Structural transition and migration of incoherent twin boundary in diamond.

Grain boundaries (GBs), with their diversity in both structure and structural transitions, play an essential role in tailoring the properties of polycrystalline materials1-5. As a unique GB subset, {112} incoherent twin boundaries (ITBs) are ubiquitous in nanotwinned, face-centred cubic materials6-9. Although multiple ITB configurations and transitions have been reported7,10, their transition mechanisms and impacts on mechanical properties remain largely unexplored, especially in regard to covalent materials. Here we report atomic observations of six ITB configurations and structural transitions in diamond at room temperature, showing a dislocation-mediated mechanism different from metallic systems11,12. The dominant ITBs are asymmetric and less mobile, contributing strongly to continuous hardening in nanotwinned diamond13. The potential driving forces of ITB activities are discussed. Our findings shed new light on GB behaviour in diamond and covalent materials, pointing to a new strategy for development of high-performance, nanotwinned materials.

Twisted-layer boron nitride ceramic with high deformability and strength.

Moiré superlattices formed by twisted stacking in van der Waals materials have emerged as a new platform for exploring the physics of strongly correlated materials and other emergent phenomena1-5. However, there remains a lack of research on the mechanical properties of twisted-layer van der Waals materials, owing to a lack of suitable strategies for making three-dimensional bulk materials. Here we report the successful synthesis of a polycrystalline boron nitride bulk ceramic with high room-temperature deformability and strength. This ceramic, synthesized from an onion-like boron nitride nanoprecursor with conventional spark plasma sintering and hot-pressing sintering, consists of interlocked laminated nanoplates in which parallel laminae are stacked with varying twist angles. The compressive strain of this bulk ceramic can reach 14% before fracture, about one order of magnitude higher compared with traditional ceramics (less than 1% in general), whereas the compressive strength is about six times that of ordinary hexagonal boron nitride layered ceramics. The exceptional mechanical properties are due to a combination of the elevated intrinsic deformability of the twisted layering in the nanoplates and the three-dimensional interlocked architecture that restricts deformation from propagating across individual nanoplates. The advent of this twisted-layer boron nitride bulk ceramic opens a gate to the fabrication of highly deformable bulk ceramics.

Coherent interfaces govern direct transformation from graphite to diamond.

Understanding the direct transformation from graphite to diamond has been a long-standing challenge with great scientific and practical importance. Previously proposed transformation mechanisms1-3, based on traditional experimental observations that lacked atomistic resolution, cannot account for the complex nanostructures occurring at graphite-diamond interfaces during the transformation4,5. Here we report the identification of coherent graphite-diamond interfaces, which consist of four basic structural motifs, in partially transformed graphite samples recovered from static compression, using high-angle annular dark-field scanning transmission electron microscopy. These observations provide insight into possible pathways of the transformation. Theoretical calculations confirm that transformation through these coherent interfaces is energetically favoured compared with those through other paths previously proposed1-3. The graphite-to-diamond transformation is governed by the formation of nanoscale coherent interfaces (diamond nucleation), which, under static compression, advance to consume the remaining graphite (diamond growth). These results may also shed light on transformation mechanisms of other carbon materials and boron nitride under different synthetic conditions.

Ultrastrong conductive in situ composite composed of nanodiamond incoherently embedded in disordered multilayer graphene.

Traditional ceramics or metals cannot simultaneously achieve ultrahigh strength and high electrical conductivity. The elemental carbon can form a variety of allotropes with entirely different physical properties, providing versatility for tuning mechanical and electrical properties in a wide range. Here, by precisely controlling the extent of transformation of amorphous carbon into diamond within a narrow temperature-pressure range, we synthesize an in situ composite consisting of ultrafine nanodiamond homogeneously dispersed in disordered multilayer graphene with incoherent interfaces, which demonstrates a Knoop hardness of up to ~53 GPa, a compressive strength of up to ~54 GPa and an electrical conductivity of 670-1,240 S m-1 at room temperature. With atomically resolving interface structures and molecular dynamics simulations, we reveal that amorphous carbon transforms into diamond through a nucleation process via a local rearrangement of carbon atoms and diffusion-driven growth, different from the transformation of graphite into diamond. The complex bonding between the diamond-like and graphite-like components greatly improves the mechanical properties of the composite. This superhard, ultrastrong, conductive elemental carbon composite has comprehensive properties that are superior to those of the known conductive ceramics and C/C composites. The intermediate hybridization state at the interfaces also provides insights into the amorphous-to-crystalline phase transition of carbon.

Extreme mechanical anisotropy in diamond with preferentially oriented nanotwin bundles.

Mechanical properties of covalent materials can be greatly enhanced with strategy of nanostructuring. For example, the nanotwinned diamond with an isotropic microstructure of interweaved nanotwins and interlocked nanograins shows unprecedented isotropic mechanical properties. How the anisotropic microstructure would impact on the mechanical properties of diamond has not been fully investigated. Here, we report the synthesis of diamond from superaligned multiwalled carbon nanotube films under high pressure and high temperature. Structural characterization reveals preferentially oriented diamond nanotwin bundles with an average twin thickness of ca. 2.9 nm, inherited from the directional nanotubes. This diamond exhibits extreme mechanical anisotropy correlated with its microstructure (e.g., the average Knoop hardness values measured with the major axis of the indenter perpendicular and parallel to nanotwin bundles are 233 ± 8 and 129 ± 9 GPa, respectively). Molecular dynamics simulation reveals that, in the direction perpendicular to the nanotwin bundles, the dense twin boundaries significantly hinder the motion of dislocations under indentation, while such a resistance is much weaker in the direction along the nanotwin bundles. Current work verifies the hardening effect in diamond via nanostructuring. In addition, the mechanical properties can be further tuned (anisotropy) with microstructure design and modification.

Heterogeneous Diamond-cBN Composites with Superb Toughness and Hardness.

The traditional hardness-toughness tradeoff poses a substantial challenge for the development of superhard materials. Due to strong covalent bonds and intrinsic brittleness, the full advantage of microstructure engineering for enhanced mechanical properties requires further exploration in superhard materials. Here heterogeneous diamond-cBN composites were synthesized from a carefully prepared precursor (hBN microflakes uniformly wrapped by onion carbon nanoparticles) through phase transitions under high pressure and high temperature. The synthesized composites inherit the architecture of the precursors: cBN regions with an anisotropic profile that spans several micrometers laterally and several hundred nanometers in thickness are embedded in a nanograined diamond matrix with high-density nanotwins. A significantly high fracture toughness of 16.9 ± 0.8 MPa m1/2 is achieved, far beyond those of single-crystal diamond and cBN, without sacrificing hardness. A detailed TEM analysis revealed multiple toughening mechanisms closely related to the microstructure. This work sheds light on microstructure engineering in superhard materials for excellent mechanical properties.

Structural Determination of a Graphite/Hexagonal Boron Nitride Superlattice Observed in the Experiment.

A previous study reported an observed unidentified graphite/hexagonal boron nitride (hBN) superlattice structure in special multilayer heterojunction devices via cross-sectional transmission electron microscopy [Haigh S. J. et al., Nat. Mater. 2012, 11, 764-767]. In this letter, we designed and confirmed two possible graphite/hBN superlattice structures (AA and Ab), which were probably the structures observed by the aforementioned experiment. The formation enthalpies of both structures were negative, indicating that they could be successfully synthesized as the previous experiment reported. The results also showed that both structures possessed dynamic stability and elastic stability. Importantly, the theoretical interlayer distances of AA and Ab were 3.34 and 3.30 Å, respectively, which were consistent with the experimental value of 3.32 Å. The X-ray diffraction patterns and Raman spectra of both structures were simulated to aid in distinguishing them. This study on the atomic structure of the graphite/hBN superlattice lays a foundation for further research and application of this material.

Three metallic BN polymorphs: 1D multi-threaded conduction in a 3D network.

In this paper, three novel metallic sp2/sp3-hybridized boron nitride (BN) polymorphs are proposed by first-principles calculations. One of them, denoted as tP-BN, is predicted based on the evolutionary particle swarm structural search. tP-BN is composed of two interlocked rings forming a tube-like 3D network. The stability and band structure calculations show that tP-BN is metastable and metallic at zero pressure. Calculations for the density of states and electron orbitals confirm that the metallicity originates from the sp2-hybridized B and N atoms, forming 1D linear conductive channels in the 3D network. According to the relationship between the atomic structure and electronic properties, another two 3D metastable metallic sp2/sp3-hybridized BN structures are constructed manually. Electronic property calculations show that both of these structures have 1D conductive channels along different axes. The polymorphs predicted in this study enrich the structures and provide a different picture of the conductive mechanism of BN compounds.

Superhard sp2-sp3 hybridized B2C3N2 with 2D metallicity.

Ternary boron-carbon-nitrogen (B-C-N) compounds are considered to possess hardness comparable to diamond and thermal stability comparable to c-BN. Explorations for desirable B-C-N phases have been continuous. However, the nonconductive properties of most B-C-N compounds narrow the applications of these compounds. Herein, we propose a sp2-sp3 hybridized phase of t-B2C3N2, which consists of diamond-like BC blocks connected with single N-N bonds. Elastic constants and phonon dispersion curves confirm that t-B2C3N2 is mechanically and dynamically stable. The structure processes 2D metallicity in a strong 3D network. Furthermore, hardness and electron-phonon calculations reveal that t-B2C3N2 is superhard and superconductive with a superconducting critical temperature reaching 2.3 K.

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.

Effect of layer and stacking sequence in simultaneously grown 2H and 3R WS2 atomic layers.

In two-dimensional layered materials, layer number and stacking order have strong effects on the optical and electronic properties. Tungsten disulfide (WS2) crystal, as one important member among transition metal dichalcogenides, has been usually prepared in a layered 2H prototype structure with space group P63/mmc ([Formula: see text]) in spite of many other expected ones such as 3R. Here, we report simultaneous growth of 2H and 3R stacked multilayer (ML) WS2 crystals in large scale by chemical vapor deposition and effects of layer number and stacking order on optical and electronic properties. As revealed in Raman and photoluminescence (PL) measurements, with an increase in layer number, 2H and 3R stacked ML WS2 crystals show similar variation of PL and Raman peaks in position and intensity. Compared to 2H stacked ML WS2, however, 3R stacked one always exhibits the larger red (blue) shift of Raman [Formula: see text] (A1g) peak and the appearance of PL A, B and I peaks at lower energies. Thereby, PL and Raman features depend on not only layer number but also stacking order. In addition, circularly polarized luminescence from two prototype WS2 crystals under circularly polarized excitation has also been investigated, showing obvious spin or valley polarization of these CVD-grown multilayer WS2 crystals.

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 m(1/2), well beyond the toughness of commercial cemented tungsten carbide, ∼10 MPa m(1/2)). 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.

Grain wall boundaries in centimeter-scale continuous monolayer WS2 film grown by chemical vapor deposition.

Centimeter-scale continuous monolayer WS2 film with large tensile strain has been successfully grown on oxidized silicon substrate by chemical vapor deposition, in which monolayer grains can be more than 200 µm in size. Monolayer WS2 grains are observed to merge together via not only traditional grain boundaries but also non-traditional ones, which are named as grain walls (GWs) due to their nanometer-scale widths. The GWs are revealed to consist of two or three layers. Though not a monolayer, the GWs exhibit significantly enhanced fluorescence and photoluminescence. This enhancement may be attributed to abundant structural defects such as stacking faults and partial dislocations in the GWs, which are clearly observable in atomically resolved high resolution transmission electron microscopy and scanning transmission electron microscopy images. Moreover, GW-based phototransistor is found to deliver higher photocurrent than that based on monolayer film. These features of GWs provide a clue to microstructure engineering of monolayer WS2 for specific applications in (opto)electronics.

Novel carbon polymorphs with cumulative double bonds in three-dimensional sp-sp2 hybrid framework.

A conspicuous amount of theoretical study has been published on the properties of carbon allotropes with alternate single and triple bonds, (-C[triple bond, length as m-dash]C-)n. However, theoretical characterizations of carbon allotropes with cumulative double bonds ([double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash])n is almost non-existent in literature. Based upon first-principles calculations, two new three-dimensional (3D) microporous carbon allotropes consisting of whorl chains connected by cumulative double bonds in a sp-sp2 hybrid framework have been proposed in this study. One of these structures, namely, Trig-C9 was obtained by an evolutionary particle swarm structural search, while the other structure, denoted as Trig-C15, was obtained by inserting double bonds into Trig-C9. Both the 3D sp-sp2 hybridized carbons have a trigonal structure with 9 and 15 atoms in the hexagonal primitive cells. The calculated results demonstrate that these polymorphs are thermodynamically, mechanically, and dynamically feasible. Trig-C9 and Trig-C15 are indirect semiconductors with band gaps of 2.70 eV and 1.25 eV, respectively. Their unique frameworks render them mechanical ductility and significant elastic anisotropy. These results open up new horizons for the exploration of new carbon phases with unique structural, mechanical, and electronic properties.

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.

Review of the unique and dominant lectin pathway of complement activation in agnathans.

As the most primitive vertebrates, lampreys are significant in understanding the early origin and evolution of the vertebrate innate and adaptive immune systems. The complement system is a biological response system with complex and precise regulatory mechanisms and plays an important role in innate and adaptive immunity. It consists of more than 30 distinct components, including intrinsic components, regulatory factors, and complement receptors. Complement system is the humoral backbone of the innate immune defense and complement-like factors have also been found in cyclostomes. Our knowledge as such in lamprey has dramatically increased in the recent years. The searching for complement components in the reissner lamprey Lethenteron reissneri genome database, together with published data, has unveiled the existence of all the orthologues of mammalian complement components identified thus far, including the complement regulatory proteins and complement receptors, in lamprey. This review, summarizes the key themes and recent updates on the complement system of agnathans and discusses the individual complement components of lampreys, and critically compare their functions to that of mammalian complement components. Interestingly, the adaptive immune system of agnathans differs from that of gnathostomes. Lamprey complement components also display some distinctive features, such as lampreys are characterized by the variable lymphocyte receptors (VLRs)-based alternative adaptive immunity. This review may serve as important literature for deducing the evolution of the immune system from invertebrates to vertebrates.

Nanocrystalline high-entropy hexaboride ceramics enable remarkable performance as thermionic emission cathodes.

The development of high-entropy borides with combined structural and functional performance holds untold scientific and technological potential, yet relevant studies have been rarely reported. In this work, we report nanocrystalline (La0.25Ce0.25Nd0.25Eu0.25)B6 high-entropy rare-earth hexaboride (HEReB6-1) ceramics fabricated through the high-pressure sintering of self-synthesized nanopowders for the first time. The as-fabricated samples exhibited a highly dense (96.3%) nanocrystalline (94 nm) microstructure with major (001) fiber textures and good grain boundaries without any impurities, resulting in a remarkable mechanical, electrical, and thermionic emission performance. The results showed that the samples possessed outstanding comprehensive mechanical properties and a high electrical resistivity from room temperature to high temperatures; these were greater than the average values of corresponding binary rare-earth hexaborides, such as a Vickers hardness of 23.4 ± 0.6 GPa and a fracture toughness of 3.0 ± 0.4 MPa•m1/2 at room temperature. More importantly, they showed high emission current densities at elevated temperatures, which were higher than the average values of the corresponding binary rare-earth hexaborides. For instance, the maximum emission current density reached 48.3 A•cm-2 at 1873 K. Such superior performance makes the nanocrystalline HEReB6-1 ceramics highly suitable for potential applications in thermionic emission cathodes.

In Situ Observation of Fracture along Twin Boundaries in Boron Carbide.

The observation of fracture behaviors in perfect and twinned B4 C crystals via in situ transmission electron microscopy (TEM) mechanical testing is reported. The crystal structure of the synthesized B4 C, composed of B11 C icosahedra connected by boron-deficient C-▫-C chains in a chemical formula of B11 C3 , is determined by state-of-the-art aberration-corrected scanning TEM. The in situ TEM observations reveal that cracking is preferentially initiated at the twin boundaries (TBs) in B4 C under both indentation and tension loading. The cracks then propagate along the TBs, thus resulting in the fracture of B4 C. These results are consistent with the theoretical calculations that show that TBs have a softening effect on B4 C with amorphous bands preferentially nucleated at the TBs. These findings elucidate the atomic arrangement and the role of planar defects in the failure of B4 C. Furthermore, they can guide the design of advanced superhard materials via planar defect control.

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.