Journal of the American Chemical Society, Vol.136, No.42, 14959-14965, 2014
Narrow Bandgap in beta-BaZn2As2 and Its Chemical Origins
beta-BaZn2As2 is known to be a p-type semiconductor with the layered crystal structure similar to that of LaZnAsO, leading to the expectation that beta-BaZn2As2 and LaZnAsO have similar bandgaps; however, the bandgap of beta-BaZn2As2 (previously reported value similar to 0.2 eV) is 1 order of magnitude smaller than that of LaZnAsO (1.5 eV). In this paper, the reliable bandgap value of beta-BaZn2As2 is determined to be 0.23 eV from the intrinsic region of the temperature dependence of electrical conductivity. The origins of this narrow bandgap are discussed based on the chemical bonding nature probed by 6 keV hard X-ray photoemission spectroscopy, hybrid density functional calculations, and the ligand theory. One origin is the direct AsAs hybridization between adjacent [ZnAs] layers, which leads to a secondary splitting of As 4p levels and raises the valence band maximum. The other is that the nonbonding Ba 5d(x2y2) orbitals form an unexpectedly deep conduction band minimum (CBM) in beta-BaZn2As2 although the CBM of LaZnAsO is formed mainly of Zn 4s. These two origins provide a quantitative explanation for the bandgap difference between beta-BaZn2As2 and LaZnAsO.