Semiconducting character of LaN: Magnitude of the bandgap and origin of the electrical conductivity

Abstract

Lanthanum nitride (LaN) has attracted research interest in catalysis due to its ability to activate the triple bonds of N2 molecules, enabling efficient and cost-effective synthesis of ammonia from N2 gas. While exciting progress has been made to use LaN in functional applications, the electronic character of LaN (metallic, semi-metallic, or semiconducting) and magnitude of its bandgap have so far not been conclusively determined. Here, we investigate the electronic properties of LaN with hybrid density functional theory calculations. In contrast to previous claims that LaN is semi-metallic, our calculations show that LaN is a direct-bandgap semiconductor with a bandgap value of 0.62 eV at the X point of the Brillouin zone. The dispersive character of the bands near the band edges leads to light electron and hole effective masses, making LaN promising for electronic and optoelectronic applications. Our calculations also reveal that nitrogen vacancies and substitutional oxygen atoms are two unintentional shallow donors with low formation energies that can explain the origin of the previously reported electrical conductivity. Our calculations clarify the semiconducting nature of LaN and reveal candidate unintentional point defects that are likely responsible for its measured electrical conductivity.