The remarkable properties of black TiO2 are due to its disordered surface shell surrounding a crystalline core. However, the chemical composition and the atomic and electronic structure of the disordered shell and its relationship to the core remain poorly understood. Using advanced transmission electron microscopy methods, we show that the outermost layer of black TiO2 nanoparticles consists of a disordered Ti2O3 shell. The measurements show a transition region that connects the disordered Ti2O3 shell to the perfect rutile core consisting first of four to five monolayers of defective rutile, containing clearly visible Ti interstitial atoms, followed by an ordered reconstruction layer of Ti interstitial atoms. Our data suggest that this reconstructed layer presents a template on which the disordered Ti2O3 layers form by interstitial diffusion of Ti ions. In contrast to recent reports that attribute TiO2 band-gap narrowing to the synergistic action of oxygen vacancies and surface disorder of nonspecific origin, our results point to Ti2O3, which is a narrow-band-gap semiconductor. As a stoichiometric compound of the lower oxidation state Ti(3+) it is expected to be a more robust atomic structure than oxygen-deficient TiO2 for preserving and stabilizing Ti(3+) surface species that are the key to the enhanced photocatalytic activity of black TiO2.

We show here that the morphological pathway of spontaneous dewetting of ultrathin Ag films on SiO 2 under nanosecond laser melting is found to be film thickness dependent. For films with thickness h between 2 ≤ h ≤ 9.5 nm, the morphology during the intermediate stages of dewetting consisted of bicontinuous structures. For films 11.5 ≤ h ≤ 20 nm, the intermediate stages consisted of regularly-sized holes. Measurement of the characteristic length scales for different stages of dewetting as a function of film thickness showed a systematic increase, which is consistent with the spinodal dewetting instability over the entire thickness range investigated. This change in morphology with thickness is consistent with observations made previously for polymer films [A. Sharma et al, Phys. Rev. Lett., v81, pp3463 (1998); R. Seemann et al, J. Phys. Cond. Matt., v13, pp4925, (2001)]. Based on the behavior of free * Corresponding author, ramki@utk.edu 1 energy curvature that incorporates intermolecular forces, we have estimated the morphological transition thickness for the intermolecular forces for Ag on SiO 2 . The theory predictions agree well with observations for Ag. These results show that it is possible to form a variety of complex Ag nanomorphologies in a consistent manner, which could be useful in optical applications of Ag surfaces, such as in surface enhanced Raman sensing.

A long-standing objective in materials research is to effectively heal fabrication defects or to remove pre-existing or environmentally induced damage in materials. Silicon carbide (SiC) is a fascinating wide-band gap semiconductor for high-temperature, high-power and high-frequency applications. Its high corrosion and radiation resistance makes it a key refractory/structural material with great potential for extremely harsh radiation environments. Here we show that the energy transferred to the electron system of SiC by energetic ions via inelastic ionization can effectively anneal pre-existing defects and restore the structural order. The threshold determined for this recovery process reveals that it can be activated by 750 and 850 keV Si and C self-ions, respectively. The results conveyed here can contribute to SiC-based device fabrication by providing a room-temperature approach to repair atomic lattice structures, and to SiC performance prediction as either a functional material for device applications or a structural material for high-radiation environments.

While the interaction of energetic ions with solids is well known to result in inelastic energy loss to electrons and elastic energy loss to atomic nuclei in the solid, the coupled effects of these energy losses on defect production, nanostructure evolution and phase transformations in ionic and covalently bonded materials are complex and not well understood due to dependencies on electron-electron scattering processes, electron-phonon coupling, localized electronic excitations, diffusivity of charged defects, and solid-state radiolysis. Here we show that a colossal synergy occurs between inelastic energy loss and pre-existing atomic defects created by elastic energy loss in single crystal strontium titanate (SrTiO3), resulting in the formation of nanometer-sized amorphous tracks, but only in the narrow region with pre-existing defects. These defects locally decrease the electronic and atomic thermal conductivities and increase electron-phonon coupling, which locally increase the intensity of the thermal spike for each ion. This work identifies a major gap in understanding on the role of defects in electronic energy dissipation and electron-phonon coupling; it also provides insights for creating novel interfaces and nanostructures to functionalize thin film structures, including tunable electronic, ionic, magnetic and optical properties.

Reduced degradation (oxidation) of silver nanoparticles (NPs) is achieved by contacting Ag with immiscible Co NPs. The relative decay of the plasmon peak (plot) shows that pure Ag NPs (blue dashed curve) decay by 25% in ca 20 days, whereas AgCo NPs last about 10 times longer, requiring nearly five months for a similar decay (red solid curve). The TEM images for both Ag and AgCo were taken after 50 days of storage under ambient conditions.