We have obtained and analyzed Raman spectra of single-crystal, hot-pressed, and chemical-vapor-deposited boron carbide materials over their single-phase region (from ∼9 to ∼20 at. % carbon). These spectra provide insight into the substitutional disorder that characterizes these structurally ordered solids. In particular, although icosahedra and chain structures occupy regular lattice positions, there is local substitutional disorder resulting from the occupancy of certain sites within the icosahedra and chains by either boron or carbon atoms. Comparison of boron carbide Raman spectra with the Raman spectra of α-rhombohedral boron, boron phosphide, and boron arsenide has confirmed the following structural model derived from theoretical considerations and electrical and thermal transport data. The boron carbide composition with nearly 20 at. % carbon is composed of ${\mathrm{B}}_{11}$C icosahedra linked by carbon-boron-carbon chains. As the carbon content is reduced toward approximately 13 at. %, carbon-boron-carbon chains are progressively replaced by carbon-boron-boron chains. Further reduction in the carbon content results in the replacement of ${\mathrm{B}}_{11}$C icosahedra with ${\mathrm{B}}_{12}$ icosahedra.

• Received 27 March 1989

DOI:https://doi.org/10.1103/PhysRevB.40.5649