Two-dimensional Hexagonal Boron Nitride Research Articles

Analytic modeling for the anisotropic thermal conductivity of polymer composites containing aligned hexagonal boron nitride

Polymer composites containing two-dimensional hexagonal boron nitride (h-BN) can achieve enhanced thermal conductivity (TC), and such enhancement is more pronounced along the orientation direction of h-BN platelets. In this paper, an analytical model was developed for simultaneously calculating the anisotropic TC of polymer composites containing aligned h-BN platelets. A unit cell was first abstracted based on the morphological observation in the literature. Then the thermal resistance method and coordinate transformation were used to derive the TC of the composites. The model was successfully validated by the experimental data from two independent literature studies over a large range of filler contents. The dependence of TC on the key parameters of the model, including the orientation angle and geometric dimension of the h-BNs, and the interfacial thermal resistance, were quantitatively analyzed and discussed.

Quantum emission from hexagonal boron nitride monolayers.

Artificial atomic systems in solids are widely considered the leading physical system for a variety of quantum technologies, including quantum communications, computing and metrology. To date, however, room-temperature quantum emitters have only been observed in wide-bandgap semiconductors such as diamond and silicon carbide, nanocrystal quantum dots, and most recently in carbon nanotubes. Single-photon emission from two-dimensional materials has been reported, but only at cryogenic temperatures. Here, we demonstrate room-temperature, polarized and ultrabright single-photon emission from a colour centre in two-dimensional hexagonal boron nitride. Density functional theory calculations indicate that vacancy-related defects are a probable source of the emission. Our results demonstrate the unprecedented potential of van der Waals crystals for large-scale nanophotonics and quantum information processing.

Scalable exfoliation process for highly soluble boron nitride nanoplatelets by hydroxide-assisted ball milling.

The scalable preparation of two-dimensional hexagonal boron nitride (h-BN) is essential for practical applications. Despite intense research in this area, high-yield production of two-dimensional h-BN with large-size and high solubility remains a key challenge. In the present work, we propose a scalable exfoliation process for hydroxyl-functionalized BN nanoplatelets (OH-BNNPs) by a simple ball milling of BN powders in the presence of sodium hydroxide via the synergetic effect of chemical peeling and mechanical shear forces. The hydroxide-assisted ball milling process results in relatively large flakes with an average size of 1.5 μm with little damage to the in-plane structure of the OH-BNNP and high yields of 18%. The resultant OH-BNNP samples can be redispersed in various solvents and form stable dispersions that can be used for multiple purposes. The incorporation of the BNNPs into the polyethylene matrix effectively enhanced the barrier properties of the polyethylene due to increased tortuosity of the diffusion path of the gas molecules. Hydroxide-assisted ball milling process can thus provide simple and efficient approaches to scalable preparation of large-size and highly soluble BNNPs. Moreover, this exfoliation process is not only easily scalable but also applicable to other layered materials.

Dielectric screening in atomically thin boron nitride nanosheets.

Two-dimensional (2D) hexagonal boron nitride (BN) nanosheets are excellent dielectric substrate for graphene, molybdenum disulfide, and many other 2D nanomaterial-based electronic and photonic devices. To optimize the performance of these 2D devices, it is essential to understand the dielectric screening properties of BN nanosheets as a function of the thickness. Here, electric force microscopy along with theoretical calculations based on both state-of-the-art first-principles calculations with van der Waals interactions under consideration, and nonlinear Thomas-Fermi theory models are used to investigate the dielectric screening in high-quality BN nanosheets of different thicknesses. It is found that atomically thin BN nanosheets are less effective in electric field screening, but the screening capability of BN shows a relatively weak dependence on the layer thickness.

Tunnel magnetoresistance with atomically thin two-dimensional hexagonal boron nitride barriers

The two-dimensional atomically thin insulator hexagonal boron nitride (h-BN) constitutes a new paradigm in tunnel based devices. A large band gap, along with its atomically flat nature without dangling bonds or interface trap states, makes it an ideal candidate for tunnel spin transport in spintronic devices. Here, we demonstrate the tunneling of spin-polarized electrons through large area monolayer h-BN prepared by chemical vapor deposition in magnetic tunnel junctions. In ferromagnet/h-BN/ferromagnet heterostructures fabricated on a chip scale, we show tunnel magnetoresistance at room temperature. Measurements at different bias voltages and on multiple devices with different ferromagnetic electrodes establish the spin polarized tunneling using h-BN barriers. These results open the way for integration of 2D monolayer insulating barriers in active spintronic devices and circuits operating at ambient temperature, and for further exploration of their properties and prospects.

Temperature dependence of the energy bandgap of two-dimensional hexagonal boron nitride probed by excitonic photoluminescence

Hexagonal boron nitride (hBN) is an emerging material for the exploration of new physics in two-dimensional (2D) systems that are complementary to graphene. Nanotubes with a diameter (∼60 nm) that is much larger than the exciton binding energy in hBN have been synthesized and utilized to probe the fundamental optical transitions and the temperature dependence of the energy bandgap of the corresponding 2D hBN sheets. An excitonic transition at 5.901 eV and its longitudinal optical phonon replica at 5.735 eV were observed. The excitonic emission line is blue shifted by about 130 meV with respect to that in hBN bulk crystals due to the effects of reduced dimensionality. The temperature evolution of the excitonic emission line measured from 300 to 800 K revealed that the temperature coefficient of the energy bandgap of hBN nanotubes with large diameters (or equivalently hBN sheets) is about 0.43 meV/0K, which is a factor of about 5 times smaller than the theoretically predicted value for the transitions between the π and π* bands in hBN bulk crystals and 6 times smaller than the measured value in AlN epilayers with a comparable energy bandgap. The observed weaker temperature dependence of the bandgap than those in 3D hBN and AlN is a consequence of the effects of reduced dimensionality in layer-structured hBN.

Characterization of two-dimensional hexagonal boron nitride using scanning electron and scanning helium ion microscopy

Characterization of the structural and physical properties of two-dimensional (2D) materials, such as layer number and inelastic mean free path measurements, is very important to optimize their synthesis and application. In this study, we characterize the layer number and morphology of hexagonal boron nitride (h-BN) nanosheets on a metallic substrate using field emission scanning electron microscopy (FE-SEM) and scanning helium ion microscopy (HIM). Using scanning beams of various energies, we could analyze the dependence of the intensities of secondary electrons on the thickness of the h-BN nanosheets. Based on the interaction between the scanning particles (electrons and helium ions) and h-BN nanosheets, we deduced an exponential relationship between the intensities of secondary electrons and number of layers of h-BN. With the attenuation factor of the exponential formula, we calculate the inelastic mean free path of electrons and helium ions in the h-BN nanosheets. Our results show that HIM is more sensitive and consistent than FE-SEM for characterizing the number of layers and morphology of 2D materials.

Heteroepitaxial Growth of Two-Dimensional Hexagonal Boron Nitride Templated by Graphene Edges

By adapting the concept of epitaxy to two-dimensional space, we show the growth of a single-atomic-layer, in-plane heterostructure of a prototypical material system--graphene and hexagonal boron nitride (h-BN). Monolayer crystalline h-BN grew from fresh edges of monolayer graphene with atomic lattice coherence, forming an abrupt one-dimensional interface, or boundary. More important, the h-BN lattice orientation is solely determined by the graphene, forgoing configurations favored by the supporting copper substrate.

The effect of grain boundaries on the mechanical properties and failure behavior of hexagonal boron nitride sheets.

In this work, the effect of grain boundaries (GBs) on the mechanical properties and failure behavior of two-dimensional hexagonal boron nitride (h-BN) sheets are systematically and comprehensively investigated using density functional theory. Results show that the formation of homoelemental bonds on GBs is an important factor, which could affect the atomic structures and stability of the h-BN sheet. The relationship between the formation energy and the misorientation angles is downward opening parabolic. The intrinsic strength shows an obvious decreasing trend with increasing inflection angles, while it shows a periodic dependence on the increase in misorientation angles. Thus, the mechanical properties of h-BN are significantly influenced by GBs. The h-BN sheets with different types of GBs show varied failure behavior, which are caused by the distinct stress distribution on GBs. The information obtained in this study would be useful for the understanding of GBs on the h-BN surface.

Stability and properties of the two-dimensional hexagonal boron nitride monolayer functionalized by hydroxyl (OH) radicals: a theoretical study

Motivated by the great advance in graphene hydroxide--a versatile material with various applications--we performed density functional theory (DFT) calculations to study the functionalization of the two-dimensional hexagonal boron nitride (h-BN) sheet with hydroxyl (OH) radicals, which has been achieved experimentally recently. Particular attention was paid to searching for the most favorable site(s) for the adsorbed OH radicals on a h-BN sheet and addressing the roles of OH radical coverage on the stability and properties of functionalized h-BN sheet. The results indicate that, for an individual OH radica, the most stable configuration is that it is adsorbed on the B site of the h-BN surface with an adsorption energy of -0.88 eV and a magnetic moment of 1.00 μ(B). Upon adsorption of more than one OH radical on a h-BN sheet, however, these adsorbates prefer to adsorb in pairs on the B and its nearest N atoms from both sides of h-BN sheet without magnetic moment. An energy diagram of the average adsorption energy of OH radicals on h-BN sheet as a function of its coverage indicates that when the OH radical coverage reaches to 60 %, the functionalized h-BN sheet is the most stable among all studied configurations. More importantly, this configuration exhibits good thermal and dynamical stability at room temperature. Owing to the introduction of certain impurity levels, the band gap of h-BN sheet gradually decreases with increasing OH coverage, thereby enhancing its electrical conductivity.

Low pressure chemical vapor deposition synthesis of hexagonal boron nitride on polycrystalline metal foils

The two-dimensional sp2-bonded material hexagonal boron nitride (h-BN) has unique electronic, thermal, mechanical, and chemical properties. It has recently found use as an ideal substrate for graphene-based electronic devices. We here describe synthesis of mono- to few-layer h-BN films using low pressure chemical vapor deposition (LPCVD) from borazine, with nickel, copper and platinum employed as catalytic substrates, and transfer of some of these films using a non-polymer method. Characterization of the films via Raman spectroscopy and transmission electron microscopy (TEM) is performed. Chemical vapor deposition synthesis of hexagonal boron nitride from borazine using metallic substrates.

Density functional study on the electronic and magnetic properties of two-dimensional hexagonal boron nitride containing vacancy

Density functional study on the electronic and magnetic properties of two-dimensional hexagonal boron nitride containing vacancy

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.

Ab-initio simulations of deformation potentials and electron mobility in chemically modified graphene and two-dimensional hexagonal boron-nitride

We present an ab-initio study of electron mobility and electron-phonon coupling in chemically modified graphene, considering fluorinated and hydrogenated graphene at different percentage coverage. Hexagonal boron carbon nitrogen is also investigated due the increased interest shown by the research community towards this material. In particular, the deformation potentials are computed by means of density functional theory, while the carrier mobility is obtained according to the Takagi model (S. Takagi, A. Toriumi, and H. Tango, IEEE Trans. Electron Devices 41, 2363 (1994)). We will show that graphene with a reduced degree of hydrogenation can compete, in terms of mobility, with silicon technology.

Characterization of thermal transport in low-dimensional boron nitride nanostructures

Recent advances in the synthesis of hexagonal boron nitride (BN) based nanostructures, similar to graphene, graphene nanoribbons, and nanotubes, have attracted significant interest into characterization of these materials. While electronic and optical properties of BN-based materials have been widely studied, the thermal transport has not been thoroughly investigated. In this paper, the thermal transport properties of these BN nanostructures are systematically studied using equilibrium molecular dynamics with a Tersoff-type empirical interatomic potential which is re-parametrized to represent experimental structure and phonon dispersion of two-dimensional hexagonal BN. Our simulations show that BN nanostructures have considerably high thermal conductivities but are still quite lower than carbon-based counterparts. Qualitatively, however, the thermal conductivity of carbon and BN nanoribbons display similar behavior with respect to the variation of width and edge structure (zigzag and armchair). Additionally, thermal conductivities of $(10,10)$ and $(10,0)$ nanotubes, both carbon and BN, are found to have very weak dependence on their chirality.

Structure transition of two-dimensional hexagonal BN under large uniaxial strain

Using the first-principles method, we have studied the structure transition of two-dimensional hexagonal boron nitride (2D h-BN) under large uniaxial strain. The strain is applied by changing the values of Lx and Ly, which correspond to the lengths of primitive cell in the directions perpendicular and parallel to B—N bonds, respectively. For the large asymmetrical tensile strain perpendicular to B—N bonds, the rhombic structure is stable when Lx≤0.3388 nm. As the strain increases, the system transforms from the rhombic structure to a rectangular structure consisting of interlaced interacting BN chains, which becomes stable when Lx≥0.3488 nm. When the strain further increases, the system finally changes into the one comprised of isolated BN chains. For the 2D h-BN with large asymmetrical tensile strain distribution parallel to B—N bonds, there is no stable rectangular structure and the system becomes the one composed of isolated BN chains when Ly>0.571 nm.

Theory of elastic and piezoelectric effects in two-dimensional hexagonal boron nitride

Starting from an empirical force constant model of valence interactions and calculating by Ewald's method the ion-ion force constants, we derive the dynamical matrix for a monolayer crystal of hexagonal boron nitride (h-BN). The phonon dispersion relations are calculated. The interplay between valence and Coulomb forces is discussed. It is shown by analytical methods that the longitudinal and the transverse optical (LO and TO) phonon branches for in-plane motion are degenerate at the $\ensuremath{\Gamma}$ point of the Brillouin zone. Away from $\ensuremath{\Gamma}$, the LO branch exhibits pronounced overbending. It is found that the nonanalytic Coulomb contribution to the dynamical matrix causes a linear increase of the LO branch with increasing wave vector starting at $\ensuremath{\Gamma}$. This effect is general for two-dimensional (2D) ionic crystals. Performing a long-wavelength expansion of the dynamical matrix, we use Born's perturbation method to calculate the elastic constants (tension coefficients). Since the crystal is noncentrosymmetric, internal displacements due to relative shifts between the two sublattices (B and N) contribute to the elastic constants. These internal displacements are responsible for piezoelectric and dielectric phenomena. The piezoelectric stress constant and the dielectric susceptibility of 2D h-BN are calculated.

Tunable bandgap structures of two-dimensional boron nitride

Electronic structures of two-dimensional (2D) hexagonal boron nitride (h-BN) with different planar strain distributions have been studied using the first principles methods. We found that the 2D h-BN without strain has a large direct bandgap and its bandgap structure strongly depends on the strength and direction of the strain. The bandgap width can be reduced significantly under both symmetrical and asymmetrical strain distributions. Moreover, the bandgap feature exhibits strong anisotropic behaviors. The bandgap remains direct under large symmetrical tensile strain or asymmetrical tensile strain perpendicular to B–N bonds. However, a small amount of symmetrical compressive strain larger than 1.5% or asymmetrical tensile strain parallel to B–N bonds larger than 1.2% turns the direct bandgap into indirect. Our results indicate that optical and electronic transport properties of 2D h-BN can be effectively tuned by applying different planar forces, offering a unique route for designing nanoscale tunable ultrathin optoelectronic devices only one atomic layer thick.

The analytical energy gradient scheme in the Gaussian based Hartree–Fock and density functional theory for two-dimensional systems using the fast multipole method

The analytical total energy gradient scheme for the Hartree–Fock and density functional crystalline orbital theory is formulated for infinitely extended periodic systems of general dimensions and implemented for those of two dimensions. Two major differences between the analytical gradient scheme for extended systems and that for molecular systems are described in detail. The first is the treatment of the long-range Coulomb interactions, which arise due to the infinite nature of the system size. The long-range effect is efficiently included by the multipole expansion technique and its extension, the fast multipole method. The use of the fast multipole method enables us to include the long-range effect up to the order of micrometer to millimeter region around the reference unit cell by virtue of the logarithmic cost scaling of the algorithm achieved by regrouping distant multipoles together and reducing the number of pairwise interactions. The second is the formulation of analytical gradient expressions with respect to unit cell parameters. In HF theory they can be calculated by accumulating forces acting on atoms multiplied by some appropriate factors, while there is an extra term which requires a special numerical treatment in grid-based density functional theory. Specifically, it is shown that the quadrature weight derivatives do not vanish even in the limit of infinitely fine grid when calculating the gradients with respect to unit cell parameters, and are essential in evaluating those gradients. Combining the analytical gradient scheme and an efficient inclusion of the long-range interaction makes it feasible to perform a full geometry optimization of extended systems at ab initio levels. As an illustration, the long-range interaction energies are computed for a two-dimensional sheet of hydrogen-fluoride. The CPU time reduction on going from the explicit evaluation of the two-electron integrals to multipole expansion, and from the multipole expansion to fast multipole method is significant. Geometry optimizations are performed on an infinite two-dimensional hexagonal boron-nitride sheet and the dependence of the gradients on various parameters are investigated.

Electrical conductivity of amine-borane-derived boron carbide nitride

Boron carbide nitride can be considered to be a graphite-like ceramic material with a partial substitution of carbon atoms by boron and nitrogen atoms in the hexagonal layers or as a two-dimensional solid solution of hexagonal boron nitride and graphite. These materials exhibit remarkable properties such as high temperature stability, chemical resistivity and semiconducting behavior.