Carbon-rich icosahedral boron carbides beyond B4C and their thermodynamic stabilities at high temperature and pressure from first principles
2016 (English)In: PHYSICAL REVIEW B, ISSN 2469-9950 (print); 2469-9969 (online), Vol. 94, no 5, 054104Article in journal (Refereed) Published
We investigate the thermodynamic stability of carbon-rich icosahedral boron carbide at different compositions, ranging from B4C to B2C, using first-principles calculations. Apart fromB4C, generally addressed in the literature, B2.5C, represented by B10C2p (C-C), where C-p and (C-C) denote a carbon atom occupying the polar site of the icosahedral cluster and a diatomic carbon chain, respectively, is predicted to be thermodynamically stable under high pressures with respect to B4C as well as pure boron and carbon phases. The thermodynamic stability of B2.5C is determined by the Gibbs free energy G as a function of pressure p and temperature T, in which the contributions from the lattice vibrations and the configurational disorder are obtained within the quasiharmonic and the mean-field approximations, respectively. The stability range of B2.5C is then illustrated through the p-T phase diagrams. Depending on the temperatures, the stability range of B2.5C is predicted to be within the range between 40 and 67 GPa. At T greater than or similar to 500 K, the icosahedral C-p atoms in B2.5C configurationally disorder at the polar sites. By investigating the properties of B2.5C, e.g., elastic constants and phonon and electronic density of states, we demonstrate that B2.5C is both mechanically and dynamically stable at zero pressure, and is an electrical semiconductor. Furthermore, based on the sketched phase diagrams, a possible route for experimental synthesis of B2.5C as well as a fingerprint for its characterization from the simulations of x-ray powder diffraction pattern are suggested.
Place, publisher, year, edition, pages
AMER PHYSICAL SOC , 2016. Vol. 94, no 5, 054104
Condensed Matter Physics
IdentifiersURN: urn:nbn:se:liu:diva-131508DOI: 10.1103/PhysRevB.94.054104ISI: 000381304300001OAI: oai:DiVA.org:liu-131508DiVA: diva2:974421
Funding Agencies|Swedish Research Council (VR) [621-2011-4417, 330-2014-6336, 2014-4750]; Marie Sklodowska Curie Actions [INCA 600398]; CeNano at Linkoping University; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]2016-09-262016-09-232016-10-19