High-pressure melt growth and transport properties of SiP, SiAs, GeP, and GeAs 2D layered semiconductors

•Layered crystals of Si- and Ge-monopnictides have been grown.•Both high-pressure melt growth and chemical vapor transport were successfully used.•Si- and Ge-monopnictides are semiconductors in a 2D-Variable-Range-Hopping regime.

Silicon and Germanium monopnictides SiP, SiAs, GeP and GeAs form a family of 2D layered semiconductors. We have succeeded in growing bulk single crystals of these compounds by melt-growth under high pressure (0.5-1 GPa) in a cubic anvil hot press. Large (mm-size), shiny, micaceous crystals of GeP, GeAs and SiAs were obtained, and could be exfoliated into 2D flakes. Small and brittle crystals of SiP were yielded by this method. High-pressure sintered polycrystalline SiP and GeAs have also been successfully used as a precursor in the Chemical Vapor Transport growth of these crystals in the presence of I2 as a transport agent. All compounds are found to crystallize in the expected layered structure and do not undergo any structural transition at low temperature, as shown by Raman spectroscopy down to T=5 K. All materials exhibit a semiconducting behavior. The electrical resistivity of GeP, GeAs and SiAs is found to depend on temperature following a 2D-Variable Range Hopping conduction mechanism. The availability of bulk crystals of these compounds opens new perspectives in the field of 2D semiconducting materials for device applications.