subjected to powder X-ray diffraction analysis, chemical analysis and were examined by scanning electron microscope. Formation of hexagonal boron nitride was found to be complete in 3 h with most forming in the initial 2 h. Boron carbide was found to exist in the reaction products of the experiments in which hexagonal boron nitride formation was not complete. The aim of this study was to investigate the role of boron carbide in the carbothermic production of hexagonal boron nitride. For this purpose, conversion reaction of boron carbide into hexagonal boron nitride was studied. Boron carbide used in these experiments was produced in the same conditions that hexagonal boron nitride was formed, but under argon atmosphere. It was found that formation of hexagonal boron nitride from boron carbide—boric oxide mixtures was slower than activated carbon—boric oxide mixtures. It was concluded that boron carbide is not a necessary intermediate product in the carbothermic production of hexagonal boron nitride.     

Nitriding of iron boride to hexagonal boron nitride

A process for preparing hexagonal boron nitride (h-BN) from iron boride (FeB) has been described for the first time. FeB powder was nitrided in ammonia at 700 K for 24 hours yielding non-crystalline BN and -Fe₂N. Subsequent annealing in ammonia for 1 hour at 1273 K resulted in a mixture of crystalline h-BN together with -Fe, -Fe₃N and -Fe₄N. The morphology of the product grains is described. This comprises an iron nitride core loosely encapsulated in a foliated BN layer. The open nature of the product layer may account for the relatively low temperature (700 K) required for the nitriding reaction. These iron containing phases were removed with dilute mineral acid leaving h-BN and trace amounts of FeB₄₉.     

Effective mechanical properties of hexagonal boron nitride nanosheets

We propose an analytical formulation to extract from energy equivalence principles the equivalent thickness and in-plane mechanical properties (tensile and shear rigidity, and Poisson's ratio) of hexagonal boron nitride (h-BN) nanosheets. The model developed provides not only very good agreement with existing data available in the open literature from experimental, density functional theory (DFT) and molecular dynamics (MD) simulations, but also highlights the specific deformation mechanisms existing in boron nitride sheets, and their difference with carbon-based graphitic systems.     

Third order elastic constants of hexagonal boron nitride

Third order elastic constants of hexagonal Boron Nitride have been evaluated using the Lannard-Jones potential. The results obtained are presented and compared with the only available measurement ofC ₃₃₃ for this material.     

Facile synthesis of hexagonal boron nitride fibers and flowers

Hexagonal boron nitride (h-BN) fibers and flowers were synthesized with a facile synthesis route. The precursor was obtained as an intermediate material by the reaction of KBH₄ and NH₄Cl at 120 °C for 48 h. h-BN was obtained by heating the intermediate material at 1250 °C for 10 h. The sample obtained was characterized by X-ray powder diffraction (XRD), Fourier transformation infrared spectroscopy (FT-IR), thermogravimetry (TG/DTA) and environment scanning electron microscopy (ESEM), which matched with h-BN. ESEM image indicated that the diameter of the BN fibers is mainly in the range of 1–2 μm.     

Effective cleaning of hexagonal boron nitride for graphene devices

Hexagonal boron nitride (h-BN) films have attracted considerable interest as substrates for graphene. ( Dean, C. R. et al. Nat. Nanotechnol. 2010 , 5 , 722 - 6 ; Wang, H. et al. Electron Device Lett. 2011 , 32 , 1209 - 1211 ; Sanchez-Yamagishi, J. et al. Phys. Rev. Lett. 2012 , 108 , 1 - 5 .) We study the presence of organic contaminants introduced by standard lithography and substrate transfer processing on h-BN films exfoliated on silicon oxide substrates. Exposure to photoresist processing adds a large broad luminescence peak to the Raman spectrum of the h-BN flake. This signal persists through typical furnace annealing recipes (Ar/H(2)). A recipe that successfully removes organic contaminants and results in clean h-BN flakes involves treatment in Ar/O(2) at 500 °C.     

Surface modification of hexagonal boron nitride nanomaterials: a review

Hexagonal boron nitride (h-BN) nanomaterials, such as boron nitride nanotubes, boron nitride nanofibers, and boron nitride nanosheets, are among the most promising inorganic nanomaterials in recent years. Their unique properties, including high mechanical stiffness, wide band gap, excellent thermal conductivity, and thermal stability, suggest many potential applications in various engineering fields. In particular, h-BN nanomaterials have been widely used as functional fillers to fabricate high-performance polymer nanocomposites. Like other nanomaterials, prior to their utilization in nanocomposites, surface modification of h-BNs is often necessary in order to prevent their strong tendency to aggregate, and to improve their dispersion and interfacial properties in polymer nanocomposites. However, the high chemical inertness and resistance to oxidation of h-BNs make it rather difficult to functionalize h-BNs. The methods frequently used to oxidize graphitic carbon nanomaterials are not quite successful on h-BNs. Therefore, many novel approaches have been studied to modify h-BN nanostructures. In this review, different surface modification strategies were discussed including various covalent and non-covalent surface modification strategies through wet or dry chemical routes. Meanwhile, the effects of these surface modification methods on the resulting material structures and properties were also reviewed. At last, a number of theoretical studies on the reactivity of h-BNs with different chemical agents have been conducted to explore new surface modification routes, which were also addressed in this review.     

High thermal conductivity of suspended few-layer hexagonal boron nitride sheets

The thermal conduction of suspended few-layer hexagonal boron nitride （h-BN） sheets was experimentally investigated using a noncontact micro-Raman spectroscopy method. The first-order temperature coefficients for monolayer （1L）, bilayer （2L） and nine-layer （9L） h-BN sheets were measured to be -（3.41 ± 0.12）× 10-2, -（3.15 ± 0.14） × 10-2 and -（3.78 ±0.16）× 10-2 cm-1.K-1, respectively. The room-temperature thermal conductivity of few-layer h-BN sheets was found to be in the range from 227 to 280 W.m-1-K-1, which is comparable to that of bulk h-BN, indicating their potential use as important components to solve heat dissipation problems in thermal management configurations.     

Direct growth of graphene/hexagonal boron nitride stacked layers

Graphene (G) and atomic layers of hexagonal boron nitride (h-BN) are complementary two-dimensional materials, structurally very similar but with vastly different electronic properties. Recent studies indicate that h-BN atomic layers would be excellent dielectric layers to complement graphene electronics. Graphene on h-BN has been realized via peeling of layers from bulk material to create G/h-BN stacks. Considering that both these layers can be independently grown via chemical vapor deposition (CVD) of their precursors on metal substrates, it is feasible that these can be sequentially grown on substrates to create the G/h-BN stacked layers useful for applications. Here we demonstrate the direct CVD growth of h-BN on highly oriented pyrolytic graphite and on mechanically exfoliated graphene, as well as the large area growth of G/h-BN stacks, consisting of few layers of graphene and h-BN, via a two-step CVD process. The G/h-BN film is uniform and continuous and could be transferred onto different substrates for further characterization and device fabrication.     

Electrostatic doping of graphene through ultrathin hexagonal boron nitride films

When combined with graphene, hexagonal boron nitride (h-BN) is an ideal substrate and gate dielectric with which to build metal|h-BN|graphene field-effect devices. We use first-principles density functional theory (DFT) calculations for Cu|h-BN|graphene stacks to study how the graphene doping depends on the thickness of the h-BN layer and on a potential difference applied between Cu and graphene. We develop an analytical model that describes the doping very well, allowing us to identify the key parameters that govern the device behavior. A predicted intrinsic doping of graphene is particularly prominent for ultrathin h-BN layers and should be observable in experiment. It is dominated by novel interface terms that we evaluate from DFT calculations for the individual materials and for interfaces between h-BN and Cu or graphene.     

Elucidation of the thermophysical mechanism of hexagonal boron nitride as nanofluids additives

This study systematically investigated the physicochemical characteristics of hexagonal boron nitride (h-BN) nanoparticles dispersed in polyalphaolefin 6 (PAO6) from a molecular level to explore the thermal stability of nano-lubricants. The nanoparticles were characterized via transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM), fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and energy-dispersive spectrometry (EDS) to analyze the chemical bonds, element distribution, and impurity. We not only theoretically reveal the rheological behavior of nano-lubricants but also propose precise models to predict the viscosity. Moreover, this study comprehensively analyzed the thermal stability of nano-lubricants under different gas environments through thermogravimetric analysis and revealed that the nanofluid thermal stability was improved owing to the small-size effect. The results show that the thermal conductivity of the nano-lubricants was significantly higher than that of PAO6. Finally, the mechanism of thermal property enhancement by the h-BN nanoparticles is revealed.     

Scanning tunnelling microscopy and spectroscopy of ultra-flat graphene on hexagonal boron nitride

Graphene has demonstrated great promise for future electronics technology as well as fundamental physics applications because of its linear energy-momentum dispersion relations which cross at the Dirac point. However, accessing the physics of the low-density region at the Dirac point has been difficult because of disorder that leaves the graphene with local microscopic electron and hole puddles. Efforts have been made to reduce the disorder by suspending graphene, leading to fabrication challenges and delicate devices which make local spectroscopic measurements difficult. Recently, it has been shown that placing graphene on hexagonal boron nitride (hBN) yields improved device performance. Here we use scanning tunnelling microscopy to show that graphene conforms to hBN, as evidenced by the presence of Moiré patterns. However, contrary to predictions, this conformation does not lead to a sizeable band gap because of the misalignment of the lattices. Moreover, local spectroscopy measurements demonstrate that the electron-hole charge fluctuations are reduced by two orders of magnitude as compared with those on silicon oxide. This leads to charge fluctuations that are as small as in suspended graphene, opening up Dirac point physics to more diverse experiments.