Strategies for gallium removal after focused ion beam patterning of ferroelectric oxide nanostructures.

As part of a study into the properties of ferroelectric single crystals at nanoscale dimensions, the effects that focused ion beam (FIB) processing can have, in terms of structural damage and ion implantation, on perovskite oxide materials has been examined, and a post-processing procedure developed to remove such effects. Single crystal material of the perovskite ferroelectric barium titanate (BaTiO3) has been patterned into thin film lamellae structures using a FIB microscope. Previous work had shown that FIB patterning induced gallium impregnation and associated creation of amorphous layers in a surface region of the single crystal material some 20 nm thick, but that both recrystallization and expulsion of gallium could be achieved through thermal annealing in air. Here we confirm this observation, but find that thermally induced gallium expulsion is associated with the formation of gallium-rich platelets on the surface of the annealed material. These platelets are thought to be gallium oxide. Etching using nitric and hydrochloric acids had no effect on the gallium-rich platelets. Effective platelet removal involved thermal annealing at 700 °C for 1 h in a vacuum followed by 1 h in oxygen, and then a post-annealing low-power plasma clean in an Ar/O atmosphere. Similar processing is likely to be necessary for the full recovery of post FIB-milled nanostructures in oxide ceramic systems in general.