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We performed a systematic investigation of the correlation between the layer stacking, structure transition, magnetic and thermal transport properties of different $\alpha$-RuCl$_3$ crystals with T$_N$ varying from 6\,K to 7.6\,K by measuring magnetic properties, specific heat, neutron single crystal diffraction, and thermal transport. A small population of stacking disorder suppresses T$_N$. $\alpha$-RuCl$_3$ crystals with a single T$_N$ in the range of 7.4\,K-7.6 K have minimal amount of stacking disorder and show a well defined structure transition around 140\,K upon cooling. For those crystals with T$_N$ below 7\,K, the structure transition occurs well below 140\,K upon cooling and is incomplete, manifested by the coexistence of both high temperature and low temperature phases down to the lowest measurement temperature. Diffuse streaks were observed for these crystals but not for those with T$_N$ above 7.4\,K. For both types of crystals, oscillatory field dependent thermal conductivity and plateau-like feature in thermal Hall resistivity were observed in the field-induced disordered state that may be a quantum spin liquid. However, $\alpha$-RuCl$_3$ crystals with with minimal amount of stacking disorder have a higher thermal conductivity that pushes the thermal Hall conductivity to be close to the half-integer quantized value. Our results demonstrate a strong correlation between the layer stacking, structure transition, magnetic and thermal transport properties, and highlight the importance of interlayer coupling in $\alpha$-RuCl$_3$ despite the weak van der Waals bonding.

In modern optics, materials with large birefringence ({\Delta}n, where n is the refractive index) are sought after for polarization control (e.g. in wave plates, polarizing beam splitters, etc.), nonlinear optics and quantum optics (e.g. for phase matching and production of entangled photons), micromanipulation, and as a platform for unconventional light-matter coupling, such as Dyakonov-like surface polaritons and hyperbolic phonon polaritons. Layered "van der Waals" materials, with strong intra-layer bonding and weak inter-layer bonding, can feature some of the largest optical anisotropy; however, their use in most optical systems is limited because their optic axis is out of the plane of the layers and the layers are weakly attached, making the anisotropy hard to access. Here, we demonstrate that a bulk crystal with subtle periodic modulations in its structure -- Sr9/8TiS3 -- is transparent and positive-uniaxial, with extraordinary index n_e = 4.5 and ordinary index n_o = 2.4 in the mid- to far-infrared. The excess Sr, compared to stoichiometric SrTiS3, results in the formation of TiS6 trigonal-prismatic units that break the infinite chains of face-shared TiS6 octahedra in SrTiS3 into periodic blocks of five TiS6 octahedral units. The additional electrons introduced by the excess Sr subsequently occupy the TiS6 octahedral blocks to form highly oriented and polarizable electron clouds, which selectively boost the extraordinary index n_e and result in record birefringence ({\Delta}n > 2.1 with low loss). The connection between subtle structural modulations and large changes in refractive index suggests new categories of anisotropic materials and also tunable optical materials with large refractive-index modulation and low optical losses., Comment: Main text + supplementary

We performed a systematic investigation of the correlation between the layer stacking, structure transition, magnetic and thermal transport properties of different $α$-RuCl$_3$ crystals with T$_N$ varying from 6\,K to 7.6\,K by measuring magnetic properties, specific heat, neutron single crystal diffraction, and thermal transport. A small population of stacking disorder suppresses T$_N$. $α$-RuCl$_3$ crystals with a single T$_N$ in the range of 7.4\,K-7.6 K have minimal amount of stacking disorder and show a well defined structure transition around 140\,K upon cooling. For those crystals with T$_N$ below 7\,K, the structure transition occurs well below 140\,K upon cooling and is incomplete, manifested by the coexistence of both high temperature and low temperature phases down to the lowest measurement temperature. Diffuse streaks were observed for these crystals but not for those with T$_N$ above 7.4\,K. For both types of crystals, oscillatory field dependent thermal conductivity and plateau-like feature in thermal Hall resistivity were observed in the field-induced disordered state that may be a quantum spin liquid. However, $α$-RuCl$_3$ crystals with with minimal amount of stacking disorder have a higher thermal conductivity that pushes the thermal Hall conductivity to be close to the half-integer quantized value. Our results demonstrate a strong correlation between the layer stacking, structure transition, magnetic and thermal transport properties, and highlight the importance of interlayer coupling in $α$-RuCl$_3$ despite the weak van der Waals bonding.

Van der Waals materials composed of stacks of individual atomic layers have attracted considerable attention due to their exotic electronic properties that can be altered by, for example, manipulating the twist angle of bilayer materials or the stacking sequence of trilayer materials. To fully understand and control the unique properties of these few-layer materials, a technique that can provide information about their local in-plane structural deformations, twist direction, and out-of-plane structure is needed. In principle, interference in overlap regions of Bragg disks originating from separate layers of a material encodes three-dimensional information about the relative positions of atoms in the corresponding layers. Here, we describe an interferometric four-dimensional scanning transmission electron microscopy technique that utilizes this phenomenon to extract precise structural information from few-layer materials with nm-scale resolution. We demonstrate how this technique enables measurement of local pm-scale in-plane lattice distortions as well as twist direction and average interlayer spacings in bilayer and trilayer graphene, and therefore provides a means to better understand the interplay between electronic properties and precise structural arrangements of few-layer 2D materials.

Two-dimensional van der Waals MnBi$_{2n}$Te$_{3n+1}$ (n = 1, 2, 3, 4) compounds have been recently found to be intrinsic magnetic topological insulators rendering quantum anomalous Hall effect and diverse topological states. Here, we summarize and compare the crystal and magnetic structures of this family, and discuss the effects of chemical composition on their magnetism. We found that a considerable fraction of Bi occupies at the Mn sites in MnBi$_{2n}$Te$_{3n+1}$ (n = 1, 2, 3, 4) while Mn is no detectable at the non-magnetic atomic sites within the resolution of neutron diffraction experiments. The occupancy of Mn monotonically decreases with the increase of n. The polarized neutron diffraction on the representative MnBi$_{4}$Te$_{7}$ reveals that its magnetization density is exclusively accumulated at the Mn site, in good agreement with the results from the unpolarized neutron diffraction. The defects of Bi at the Mn site naturally explain the continuously reduced saturated magnetic moments from n = 1 to n = 4. The experimentally estimated critical exponents of all the compounds generally suggest a three-dimensional character of magnetism. Our work provides material-specified structural parameters that may be useful for band structure calculations to understand the observed topological surface states and for designing quantum magnetic materials through chemical doping., Comment: 5 figures, typos corrected

Production of syngas with tunable CO/H2 ratio from renewable resources is an ideal way to provide a carbon-neutral feedstock for liquid fuel production. Ag is a benchmark electrocatalysts for CO2-to-CO conversion but high overpotential limits the efficiency. We synthesize AgP2 nanocrystals (NCs) with a greater than 3-fold reduction in overpotential for electrochemical CO2-to-CO reduction compared to Ag and greatly enhanced stability. Density functional theory calculations reveal a significant energy barrier decrease in the formate intermediate formation step. In situ X-ray absorption spectroscopy (XAS) shows that a maximum Faradaic efficiency is achieved at an average silver valence state of +1.08 in AgP2 NCs. A photocathode consisting of a n+p-Si wafer coated with ultrathin Al2O3 and AgP2 NCs achieves an onset potential of 0.2 V vs. RHE for CO production and a partial photocurrent density for CO at −0.11 V vs. RHE (j−0.11, CO) of −3.2 mA cm−2., Conversion of CO2 into value-added chemicals by use of renewable energy is promising to achieve a carbon-neutral energy cycle. Here, the authors show that AgP2 is a stable, selective and efficient syngas catalyst for solar-to-fuel conversion with a 3-fold lower overpotential compared to the benchmark Ag catalyst.

The effects of N-doping and the lithiation mechanism of TiO2 nanotubes were elucidated by integrated in situ microscopy and electrochemical measurements.

Lithium-ion batteries (LIBs) commercially dominate portable energy storage and have been extended to hybrid/electric vehicles by utilizing electrode materials with enhanced energy density. However, the energy density and cycling life of LIBs must extend beyond the current reach of commercial electrodes to meet the performance requirements for transportation applications. Carbon-based anodes, serving as the main negative electrodes in LIBs, have an intrinsic capacity limitation due to the intercalation mechanism. Some nanostructured carbon materials offer very interesting reversible capacities and can be considered as future anode materials. However, their fabrication processes are often complicated and expensive. Theoretically, using a lithium metal anode is the best way of delivering high energy density due to its largest theoretical capacity of more than 3800 mAh g-1; however, lithium metal is highly reactive with liquid electrolytes. Alternative anodes are being explored, including other lithium-reactive metals, such as Si, Ge, Zn, V, and so forth. These metals react reversibly with a large amount of Li per formula unit to form lithium-metal alloys, rendering these materials promising candidates for next-generation LIBs with high energy density. Though, most of these pure metallic anodes experience large volume changes during lithiation and delithiation processes that often results in cracking of the anode material and a loss electrical contact between the particles. Nanosized metal sulfides were recently found to possess better cycling stability and larger reversible capacities over pure metals. Further improvements and developments of metal sulfide-based anodes rely on a fundamental understanding of their electrochemical cycling mechanisms. Not only must the specific electrochemical reactions be correctly identified, but also the microstructural evolution upon electrochemical cycling, which often dictates the cyclability and stability of nanomaterials in batteries, must be clearly understood. Probing these dynamic evolution processes, i.e. the lithiation reactions and morphology evolutions, are often challenging. It requires both high-resolution chemical analysis and microstructural identification. In situ transmission electron microscopy (TEM) coupled with electron energy loss spectroscopy (EELS) has recently been raised as one of the most powerful techniques for monitoring electrochemical processes in anode materials for LIBs. In this work, we focus on elucidating the origin of the structural stability of SnS2 during electrochemical cycling by revealing the microstructural evolution of SnS2 upon lithiation using in situ TEM. Crystalline SnS2 was observed to undergo a two-step reaction after the initial lithium intercalation: (1) irreversible formation of metallic tin and amorphous lithium sulfide and (2) reversible transformation of metallic tin to Li-Sn alloys, which is determined to be the rate-determining step. More interestingly, it was discovered that a self-assembled composite framework formed during the irreversible conversion reaction, which has not been previously reported. Crystalline Sn nanoparticles are well arranged within an amorphous Li2S "matrix" in this self-assembled framework. This nanoscale framework confines the locations of individual Sn nanoparticles and prevents particle agglomeration during the subsequent cycling processes, therefore providing desired structural tolerance and warranting a sufficientelectron pathway. Our results not only explain the outstanding cycling stability of SnS2 over metallic tin anodes, but also provide important mechanistic insights into the design of high-performance electrodes for next-generation LIBs through the integration of a unique nanoframework.

The effects of N-doping and the lithiation mechanism of TiO2 nanotubes were elucidated by integrated in situ microscopy and electrochemical measurements.

Control of structure at the atomic level can precisely and effectively tune catalytic properties of materials, enabling enhancement in both activity and durability. We synthesized a highly active and durable class of electrocatalysts by exploiting the structural evolution of platinum-nickel (Pt-Ni) bimetallic nanocrystals. The starting material, crystalline PtNi3 polyhedra, transforms in solution by interior erosion into Pt3Ni nanoframes with surfaces that offer three-dimensional molecular accessibility. The edges of the Pt-rich PtNi3 polyhedra are maintained in the final Pt3Ni nanoframes. Both the interior and exterior catalytic surfaces of this open-framework structure are composed of the nanosegregated Pt-skin structure, which exhibits enhanced oxygen reduction reaction (ORR) activity. The Pt3Ni nanoframe catalysts achieved a factor of 36 enhancement in mass activity and a factor of 22 enhancement in specific activity, respectively, for this reaction (relative to state-of-the-art platinum-carbon catalysts) during prolonged exposure to reaction conditions.

Improved methods for the flux growth of single crystals of the important battery material LiFePO4 have been developed, allowing the facile preparation of single crystals up to 1 cm across with well-developed facets at relatively low temperatures. The structural characterization of these samples by both powder X-ray diffraction and single crystal diffraction (X-ray and neutron) indicates that the samples are typically stoichiometric with a very low concentration of Fe defects on the Li site, though crystals with larger concentrations of defects can be specifically grown using Fe-rich fluxes. These defects occur through the formation of a Fe-rich (Li1-2xFe x)FePO4 partial solid solution, in contrast to the antisite defects more commonly discussed in the literature which would preserve the ideal LiFePO4 stoichiometry. The LiFePO4 defects are shown to be sarcopside-like (2 Li+ → Fe2+ + vacancy) based on compositions refined from single crystal diffraction data, the observed dependence of unit cell parameters on defect concentration, and their observed phase behavior (defects only appear in growths from fluxes which are Fe-rich relative to stoichiometric LiFePO4). The distribution of defects has been studied by aberration corrected scanning transmission electron microscopy and was found to be highly inhomogenous, suggesting that defect-containing crystals may consist of endotaxial intergrowths of olivine LiFePO4 and sarcopside Fe3(PO4)2 in a manner that minimizes the detrimental influence of FeLi defects on the rate of Li-ion transport within crystallites. © 2013 American Chemical Society.

A growth diagram of Lu-Fe-O compounds on MgO (111) substrates using pulsed laser deposition is constructed based on extensive growth experiments. The LuFe$_2$O$_4$ phase can only be grown in a small range of temperature and O$_2$ pressure conditions. An understanding of the growth mechanism of Lu-Fe-O compound films is offered in terms of the thermochemistry at the surface. Superparamagnetism is observed in LuFe$_2$O$_4$ film and is explained in terms of the effect of the impurity h-LuFeO$_3$ phase and structural defects .

The atomic and electronic structures at interfaces in thin films are typically different from the bulk and are vitally important in determining the physical properties of thin films. The interface between SrVO3, chosen as a prototype for vanadium-based perovskite materials in this work, and LaAlO3 substrate is investigated by scanning transmission electron microscopy, electron energy-loss spectroscopy, and theoretical multi-electron calculations. Extra electrons have been detected on the interface layer by comparing the energy-loss near-edge structures of V-L3,2 edges to those from the film far from the interface. Monochromated EELS and theoretical calculations for SrVO3, VO2, and V2O 3 support this conclusion. The extra electrons appear to originate from a change in the local bonding configuration of V at the La-O terminated substrate surface as determined by Z-contrast imaging. © 2011 American Institute of Physics.

著者人数: 183名, 資料番号: SA1003701000

Using a spherical aberration (Cs)-corrected scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS), we Investigated a 6 degrees low-angle [001] tilt grain boundary in SrTiO(3). The enhanced spatial resolution of the aberration corrector leads to the observation of a number Of Structural variations ill the edge dislocations along the grain boundary that neither resemble the standard edge dislocations nor partial dislocations for SrTiO(3). Although there appear to be many variants in the structure that can be interpreted as compositional effects, three main classes of core structure are found to be prominent. From EELS analysis, these classifications seem to be related to Sr deficiencies, with the final variety of the cores being consistent with an embedded TiO(x) rocksalt-like structure.

The bulk of the comet 81P/Wild 2 ( hereafter Wild 2) samples returned to Earth by the Stardust spacecraft appear to be weakly constructed mixtures of nanometer-scale grains, with occasional much larger ( over 1 micrometer) ferromagnesian silicates, Fe-Ni sulfides, Fe-Ni metal, and accessory phases. The very wide range of olivine and low-Ca pyroxene compositions in comet Wild 2 requires a wide range of formation conditions, probably reflecting very different formation locations in the protoplanetary disk. The restricted compositional ranges of Fe-Ni sulfides, the wide range for silicates, and the absence of hydrous phases indicate that comet Wild 2 experienced little or no aqueous alteration. Less abundant Wild 2 materials include a refractory particle, whose presence appears to require radial transport in the early protoplanetary disk.

The Stardust spacecraft collected thousands of particles from comet 81P/Wild 2 and returned them to Earth for laboratory study. The preliminary examination of these samples shows that the nonvolatile portion of the comet is an unequilibrated assortment of materials that have both presolar and solar system origin. The comet contains an abundance of silicate grains that are much larger than predictions of interstellar grain models, and many of these are high-temperature minerals that appear to have formed in the inner regions of the solar nebula. Their presence in a comet proves that the formation of the solar system included mixing on the grandest scales.