▪ Abstract The synthesis of the two currently used superhard materials, diamond and cubic boron nitride, is briefly described with indications of the factors influencing the quality of the crystals obtained. The physics of hardness is discussed and the importance of covalent bonding and fixed atomic positions in the crystal structure, which determine high hardness values, is outlined. The materials investigated to date are described and new potentially superhard materials are presented. No material that is thermodynamically stable under ambient conditions and composed of light (small) atoms will have a hardness greater than that of diamond. Materials with hardness values similar to that of cubic boron nitride (cBN) can be obtained. However, increasing the capabilities of the high-pressure devices could lead to the production of better quality cBN compacts without binders.

Synthesis and Design of Superhard Materials

Single atomic layer nanosheet materials show great application potential in many fields due to their enhanced intrinsic properties compared to their counterparts and newly born properties. Herein, g-C3N4 nanosheets with a single atomic layer structure are prepared by a simple chemical exfoliation method. The as-prepared nanosheets show a single atomic thickness of 0.4 nm and a lateral size of micrometers. The structure and photocatalytic properties of the as-prepared single layer g-C3N4 are then studied. Compared with the bulk g-C3N4, single layer g-C3N4 nanosheets show great superiority in photogenerated charge carrier transfer and separation. Accordingly, the photocatalytic H2 production and pollutant decomposition activities and photocurrent generation of single layer g-C3N4 nanosheets are much higher than those of the bulk g-C3N4, indicating the great application potential of single layer g-C3N4 nanosheets in photocatalysis and photosynthesis.

Chemical exfoliation of graphitic carbon nitride for efficient heterogeneous photocatalysis

Advances in the accuracy and efficiency of first-principles electronic structure calculations have allowed detailed studies of the energetics of materials under high pressures. At the same time, improvements in the resolution of powder x-ray diffraction experiments and more sophisticated methods of data analysis have revealed the existence of many new and unexpected high-pressure phases. The most complete set of theoretical and experimental data obtained to date is for the group-IVA elements and the group-IIIA--VA and IIB--VIA compounds. Here the authors review the currently known structures and high-pressure behavior of these materials and the theoretical work that has been done on them. The capabilities of modern first-principles methods are illustrated by a full comparison with the experimental data.

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High-pressure phases of group-IV, III–V, and II–VI compounds

Boron is an element of fascinating chemical complexity. This arises from frustration: situated between metals and insulators in the periodic table, boron has only three valence electrons that could in principle favour metallicity, yet they are sufficiently localized to give rise to an insulating state. This delicately balanced electronic structure is easily modified by pressure, temperature and impurities, making it difficult to establish boron's structure and properties. Oganov et al. have now explored the high-pressure behaviour of boron and uncovered a previously unknown ionic phase consisting of negatively charged icosahedral B12 clusters and positively charged B2 pairs. The ionicity of the new phase strongly affects many of its properties, and arises from the different electronic properties of the B12 clusters and B2 pairs and the resultant charge transfer between them. This paper has explored the high-pressure behaviour of boron and uncovered a new phase that consists of negatively charged icosahedral B12 clusters and positively charged B2 pairs. The ionicity of the new phase strongly affects many of its properties, and arises from the different electronic properties of the B12 clusters and B2 pairs and the resultant charge transfer between them. Boron is an element of fascinating chemical complexity. Controversies have shrouded this element since its discovery was announced in 1808: the new ‘element’ turned out to be a compound containing less than 60–70% of boron, and it was not until 1909 that 99% pure boron was obtained1. And although we now know of at least 16 polymorphs2, the stable phase of boron is not yet experimentally established even at ambient conditions3. Boron’s complexities arise from frustration: situated between metals and insulators in the periodic table, boron has only three valence electrons, which would favour metallicity, but they are sufficiently localized that insulating states emerge. However, this subtle balance between metallic and insulating states is easily shifted by pressure, temperature and impurities. Here we report the results of high-pressure experiments and ab initio evolutionary crystal structure predictions4,5 that explore the structural stability of boron under pressure and, strikingly, reveal a partially ionic high-pressure boron phase. This new phase is stable between 19 and 89 GPa, can be quenched to ambient conditions, and has a hitherto unknown structure (space group Pnnm, 28 atoms in the unit cell) consisting of icosahedral B12 clusters and B2 pairs in a NaCl-type arrangement. We find that the ionicity of the phase affects its electronic bandgap, infrared adsorption and dielectric constants, and that it arises from the different electronic properties of the B2 pairs and B12 clusters and the resultant charge transfer between them.

Ionic high-pressure form of elemental boron

A central challenge to modern materials science is the rational design and synthesis of new materials possessing exceptional properties. Recent advances in first-principles modeling methods and the availability of increasingly powerful computational resources make this goal increasingly achievable. The strength of these modeling methods lies in their predictive ability. They are able to reproduce the crystal structures and elastic properties of a large class of materials to within 2–3% of experimental values and have predicted a number of phase transitions that have been verified experimentally.Despite the power of these methods, the process of designing materials from first principles is not usually a straight-forward or simple one. It requires overcoming a number of obstacles, some of them quite formidable. First a calculable figure of merit that correlates well with the desired property must be identified. While this may be straightforward in some cases, in others—such as predicting the ability of a material to isolate radionuclides over million-year time scales—the process of reducing complex properties to a few calculable variables can be rather difficult. Next a promising chemical system and a realistic set of crystal structures must be selected. This is not trivial because predicting the structures that can crystallize in a given system can be exceedingly challenging. However a wide variety of methods are available to aid in the generation of promising structures — comparative crystallography, algorithms based upon the concepts of crystalline nets and close packing, modern alloy theory methods, and simulated annealing strategies being some examples.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0883769400031420

Computational Alchemy: The Search for New Superhard Materials

Synthesis of diamond from graphite-carbonate system under very high temperature and pressure

https://www.jstage.jst.go.jp/article/pjab1977/66/1/66_1_7/_pdf

High pressure synthesis of rocksalt type of AlN.

Segregative Crystallization of Several Diamond-like Phases from the Graphitic BC2N without an Additive at 7.7 GPa

Graphite BC[sub 2]N has been compressed with Co metal at a pressure of 5.5 GPa and temperatures of 1400-1600[degrees]C. The principal resulting products were crystals (average dimension 3 [mu]m) with cubiclike facets. The powder X-ray diffraction pattern revealed two kinds of cubic phase, in approximately equal amounts, which were identified as diamond and cBN on the basis of their lattice parameters. Microelemental analyses on individual crystal fragments by K-edge electron energy-loss spectroscopy confirmed this disproportionating crystallization scheme: half of the grains were composed of carbon-only signals of which gave fine-structure characteristic of sp[sup 3] bonding and the other half gave spectra characteristic of sp[sup 3] boron and nitrogen. The crystallization of cBN as well as diamond in the catalytic solvent of pure Co metal is observed here for the first time and is of relevance to the mechanism of the accepted catalytic action of cobalt on the hexagonal/cubic transformation. 26 refs., 4 figs., 2 tabs.

Simultaneous crystallization of diamond and cubic boron nitride from the graphite relative boron carbide nitride (BC2N) under high pressure/high temperature conditions

As diamond-producing catalysts, 12 transition metals such as iron, cobalt, and nickel were first reported by General Electric researchers more than 30 years ago. Since then, no additional elemental catalyst has been reported. An investigation of the catalytic action of group V elements is of great interest from the viewpoint of producing an n-type semiconducting diamond crystal. In the present study, diamond was synthesized from graphite in the presence of elemental phosphorus at high pressure and temperature (7.7 gigapascals and 1800 degrees C). Furthermore, single-crystal diamond was grown on a diamond seed crystal.

https://science.sciencemag.org/content/sci/259/5101/1592.full.pdf

Minoru Akaishi

Papers

Synthesis of diamond from graphite-carbonate system under very high temperature and pressure

High pressure synthesis of rocksalt type of AlN.

Segregative Crystallization of Several Diamond-like Phases from the Graphitic BC2N without an Additive at 7.7 GPa

Simultaneous crystallization of diamond and cubic boron nitride from the graphite relative boron carbide nitride (BC2N) under high pressure/high temperature conditions

Phosphorus: An Elemental Catalyst for Diamond Synthesis and Growth