Abstract
Boron is a unique element, being the only element, all known polymorphs of which are superhard, and all of its crystal structures are distinct from any other element. The electron-deficient bonding in boron explains its remarkable sensitivity to even small concentrations of impurity atoms and allows boron to form peculiar chemical compounds with very different elements. These complications made the study of boron a great challenge, creating also a unique and instructive chapter in the history of science. Strange though it may sound, the discovery of boron in 1808 was ambiguous, with pure boron polymorphs established only starting from the 1950s–1970s, and only in 2007 was the stable phase at ambient conditions determined. The history of boron research from its discovery to the latest discoveries pertaining to the phase diagram of this element, the structure and stability of β-boron, and establishment of a new high-pressure polymorph, γ-boron is reviewed.
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Oganov, A.R., Chen, J., Gatti, C., Ma, Y.-M., Yu, T., Liu, Z., Glass, C.W., Ma, Y.-Z., Kurakevych, O.O., and Solozhenko, V.L., Ionic High-Pressure Form of Elemental Boron, Nature, 2009, vol. 457, pp. 863–867.
Gay-Lussac, J.L. and Thenard, L.J., Sur la Décomposition et la Recomposition de l’Acide Boracique, Ann. Chim. Phys., 1808, vol. 68, pp. 169–174.
Davy, H., Electro-Chemical Researches, on the Decomposition of the Earths; With Observations on the Metals Obtained from the Alkaline Earths, and on the Amalgam Procured from Ammonia (Read June 30, 1808), Phil. Trans. R. Soc. Lond., 1808, vol. 98, pp. 333–370.
Moissan, H., Etude du Bore Amorphe, Ann. Chim. Phys., 1895, vol. 6, pp. 296–320.
Weintraub, E., On the Properties and Preparation of the Element Boron, J. Ind. Eng. Chem., 1911, vol. 3, no. 5, pp. 299–301.
Sainte-Claire Deville, H. and Wöhler, F., Ueber das Bor, Ann. Physik, 1857, vol. 176, no. 4, pp. 635–646.
Wöhler, F. and Sainte-Claire Deville, H., Du Bore, Ann. Chim. Phys., 1858, vol. 52, no. 3, pp. 63–92.
Douglas, B.E. and Ho, S.-M., Structure and Chemistry of Crystalline Solids, New York: Springer, 2006.
Richards, S.M. and Kasper, J.S., The Crystal Structure of YB66, Acta Cryst., 1969, vol. B25, pp. 237–251.
Amberger, E. and Ploog, K., Bildung der Gitter des Reinen Bors, J. Less-Common Metals, 1971, vol. 23, pp. 21–31.
Will, G. and Ploog, K., Crystal Structure of I-Tetragonal Boron, Nature, 1974, vol. 251, pp. 406–408.
Laubengayer, A.W., Hurd, D.T., Newkirk, A.E., and Hoard, J.L., Boron. I. Preparation and Properties of Pure Crystalline Boron, J. Am. Chem. Soc., 1943, vol. 65, pp. 1924–1931.
Hoard, J.L., Geller, S., and Hughes, R.E., On the Structure of Elementary Boron, J. Am. Chem. Soc., 1951, vol. 73, pp. 1892–1893.
Hoard, J.L., Hughes, R.E., and Sands, D.E., The Structure of Tetragonal Boron, J. Am. Chem. Soc., 1958, vol. 80, 4507–4515.
Pauling, L., The Nature of the Chemical Bond, Ithaca, New York: Cornell University Press, 1960.
Ploog, K. and Amberger, E., Kohlenstoff-Induzierte Gitter beim Bor: I-Tetragonales (B12)4B2C und (B12)4B2C2, J. Less-Comm. Metals, 1971, vol. 23, pp. 33–42.
Sands, D.E. and Hoard, J.L., Rhombohedral Elemental Boron, J. Am. Chem. Soc., 1957, vol. 79, pp. 5582–5583.
Hughes, R.E., Kennard, C.H.L., Sullenger, D.B., Weakliem, H.A., Sands, D.E., and Hoard, J.L., The Structure of β-Rhombohedral Boron, J. Am. Chem. Soc., 1963, vol. 85, 361–362.
McCarty, L.V., Kasper, J.S., Horn, F.H., Decker, B.F., and Newkirk, A.F., A New Crystalline Modification of Boron, J. Am. Chem. Soc., 1958, vol. 80, p. 2592.
Talley, C.P., A New Polymorph of Boron, Acta Cryst., 1960, vol. 13, pp. 271–272.
Vlasse, M., Naslain, R., Kasper, J.S., and Ploog, K., Crystal Structure of Tetragonal Boron Related to α-AlB12, J. Sol. State Chem., 1979, vol. 28, 289–301.
Chase M.W., Jr., NIST-JANAF Thermochemical Tables, Fourth Edition, J. Phys. Chem. Ref. Data Monographs & Suppl., 1998, Monograph no. 9, American Chemical Society, American Institute of Physics, National Institute of Standards and Technology.
Wentorf, R.H., Jr., Boron: Another Form, Science, 1965, vol. 147, pp. 49–50.
Nagamatsu, J., Nakagawa, N., Muranaka, T., Zenitani, Y., and Akimitsu, J., Superconductivity at 39 K in Magnesium Diboride, Nature, 2001, vol. 410, pp. 63–64.
Ma, Y., Wang, Y., and Oganov, A.R., Absence of Superconductivity in the Novel High-Pressure Polymorph of MgB2, Phys. Rev. B, 2009, vol. 79, p. 054101.
Eremets, M.I., Struzhkin, V.W., Mao, H.K., and Hemley, R.J., Superconductivity in Boron, Science, 2001, vol. 293, pp. 272–274.
Sanz, D.N., Loubeyre, P., Mezouar, M., Equation of State and Pressure-Induced Amorphization of Beta-Boron from X-Ray Measurements up to 100 GPa, Phys. Rev. Lett., 2001, vol. 89, pp. 245501.
Ma, Y.Z., Prewitt, C.T., Zou, G.T., Mao, H.K., and Hemley, R.J., High-Pressure High-Temperature X-ray Diffraction of beta-Boron to 30 GPa, Phys. Rev. B, 2003, vol. 67, p. 174116.
Van Setten, M.J., Uijttewaal, M.A., de Wijs, G.A., and de Groot, R.A., Thermodynamic Stability of Boron: The Role of Defects and Zero Point Motion, J. Am. Chem. Soc, 2007, vol. 129, pp. 2458–2465.
Widom, M. and Mikhalkovic, M., Symmetry-Broken Crystal Structure of Elemental Boron at Low Temperature, Phys. Rev. B, 2008, vol. 77, pp. 064113.
Ogitsu, T., Gygi, F., Reed, J., Motome, Y., Schwegler, E., and Galli, G., Imperfect Crystal and Unusual Semiconductor: Boron, a Frustrated Element, J. Am. Chem. Soc., 2009, vol. 131, pp. 1903–1909.
Oganov, A.R. and Glass C.W., Crystal Structure Prediction Using ab initio Evolutionary Techniques: Principles and Applications, J. Chem. Phys., 2006, vol. 124, p. 244704.
Solozhenko, V.L., Kurakevych, O.O., and Oganov, A.R., On the Hardness of a New Boron Phase, Orthorhombic γ-B28, J. Superhard Mater., 2008, vol. 30, pp. 428–429.
Gabunia, D., Tsagareishvili, O., Darsavelidze, G., Lezhava, D., Antadze, M., and Gabunia, L., Preparation, Structure and Some Properties of Boron Crystals with Different Content of 10B and 11B Isotopes, J. Solid State Chem., 2004, vol. 177, pp. 600–604.
Amberger, E. and Stumpf, W., in Gmelin Handbook of Inorganic Chemistry. Elemental Boron, Boron Carbides, 8th ed., Suppl. vol. 2, SN 13, Ex. 19, Berlin: Springer-Verlag, 1981, pp. 1–112.
Zarechnaya, E.Y., Dubrovinsky, L., Dubrovinskaia, N., Filinchuk, Y., Chernyshov, D., Dmitriev, V., Miyajima, N., El Goresy, A., Braun, H.F., Vansmaalen, S., Kantor, I., Kantor, A., Prakapenka, V., Hanfland, M., Mikhailushkin, A.S., Abrikosov, I.A., and Simak, S.I., Superhard Semiconducting Optically Transparent High Pressure Phase of Boron, Phys. Rev. Lett., 2009, vol. 102, p. 185501.
Zarechnaya, E.Y., Dubrovinsky, L., Dubrovinskaia, N., Miyajima, N., Filinchuk, Y., Chernyshov, D., and Dmitriev, V., Synthesis of an Orthorhombic High Pressure Boron Phase, Sci. Tech. Adv. Mat., 2008, vol. 9, p. 044209.
Oganov, A.R., Solozhenko, V.L., Kurakevych, O.O., Gatti, C., Ma, Y., Chen, J., Liu, Z., and Hemley, R.J., Comment on “Superhard Semiconducting Optically Transparent High Pressure Phase of Boron”, 2009, http://arxiv.org/abs/0908.2126.
Le Godec, Y., Kurakevych, O.O., Munsch, P., Garbarino, G., and Solozhenko, V.L., Equation of State of Orthorhombic Boron, γ-B28., Solid State Comm., 2009, vol. 149, 1356–1358.
Rulis, P., Wang, L., and Ching, W.Y., Prediction of γ-B28 ELNES with Comparison to α-B12., Phys. Stat. Sol. (RRL), 2009, vol. 3, pp. 133–135.
Jiang, C., Lin, Z., Zhang, J., and Zhao, Y., First-Principles Prediction of Mechanical Properties of gamma-Boron, Appl. Phys. Lett., 2009, vol. 94, p. 191906.
Segall, D.E. and Arias, T.A., Ab initio Approach for High-Pressure Systems with Application to High-Pressure Phases of Boron: Perturbative Momentum-Space Potentials, Phys. Rev. B, 2003, vol. 67, p. 064105.
Haussermann, U., Simak, S.I., Ahuja, R., and Johansson, B., Metal-Nonmetal Transition in the Boron Group Elements, Phys. Rev. Lett., 2003, vol. 90, p. 065701.
Ma, Y.M., Tse, J.S., Klug, D.D., and Ahuja, R., Electron-Phonon Coupling of α-Ga Boron, Phys. Rev. B, 2004, vol. 70, p. 214107.
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Original Russian Text © A.R. Oganov, V.L. Solozhenko, 2009, published in Sverkhtverdye Materialy, 2009, Vol. 31, No. 5, pp. 3–11.
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Oganov, A.R., Solozhenko, V.L. Boron: a hunt for superhard polymorphs. J. Superhard Mater. 31, 285–291 (2009). https://doi.org/10.3103/S1063457609050013
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DOI: https://doi.org/10.3103/S1063457609050013