Interface engineering for a stable chemical structure of oxidized-black phosphorus via self-reduction in AlO x atomic layer deposition.

We evaluated the change in the chemical structure between dielectrics (AlOx and HfOx) grown by atomic layer deposition (ALD) and oxidized black phosphorus (BP), as a function of air exposure time. Chemical and structural analyses of the oxidized phosphorus species (PxOy) were performed using atomic force microscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, first-principles density functional theory calculations, and the electrical characteristics of field-effect transistors (FETs). Based on the combined experiments and theoretical investigations, we clearly show that oxidized phosphorus species (PxOy, until exposed for 24 h) are significantly decreased (self-reduction) during the ALD of AlOx. In particular, the field effect characteristics of a FET device based on Al2O3/AlOx/oxidized BP improved significantly with enhanced electrical properties, a mobility of ∼253 cm2 V-1 s-1 and an on-off ratio of ∼105, compared to those of HfO2/HfOx/oxidized BP with a mobility of ∼97 cm2 V-1 s-1 and an on-off ratio of ∼103-104. These distinct differences result from a significantly decreased interface trap density (Dit ∼ 1011 cm-2 eV-1) and subthreshold gate swing (SS ∼ 270 mV dec-1) in the BP device caused by the formation of stable energy states at the AlOx/oxidized BP interface, even with BP oxidized by air exposure.