We used temperature-dependent x-ray absorption fine structure (XAFS) measurements to examine the local structural properties around vanadium atoms at the V K edge from VO2 films. A direct comparison of the simultaneously-measured resistance and XAFS regarding the VO2 films showed that the thermally-driven structural transition occurred prior to the resistance transition during a heating, while this change simultaneously occured during a cooling. Extended-XAFS (EXAFS) analysis revealed significant increases of the Debye-Waller factors of the V-O and V-V pairs in the {111} direction of the R-phase VO2 that are due to the phonons of the V-V arrays along the same direction in a metallic phase. The existance of a substantial amount of structural disorder on the V-V pairs along the c-axis in both M1 and R phases indicates the structural instability of V-V arrays in the axis. The anomalous structural disorder that was observed on all atomic sites at the structural phase transition prevents the migration of the V 3d1 electrons, resulting in a Mott insulator in the M2-phase VO2.
Mott proposed that impurity bands in corundum-symmetry Ti2O3 at high temperatures caused a collapse in the bandgap. However, the origin of the impurity bands has not yet been clarified. We examine the local structural properties of metal-to-insulator-transition Ti2O3 using in-situ x-ray absorption fine structure (XAFS) measurements at the Ti K edge in the temperature range from 288 to 739 K. The Ti2O3 powder is synthesized by using a chemical reaction method. X-ray diffraction (XRD) measurements from Ti2O3 with a Rietveld refinement demonstrate a single-phased R-3c symmetry without additional distortion. Extended-XAFS combined with XRD reveals a zigzag patterned Ti position and an anomalous structural disorder in Ti-Ti pairs, accompanied by a bond length expansion of the Ti-Ti pairs along the c-axis for T > 450 K. The local structural distortion and disorder of the Ti atoms would induce impurity levels in the band gap between the Ti 3d a1g and egπ bands, resulting in a collapse of the band gap for T > 450 K.
The local structural properties of TiO 2 nanoparticles (NPs) were investigated under ultraviolet light (UV) using in-situ X-ray absorption fine structure measurements at the Ti K edge. XAFS analysis showed that the bond lengths of the atomic pairs were distorted by 0.1 Å and that the Debye-Waller factors of the atomic pairs were increased substantially under UV light, compared with those of no UV light. These results suggested that the local structural changes were caused by the photocatalyst reactivity of oxygen atoms in the NPs. Unlike other techniques, in-situ XAFS is sensitive to detect local structural changes during the photocatalytic reactivity.
Uniformly and vertically well-aligned ZnO nanorods were fabricated in-situ and ex-situ on ZnO films using a catalyst-free metal-organic chemical vapor process. Microstructural properties of the initial growth of ZnO nanorods on ZnO films with different surface roughnesses were investigated. We observed that the ZnO nanorods grown on ZnO films with surface roughness of less than 1.0 nm were well-aligned along the c-axis and in the ab-plane. When the nanorods grew on ZnO films with a large surface roughness, they had three different growth directions of 28 degrees, 62 degrees, and 90 degrees to the film surface. The slant angle of 62 degrees corresponds to the angle between the ZnO(001) and (101) planes. The initial growth direction difference caused structural disorder at the interface of the ZnO nanorod and film, and prevented epitaxial growth and the alignment of the nanorods.
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