Atomic Structure, Stoichiometry, and Polytypism
T HE sively discussed in the literature. atomic structure of boron carbide has been exten- 1–8 The primary structural units of boron carbide are the 12-atom icosahedra
located at the vertices of a rhombohedral lattice of trigonal
symmetry (R3m space group), and the 3-atom linear chains
that link the icosahedra along the (111) rhombohedral axis,
as illustrated in Fig. 1. This structure can also be described
in terms of a hexagonal lattice based on a nonprimitive unit
cell, in which case the [0001] axis of the hexagonal lattice
corresponds to the [111] rhombohedral direction (Fig. 1).
The presence of icosahedra within the boron carbide structure is a consequence of elemental boron’s ability to form
caged structures of a variety of sizes5,9; the icosahedra in
boron carbide are essentially two pentagonal pyramids
bonded together.10 As such, two types of chemically distinct
sites, polar and equatorial, are possible within an individual
icosahedron. The polar sites correspond to those atoms that
link the icosahedra together. The polar atoms within the cage