Impurity-derived P-Type Conductivity in Cubic Boron Arsenide

Cubic boron arsenide (c-BAs) exhibits an ultrahigh thermal conductivity (κ) approaching 1300 Wm−1 K−1 at room temperature. However, c-BAs is believed to incorporate high concentrations of crystal imperfections that can both quench κ and act as sources of unintentional p-type conductivity. Although this behavior has been attributed to native defects, we show here, using optical and magnetic resonance spectroscopies together with first-principles calculations, that unintentional acceptor impurities such as silicon and/or carbon are more likely candidates for causing the observed conductivity. These results also clarify that the true low-temperature bandgap of c-BAs is 0.3 eV higher than the widely reported value of ∼1.5 eV. Low-temperature photoluminescence measurements of c-BAs crystals reveal impurity-related recombination processes (including donor-acceptor pair recombination), and electron paramagnetic resonance experiments show evidence for effective mass-like shallow acceptors. Our hybrid density functional calculations indicate that native defects are incapable of giving rise to such signals. Instead, we find that group-IV impurities readily incorporate on the As site and act as shallow acceptors. Such impurities can dominate the electrical properties of c-BAs, and their influence on phonon scattering must be considered when optimizing thermal conductivity.