ABSTRACT
X-ray absorption fine-structure (XAFS) data were obtained for the V K-edge for a series of anisotropic single crystals of (Cr(x)V(1-x))(2)O(3). The data and the results were compared for the as-prepared bulk single crystals (measured in fluorescence in two different orientations) and those ground to powder (measured in transmission). For the bulk single crystals, the glancing-emergent-angle (GEA) method was used to minimize fluorescence distortion. The reliability of the GEA technique was tested by comparing the polarization-weighted single-crystal XAFS data with the experimental powder data. These data were found to be in excellent agreement throughout the entire energy range. Thus, it was possible to reliably measure individual V-V contributions parallel and perpendicular to the c axis of the single crystals, i.e. those unavailable by powder data XAFS analysis. These experiments demonstrate that GEA is a premiere method for non-destructive high-photon-count in situ studies of local structure in bulk single crystals.
ABSTRACT
Structural transformations around both V and Cr atoms in (V1-xCrx)2O3 across its metal-insulator transition (MIT) at x approximately 0.01 are studied by extended x-ray absorption fine-structure technique. Our new results for Cr made possible by the use of a novel x-ray analyzer that we developed reveal the substitutional mechanism of Cr doping. We find that this system has a buckled structure with short Cr-V and long V-V bonds. This system of bonds is disordered around the average trigonal lattice ascertained by x-ray diffraction. Such local distortions can result in a long range strain field that sets in around dilute Cr atoms in microscopic regions. We suggest that such locally strained regions should be insulating even at small x. The possibility of local insulating regions within a metallic phase, first suggested by Rice and Brinkman in 1972, remains unaccounted for in modern MIT theories.
