Advanced microstructure of boron carbide

The rhombohedral elementary cell of the complex boron carbide structure is composed of B(12) or B(11)C icosahedra and CBC, CBB or B□B (□, vacancy) linear arrangements, whose shares vary depending on the actual chemical compound. The evaluation of the IR phonon spectra of isotopically pure boron carbide yields the quantitative concentrations of these components within the homogeneity range. The structure formula of B(4.3)C at the carbon-rich limit of the homogeneity range is (B(11)C) (CBC)(0.91) (B□B)(0.09) (□, vacancy); and the actual structure formula of B(13)C(2) is (B(12))(0.5)(B(11)C)(0.5)(CBC)(0.65)(CBB)(0.16) (B□B)(0.19), and deviates fundamentally from (B(12))CBC, predicted by theory to be the energetically most favourable structure of boron carbide. In reality, it is the most distorted structure in the homogeneity range. The spectra of (nat)B(x)C make it evident that boron isotopes are not randomly distributed in the structure. However, doping with 2% silicon brings about a random distribution.     

Electrooptical effect in the plasmon structure glass–In<Subscript>2</Subscript>O<Subscript>3</Subscript>: Sn–ferroelectric–Al with a subwavelength grating

We have constructed the equations of state for crystalline boron carbide B₁₁C (C–B–C) and its melt under high dynamic and static pressures. A kink on the shock adiabat for boron carbide has been revealed in the pressure range near 100 GPa, and the melting curve with negative curvature in the pressure range 0–120 GPa has been calculated. The results have been used for interpreting the kinks on the shock adiabat for boron carbide in the pressure range of 0–400 GPa.     

Superconductivity in boron carbide? Clarification by low-temperature MIR/FIR spectra

The electronic structure and phonon density of B(13)B(2) boron carbide calculated by Calandra et al (2004 Phys. Rev. B 69 224505) defines this compound as metallic, and the authors predict superconductivity with T(C)s up to 36.7 K. Their results are affected by the same deficiencies as former band structure calculations on boron carbides based on hypothetical crystal structures deviating significantly from the real ones. We present optical mid IR/far IR (MIR/FIR) spectra of boron carbide with compositions between B(4.3)C and B(10.37)C, evidencing semiconducting behaviour at least down to 30 K. There is no indication of superconductivity. The spectra yield new information on numerous localized gap states close to the valence band edge.     

Single crystalline boron carbide nanobelts: synthesis and characterization

This paper reports that the large-scale single crystalline boron carbide nanobelts have been fabricated through a simple carbothermal reduction method with B/B2O3/C/Fe powder as precursors at 1100℃. Transmission electron microscopy and selected area electron diffraction characterizations show that the boron carbide nanobelt has a B4C rhomb-centred hexagonal structure with good crystallization. Electron energy loss spectroscopy analysis indicates that the nanobelt contains only B and C, and the atomic ratio of B to C is close to 4：1. High resolution transmission electron microscopy results show that the preferential growth direction of the nanobelt is [101]. A possible growth mechanism is also discussed.     

溅射功率对碳化硼薄膜组分与力学性能的影响

采用射频磁控溅射技术,在不同溅射功率条件下制备了碳化硼薄膜,并用X射线光电子能谱(XPS)和傅里叶变换红外吸收光谱(FT-IR)对碳化硼薄膜的组分进行了定量表征,分析了功率变化对碳化硼组分的影响。利用纳米压入仪通过连续刚度法(CSM)对碳化硼薄膜的硬度和模量等力学性能进行了分析。研究表明:随着功率的增大,硼与碳更易结合形成BC键,在功率增大到250 W时,BC键明显增多;在250 W时,硼与碳的原子分数比出现了最大值5.66;碳化硼薄膜的硬度与模量都随功率的增大呈现出先增大后减小的趋势,且在250 W时均出现了最大值,分别为28.22 GPa和314.62 GPa。     

溅射功率对碳化硼薄膜组分与力学性能的影响

采用射频磁控溅射技术,在不同溅射功率条件下制备了碳化硼薄膜,并用X射线光电子能谱(XPS)和傅里叶变换红外吸收光谱(FT-IR)对碳化硼薄膜的组分进行了定量表征,分析了功率变化对碳化硼组分的影响。利用纳米压入仪通过连续刚度法(CSM)对碳化硼薄膜的硬度和模量等力学性能进行了分析。研究表明：随着功率的增大,硼与碳更易结合形成BC键,在功率增大到250 W时,BC键明显增多;在250 W时,硼与碳的原子分数比出现了最大值5.66;碳化硼薄膜的硬度与模量都随功率的增大呈现出先增大后减小的趋势,且在250 W时均出现了最大值,分别为28.22 GPa和314.62 GPa。     

Photo-induced site-specific nitridation of plasma-deposited B10C2Hx films: A new pathway toward post-deposition doping of semiconducting boron carbides

We show that dopant impurities can be introduced in a controlled, site-specific manner into pre-deposited semiconducting boron carbide films. B―N bond formation has been characterized by X-ray photoelectron spectroscopy for semiconducting B₁₀C₂H_x films exposed to vacuum ultraviolet photons in the presence of NH₃. Core level photoemission data indicate that B―NH₂ bonds are formed at B sites bonded to other boron atoms (B―B), and not at boron atoms adjacent to carbon atoms (B―C) or at carbon atom sites. Nitridation obeys diffusion-limited kinetics. These results indicate that dopant species can be introduced in a controlled, site-specific manner into pre-deposited boron carbide films, as opposed to currently required dopant incorporation during the deposition process.     

Synthesis and photoluminescence property of boron carbide nanowires

Large scale, high density boron carbide nanowires have been synthesized by using an improved carbothermal reduction method with B/B203/C powder precursors under an argon flow at 1100℃. The boron carbide nanowires are 5-10 μm in length and 80-100 nm in diameter. Transmission electron microscopy （TEM） and selected area electron diffraction （SAED） characterizations show that the boron carbide nanowire has a B4C rhombohedral structure with good crystallization. The Raman spectrum of the as-grown boron carbide nanowires is consistent with that of a B4C structure consisting of B11C icosahedra and C-B-C chains. The room temperature photoluminescence spectrum of the boron carbide nanowires exhibits a visible range of emission centred at 638 nm.     

Possibilities of the formation of carbides and borides by ion implantation

In the system of boron and carbon, the formation of boron carbide was investigated after ion implantation of 25 keV B ions into carbon or of 25 keV C ions into boron and subsequent annealing. TEM and electron diffraction studies showed that the crystallization of boron carbide begins only at temperatures above 1050°C. By implantation of 20 keV C ions into iron (ion dose 10¹⁷ C ions/cm²) only the metastable ε-Fe₂O will be generated, which at above 220°C transforms into the stable cementite Fe₃C. After implantation of 20 keV B ions into iron, no formation of iron boride could be found. These experimental facts can be understood qualitatively with the help of the thermal-spike model. The energy density or the temperature in the thermal spikes is not sufficient for the generation of cementite iron boride or boron carbide.     

Deformation twinning in boron carbide particles within nanostructured Al 5083/B4C metal matrix composites

The presence of deformation twins is documented in boron carbide reinforcement particles within a nanostructured Al 5083/B₄C metal matrix composite. High resolution transmission electron microscopy analysis suggests that these are (0001) twins. This work discusses the mechanisms responsible for their formation based on crystallographic analysis and mechanical loading conditions. Specifically, we propose that there are two potential models that can be used to describe twin formation in boron carbide particles. The structural models involve slip in the 1/3[1100] (0110) or 1/3[0110] (0110) planes of C–C–C chains and the appropriate reconfiguration of B–C bonds. Analysis of the loading conditions experienced by the boron carbide particles indicates that local high stress intensity and the presence of a high shear force around the boron carbide particles are two factors that contribute to twin formation.     

Properties of B_4C-TiB_2 ceramics prepared by spark plasma sintering

By doping titanium hydride(TiH2) into boron carbide(B4C), a series of B4C + x wt% TiH2(x = 0, 5, 10, 15, and 20)composite ceramics were obtained through spark plasma sintering(SPS). The effects of the sintering temperature and the amount of TiH2 additive on the microstructure, mechanical and electrical properties of the sintered B4C-TiB2 composite ceramics were investigated. Powder mixtures of B4C with 0–20 wt% TiH2 were heated from 1400℃ to 1800℃ for 20 min under 50 MPa. The results indicated that higher sintering temperatures contributed to greater ceramic density. With increasing TiH2 content, titanium diboride(TiB2) formed between the TiH2 and B4C matrix. This effectively improved Young’s modulus and fracture toughness of the composite ceramics, significantly improving their electrical properties: the electrical conductivity reached 114.9 S·cm-1 at 1800℃ when x = 20. Optimum mechanical properties were obtained for the B4C ceramics sintered with 20 wt% TiH2, which had a relative density of 99.9±0.1%, Vickers hardness of 31.8 GPa,and fracture toughness of 8.5 MPa·m1/2. The results indicated that the doping of fine Ti particles into the B4C matrix increased the conductivity and the fracture toughness of B4C.     

Structural and electronic properties of boron-doped double-walled silicon carbide nanotubes

The effects of boron doping on the structural and electronic properties of (6,0)@(14,0) double-walled silicon carbide nanotube (DWSiCNT) are investigated by using spin-polarized density functional theory. It is found that boron atom could be more easily doped in the inner tube. Our calculations indicate that a Si site is favorable for B under C-rich condition and a C site is favorable under Si-rich condition. Additionally, B-substitution at either single carbon or silicon atom site in DWSiCNT could induce spontaneous magnetization.     

Studies on the influence of surface pre-treatments on electroless copper coating of boron carbide particles

Boron carbide is one of the hard ceramic particles which find application as structural materials and neutron shielding material due to its high neutron capture cross section. Copper coating on boron carbide particle is essential for the synthesis of metal-ceramic composites with enhanced sinterability and dispersibility. Surface characteristics of the substrate and the coating parameters play a foremost role in the formation of effective electroless coating. The effect of surface pre-treatment conditions and pH on electroless copper coating of boron carbide particles has been studied. Surface pre-treatement of B₄C when compared to acid treated and alkali treated particles were carried out. Uniform copper coating was observed at pH 12 in alkali treated particles when compared to others due to the effective removal of inevitable impurities during the production and processing of commercially available B₄C. A threshold pH 11 was required for initiation of copper coating on boron carbide particles. The growth pattern of the copper coating also varies depending on the surface conditions from acicular to spherical morphology.     

The local physical structure of amorphous hydrogenated boron carbide: insights from magic angle spinning solid-state NMR spectroscopy

Magic angle spinning solid-state nuclear magnetic resonance spectroscopy techniques are applied to the elucidation of the local physical structure of an intermediate product in the plasma-enhanced chemical vapour deposition of thin-film amorphous hydrogenated boron carbide (B(x)C:H(y)) from an orthocarborane precursor. Experimental chemical shifts are compared with theoretical shift predictions from ab initio calculations of model molecular compounds to assign atomic chemical environments, while Lee-Goldburg cross-polarization and heteronuclear recoupling experiments are used to confirm atomic connectivities. A model for the B(x)C:H(y) intermediate is proposed wherein the solid is dominated by predominantly hydrogenated carborane icosahedra that are lightly cross-linked via nonhydrogenated intraicosahedral B atoms, either directly through B-B bonds or through extraicosahedral hydrocarbon chains. While there is no clear evidence for extraicosahedral B aside from boron oxides, ～40% of the C is found to exist as extraicosahedral hydrocarbon species that are intimately bound within the icosahedral network rather than in segregated phases.     

Thermodynamic study of the solubility process of boron in silicon carbide,grown from the vapour phase

The thermodynamics of the solubility process of the acceptor impurity boron in silicon carbide is investigated. The thermodynamic analysis of equilibrium in the Si-C-B system has been carried out and the temperature dependences of the partial pressures of interacting components are determined for the temperature interval (1800–3000) K.The calculation of the Fermi level in p-SiC(B) is carried out. The heat of solution and the distribution coefficient of boron in silicon carbide are determined on the basis of the thermodynamic analysis of the Si-C-B system, the experimental temperature dependence of boron solubility and the calculation of the Fermi level and Fermi-Dirac distribution in p-SiC(B).     

Is the established structure of α-rhombohedral boron correct? Comparative study of IR-active phonons with B6O, B4.3C and β-rhombohedral boron

The established structure of α-rhombohedral boron, based on one B(12) icosahedron per unit cell only, is put in question. A careful evaluation of the IR-active phonons in comparison with B(6)O, B(4.3)C and β-rhombohedral boron makes it evident that-aside from the B(12) icosahedra-the α-rhombohedral boron structure also contains single boron atoms. We assume these single atoms replace the currently assumed inter-icosahedral three-centre-bonds by covalently saturating the outward directing bonds of the equatorial atoms of the three adjacent icosahedra. Indeed, the implied structure formula B(12)B(2) is not supported by previous density measurements. The IR-phonon spectra of the related structures are correlated and merely shifted relative to one another; significant features depend quantitatively on the actual structure, but they can be easily allocated.     

Theoretical study on transport properties of a BN co-doped SiC nanotube

We investigate the electronic transport properties of silicon carbide nanotubes (SiCNT) in presence of both boron (B) and nitrogen (N) impurities. The results show that co-doping BN impurities suppresses the important negative differential resistance (NDR) property. NDR suppression is attributed to the introduction of new electronic states near the Fermi level followed by weak orbital localization. BN co-doping results in exponential current-voltage (I-V) characteristics which is in contrast to linear I-V characteristics for individual boron and nitrogen doped SiCNTs. HOMO has no contribution from B impurity, whereas, LUMO has contribution from N impurity at low and high bias.     

Stuffing improves the stability of fullerenelike boron clusters

First-principles electronic structure calculations show that boron clusters B98, B99, B100, B101, and B102 based on icosahedral-B12 stuffed fullerenes are more stable than the fullerenelike boron clusters. These more stable structures are envisaged as an icosahedral B12 each vertex of which is connected to the apex of a pentagonal pyramid (B6) via radial 2c-2e sigma bonds. The resulting B84 (B(12)@B(12)@B(60)) retains the same symmetry as C60, and the B(n) (n=84-116) clusters are generated around it. We further project the possibility of producing such B12 based giant clusters.     

Elemental and chemical-state mapping of boron carbide fracture surfaces

Samples of commercial B₄C and of reactive hot-pressed B₉C were fractured in situ in a scanning Auger microscopy (SAM) system. The B₄C fracture surfaces showed small areas of pore structures, as well as larger relatively smooth areas. Impurities (Cu, Si, S, Ca, N, O and Cr) were found in trace amounts in the pore areas. SAM maps were made of most of these impurities. The nitrogen was found by Auger lineshape in point Auger electron spectroscopy scans to be in the compound BN. Carbon was found on the surface in both boron carbide and as graphite. SAM was used to seperately map B in B₄C and B in BN, as well as C in B₄C and C in graphite, in a pore region. In the smooth areas of B₄C fracture surfaces fewer impurities were found. The carbon occured in B₄C and in localized carbon-rich areas which had graphite surface layers. In contrast, only B and C were found on the B₉C fracture surfaces; but the distributions of these elements were not homogenous. Carbon was found both in elemental form as graphite and chemically bound to boron as a carbide. In comparison with the graphite regions on the B₄C surfaces, the graphite areas on the B₉C fracture surfaces were not localized. The total surface area was nearly balanced between graphite and carbide regions. Argon ion bombardment revealed the graphite areas to be less than 100 nm thick.     

The properties of boron carbide/silicon heterojunction diodes fabricated by Plasma-Enhanced Chemical Vapor Deposition

p-n heterojunction diodes have been fabricated from boron carbide (B_1–x C _x ) and n-type Si(111). Boron carbide thin films were deposited on Si(111) using Plasma-Enhanced Chemical Vapor Deposition (PECVD) from nido-pentaborane (B₅H₉) and methane (CH₄). Composition of boron carbide thin films was controlled by changing the relative partial pressure ratio between nido-pentaborane and methane. The properties of the diodes were strongly affected by the composition and thickness of boron carbide layer and operation temperatures. Boron carbide/silicon heterojunction diodes show rectifying properties at temperatures below 300° C. The temperature dependence of reverse current is strongly dependent upon the energy of the band gap of the boron carbide films.