Surface conditions for the observation of metal–insulator transitions on Cr-doped V2O3

Chromium-doped vanadium sesquioxide, (V1−xCrx)2O3, displays two metal–insulator transitions with temperature for 0.005<x<0.0179. The high-temperature (∼300 K) transition occurs in a temperature range that is of interest for catalysis; the physics of the transition is also of fundamental interest. However, so far that transition has been observed only on cleaved samples. Due to the difficulty in obtaining doped single crystals for cleaving, alternate preparation methods are required. (V0.985Cr0.015)2O3 (0001) was prepared both by scraping with a diamond file and by ion bombardment followed by annealing in oxygen; the resulting surfaces were examined by ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS) for evidence of the high-temperature metal–insulator transition. Although resistance measurements across the transition temperature showed that a transition had taken place in the bulk, no changes were observed in photoemission spectra of scraped samples; they appeared insulating both above and below the transition. Annealed samples, on the other hand, displayed a clear increase in the density of states at EF, as well as changes in core-level XPS consistent with a metallic surface, as the temperature was lowered through the transition. Sharp (1×1) low energy electron diffraction (LEED) patterns were obtained from annealed surfaces, and Auger spectra showed no evidence of chromium segregation following annealing.