Axis dependent conduction polarity in the air-stable semiconductor, PdSe₂

Axis-dependent conduction polarity (ADCP) is a unique electronic phenomena in which the charge polarity of carrier conduction can differ from p-type to n-type depending on the direction of travel through the crystal. Most materials that exhibit ADCP are metals, and very few semiconducting materials exhibit this effect. Here, we establish that PdSe₂, a ∼0.5 eV band gap semiconductor that is air- and water-stable, exhibits ADCP, through the growth and characterization of the transport properties of crystals with extrinsic p- and n-type doping levels of Ir and Sb, respectively, in the 10¹⁶-10¹⁸ cm^-3 range. Electron doped PdSe₂ exhibits p-type conduction in the cross-plane direction and n-type conduction along the in-plane directions above an onset temperature of 100-200 K that varies with doping level. Lightly p-doped samples show p-type thermopower in all directions at low temperatures, but above ∼360 K the in-plane thermopower turns negative. Density functional theory calculations indicate that the origin of ADCP arises from the complementary effective mass anisotropies in the valence and conduction bands in this material, which facilitate hole transport in the cross-plane direction, and electron transport along the in-plane directions. ADCP occurs at temperatures with sufficient thermal population of both carrier types to overcome the extrinsic doping levels to exploit the effective mass anisotropy. In total, the development of this stable semiconductor in which thermally or optically excited holes and electrons inherently migrate along different directions opens up numerous potential applications in a multitude of technologies.