Controlling Surface Structure and Primary Particle Size to Enhance Performance and Reduce Gas Evolution in Lithium- and Manganese-Rich Layered Oxide Cathodes.

Practical application of lithium- and manganese-rich layered oxide cathodes has been hindered despite their high performance and low cost owing to high gas evolution accompanying capacity loss even in a conservative voltage window. Here, we control the surface structure and primary particle size of lithium- and manganese-rich layered oxide cathodes not only to enhance the electrochemical performance but also to reduce gas evolution. Sulfur-coated Fm3̅m/R3̅m double reduced surface layers and Mo doping dramatically reduce gas evolution, which entails the improvement of electrochemical performance. With the optimization, we prove that it is competitive enough to conventional high-nickel cathodes in the aspects of gas evolution as well as electrochemical performance in the conservative voltage window of 2.5-4.4 V. Our findings provide invaluable insights on the improvement of electrochemical performance and gas evolution properties in lithium- and manganese-rich layered oxide cathodes.

Heterointerface Effect on Two-Step Nucleation Mechanism of Bi Particles.

The nucleation and crystallization of Bi particles on two matrices, crystalline bismuth sulfide (c-Bi2S3) and amorphized bismuth titanium oxide (a-Bi12TiO20), were studied by using in situ transmission electron microscopy (TEM) analysis. The atomic structures of the Bi particles were monitored by acquiring high-resolution TEM images in real time. The Bi particles were grown on c-Bi2S3 and a-Bi12TiO20 via a two-step nucleation mechanism; dense liquid clusters were clearly observed at the initial stage of nucleation, and the coalescence of clusters was frequently observed during the growth. However, the nucleation and crystallization behaviors of Bi particles were governed by the matrix; in particular, the evolution of their morphology and atomic structure was confined on c-Bi2S3 but free from matrix effects on a-Bi12TiO20. The matrix effect on the two-step nucleation mechanism was demonstrated from a thermodynamic point of view.

Metallic line defect in wide-bandgap transparent perovskite BaSnO3.

A line defect with metallic characteristics has been found in optically transparent BaSnO3 perovskite thin films. The distinct atomic structure of the defect core, composed of Sn and O atoms, was visualized by atomic-resolution scanning transmission electron microscopy (STEM). When doped with La, dopants that replace Ba atoms preferentially segregate to specific crystallographic sites adjacent to the line defect. The electronic structure of the line defect probed in STEM with electron energy-loss spectroscopy was supported by ab initio theory, which indicates the presence of Fermi level-crossing electronic bands that originate from defect core atoms. These metallic line defects also act as electron sinks attracting additional negative charges in these wide-bandgap BaSnO3 films.

STEM beam channeling in BaSnO3/LaAlO3 perovskite bilayers and visualization of 2D misfit dislocation network.

A study of the STEM probe channeling in a heterostructured crystalline bilayer specimens is presented here with a goal to guide STEM-based characterization of multilayer structures. STEM analysis of perovskite BaSnO3/LaAlO3 bilayers is performed and the dominating effects of beam channeling on HAADF- and LAADF-STEM are illustrated. To study the electron beam channeling through BaSnO3/LaAlO3 bilayers, probe intensity depth profiles are calculated, and the effects of probe defocus and atomic column alignment are discussed. Characteristics of the beam channeling are correlated to resulting ADF-STEM images, which is then tested by comparing focal series of plan-view HAADF-STEM images to those recorded experimentally. Additionally, discussions on how to visualize the misfit dislocation network at the BaSnO3/LaAlO3 interface using HAADF- and LAADF-STEM images are provided.

Subatomic Channeling and Helicon-Type Beams in SrTiO_{3}.

Inspired by recent experimental subatomic measurements using analytical aberration-corrected scanning transmission electron microscopes, we study electron probe propagation in crystalline SrTiO_{3} at the subatomic length scale. Here, we report the existence of subatomic channeling and the formation of a helicon-type beam at this scale. The results of beam propagation simulations, which are performed at various crystal temperatures, STEM probe convergence angles (10-50 mrad), and beam energies (80-300 keV), showed that reducing the ambient temperature can enhance the subatomic channeling and STEM probe parameters can be used to control the features of helicon-type beams.

Microstructure characterization of BaSnO3 thin films on LaAlO3 and PrScO3 substrates from transmission electron microscopy.

Detailed microstructure analysis of epitaxial thin films is a vital step towards understanding essential structure-property relationships. Here, a combination of transmission electron microscopy (TEM) techniques is utilized to determine in detail the microstructure of epitaxial La-doped BaSnO3 films grown on two different perovskite substrates: LaAlO3 and PrScO3. These BaSnO3 films are of high current interest due to outstanding electron mobility at ambient. The rotational disorder of low-angle grain boundaries, namely the in-plane twist and out-of-plane tilt, is visualized by conventional TEM under a two-beam condition, and the degree of twists in grains of such films is quantified by selected-area electron diffraction. The investigation of the atomic arrangement near the film-substrate interfaces, using high-resolution annular dark-field scanning TEM imaging, reveals that edge dislocations with a Burgers vector along [001] result in the out-of-plane tilt. It is shown that such TEM-based analyses provide detailed information about the microstructure of the films, which, when combined with complimentary high-resolution X-ray diffraction, yields a complete structural characterization of the films. In particular, stark differences in out-of-plane tilt on the two substrates are shown to result from differences in misfit dislocation densities at the interface, explaining a puzzling observation from X-ray diffraction.

A New Line Defect in NdTiO3 Perovskite.

Perovskite oxides form an eclectic class of materials owing to their structural flexibility in accommodating cations of different sizes and valences. They host well-known point and planar defects, but so far no line defect has been identified other than dislocations. Using analytical scanning transmission electron microscopy (STEM) and ab initio calculations, we have detected and characterized the atomic and electronic structures of a novel line defect in NdTiO3 perovskite. It appears in STEM images as a perovskite cell rotated by 45°. It consists of self-organized Ti-O vacancy lines replaced by Nd columns surrounding a central Ti-O octahedral chain containing Ti4+ ions, as opposed to Ti3+ in the host. The distinct Ti valence in this line defect introduces the possibility of engineering exotic conducting properties in a single preferred direction and tailoring novel desirable functionalities in this Mott insulator.

Improving Signal-to-Noise Ratio in Scanning Transmission Electron Microscopy Energy-Dispersive X-Ray (STEM-EDX) Spectrum Images Using Single-Atomic-Column Cross-Correlation Averaging.

Acquiring an atomic-resolution compositional map of crystalline specimens has become routine practice, thus opening possibilities for extracting subatomic information from such maps. A key challenge for achieving subatomic precision is the improvement of signal-to-noise ratio (SNR) of compositional maps. Here, we report a simple and reliable solution for achieving high-SNR energy-dispersive X-ray (EDX) spectroscopy spectrum images for individual atomic columns. The method is based on standard cross-correlation aided by averaging of single-column EDX maps with modifications in the reference image. It produces EDX maps with minimal specimen drift, beam drift, and scan distortions. Step-by-step procedures to determine a self-consistent reference map with a discussion on the reliability, stability, and limitations of the method are presented here.

Direct observation of the core/double-shell architecture of intense dual-mode luminescent tetragonal bipyramidal nanophosphors.

Highly efficient downconversion (DC) green-emitting LiYF4:Ce,Tb nanophosphors have been synthesized for bright dual-mode upconversion (UC) and DC green-emitting core/double-shell (C/D-S) nanophosphors-Li(Gd,Y)F4:Yb(18%),Er(2%)/LiYF4:Ce(15%),Tb(15%)/LiYF4-and the C/D-S structure has been proved by extensive scanning transmission electron microscopy (STEM) analysis. Colloidal LiYF4:Ce,Tb nanophosphors with a tetragonal bipyramidal shape are synthesized for the first time and they show intense DC green light via energy transfer from Ce(3+) to Tb(3+) under illumination with ultraviolet (UV) light. The LiYF4:Ce,Tb nanophosphors show 65 times higher photoluminescence intensity than LiYF4:Tb nanophosphors under illumination with UV light and the LiYF4:Ce,Tb is adapted into a luminescent shell of the tetragonal bipyramidal C/D-S nanophosphors. The formation of the DC shell on the core significantly enhances UC luminescence from the UC core under irradiation of near infrared light and concurrently generates DC luminescence from the core/shell nanophosphors under UV light. Coating with an inert inorganic shell further enhances the UC-DC dual-mode luminescence by suppressing the surface quenching effect. The C/D-S nanophosphors show 3.8% UC quantum efficiency (QE) at 239 W cm(-2) and 73.0 ± 0.1% DC QE. The designed C/D-S architecture in tetragonal bipyramidal nanophosphors is rigorously verified by an energy dispersive X-ray spectroscopy (EDX) analysis, with the assistance of line profile simulation, using an aberration-corrected scanning transmission electron microscope equipped with a high-efficiency EDX. The feasibility of these C/D-S nanophosphors for transparent display devices is also considered.

Giant Spin Pumping and Inverse Spin Hall Effect in the Presence of Surface and Bulk Spin-Orbit Coupling of Topological Insulator Bi2Se3.

Three-dimensional (3D) topological insulators are known for their strong spin-orbit coupling (SOC) and the existence of spin-textured surface states that might be potentially exploited for "topological spintronics." Here, we use spin pumping and the inverse spin Hall effect to demonstrate successful spin injection at room temperature from a metallic ferromagnet (CoFeB) into the prototypical 3D topological insulator Bi2Se3. The spin pumping process, driven by the magnetization dynamics of the metallic ferromagnet, introduces a spin current into the topological insulator layer, resulting in a broadening of the ferromagnetic resonance (FMR) line width. Theoretical modeling of spin pumping through the surface of Bi2Se3, as well as of the measured angular dependence of spin-charge conversion signal, suggests that pumped spin current is first greatly enhanced by the surface SOC and then converted into a dc-voltage signal primarily by the inverse spin Hall effect due to SOC of the bulk of Bi2Se3. We find that the FMR line width broadens significantly (more than a factor of 5) and we deduce a spin Hall angle as large as 0.43 in the Bi2Se3 layer.

Facile synthesis of intense green light emitting LiGdF4:Yb,Er-based upconversion bipyramidal nanocrystals and their polymer composites.

A pathway for achieving intense green light emitting LiGdF4:Yb,Er upconversion nanophosphors (UCNPs) via Y(3+) doping is demonstrated. It was revealed that Y(3+) doping initiated the formation of a tetragonal phase and affected the particle size. Single tetragonal-phase LiGd0.4Y0.4F4:Yb(18%),Er(2%) (LGY0.4F:Yb,Er) UCNPs exhibited strong upconversion (UC) green luminescence and tetragonal bipyramidal morphologies. They showed 1325 and 325-fold higher photoluminescence intensity than the 0 and 80 mol% Y(3+)-doped LiGdF4:Yb,Er UCNPs, respectively. Additionally the particle size (edge length) of LiGdF4:Yb,Er-based upconversion tetragonal bipyramids (UCTBs) was controlled from 60.5 nm to an ultrasmall size of 9.3 nm with varying Y(3+) doping concentration. In an LGY0.4F:Yb,Er UCTB, uniform distribution of all constituent elements was directly confirmed by using high-angle annular dark-field scanning transmission electron microscopy and energy-filtered transmission electron microscopy (EFTEM) image analyses. In particular, existence of activator Er(3+) ions with extremely small quantity was clearly seen over a particle on the EFTEM image. Moreover, the LGY0.4F:Yb,Er UCTBs were successfully incorporated into the polydimethylsiloxane (PDMS) polymer and the highly transparent UCTB-PDMS composites showed bright green light under the excitation of 980 nm infrared light.

Disproportionation of (Mg,Fe)SiO3 perovskite in Earth's deep lower mantle.

The mineralogical constitution of the Earth's mantle dictates the geophysical and geochemical properties of this region. Previous models of a perovskite-dominant lower mantle have been built on the assumption that the entire lower mantle down to the top of the D″ layer contains ferromagnesian silicate [(Mg,Fe)SiO3] with nominally 10 mole percent Fe. On the basis of experiments in laser-heated diamond anvil cells, at pressures of 95 to 101 gigapascals and temperatures of 2200 to 2400 kelvin, we found that such perovskite is unstable; it loses its Fe and disproportionates to a nearly Fe-free MgSiO3 perovskite phase and an Fe-rich phase with a hexagonal structure. This observation has implications for enigmatic seismic features beyond ~2000 kilometers depth and suggests that the lower mantle may contain previously unidentified major phases.

Observation of electrically-inactive interstitials in Nb-doped SrTiO3.

Despite rapid recent progress, controlled dopant incorporation and attainment of high mobility in thin films of the prototypical complex oxide semiconductor SrTiO3 remain problematic. Here, analytical scanning transmission electron microscopy is used to study the local atomic and electronic structure of Nb-doped SrTiO3 both in ideally substitutionally doped bulk single crystals and epitaxial thin films. The films are deposited under conditions that would yield highly stoichiometric undoped SrTiO3, but are nevertheless insulating. The Nb incorporation in such films was found to be highly inhomogeneous on nanoscopic length-scales, with large quantities of what we deduce to be interstitial Nb. Electron energy loss spectroscopy reveals changes in the electronic density of states in Nb-doped SrTiO3 films compared to undoped SrTiO3, but without the clear shift in the Fermi edge seen in bulk single crystal Nb-doped SrTiO3. Analysis of atomic-resolution annular dark-field images allows us to conclude that the interstitial Nb is in the Nb(0) state, confirming that it is electrically inactive. We argue that this approach should enable future work establishing the vitally needed relationships between synthesis/processing conditions and electronic properties of Nb-doped SrTiO3 thin films.

Phosphorus-doped silicon nanocrystals exhibiting mid-infrared localized surface plasmon resonance.

Localized surface plasmon resonances (LSPRs) enable tailoring of the optical response of nanomaterials through their free carrier concentration, morphology, and dielectric environment. Recent efforts to expand the spectral range of usable LSPR frequencies into the infrared successfully demonstrated LSPRs in doped semiconductor nanocrystals. Despite silicon's importance for electronic and photonic applications, no LSPRs have been reported for doped silicon nanocrystals. Here we demonstrate doped silicon nanocrystals synthesized via a nonthermal plasma technique that exhibits tunable LSPRs in the energy range of 0.07-0.3 eV or mid-infrared wavenumbers of 600-2500 cm(-1).

Electron holography of magnetic field generated by a magnetic recording head.

The magnetic field generated by a magnetic recording head is evaluated using electron holography. A magnetic recording head, which is connected to an electric current source, is set on the specimen holder of a transmission electron microscope. Reconstructed phase images of the region around the magnetic pole show the change in the magnetic field distribution corresponding to the electric current applied to the coil of the head. A simulation of the magnetic field, which is conducted using the finite element method, reveals good agreement with the experimental observations.

Electron holography study of remanence states in exchange-biased MnPd/Fe bilayers grown epitaxially on MgO(001).

We investigated magnetic remanence states of epitaxially grown, exchange-biased MnPd/Fe bilayers by electron holography emphasizing the crystallographic orientations of the layers. Thin-foil transmission electron microscopy (TEM) specimens were carefully prepared along both hard and easy axes of the Fe layer. The ex situ magnetization-reversal process was carried out using the TEM specimens, and magnetic flux densities of the ultra-thin Fe layers were evaluated at different remanence states. We show that a spin configuration in the TEM specimens is determined by the competition between an exchange coupling at the MnPd/Fe bilayer interface, shape anisotropy of TEM specimens and intrinsic magnetocrystalline anisotropy of Fe.

Investigation of initial growth of ZnO nanowires and their growth mechanism.

ZnO nanowires were synthesized on Si substrates by a simple metal vapor deposition method without any catalysts. The initial growth and the growth mechanism of the ZnO nanowires were studied using scanning and transmission electron microscopy. We found that the ZnO nanowires grew on the Si substrate via a self-seeding vapor-solid mechanism. The growth process of the ZnO nanowires consisted of four steps: self-seeding, one-dimensional epitaxial growth of the nanowires on the seeds by a base-growth mode, further acceleration of nanowire growth with additional seeding, and active formation of the nanowires.

The synthesis and growth mechanism of bamboo-like In2O3 nanowires.

Bamboo-like In(2)O(3) nanowires are successfully synthesized at 850 degrees C by a simple thermal evaporation method with an Au catalyst. The morphology of In(2)O(3) nanowires is controlled by the N(2) flow rate. Three different morphologies-straight, bamboo-like, and bent and tangled-are obtained under N(2) flow rates of 500, 700, and 1000 sccm, respectively. A possible growth mechanism of the bamboo-like In(2)O(3) nanowires is proposed. The bamboo-like In(2)O(3) nanowires consist of a stem and nodes, which are formed by rapid precipitation and oxidation processes of indium from an In-rich Au-In alloy at the bottom of an Au catalyst during their growth. Low-temperature photoluminescence of the In(2)O nanowires shows a sharp blue emission at 440 nm and a broad orange emission centered at 620 nm. The possible origin of the orange emission is discussed.

Synthesis of diamond-shape titanate molecular sheets with different sizes and realization of quantum confinement effect during dimensionality reduction from two to zero.

Synthesis of semiconductor nanoparticles with uniform shapes, sizes, and compositions in series with a gradual size reduction has not been achieved for two-dimensional molecular sheets. We report a large-scale (>2.6 g) synthesis of 0.75-nm-thick diamond-shape lepidocrocite-type titanate molecular sheets with the sizes decreasing from (27.3, 19.1) to (7.7, 5.5), where the numbers in parentheses represent the long and short diagonal lengths, respectively, in nm. This is the first example of synthesizing semiconductor nanoparticles in series with the dimensionality reduction from two to zero, without coating the surfaces with surface-passivating ligands. The titanate molecular sheets showed three exciton-absorption bands in the 4.0-6.5 eV region, the absorption energies of which increased with decreasing the area. Contrary to the common belief, the per-unit cell oscillator strengths gradually increased with increasing area and the per-particle oscillator strengths increased in proportion to the area. The average reduced exciton masses along the two diagonal axes were 0.10 and 0.11 m e, respectively, which were much smaller than those of bulk titanates (by 60-130 times). The estimated average Bohr radii along the two-diagonal axes were 4.8 and 4.3 nm, respectively.