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Metal fluoride (MF) conversion cathodes theoretically show higher gravimetric and volumetric capacities than Ni- or Co-based intercalation oxide cathodes, which makes metal fluoride-lithium batteries promising candidates for next-generation high-energy-density batteries. However, their high-energy characteristics are clouded by low-capacity utilization, large voltage hysteresis, and poor cycling stability of transition MF cathodes. A variety of reasons is responsible for this: poor reaction kinetics, low conductivities, unstable MF/electrolyte interfaces and dissolution of active species upon cycling. Herein, we combine the synthesis of the metal-organic-framework (MOF) with the low-temperature fluorination to prepare MOF-shaped CoF2@C nanocomposites that exhibit confinement of the CoF2 nanoparticles and efficient mixed-conducting wiring in the produced architecture. The ultrasmall CoF2 nanoparticles (5-20 nm on average) are uniformly covered by graphitic carbon walls and embedded in the porous carbon framework. Within the CoF2@C nanocomposite, the cross-linked carbon wall and interconnected nanopores serve as electron- and ion-conducting pathways, respectively, enabling a highly reversible conversion reaction of CoF2. As a result, the produced CoF2@C composite cathodes successfully restrain the above-mentioned challenges and demonstrate high-capacity utilization of ∼500 mAh g-1 at 0.2C, good rate capability (up to 2C), and long-term cycle stability over 400 cycles. Overall, the presented study not only reports on a simple composite design to achieve high-energy characteristics in CoF2-Li batteries but also may provide a general solution for many other metal fluoride-lithium batteries.

Electron transparent TEM lamella with unaltered microstructure and chemistry is the prerequisite for successful TEM explorations. Currently, TEM specimen preparation of quantum nanostructures, such as quantum dots (QDs), remains a challenge. In this work, we optimize the sample-preparation routine for achieving high-quality TEM specimens consisting of SrRuO3 (SRO) QDs grown on SrTiO3 (STO) substrates. We demonstrate that a combination of ion-beam-milling techniques can produce higher-quality specimens of quantum nanostructures compared to TEM specimens prepared by a combination of tripod polishing followed by Ar+ ion milling. In the proposed method, simultaneous imaging in a focused ion-beam device enables accurate positioning of the QD regions and assures the presence of dots in the thin lamella by cutting the sample inclined by 5{\deg} relative to the dots array. Furthermore, the preparation of TEM lamellae with several large electron-transparent regions that are separated by thicker walls effectively reduces the bending of the specimen and offers broad thin areas. The final use of a NanoMill efficiently removes the amorphous layer without introducing any additional damage., Comment: 20 pages, 6 figures, 1 table

Terrestrial isopods possess large sensory setae on their walking legs. Increased fracture resistance of these elongated structures is of crucial importance, making the exoskeleton forming the setae an interesting durable material that may inspire biomimetic designs. We studied the cuticle of the sensory setae with analytical electron microscopy in order to gain detailed insights into its structure and composition at the nanometer scale and identify features that increase the fracture resistance of these minute skeletal elements. The setae are stiff structures formed by mineralized cuticle that are connected to the leg exoskeleton by a non-mineralized joint membrane. Our results demonstrate that different layers of the setal cuticle display contrasting organizations of the chitin-protein fibers and mineral particles. While in the externally positioned exocuticle organic fibers shift their orientation helicoidally in sequential layers, the fibers are aligned axially in the internally positioned endocuticle. In the setal cuticle, layers of structurally anisotropic cuticle likely providing strength in the axial direction are combined with layers of isotropic cuticle which may allow the setae to better resist perpendicular loading. They are further strengthened with amorphous calcium phosphate, a highly fracture resistant mineral rarely observed in invertebrate skeletons.

Sodium-ion batteries (SIB) are regarded as the most promising competitors to lithium-ion batteries in spite of expected electrochemical disadvantages. Here a “cross-linking” strategy is proposed to mitigate the typical SIB problems. We present a SIB full battery that exhibits a working potential of 3.3 V and an energy density of 180 Wh kg–1 with good cycle life. The anode is composed of cross-linking hollow carbon sheet encapsulated CuP2 nanoparticles (CHCS-CuP2) and a cathode of carbon coated Na3V2(PO4)2F3 (C-NVPF). For the preparation of the CHCS-CuP2 nanocomposites, we develop an in situ phosphorization approach, which is superior to mechanical mixing. Such CHCS-CuP2 nanocomposites deliver a high reversible capacity of 451 mAh g–1 at 80 mA g–1, showing an excellent capacity retention ratio of 91% in 200 cycles together with good rate capability and stable cycling performance. Post mortem analysis reveals that the cross-linking hollow carbon sheet structure as well as the initially formed SEI layers are...

Iron disilicide nanowhiskers and nanoblades are synthesized by depositing Fe onto Si(100) substrates at about 900 °C via electron beam physical vapor deposition. The nanostructures are determined as single crystalline α-FeSi2 with tetragonal lattice. The nanostructures are stable with prolong exposure under ambient condition, and no transformation towards β-FeSi2 is detected after 2 h annealing at 500 °C and 800 °C under high vacuum condition (10−6 mbar). The growth directions of the whiskers are found as either [001] or [100]. However, in the blades we observe grow only in [100] crystallographic direction. Changing cross-sectional shape of the α-FeSi2 whiskers from octagon at the root to rectangle at the upper part is observed and believed to be a result of the thermodynamic and kinetic anisotropy. SiO2 layer formed on the surface of the structures because of its lower surface energy compared to all iron oxides. By this a passivation, which prevents further oxidization, of the nanowhiskers is achieved. The α-FeSi2 whiskers form by root growth. Keywords: Electron beam evaporation, α-FeSi2, Whisker, Transmission electron microscopy, Atom probe tomography, Physical vapor deposition

We present the fabrication and exploration of arrays of nanodots of $SrRuO_3$ with dot sizes between 500 nm and 15 nm. Down to the smallest dot size explored, the samples were found to be magnetic with a maximum of the Curie temperature $T_C$ achieved by dots of 30 nm diameter. This peak in $T_C$ is associated with a dot-size-induced relief of the epitaxial strain, as evidenced by scanning transmission electron microscopy.

Metal fluoride-lithium batteries with potentially high energy densities, even higher than lithium-sulfur batteries, are viewed as very promising candidates for next-generation lightweight and low-cost rechargeable batteries. However, so far, metal fluoride cathodes have suffered from poor electronic conductivity, sluggish reaction kinetics and side reactions causing high voltage hysteresis, poor rate capability, and rapid capacity degradation upon cycling. Herein, it is reported that an FeF3 @C composite having a 3D honeycomb architecture synthesized by a simple method may overcome these issues. The FeF3 nanoparticles (10-50 nm) are uniformly embedded in the 3D honeycomb carbon framework where the honeycomb walls and hexagonal-like channels provide sufficient pathways for the fast electron and Li-ion diffusion, respectively. As a result, the as-produced 3D honeycomb FeF3 @C composite cathodes even with high areal FeF3 loadings of 2.2 and 5.3 mg cm-2 offer unprecedented rate capability up to 100 C and remarkable cycle stability within 1000 cycles, displaying capacity retentions of 95%-100% within 200 cycles at various C rates, and ≈85% at 2C within 1000 cycles. The reported results demonstrate that the 3D honeycomb architecture is a powerful composite design for conversion-type metal fluorides to achieve excellent electrochemical performance in metal fluoride-lithium batteries.

Focusing X-rays to single nanometer dimensions is impeded by the lack of high-quality, high-resolution optics. Challenges in fabricating high aspect ratio 3D nanostructures limit the quality and the resolution. Multilayer zone plates target this challenge by offering virtually unlimited and freely selectable aspect ratios. Here, a full-ceramic zone plate is fabricated via atomic layer deposition of multilayers over optical quality glass fibers and subsequent focused ion beam slicing. The quality of the multilayers is confirmed up to an aspect ratio of 500 with zones as thin as 25 nm. Focusing performance of the fabricated zone plate is tested toward the high-energy limit of a soft X-ray scanning transmission microscope, achieving a 15 nm half-pitch cut-off resolution. Sources of adverse influences are identified, and effective routes for improving the zone plate performance are elaborated, paving a clear path toward using multilayer zone plates in high-energy X-ray microscopy. Finally, a new fabrication concept is introduced for making zone plates with precisely tilted zones, targeting even higher resolutions.

The lithium-sulfur battery is considered as one of the most promising energy storage systems and has received enormous attentions due to its high energy density and low cost. However, polysulfide dissolution and the resulting shuttle effects hinder its practical application unless very costly solutions are considered. Herein, a sulfur-rich polymer termed sulfur-limonene polysulfide is proposed as powerful electroactive material that uniquely combines decisive advantages and leads out of this dilemma. It is amenable to a large-scale synthesis by the abundant, inexpensive, and environmentally benign raw materials sulfur and limonene (from orange and lemon peels). Moreover, owing to self-protection and confinement of lithium sulfide and sulfur, detrimental dissolution and shuttle effects are successfully avoided. The sulfur-limonene-based electrodes (without elaborate synthesis or surface modification) exhibit excellent electrochemical performances characterized by high discharge capacities (≈1000 mA h g-1 at C/2) and remarkable cycle stability (average fading rate as low as 0.008% per cycle during 300 cycles).

The influences of different transmission electron microscopy (TEM) specimen preparation techniques on the chemical composition of Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) single crystals was studied. Ion-milled samples where no cooling with liquid nitrogen (L-N2) was applied show permanently changed composition also deep inside the bulk material. When the PMN-PT samples were cooled to L-N2 temperature during the ion-milling process and in addition lower accelerating voltages were used, the chemical composition was altered only in the thinnest parts close to the specimen edge. Samples prepared using only tripod polishing technique show compositional irregularities close to the specimen edge. For the preparation of lead-containing samples, such as PMN-PT single crystals, a combination of tripod polishing and short Ar-ion-milling at low accelerating voltages while cooling the samples to liquid nitrogen temperature proved to be the most suitable to obtain artefact-free electron-transparent TEM lamellae.

Teeth are an excellent example where optimally designed nanoarchitectures with precisely constructed components consist of simple compounds. Typically, these simple constituent phases with insignificant properties show mechanical property amplifications when formed into composite architectures. Material properties of functional composites are generally regulated on the nanoscale, which makes their characterization particularly demanding. Using advanced analytical and imaging transmission electron microscopy techniques, we identified innovative microstructural adjustments combined with astonishing compositional adaptations in incisors of coypu. Unique constituents, recognized as an additional amorphous Fe-rich surface layer followed by a transition zone covering pigmented enamel, provide the required structural stability to withstand repeated mechanical load. The chemically diverse Fe-rich surface layer, including ferrihydrite and iron-calcium phosphates, gives the typical orange-brown coloration to the incisors. Within the spaces between elongated hydroxyapatite crystals in the pigmented enamel, only ferrihydrite was found, implying that enamel pigmentation is a very strictly controlled process. Most significantly, an unprecedentedly high amount of Mg was measured in the amorphous flake-like material within the dentinal tubules of the incisors, suggesting the presence of a (Mg,Ca) phosphate phase. This unusually high influx of Mg into the dentin of incisors, but not molars, suggests a substantial functionality of Mg in the initial formation stages and constant growth of incisors. The present results emphasize the strong mutual correlation among the microstructure, chemical composition, and mechanical properties of mineralized dental tissues.

This paper describes a method to pattern surfaces with Au-Ag hybrid nanoparticles. We used block copolymer micelle lithography of Au nanoparticles and electroless deposition of Ag. The combination of these two methods enables independent tuning of nanoparticle spacing and Ag-shell size. For this purpose, 8 nm large patterned Au nanoparticle seeds served as nuclei for the electroless deposition of silver that is based on a modified Tollens process with glucose. By adjusting the reaction conditions, specific growth of Ag on top of the Au seeds has been accomplished and analyzed by SEM, HRTEM, XEDS, and UV-vis spectroscopy. We could show that this versatile and green method is feasible on glass as well as on biomedical-relevant polymers like poly(ethylene glycol) hydrogels and amorphous Teflon. In conclusion, this method provides a new route to pattern glass and polymeric surfaces with Au-Ag hybrid nanoparticles. It will have many uses in applications such as surface enhanced Raman spectroscopy (SERS) or antimicrobial coatings for which hybrid nanoparticle density, size, and morphology are important.

Platinum/yttria stabilized zirconia (Pt/YSZ) interfaces with two different orientation relationships were characterized using advanced analytical transmission electron microscopy methods. Quantitative X-ray energy dispersive spectroscopy (XEDS) was performed by the recently developed ζ-factor method. Neither interdiffusion nor segregation was detected across the Pt/YSZ interfaces of both orientation conditions within the resolution limit of the technique. The interface specific components of the electron energy-loss near-edge structures (ELNES) were extracted by employing the spatial difference technique. Features of the O–K ELNES at the interface are distinctly different from that at bulk YSZ indicating Pt–O bonding. The experimentally observed changes in the O–K ELNES are in good agreement with the results of ab-initio full multiple scattering calculation, based on structure modeling at the interfaces.

We report the use of reverse PS-b-P2VP diblock copolymer micelles as true nanoscale-sized reactor vessels to synthesize ZnO nanoparticles. The reverse micelles were formed in toluene and then sequentially loaded with zinc acetate dihydrate and tetramethylammonium hydroxide reactants. Moreover, high spatial resolution Z-contrast imaging and EDX spectroscopy techniques were used to confirm the segregation of the Zn cation to the core of the loaded micelles. Determining the chemical distribution with high nanoscale spatial resolution is shown to complement the less direct characterization by AFM, DLS and FTIR, thus demonstrating broader implications for the characterization of hybrid nanocomposite systems.

The extraordinary combination of strength and toughness attained by nature's highly sophisticated structural design in nacre has inspired the synthesis of novel nanocomposites. In this context, the organic-inorganic hierarchical design of nacre has been mimicked. However, two key features of nacre, namely the scaling of the structural components and the low content of the organic phase, have not been replicated yet. Here, we present thin nanocomposite films with properly adjusted thicknesses of the organic and inorganic layers, as well as a microstructure that closely resembles that of nacre. These films, which are obtained by the combination of low-temperature chemical bath deposition of titania with layer-by-layer assembly of polyelectrolytes, exhibit enhancement in a fracture toughness by a factor of 4, combined with notable increase in hardness, while the Young's modulus is largely preserved in comparison to the single titania layer. Our findings highlight the significance of the 10:1 inorganic/organic layer thickness ratio evolved by nature, and provide novel perspectives for the future development of efficient bioinspired thin films.

The mechanisms of the platinum germanide formation by RTA processes in the Ge/Pt/Ge/SiO 2 /Si structure in the temperature range from 200 °C to 600 °C were investigated by means of transmission electron microscopy (TEM) techniques. The studies were focused on the observations of the layer microstructure and of Ge/Pt/Ge interfaces at an atomic scale by high resolution TEM (HRTEM), as well as on the identification of formed phases using analytical TEM and diffraction techniques. The formation of platinum germanides in the Ge/Pt/Ge/SiO 2 /Si structure is visible at 200 °C. However, at this temperature only a part of Ge reacted with the whole Pt during annealing. The whole Ge layer reacted with the Pt layer at 300 °C. The formed Pt–Ge layer is not a mono-layer but consists of two platinum germanides layers. The results of the annealing of Ge/Pt/Ge/SiO 2 /Si structure at higher temperatures are very similar to the results obtained at 300 °C. Various Pt–Ge phases have been found in the samples studied. The PtGe phase in the germanide layer of the sample annealed at 200 °C was found by means of TEM diffraction analysis and the energy-dispersive X-ray spectroscopy (EDXS) in scanning TEM. At 300 °C the diffraction pattern reveals the reflections corresponding to PtGe and Pt 2 Ge 3 phases. Analytical TEM studies showed that the phase composition depends on annealing temperature and that the Ge content in the Pt–Ge phases increases with temperature.

A nano-sized CeO2 powder was synthesized by a modified glycine nitrate process (MGNP). The synthesized powder was characterized by X-ray diffraction (XRD), the Brunauer Emmett Teller (BET) method, and transmission electron microscopy (TEM). The lattice parameter and crystallite size were determined by the Rietveld refinement of X-ray diffraction patterns. The shrinkage kinetics of the green body was continuously monitored in air and in oxygen atmospheres using a high temperature dilatometer up to 1500°C. During the high temperature sintering in air a redox reaction occurred (Ce4+ was partially reduced to Ce3+, and oxygen gas was released). The redox reaction influenced the sintering behaviour of CeO2, resulting in a decrease in density. On the basis of shrinkage kinetics data in oxygen atmosphere a master sintering curve for CeO2 was constructed. Using the concept of the master sintering curve, the densification behaviour in oxygen atmosphere was successfully predicted from early to final stages of sintering. During sintering of CeO2 at lower temperature in air atmosphere a significant contribution of the surface diffusion was observed.

Platinum films with thicknesses up to 1 μm have been deposited on YSZ(111) and on YSZ(100) by pulsed laser deposition (YSZ: yttria-stabilized zirconia). The as-deposited platinum films are nanocrystalline with a grain size in the order of 30 nm. During thermal treatment at 1023 K the microstructure of the films changes due to grain growth, leading to well adhering and well orientated films. Closed cavities are created within the film during the growth. The microstructure and morphology of the films are documented by HRSEM, XRD and XRD pole figures. The high quality of the Pt/YSZ interfaces is documented by high-resolution transmission electron microscopy (HRTEM). The platinum films on (100)-orientated YSZ are polycrystalline with large grains whereas the platinum films on (111)-orientated YSZ are single crystalline with a negligible concentration of grain boundaries. Since these platinum films on YSZ(111) are virtually impermeable for oxygen, microstructures on the basis of these epitaxial films may be used as geometrically and microstructurally well defined model-type electrodes for the study of electrochemical processes at the triple phase boundary Pt(O2)/YSZ and on the surface of platinum.

Superconductors in proximity to topological insulators (TIs) have the potential to unlock exotic quantum phenomena, such as Majorana fermions. Quasi-one-dimensional structures are particularly suited to host these quantum states. Despite the growth of TI nanostructures being relatively straightforward, the in situ synthesis of superconductor-TI structures has been challenging. Here, we present a systematic study of the growth of the s-wave superconductor Sn on the TI Bi2Te3 by physical vapor transport. If Sn does not enter the Bi2Te3 lattice as a dopant, two types of structures are formed: Sn nanoparticles, that cover Bi2Te3 plates and belts in a cloud-like shape, and thin Sn layers on Bi2Te3 plates, that appear in puddle-like recessions. These heterostructures have potential applications as novel quantum devices.

In this paper, we report a novel synthetic approach towards electrically conductive ZnO nanowires close to ambient conditions using lambda-DNA as a template. Initially, the suitability of DNA to assemble ZnO nanocrystals into thin coatings was investigated. The ZnO nanowires formed on stretched and aligned lambda-DNA molecules were prepared via chemical bath deposition (CBD) of zinc acetate in methanol solution in the presence of polyvinylpyrrolidone (PVP). After 10 deposition cycles, the nanowires exceed 10 microm in length and the height can be varied from 12 to around 40 nm. The nanocrystalline structure of the ZnO wires was confirmed by high-resolution transmission electron microscopy (HRTEM). The electrical conductivity was found to be of the order of several Omega cm at room temperature in two terminal measurements.

Epitaxial CeO2 films with different thickness were grown on Y2O3 stabilised Zirconia substrates. Reduction of cerium ions at the interface between CeO2 films and yttria stabilised zirconia substrates is demonstrated using aberration-corrected scanning transmission electron microscopy combined with electron energy-loss spectroscopy. It is revealed that most of the Ce ions were reduced from Ce 4+ to Ce3+ at the interface region with a decay of several nanometers. Several possibilities of charge compensations are discussed. Irrespective of the details, such local non-stoichiometries are crucial not only for understanding charge transport in such hetero-structures but also for understanding ceria catalytic properties.

The last three decades have seen a growing trend toward studying the interfacial phenomena in complex oxide heterostructures. Of particular concern is the charge distribution at interfaces, which is a crucial factor in controlling the interface transport behavior. However, the study of the charge distribution is very challenging due to its small length scale and the intricate structure and chemistry at interfaces. Furthermore, the underlying origin of the interfacial charge distribution has been rarely studied in-depth and is still poorly understood. Here, by a combination of aberration-corrected scanning transmission electron microscopy (STEM) and spectroscopy techniques, we identify the charge accumulation in the SrMnO3 (SMO) side of SrMnO3/SrTiO3 heterointerfaces and find that the charge density attains the maximum of 0.13 ± 0.07 e-/unit cell (uc) at the first SMO monolayer. Based on quantitative atomic-scale STEM analyses and first-principle calculations, we explore the origin of interfacial charge accumulation in terms of epitaxial strain-favored oxygen vacancies, cationic interdiffusion, interfacial charge transfer, and space-charge effects. This study, therefore, provides a comprehensive description of the charge distribution and related mechanisms at the SMO/STO heterointerfaces, which is beneficial for the functionality manipulation via charge engineering at interfaces.