Dongli Yu

Ultrahard nanotwinned cubic boron nitride

Cubic boron nitride (cBN) is a well known superhard material that has a wide range of industrial applications. Nanostructuring of cBN is an effective way to improve its hardness by virtue of the Hall–Petch effect—the tendency for hardness to increase with decreasing grain size. Polycrystalline cBN materials are often synthesized by using the martensitic transformation of a graphite-like BN precursor, in which high pressures and temperatures lead to puckering of the BN layers. Such approaches have led to synthetic polycrystalline cBN having grain sizes as small as ∼14 nm (refs 1, 2, 4, 5). Here we report the formation of cBN with a nanostructure dominated by fine twin domains of average thickness ∼3.8 nm. This nanotwinned cBN was synthesized from specially prepared BN precursor nanoparticles possessing onion-like nested structures with intrinsically puckered BN layers and numerous stacking faults. The resulting nanotwinned cBN bulk samples are optically transparent with a striking combination of physical properties: an extremely high Vickers hardness (exceeding 100 GPa, the optimal hardness of synthetic diamond), a high oxidization temperature (∼1,294 °C) and a large fracture toughness (>12 MPa m1/2, well beyond the toughness of commercial cemented tungsten carbide, ∼10 MPa m1/2). We show that hardening of cBN is continuous with decreasing twin thickness down to the smallest sizes investigated, contrasting with the expected reverse Hall–Petch effect below a critical grain size or the twin thickness of ∼10–15 nm found in metals and alloys.

Nanotwinned diamond with unprecedented hardness and stability

Although diamond is the hardest material for cutting tools, poor thermal stability has limited its applications, especially at high temperatures. Simultaneous improvement of the hardness and thermal stability of diamond has long been desirable. According to the Hall−Petch effect, the hardness of diamond can be enhanced by nanostructuring (by means of nanograined and nanotwinned microstructures), as shown in previous studies. However, for well-sintered nanograined diamonds, the grain sizes are technically limited to 10−30 nm (ref. 3), with degraded thermal stability compared with that of natural diamond. Recent success in synthesizing nanotwinned cubic boron nitride (nt-cBN) with a twin thickness down to ∼3.8 nm makes it feasible to simultaneously achieve smaller nanosize, ultrahardness and superior thermal stability. At present, nanotwinned diamond (nt-diamond) has not been fabricated successfully through direct conversions of various carbon precursors (such as graphite, amorphous carbon, glassy carbon and C60). Here we report the direct synthesis of nt-diamond with an average twin thickness of ∼5 nm, using a precursor of onion carbon nanoparticles at high pressure and high temperature, and the observation of a new monoclinic crystalline form of diamond coexisting with nt-diamond. The pure synthetic bulk nt-diamond material shows unprecedented hardness and thermal stability, with Vickers hardness up to ∼200 GPa and an in-air oxidization temperature more than 200 °C higher than that of natural diamond. The creation of nanotwinned microstructures offers a general pathway for manufacturing new advanced carbon-based materials with exceptional thermal stability and mechanical properties.

Tetragonal Allotrope of Group 14 Elements

Group 14 elements (C, Si, and Ge) exist as various stable and metastable allotropes, some of which have been widely applied in industry. The discovery of new allotropes of these elements has long attracted considerable attention; however, the search is far from complete. Here we computationally discovered a tetragonal allotrope (12 atoms/cell, named T12) commonly found in C, Si, and Ge through a particle swarm structural search. The T12 structure employs sp(3) bonding and contains extended helical six-membered rings interconnected by pairs of five- and seven-membered rings. This arrangement results in favorable thermodynamic conditions compared with most other experimentally or theoretically known sp(3) species of group 14 elements. The T12 polymorph naturally accounts for the experimental d spacings and Raman spectra of synthesized metastable Ge and Si-XIII phases with long-puzzling unknown structures, respectively. We rationalized an alternative experimental route for the synthesis of the T12 phase via decompression from the high-pressure Si- or Ge-II phase.

Hardness of covalent compounds: Roles of metallic component and d valence electrons

Based on the detailed analysis of chemical bonds, we present a Vickers hardness expression for the covalency-dominant crystals such as transition-metal carbides and nitrides. Hardness is dependent not only on bond length, bond density, and ionicity of bond [F. M. Gao et al., Phys. Rev. Lett. 91, 015502 (2003)] but also on the metallicity of bond and orbital form in the crystal structure of a compound, and all of these parameters can be determined by first-principles calculations. The calculated hardness using our expression has a good agreement with the experimental values for known monocarbides, mononitrides of transition metals, and cubic Zr3N4 with Th3P4 structure. In addition, we have predicted the Vickers hardness of the recently predicted tetragonal BC3 and tetragonal B2CN, and the recently synthesized pyrite PtN2 and marcasite OsN2. Our method offers one useful technique to search for superhard materials in transition-metal carbides and nitrides.

Direct Band Gap Silicon Allotropes

Elemental silicon has a large impact on the economy of the modern world and is of fundamental importance in the technological field, particularly in solar cell industry. The great demand of society for new clean energy and the shortcomings of the current silicon solar cells are calling for new materials that can make full use of the solar power. In this paper, six metastable allotropes of silicon with direct or quasidirect band gaps of 0.39-1.25 eV are predicted by ab initio calculations at ambient pressure. Five of them possess band gaps within the optimal range for high converting efficiency from solar energy to electric power and also have better optical properties than the Si-I phase. These Si structures with different band gaps could be applied to multiple p-n junction photovoltaic modules.

Compressed carbon nanotubes: A family of new multifunctional carbon allotropes

The exploration of novel functional carbon polymorphs is an enduring topic of scientific investigations. In this paper, we present simulations demonstrating metastable carbon phases as the result of pressure induced carbon nanotube polymerization. The configuration, bonding, electronic, and mechanical characteristics of carbon polymers strongly depend on the imposed hydrostatic/non-hydrostatic pressure, as well as on the geometry of the raw carbon nanotubes including diameter, chirality, stacking manner, and wall number. Especially, transition processes under hydrostatic/non-hydrostatic pressure are investigated, revealing unexpectedly low transition barriers and demonstrating sp2→sp3 bonding changes as well as peculiar oscillations of electronic property (e.g., semiconducting→metallic→semiconducting transitions). These polymerized nanotubes show versatile and superior physical properties, such as superhardness, high tensile strength and ductility, and tunable electronic properties (semiconducting or metallic).

Enhanced thermoelectric figure of merit in nanocrystalline Bi2Te3 bulk

Nanocrystalline Bi2Te3 bulks were synthesized via a nanostructuring method that included steps of ball milling, cold pressing, and sintering. In the temperature range of 325–525 K, nanocrystalline Bi2Te3 bulks exhibit good thermoelectric properties with a peak ZT of 0.94. The experimental results suggest that the partially coherent boundaries allow the maintenance of low grain growth rate and low resistivity. The enhancement of ZT comes from a large reduction in the phonon thermal conductivity and a strong suppression of the bipolar effect at high temperature.

Hardness of cubic spinel Si3N4

The hardness of cubic spinel Si3N4 was calculated by using our microscopic model of hardness combined with first principles calculation. The calculated Vickers hardness is only 33.3GPa in good agreement with its experimental values reported recently, indicating that the cubic spinel Si3N4 is not a superhard material. Our calculation results also implicate a more important fact that predicting the hardness of a material based on its bulk modulus or shear modulus is impertinent.

Great thermoelectric power factor enhancement of CoSb3 through the lightest metal element filling

Lithium, the lightest metal element with a small ionic radius, is successfully filled into the voids of CoSb3 by utilizing the high pressure synthesis technique. The synthesized Li0.4Co4Sb12 shows the largest thermoelectric power factor of 6000 μW m−1 K−2 among all elemental filled CoSb3 materials. This significantly enhanced thermoelectric power factor is attributed to the large carrier mobility of Li0.4Co4Sb12, 61 cm2 V−1 s−1, featuring a good electron crystal property for the Li-filled CoSb3 samples.

Orthorhombic B2CN crystal synthesized by high pressure and temperature

Abstract B0.54C0.28N0.18 precursor powder with turbostratic structure was prepared by using melamine and boric acid. The precursor was transformed into orthorhombic B2CN under definite high pressure and temperature conditions. The composition of the orthorhombic B2CN powder is B0.47C0.23N0.30. Its lattice parameters are a=0.4776 nm, b=0.4585 nm and c=0.3629 nm. A strong absorption band from 1088 to 1385 cm −1 of orthorhombic B2CN was observed by infrared measurement. In the photoluminescence (PL) spectrum of orthorhombic B2CN powder measured at room temperature, a broad peak corresponding to its band-edge emission centers at 374 nm.