Role of Vacancy Condensation in the Formation of Voids in Rutile TiO₂ Nanowires

Titanium dioxide nanowire (NW) arrays are incorporated in many devices for energy conversion, energy storage, and catalysis. A common approach to fabricate these NWs is based on hydrothermal synthesis strategies. A drawback of this low-temperature method is that the NWs have a high density of defects, such as stacking faults, dislocations, and oxygen vacancies. These defects compromise the performance of devices. Here, we report a postgrowth thermal annealing procedure to remove these lattice defects and propose a mechanism to explain the underlying changes in the structure of the NWs. A detailed transmission electron microscopy study including in situ observation at elevated temperatures reveals a two-stage process. Additional spectroscopic analyses and X-ray diffraction experiments clarify the underlying mechanisms. In an early, low-temperature stage, the as-grown mesocrystalline NW converts to a single crystal by the dehydration of surface-bound OH groups. At temperatures above 500 °C, condensation of oxygen vacancies takes place, which leads to the fabrication of NWs with internal voids. These voids are faceted and covered with Ti³⁺-rich amorphous TiO_<i>x</i>

Activation and Fluoride-Assisted Phosphating of Aluminum-Silicon-Coated Steel

Phosphating is a crucial process in the corrosion protection of metals. Here, activation and fluoride-assisted tricationic phosphating is investigated on aluminum–silicon (AS) coated steel surfaces. Dynamic light scattering results from the activation bath show a bimodal size distribution, with hydrodynamic radii of ∼400 nm and ∼10 μm. For the smaller particle fraction, static light scattering results are consistent with the interpretation of disklike particles as scattering objects. Particles of the larger fraction sediment with time. In the presence of electrolyte, the scattering intensity from the larger particle fraction increases. Coagulation with time is suggested to be related to the decrease in activity of the activation bath. Scanning Auger microscopy (SAM) shows a higher phosphorus concentration after titanium phosphate activation in the Al-rich areas compared to the Si-rich areas of the AS coatings. There is no correlation between the size of the species in the activation bath, and the size of the phosphate-containing regions on the activated surface. Phosphating was performed in the presence of hexafluorosilicic acid, H₂SiF₆, ammonium hydrogen difluoride, NH₄HF₂, and both, at an initial pH of 2.5. The absence of crystals after phosphating with H₂SiF₆ is an indication that SiF₆^2– is the final product of the oxide dissolution in the presence of fluoride. In the presence of NH₄HF₂, the Si-rich regions of the surface are phosphated before the Si-poor (Al-rich) regions. Hence, the phosphate distribution after activation and after phosphating are opposite. These results show that a high surface concentration of phosphate after activation is not sufficient for a high coverage with phosphate crystals after phosphating

Low-Copy Number Protein Detection by Electrode Nanogap-Enabled Dielectrophoretic Trapping for Surface-Enhanced Raman Spectroscopy and Electronic Measurements

We report a versatile analysis platform, based on a set of nanogap electrodes, for the manipulation and sensing of biomolecules, as demonstrated here for low-copy number protein detection. An array of Ti nanogap electrode with sub-10 nm gap size function as templates for alternating current dielectrophoresis-based molecular trapping, hot spots for surface-enhanced Raman spectroscopy as well as electronic measurements, and fluorescence imaging. During molecular trapping, recorded Raman spectra, conductance measurements across the nanogaps, and fluorescence imaging show unambiguously the presence and characteristics of the trapped proteins. Our platform opens up a simple way for multifunctional low-concentration heterogeneous sample analysis without the need for target preconcentration