Elemental boron has many interesting properties, such as high melting point, low density, high hardness, high Young’s modulus, good oxidation resistance, resulting from its complex crystalline structure from its electron-deficient nature. Boron forms complex crystalline structures according to the various arrangements of B12 icosahedra in the lattice, such as α (B12)- and β (B105)-rhombohedral and α (B50)- and β (B196)-tetragonal boron polymorphs, among others. Even though considerable materials research has been conducted over the past half century on boron and boron-based compounds, investigating their unique structures and corresponding properties, our understanding of this complex class of materials is still poor, compared to some other well-studied materials with much simpler structures such as silicon. Thermal transport studies through bulk boron have been performed mainly on β-rhombohedral and amorphous boron, because of the difficulty to grow high quality bulk α-rhombohedral boron samples [1–3]. Some efforts have been made to measure B12As2, B12P2, AlB12 samples that have an α-rhombohedral form [2,3]. There is almost no information available on α-tetragonal boron. However, Slack predicted the thermal conductivity of α-boron should be ∼200 W/m-K at room temperature, which is 1/2 that of copper. Large phonon mean free path has been predicted for α-boron (from ∼200 nm at room temperature to 6 nm at the Debye temperature), which could lead to interesting thermal transport properties for low dimensional boron structures.

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