Destabilization of Sn2+ 5s2 Lone-Pair States of SnO through Dimensional Crossover.

Materials exhibiting unique electronic properties arising from a characteristic crystal structure have physical properties that are sensitive to structural dimensionality. This study involves the destabilization of Sn 5s2 lone-pair states of SnO films by decreasing their structural dimensionality in the out-of-plane direction. The inherent dispersive band structure of the SnO films remained unchanged between 80 and 11 nm. Below 11 nm, their dispersive band structure disappeared, the O/Sn ratio increased, and the carrier type changed from the p type to the n type, whereas the Sn valency remained constant at +2. These unconventional changes arose from the electronic separation corresponding to the Debye length, which is proportional to permittivity, and were attributed to weakened interactions between Sn 5s2 lone-pair electrons. Therefore, designing low-permittivity materials is beneficial for reducing the crystallite size required for stabilizing lone-pair states. These results are essential for designing emergent p-type oxides and improving their semiconducting properties and performance in transparent or high-power electronics.

Semiconductor nanochannels in metallic carbon nanotubes by thermomechanical chirality alteration.

Carbon nanotubes have a helical structure wherein the chirality determines whether they are metallic or semiconducting. Using in situ transmission electron microscopy, we applied heating and mechanical strain to alter the local chirality and thereby control the electronic properties of individual single-wall carbon nanotubes. A transition trend toward a larger chiral angle region was observed and explained in terms of orientation-dependent dislocation formation energy. A controlled metal-to-semiconductor transition was realized to create nanotube transistors with a semiconducting nanotube channel covalently bonded between a metallic nanotube source and drain. Additionally, quantum transport at room temperature was demonstrated for the fabricated nanotube transistors with a channel length as short as 2.8 nanometers.

Electrical conduction and field emission of a single-crystalline GdB44Si2 nanowire.

The electronic transport and field emission properties of a single-crystalline GdB44Si2 nanowire are studied. The atomic structure and elemental composition of the GdB44Si2 nanowire are characterized by transmission electron microscopy (TEM) using atomic imaging, energy-dispersive X-ray spectroscopy (EDS), and electron energy-loss spectroscopic (EELS) mapping. The electrical conductivity of the single GdB44Si2 nanowire is in the range of 46.8-60.1 S m-1. The in situ TEM field emission measurement reveals that it has a low work function of 2.4 eV. To realize a converged electron emission, a field evaporation pretreatment was used to clean the emission surface and to make a sharpened tip. The field emission probe measurement results show that the electron emission from the sharp GdB44Si2 nanowire is converged to a single field emission spot and it has a work function of 2.6 eV which is in agreement with the in situ TEM measurement. The stability of field emission current is also very good with a fluctuation of 1.4% in 20 min. With a low work function and stable emission current, the GdB44Si2 nanowire shows great promise for field emission applications.

Emerging Atomic Energy Levels in Zero-Dimensional Silicon Quantum Dots.

Driven by the emergence of colloidal semiconductor quantum dots (QDs) of tunable emission wavelengths, characteristic of exciton absorption peaks, outstanding photostability and solution processability in device fabrication have become a key tool in the development of nanomedicine and optoelectronics. Diamond cubic crystalline silicon (Si) QDs, with a diameter larger than 2 nm, terminated with hydrogen atoms are known to exhibit bulk-inherited spin and valley properties. Herein, we demonstrate a newly discovered size region of Si QDs, in which a fast radiative recombination on the order of hundreds of picoseconds is responsible for photoluminescence (PL). Despite retaining a crystallographic structure like the bulk, controlling their diameters in the 1.1-1.7 nm range realizes the strong PL with continuous spectral tunability in the 530-580 nm window, the narrow spectral line widths without emission tails, and the fast relaxation of photogenerated carriers. In contrast, QDs with diameters greater than 1.8 nm display the decay times on the microsecond order as well as the previous Si QDs. In addition to the five-orders-of-magnitude variation in the PL decay time, a systematic study on the temperature dependence of PL properties suggests that the energy structure of the smaller QDs does not retain an indirect band gap character. It is discussed that a 1.7 nm diameter is critical to undergo changes in energy structure from bulky to molecular configurations.

Chirality transitions and transport properties of individual few-walled carbon nanotubes as revealed by in situ TEM probing.

Physical properties of carbon nanotubes (CNTs) are closely related to the atomic structure, i.e. the chirality. It is highly desirable to develop a technique to modify their chirality and control the resultant transport properties. Herein, we present an in situ transmission electron microscopy (TEM) probing method to monitor the chirality transition and transport properties of individual few-walled CNTs. The changes of tube structure including the chirality are stimulated by programmed bias pulses and associated Joule heating. The chirality change of each shell is analyzed by nanobeam electron diffraction. Supported by molecular dynamics simulations, a preferred chirality transition path is identified, consistent with the Stone-Wales defect formation and dislocation sliding mechanism. The electronic transport properties are measured along with the structural changes, via fabricating transistors using the individual nanotubes as the suspended channels. Metal-to-semiconductor transitions are observed along with the chirality changes as confirmed by both the electron diffraction and electrical measurements. Apart from providing an alternative route to control the chirality of CNTs, the present work demonstrates the rare possibility of obtaining the dynamic structure-properties relationships at the atomic and molecular levels.

Graphene composites with dental and biomedical applicability.

Pure graphene in the form of few-layer graphene (FLG) - 1 to 6 layers - is biocompatible and non-cytotoxic. This makes FLG an ideal material to incorporate into dental polymers to increase their strength and durability. It is well known that graphene has high mechanical strength and has been shown to enhance the mechanical, physical and chemical properties of biomaterials. However, for commercial applicability, methods to produce larger than lab-scale quantities of graphene are required. Here, we present a simple method to make large quantities of FLG starting with commercially available multi-layer graphene (MLG). This FLG material was then used to fabricate graphene dental-polymer composites. The resultant graphene-modified composites show that low concentrations of graphene (ca. 0.2 wt %) lead to enhanced performance improvement in physio-mechanical properties - the mean compressive strength increased by 27% and the mean compressive modulus increased by 22%. Herein we report a new, cheap and simple method to make large quantities of few-layer graphene which was then incorporated into a common dental polymer to fabricate graphene-composites which shows very promising mechanical properties.

Fabrication and characterization of branched carbon nanostructures.

Carbon nanotubes (CNTs) have atomically smooth surfaces and tend not to form covalent bonds with composite matrix materials. Thus, it is the magnitude of the CNT/fiber interfacial strength that limits the amount of nanomechanical interlocking when using conventional CNTs to improve the structural behavior of composite materials through reinforcement. This arises from two well-known, long standing problems in this research field: (a) inhomogeneous dispersion of the filler, which can lead to aggregation and (b) insufficient reinforcement arising from bonding interactions between the filler and the matrix. These dispersion and reinforcement issues could be addressed by using branched multiwalled carbon nanotubes (b-MWCNTs) as it is known that branched fibers can greatly enhance interfacial bonding and dispersability. Therefore, the use of b-MWCNTs would lead to improved mechanical performance and, in the case of conductive composites, improved electrical performance if the CNT filler was better dispersed and connected. This will provide major benefits to the existing commercial application of CNT-reinforced composites in electrostatic discharge materials (ESD): There would be also potential usage for energy conversion, e.g., in supercapacitors, solar cells and Li-ion batteries. However, the limited availability of b-MWCNTs has, to date, restricted their use in such technological applications. Herein, we report an inexpensive and simple method to fabricate large amounts of branched-MWCNTs, which opens the door to a multitude of possible applications.

Origin of the Photoluminescence Quantum Yields Enhanced by Alkane-Termination of Freestanding Silicon Nanocrystals: Temperature-Dependence of Optical Properties.

On the basis of the systematic study on temperature dependence of photoluminescence (PL) properties along with relaxation dynamics we revise a long-accepted mechanism for enhancing absolute PL quantum yields (QYs) of freestanding silicon nanocrystals (ncSi). A hydrogen-terminated ncSi (ncSi:H) of 2.1 nm was prepared by thermal disproportination of (HSiO1.5)n, followed by hydrofluoric etching. Room-temperature PL QY of the ncSi:H increased twentyfold only by hydrosilylation of 1-octadecene (ncSi-OD). A combination of PL spectroscopic measurement from cryogenic to room temperature with structural characterization allows us to link the enhanced PL QYs with the notable difference in surface structure between the ncSi:H and the ncSi-OD. The hydride-terminated surface suffers from the presence of a large amount of nonradiative relaxation channels whereas the passivation with alkyl monolayers suppresses the creation of the nonradiative relaxation channels to yield the high PL QY.

Control of the spatial distribution and crystal orientation of self-organized Au nanoparticles.

Ordered, two-dimensional, self-organized Au nanoparticles were fabricated using radiofrequency (RF) magnetron sputtering. The particles were uniformly spherical in shape and ultrafine in size (3-7 nm) and showed an ultrahigh density in the order of ∼10(12) inch(-2). A custom-developed sputtering apparatus that employs low sputtering power density and a minimized sputtering time (1 min) was used to markedly simplify the preparation conditions for Au nanoparticle fabrication. The spatial distribution of Au nanoparticles was rigorously controlled by placing a Ta interfacial layer between the Au nanoparticles and substrate as well as by post-annealing samples in an Ar atmosphere after the formation of Au nanoparticles. The interfacial layer and the post-annealing step caused approximately 40% of the Au nanoparticles on the substrate surface to orient in the (111) direction. This method was shown to produce ultrafine Au nanoparticles showing an ultrahigh surface density. The crystal orientation of the nanoparticles can be precisely controlled with respect to the substrate surface. Therefore, this technique promises to deliver tunable nanostructures for applications in the field of high-performance electronic devices.

Synthesis, crystal structure, and electronic properties of high-pressure PdF2-type oxides MO2 (M = Ru, Rh, Os, Ir, Pt).

The polycrystalline MO2's (HP-PdF2-type MO2, M = Rh, Os, Pt) with high-pressure PdF2 compounds were successfully synthesized under high-pressure conditions for the first time, to the best of our knowledge. The crystal structures and electromagnetic properties were studied. Previously unreported electronic properties of the polycrystalline HP-PdF2-type RuO2 and IrO2 were also studied. The refined structures clearly indicated that all compounds crystallized into the HP-PdF2-type structure, M(4+)O(2-)2, rather than the pyrite-type structure, M(n+)(O2)(n-) (n < 4). The MO2 compounds (M = Ru, Rh, Os, Ir) exhibited metallic conduction, while PtO2 was highly insulating, probably because of the fully occupied t2g band. Neither superconductivity nor a magnetic transition was detected down to a temperature of 2 K, unlike the case of 3d transition metal chalcogenide pyrites.

In situ TEM observation of a microcrucible mechanism of nanowire growth.

The growth of metal oxide nanowires can proceed via a number of mechanisms such as screw dislocation, vapor-liquid-solid process, or seeded growth. Transmission electron microscopy (TEM) can resolve nanowires but invariably lacks the facility for direct observation of how nanowires form. We used a transmission electron microscope equipped with an in situ heating stage to follow the growth of quaternary metal oxide nanowires. Video-rate imaging revealed barium carbonate nanoparticles diffusing through a porous matrix containing copper and yttrium oxides to subsequently act as catalytic sites for the outgrowth of Y2BaCuO5 nanowires on reaching the surface. The results suggest that sites on the rough surface of the porous matrix act as microcrucibles and thus provide insights into the mechanisms that drive metal oxide nanowire growth at high temperatures.

Synthesis of highly strained mesostructured SrTiO(3)/BaTiO(3) composite films with robust ferroelectricity.

A new class of highly stable ferroelectric material, that is, a mesostructured SrTiO(3)/BaTiO(3) composite film, obtained by a surfactant-templated sol-gel method is reported. Due to the concave surface geometry and abundant hetero-interface between SrTiO(3) (ST) and BaTiO(3) (BT) phases, a large number of strains can be created in the composite film, thereby leading to dramatic enhancement of ferroelectric property (see scheme).

Synthesis of MoO3 nanotubes by thermal mesostructural transition of spherical triblock copolymer micelle templates.

Here we report a new method of synthesizing one-dimensional metal oxide nanotubes (MoO(3)) via thermal mesostructural transition of spherical micelle templates. This nanotube formation is realized by entanglement of adjacent spherical core-shell nanoparticles templated from block copolymer micelles.

Electrochemical design of mesoporous Pt-Ru alloy films with various compositions toward superior electrocatalytic performance.

Mesoporous Pt-Ru alloy films with various compositions were synthesized by electrochemical plating in an aqueous surfactant solution. After the removal of surfactants, continuous mesoporous Pt-Ru alloy films possessing uniform mesopores with diameter about 7 nm were obtained. The Ru content in the films could be controlled from 0 to 13 at % by changing the precursor compositions. For all the films, the mesostructural periodicities and the mesopore sizes in the films were not changed. Due to the mesoporous structure and the doped Ru content, our mesoporous Pt-Ru films showed superior electrocatalytic activity for methanol oxidation reaction in comparison with the commercially available Pt catalyst.

Fullerene/cobalt porphyrin hybrid nanosheets with ambipolar charge transporting characteristics.

A novel supramolecular nanoarchitecture, comprising C(60)/Co porphyrin nanosheets, was prepared by a simple liquid-liquid interfacial precipitation method and fully characterized by means of optical microscopy, AFM, STEM, TEM, and XRD. It is established that the highly crystalline C(60)/Co porphyrin nanosheets have a simple (1:1) stoichiometry, and when incorporated in bottom-gate, bottom-contact field-effect transistors (FETs), they show ambipolar charge transport characteristics.

Electrochemical synthesis of mesoporous Pt-Au binary alloys with tunable compositions for enhancement of electrochemical performance.

Mesoporous Pt-Au binary alloys were electrochemically synthesized from lyotropic liquid crystals (LLCs) containing corresponding metal species. Two-dimensional exagonally ordered LLC templates were prepared on conductive substrates from diluted surfactant solutions including water, a nonionic surfactant, ethanol, and metal species by drop-coating. Electrochemical synthesis using such LLC templates enabled the preparation of ordered mesoporous Pt-Au binary alloys without phase segregation. The framework composition in the mesoporous Pt-Au alloy was controlled simply by changing the compositional ratios in the precursor solution. Mesoporous Pt-Au alloys with low Au content exhibited well-ordered 2D hexagonal mesostructures, reflecting those of the original templates. With increasing Au content, however, the mesostructural order gradually decreased, thereby reducing the electrochemically active surface area. Wide-angle X-ray diffraction profiles, X-ray photoelectron spectra, and elemental mapping showed that both Pt and Au were atomically distributed in the frameworks. The electrochemical stability of mesoporous Pt-Au alloys toward methanol oxidation was highly improved relative to that of nonporous Pt and mesoporous Pt films, suggesting that mesoporous Pt-Au alloy films are potentially applicable as electrocatalysts for direct methanol fuel cells. Also, mesoporous Pt-Au alloy electrodes showed a highly sensitive amperometric response for glucose molecules, which will be useful in next-generation enzyme-free glucose sensors.

Synthesis of olive-shaped mesoporous platinum nanoparticles (MPNs) with a hard-templating method using mesoporous silica (SBA-15).

Well-ordered mesoporous Pt nanoparticles (MPNs) with uniform olive shapes are synthesized by using two-dimensional (2D) hexagonal mesoporous silica (SBA-15) as a hard template. The average particle sizes are controllable in the range of 150 to 230 nm by changing the reduction time. Low-angle XRD profiles for the obtained MPNs show three distinct peaks assignable to the (10), (11), and (20) planes of a highly ordered 2D hexagonal symmetry. From high-magnification SEM images, periodically arranged Pt nanowires are observed clearly, which are a negative replica of the 2D hexagonally ordered mesoporous silica (SBA-15). Furthermore, the single crystallinity of the Pt fcc structure coherently extends over the whole particles. As a result of such unique character as well as high surface area, the obtained MPNs show distinctly enhanced electrocatalytic properties for methanol oxidation reaction compared to other Pt samples, such as Pt black.

Synthesis of continuous mesoporous Ga-doped titania films with anatase crystallized framework.

Here we report synthesis of ordered mesoporous titania films with various amounts of Ga content. The influence of Ga contents on mesostructural ordering, surface morphology, thermal stability, and anatase crystallinity is carefully investigated, by using grazing incidence small angle X-ray scattering (GISAXS), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), and Raman spectroscopy. The presence of highly dispersed Ga contents in the titania frameworks can promote the thermal stability of mesoporous titania structures, resulting that the anatase crystallization successfully proceeds without collapse of mesostructures.