(172d) Electrostatic Coupling of Surface Charge to Bulk Defect Behavior In Metal Oxides

Gorai, P., University of Illinois
Hollister, A. G., University of Illinois
Pangan-Okimoto, K., University of Illinois

The technologically useful properties of semiconductor oxides such as titania and zinc oxide often depend on the concentration and diffusion of point defects. Near-surface effects are particularly important in nanoscale devices because most of the bulk is located in the vicinity of the surface. Past work in our laboratory with silicon and titania has shown that semiconductor surfaces serve as efficient pathways for generation and annihilation of point defects in the underlying bulk. Surfaces can, in addition, support electrically charged defects which create near-surface strong electric fields that can influence the local motion of charged defects resulting in the formation of space-charge layers. The electric field-driven accumulation or depletion of charged oxygen defects in such space-charge regions in metal oxides have direct implications on the performance of nanoscale devices such as gas sensors and memory resistors. Oxygen diffusion behavior was studied by exposing natural-abundance single-crystal rutile to isotopically labeled oxygen gas.  The resulting profiles were measured by secondary ion mass spectrometry and subsequently modeled with continuum equations for the reaction, Fickian diffusion and electric field-driven diffusion of the key point defects. The degree of charge build-up at the surface can be quantified by an electric potential (Vi). The profiles calculated show a characteristic steep concentration gradient near the surface followed by a normal bulk diffusion profile. By identifying the charge-mediated field-driven diffusion mechanism as the controlling factor for the near-surface pile-up of oxygen, we demonstrate that this method allows the spatially resolved characterization of space charge regions near the surfaces of crystalline semiconductor metal oxides. The capability to predict oxygen pile-up in nanoscale metal oxide devices may be beneficial in device improvement via defect engineering of surfaces.