Design, Synthesis, and Optoelectronic Properties of the High-Purity Phase in Layered AETMN₂(AE = Sr, Ba; TM = Ti, Zr, Hf) Semiconductors

We report the synthesis and optoelectronic properties of high phase-purity (>94 mol %) bulk polycrystals of KCoO2-type layered nitrides AETMN2 (AE = Sr, Ba; and TM = Ti, Zr, Hf), which are expected to exhibit unique electron transport properties originating from their natural two-dimensional (2D) electronic structure, but high-purity intrinsic samples have yet been reported. The bulks were synthesized using a solid-state reaction between AENH and TMN precursors with NaN3 to achieve high N chemical potential during the reaction. The AETMN2 bulks are n-type semiconductors with optical band gaps of 1.63 eV for SrTiN2, 1.97 eV for BaZrN2, and 2.17 eV for BaHfN2. SrTiN2 and BaZrN2 bulks show degenerated electron conduction due to the natural high-density electron doping and paramagnetic behavior in all of the temperature ranges examined, while such unintentional carrier generation is largely suppressed in BaHfN2, which exhibits nondegenerated electron conduction. The BaHfN2 sample also exhibits weak ferromagnetic behavior at temperatures lower than 35 K. Density functional theory calculations suggest that the high-density electron carriers in SrTiN2 come from oxygen impurity substitution at the N site (ON) acting as a shallow donor even if the high-N chemical potential synthesis conditions are employed. On the other hand, the formation energy of ON becomes larger in BaHfN2 because of the stronger TM-N chemical bonds. Present results demonstrate that the easiness of impurity incorporation is designed by density functional calculations to produce a more intrinsic semiconductor in wider chemical conditions, opening a way to cultivating novel functional materials that are sensitive to atmospheric impurities and defects.