The idealized rhombohedral unit cell of boron carbide is formed by a 12-atom icosahedron and a 3-atom linear chain. Phase transitions are second order and caused by the exchange of B and C sites or by vacancies in the structure. Nevertheless, the impact of such minimal structural changes on the properties can be significant. As the X-ray scattering cross sections of B and C isotopes are very similar, the capability of X-ray fine structure investigation is substantially restricted. Phonon spectroscopy helps close this gap as the frequency and strength of phonons sensitively depend on the bonding force and mass of the vibrating atoms concerned. Phase transitions known to date have been identified due to significant changes of properties: (1) The phase transition near the chemical composition B8C by clear change of the electronic structure; (2) the endothermic temperature-dependent phase transition at 712 K according to the change of specific heat; (3) the high-pressure phase transition at 33.2 GPa by the drastic change of optical appearance from opacity to transparency. These phase transitions affect IR- and Raman-active phonons and other solid-state properties. The phase transitions at B~8C and 712 K mean that a well-defined distorted structure is converted into another one. In the high-pressure phase transition, an apparently well-defined distorted structure changes into a highly ordered one. In all these cases, the distribution of polar C atoms in the icosahedra plays a crucial role.
Keywords: boron carbide; electronic properties; phase transition; phonons; structural disorder.