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Register a new userStrong shape dependence of the Morin transition in alpha-Fe2O3 single-crystalline nanostructures
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Single-crystalline alpha-Fe2O3 nanorings (short nanotubes) and nanotubes were synthesized by a hydrothermal method. High-resolution transmission electron microscope and selected-area electron diffraction confirm that the axial directions of both nanorings and nanotubes are parallel to the crystalline c-axis. What is intriguing is that the Morin transition occurs at about 210 K in the short nanotubes with a mean tube length of about 115 nm and a mean outer diameter of 169 nm while it disappears in the nanotubes with a mean tube length of about 317 nm and a mean outer diameter of 148 nm. Detailed analyses of magnetization data, x-ray diffraction spectra, and room-temperature Mossbauer spectra demonstrate that this very strong shape dependence of the Morin transition is intrinsic to hematite. We can quantitatively explain this intriguing shape dependence in terms of opposite signs of the surface magnetic anisotropy constants in the surface planes parallel and perpendicular to the c-axis (that is, K_parallel = -0.37 erg/cm^2 and K_perp = 0.42 erg/cm^{2}).
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The production of hydrogen from water using only a catalyst and solar energy is one of the most challenging and promising outlets for the generation of clean and renewable energy. Semiconductor photocatalysts for solar hydrogen production by water photolysis must employ stable, non-toxic, abundant and inexpensive visible-light absorbers capable of harvesting light photons with adequate potential to reduce water. Here, we show that a-Fe2O3 can meet these requirements by means of using hydrothermally prepared nanorings. These iron oxide nanoring photocatalysts proved capable of producing hydrogen efficiently without application of an external bias. In addition, Co(OH)2 nanoparticles were shown to be efficient co-catalysts on the nanoring surface by improving the efficiency of hydrogen generation. Both nanoparticle-coated and uncoated nanorings displayed superior photocatalytic activity for hydrogen evolution when compared with TiO2 nanoparticles, showing themselves to be promising materials for water-splitting using only solar light.
Electrochemical oxidation of hematite ({alpha}-Fe2O3) nano-particulate films at 600 mV vs. Ag+/AgCl reference in KOH electrolyte forms a species at the hematite surface which causes a new transition in the upper Hubbard band between the Fe(3d)-O(2p) state region and the Fe(4sp)-O(2p) region, as evidenced by oxygen near edge x-ray absorption fine structure (NEXAFS) spectra. The electrochemical origin of this transition suggests that it is related with a surface state. This transition, not known for pristine {alpha}-Fe2O3 is at about the same x-ray energy, where pristine 1% Si doped Si:Fe2O3 has such transition. Occurrence of this state coincides with the onset of an oxidative dark current wave at around 535 mV - a potential range, where the tunneling exchange current has been previously reported to increase by three orders of magnitude with the valence band and the transfer coefficient by a factor of 10. Oxidation to only 200 mV does not form such extra NEXAFS feature, supporting that a critical electrochemical potential between 200 and 600 mV is necessary to change the electronic structure of the iron oxide at the surface. Decrease of the surface roughness, as suggested by visual inspection, profilometry and x-ray reflectivity, points to faceting as potential structural origin of the surface state.
We determined frictional figures of merit for a pair of layered honeycomb nanostructures, such as graphane, fluorographene, MoS$_2$ and WO$_2$ moving over each other, by carrying out ab-initio calculations of interlayer interaction under constant loading force. Using Prandtl-Tomlinson model we derived critical stiffness required to avoid stick-slip behavior. We showed that these layered structures have low critical stiffness even under high loading forces due to their charged surfaces repelling each other. The intrinsic stiffness of these materials exceed critical stiffness and thereby avoid the stick-slip regime and attain nearly dissipationless continuous sliding. Remarkably, tungsten dioxide displays much better performance relative to others and heralds a potential superlubricant. The absence of mechanical instabilities leading to conservative lateral forces is also confirmed directly by the simulations of sliding layers.
Deep subwavelength integration of high-definition plasmonic nanostructures is of key importance for the development of future optical nanocircuitry for high-speed communication, quantum computation and lab-on-a-chip applications. So far the experimental realization of proposed extended plasmonic networks consisting of multiple functional elements remains challenging, mainly due to the multi-crystallinity of commonly used thermally evaporated gold layers. Resulting structural imperfections in individual circuit elements will drastically reduce the yield of functional integrated nanocircuits. Here we demonstrate the use of very large (>100 micron^2) but thin (<80 nm) chemically grown single-crystalline gold flakes, which, after immobilization, serve as an ideal basis for focused-ion beam milling and other top-down nanofabrication techniques on any desired substrate. Using this methodology we obtain high-definition ultrasmooth gold nanostructures with superior optical properties and reproducible nano-sized features over micrometer length scales. Our approach provides a possible solution to overcome the current fabrication bottleneck and to realize high-definition plasmonic nanocircuitry.
Single GaN nanowires formed spontaneously on a given substrate represent nanoscopic single crystals free of any extended defects. However, due to the high area density of thus formed GaN nanowire ensembles, individual nanowires coalesce with others in their immediate vicinity. This coalescence process may introduce strain and structural defects, foiling the idea of defect-free material due to the nanowire geometry. To investigate the consequences of this process, a quantitative measure of the coalescence of nanowire ensembles is required. We derive objective criteria to determine the coalescence degree of GaN nanowire ensembles. These criteria are based on the area-perimeter relationship of the cross-sectional shapes observed, and in particular on their circularity. Employing these criteria, we distinguish single nanowires from coalesced aggregates in an ensemble, determine the diameter distribution of both, and finally analyze the coalescence degree of nanowire ensembles with increasing fill factor.
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