Origins and Importance of Intragranular Cracking in Layered Lithium Transition Metal Oxide Cathodes.

Li-ion batteries have a pivotal role in the transition toward electric transportation. Ni-rich layered transition metal oxide (LTMO) cathode materials promise high specific capacity and lower cost but exhibit faster degradation compared with lower Ni alternatives. Here, we employ high-resolution electron microscopy and spectroscopy techniques to investigate the nanoscale origins and impact on performance of intragranular cracking (within primary crystals) in Ni-rich LTMOs. We find that intragranular cracking is widespread in charged specimens early in cycle life but uncommon in discharged samples even after cycling. The distribution of intragranular cracking is highly inhomogeneous. We conclude that intragranular cracking is caused by local stresses that can have several independent sources: neighboring particle anisotropic expansion/contraction, Li- and TM-inhomogeneities at the primary and secondary particle levels, and interfacing of electrochemically active and inactive phases. Our results suggest that intragranular cracks can manifest at different points of life of the cathode and can potentially lead to capacity fade and impedance rise of LTMO cathodes through plane gliding and particle detachment that lead to exposure of additional surfaces to the electrolyte and loss of electrical contact.

Cation Disorder in Ferroelectric Ba4M2Nb10O30 (M = Na, K, and Rb) Tetragonal Tungsten Bronzes.

The crystal structure of tetragonal tungsten bronzes, with the general formula A12A24C4B12B28O30, is flexible both from a chemical and structural viewpoint, resulting in a multitude of compositions. The A1 and A2 lattice sites, with different coordination environments, are usually regarded to be occupied by two different cations such as in Ba4Na2Nb10O30 with Na+ and Ba2+ occupying the A1 and A2 sites, respectively. Here, we report on a systematic study of the lattice site occupancy on the A1 and A2 sites in the series Ba4M2Nb10O30 (M = Na, K, and Rb). The three compounds were synthesized by a two-step solid-state method. The site occupancy on the A1 and A2 sites were investigated by a combination of Rietveld refinement of X-ray diffraction patterns and scanning transmission electron microscopy with simultaneous energy-dispersive spectroscopy. The two methods demonstrated consistent site occupancy of the cations on the A1 and A2 sites, rationalized by the variation in the size of the alkali cations. The cation order-disorder phenomenology in the tungsten bronzes reported is discussed using a thermodynamic model of O'Neill and Navrotsky, originally developed for cation interchange in spinels.

Tailoring the Vertical and Planar Growth of 2D WS2 Thin Films Using Pulsed Laser Deposition for Enhanced Gas Sensing Properties.

In this study, pulsed laser deposition has been utilized for the controllable synthesis of WS2 thin films with growth orientation ranging from vertically to horizontally aligned layers, and the effect of growth parameters has been investigated. The growth of thin films on SiO2 substrates at three different pressures (30, 50, and 70 mTorr) and three different temperatures (400, 500, and 600 °C) has been studied. Detailed characterizations carried out on the as-grown layers clearly show the formation of the 2H-WS2 phase and its morphological evolution with deposition conditions. Atomic force microscopy and cross-sectional transmission electron microscopy have been used to deduce the growth mechanism of the vertical and planar films with different deposition parameters. The samples grown with a combination of lower temperatures and higher pressures exhibit a vertical flake-like growth with a flake thickness of ∼2-5 nm. However, at higher temperatures and lower pressures, the film growth is observed to be rather planar. The gas sensing parameters and the underlying mechanism have been observed to be quite different for vertically and horizontally grown layers. The vertical layers showed a selective response toward NO2 gas at room temperature (RT) with a limit of detection less than 50 ppb. In comparison, a very subdued and poor gas sensing response was recorded for the planar film at RT. A large specific area and abundance of active edge sites along with the flat basal plane present in the vertically grown layers seem to be responsible for efficient gas sensing toward NO2.

Direct Integration of Strained-Pt Catalysts into Proton-Exchange-Membrane Fuel Cells with Atomic Layer Deposition.

The design and fabrication of lattice-strained platinum catalysts achieved by removing a soluble core from a platinum shell synthesized via atomic layer deposition, is reported. The remarkable catalytic performance for the oxygen reduction reaction (ORR), measured in both half-cell and full-cell configurations, is attributed to the observed lattice strain. By further optimizing the nanoparticle geometry and ionomer/carbon interactions, mass activity close to 0.8 A mgPt -1 @0.9 V iR-free is achievable in the membrane electrode assembly. Nevertheless, active catalysts with high ORR activity do not necessarily lead to high performance in the high-current-density (HCD) region. More attention shall be directed toward HCD performance for enabling high-power-density hydrogen fuel cells.

Detecting minute amounts of nitrogen in GaNAs thin films using STEM and CBED.

Nitrogen (N) is a common element added to GaAs for band gap engineering and strain compensation. However, detection of small amounts of N is difficult for electron microscopy as well as for other chemical analysis techniques. In this work, N in GaAs is examined by using different transmission electron microscopy (TEM) techniques. While both dark-field TEM imaging using the composition sensitive (002) reflections and selected area diffraction reveal a significant difference between the doped thin-film and the GaAs substrate, spectroscopy techniques such as electron energy loss and energy dispersive X-ray spectroscopy are not able to detect N. To quantify the N content, quantitative convergent beam electron diffraction (QCBED) is used, which gives a direct evidence of N substitution and As vacancies. The measurements are enabled by the electron energy-filtered scanning CBED technique. These results demonstrate a sensitive method for composition analysis based on quantitative electron diffraction.

Observation of Electric-Field-Induced Structural Dislocations in a Ferroelectric Oxide.

Dislocations are 1D topological defects with emergent electronic properties. Their low dimensionality and unique properties make them excellent candidates for innovative device concepts, ranging from dislocation-based neuromorphic memory to light emission from diodes. To date, dislocations are created in materials during synthesis via strain fields or flash sintering or retrospectively via deformation, for example, (nano)-indentation, limiting the technological possibilities. In this work, we demonstrate the creation of dislocations in the ferroelectric semiconductor Er(Mn,Ti)O3 with nanoscale spatial precision using electric fields. By combining high-resolution imaging techniques and density functional theory calculations, direct images of the dislocations are collected, and their impact on the local electric transport behavior is studied. Our approach enables local property control via dislocations without the need for external macroscopic strain fields, expanding the application opportunities into the realm of electric-field-driven phenomena.

Publisher Correction: Conductivity control via minimally invasive anti-Frenkel defects in a functional oxide.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Conductivity control via minimally invasive anti-Frenkel defects in a functional oxide.

Utilizing quantum effects in complex oxides, such as magnetism, multiferroicity and superconductivity, requires atomic-level control of the material's structure and composition. In contrast, the continuous conductivity changes that enable artificial oxide-based synapses and multiconfigurational devices are driven by redox reactions and domain reconfigurations, which entail long-range ionic migration and changes in stoichiometry or structure. Although both concepts hold great technological potential, combined applications seem difficult due to the mutually exclusive requirements. Here we demonstrate a route to overcome this limitation by controlling the conductivity in the functional oxide hexagonal Er(Mn,Ti)O3 by using conductive atomic force microscopy to generate electric-field induced anti-Frenkel defects, that is, charge-neutral interstitial-vacancy pairs. These defects are generated with nanoscale spatial precision to locally enhance the electronic hopping conductivity by orders of magnitude without disturbing the ferroelectric order. We explain the non-volatile effects using density functional theory and discuss its universality, suggesting an alternative dimension to functional oxides and the development of multifunctional devices for next-generation nanotechnology.

The influence of AlN buffer layer on the growth of self-assembled GaN nanocolumns on graphene.

GaN nanocolumns were synthesized on single-layer graphene via radio-frequency plasma-assisted molecular beam epitaxy, using a thin migration-enhanced epitaxy (MEE) AlN buffer layer as nucleation sites. Due to the weak nucleation on graphene, instead of an AlN thin-film we observe two distinguished AlN formations which affect the subsequent GaN nanocolumn growth: (i) AlN islands and (ii) AlN nanostructures grown along line defects (grain boundaries or wrinkles) of graphene. Structure (i) leads to the formation of vertical GaN nanocolumns regardless of the number of AlN MEE cycles, whereas (ii) can result in random orientation of the nanocolumns depending on the AlN morphology. Additionally, there is a limited amount of direct GaN nucleation on graphene, which induces non-vertical GaN nanocolumn growth. The GaN nanocolumn samples were characterized by means of scanning electron microscopy, transmission electron microscopy, high-resolution X-ray diffraction, room temperature micro-photoluminescence, and micro-Raman measurements. Surprisingly, the graphene with AlN buffer layer formed using less MEE cycles, thus resulting in lower AlN coverage, has a lower level of nitrogen plasma damage. The AlN buffer layer with lowest AlN coverage also provides the best result with respect to high-quality and vertically-aligned GaN nanocolumns.

On the biogenicity of Fe-oxyhydroxide filaments in silicified low-temperature hydrothermal deposits: Implications for the identification of Fe-oxidizing bacteria in the rock record.

Microaerophilic Fe(II)-oxidizing bacteria produce biomineralized twisted and branched stalks, which are promising biosignatures of microbial Fe oxidation in ancient jaspers and iron formations. Extracellular Fe stalks retain their morphological characteristics under experimentally elevated temperatures, but the extent to which natural post-depositional processes affect fossil integrity remains to be resolved. We examined siliceous Fe deposits from laminated mounds and chimney structures from an extinct part of the Jan Mayen Vent Fields on the Arctic Mid-Ocean Ridge. Our aims were to determine how early seafloor diagenesis affects morphological and chemical signatures of Fe-oxyhydroxide biomineralization and how extracellular stalks differ from abiogenic features. Optical and scanning electron microscopy in combination with focused ion beam-transmission electron microscopy (FIB-TEM) was used to study the filamentous textures and cross sections of individual stalks. Our results revealed directional, dendritic, and radial arrangements of biogenic twisted stalks and randomly organized networks of hollow tubes. Stalks were encrusted by concentric Fe-oxyhydroxide laminae and silica casings. Element maps produced by energy dispersive X-ray spectroscopy (EDS) in TEM showed variations in the content of Si, P, and S within filaments, demonstrating that successive hydrothermal fluid pulses mediate early diagenetic alteration and modify the chemical composition and surface features of stalks through Fe-oxyhydroxide mineralization. The carbon content of the stalks was generally indistinguishable from background levels, suggesting that organic compounds were either scarce initially or lost due to percolating hydrothermal fluids. Dendrites and thicker abiotic filaments from a nearby chimney were composed of nanometer-sized microcrystalline iron particles and silica and showed Fe growth bands indicative of inorganic precipitation. Our study suggests that the identification of fossil stalks and sheaths of Fe-oxidizing bacteria in hydrothermal paleoenvironments may not rely on the detection of organic carbon and demonstrates that abiogenic filaments differ from stalks and sheaths of Fe-oxidizing bacteria with respect to width distribution, ultrastructure, and textural context.

Silicon-Carbon composite anodes from industrial battery grade silicon.

In this work, silicon/carbon composites for anode electrodes of Li-ion batteries are prepared from Elkem's Silgrain® line. Gentle ball milling is used to reduce particle size of Silgrain, and the resulting Si powder consists of micrometic Si with some impurities. Silicon/carbon composite with CMC/SBR as a dual binder can achieve more than 1200 cycles with a capacity of 1000 mAh g-1 of Si. This excellent electrochemical performance can be attributed to the use of a buffer as a solvent to control the pH of the electrode slurry, and hence the bonding properties of the binder to the silicon particles. In addition, the use of FEC as an electrolyte additive is greatly contributing to a stabilized cycling by creating a more robust SEI layer. This work clearly demonstrates the potential of industrial battery grade silicon from Elkem.

Critically testing olivine-hosted putative martian biosignatures in the Yamato 000593 meteorite-Geobiological implications.

On rocky planets such as Earth and Mars the serpentinization of olivine in ultramafic crust produces hydrogen that can act as a potential energy source for life. Direct evidence of fluid-rock interaction on Mars comes from iddingsite alteration veins found in martian meteorites. In the Yamato 000593 meteorite, putative biosignatures have been reported from altered olivines in the form of microtextures and associated organic material that have been compared to tubular bioalteration textures found in terrestrial sub-seafloor volcanic rocks. Here, we use a suite of correlative, high-sensitivity, in situ chemical, and morphological analyses to characterize and re-evaluate these microalteration textures in Yamato 000593, a clinopyroxenite from the shallow subsurface of Mars. We show that the altered olivine crystals have angular and micro-brecciated margins and are also highly strained due to impact-induced fracturing. The shape of the olivine microalteration textures is in no way comparable to microtunnels of inferred biological origin found in terrestrial volcanic glasses and dunites, and rather we argue that the Yamato 000593 microtextures are abiotic in origin. Vein filling iddingsite extends into the olivine microalteration textures and contains amorphous organic carbon occurring as bands and sub-spherical concentrations <300 nm across. We propose that a martian impact event produced the micro-brecciated olivine crystal margins that reacted with subsurface hydrothermal fluids to form iddingsite containing organic carbon derived from abiotic sources. These new data have implications for how we might seek potential biosignatures in ultramafic rocks and impact craters on both Mars and Earth.

Epitaxial K0.5Na0.5NbO3 thin films by aqueous chemical solution deposition.

We report on an environmentally friendly and versatile aqueous chemical solution deposition route to epitaxial K0.5Na0.5NbO3 (KNN) thin films. The route is based on the spin coating of an aqueous solution of soluble precursors on SrTiO3 single crystal substrates followed by pyrolysis at 400°C and annealing at 800°C using rapid thermal processing. Strongly textured films with homogeneous thickness were obtained on three different crystallographic orientations of SrTiO3. Epitaxial films were obtained on (111) SrTiO3 substrates, while films consisting of an epitaxial layer close to the substrate followed by an oriented polycrystalline layer were obtained on (100) and (110) SrTiO3 substrates. A K2Nb4O11 secondary phase was observed on the surface of the thin films due to the evaporation of alkali species, while the use of an NaCl/KCl flux reduced the amount of the secondary phase. Ferroelectric behaviour of the films was investigated by PFM, and almost no dependence on the film crystallographic orientation was observed. The permittivity and loss tangent of the films with the NaCl/KCl flux were 870 and 0.04 (100-orientation) and 2250 and 0.025 (110-orientation), respectively, at 1 kHz.

GaN/AlGaN Nanocolumn Ultraviolet Light-Emitting Diode Using Double-Layer Graphene as Substrate and Transparent Electrode.

The many outstanding properties of graphene have impressed and intrigued scientists for the last few decades. Its transparency to light of all wavelengths combined with a low sheet resistance makes it a promising electrode material for novel optoelectronics. So far, no one has utilized graphene as both the substrate and transparent electrode of a functional optoelectronic device. Here, we demonstrate the use of double-layer graphene as a growth substrate and transparent conductive electrode for an ultraviolet light-emitting diode in a flip-chip configuration, where GaN/AlGaN nanocolumns are grown as the light-emitting structure using plasma-assisted molecular beam epitaxy. Although the sheet resistance is increased after nanocolumn growth compared with pristine double-layer graphene, our experiments show that the double-layer graphene functions adequately as an electrode. The GaN/AlGaN nanocolumns are found to exhibit a high crystal quality with no observable defects or stacking faults. Room-temperature electroluminescence measurements show a GaN related near bandgap emission peak at 365 nm and no defect-related yellow emission.

Vertical GaN nanocolumns grown on graphene intermediated with a thin AlN buffer layer.

We report on the self-assembled growth of high-density and vertically-oriented n-doped GaN nanocolumns on graphene by radio-frequency plasma-assisted molecular beam epitaxy. Graphene was transferred to silica glass, which was used as the substrate carrier. Using a migration enhanced epitaxy grown AlN buffer layer for the nucleation is found to enable a high density of vertical GaN nanocolumns with c-axis growth orientation on graphene. Furthermore, micro-Raman spectroscopy indicates that the AlN buffer reduces damage on the graphene caused by impinging active N species generated by the radio-frequency plasma source during the initial growth stage and nucleation of GaN. In addition, the grown GaN nanocolumns on graphene are found to be virtually stress-free. Micro-photoluminescence measurements show near band-edge emission from wurtzite GaN, exhibiting higher GaN bandgap related photoluminescence intensity relative to a reference GaN bulk substrate and the absence of both yellow luminescence and excitonic defect emission. Transmission electron microscopy reveals the interface of GaN nanocolumns on graphene via a thin AlN buffer layer. Even though the first few monolayers of AlN on top of graphene are strained due to in-plane lattice mismatch between AlN and graphene, the grown GaN nanocolumns have a wurtzite crystal structure without observable defects. The results of this initial work pave the way towards realizing low-cost and high-performance electronic and optoelectronic devices based on III-N semiconductors grown on graphene.

High Interfacial Charge Storage Capability of Carbonaceous Cathodes for Mg Batteries.

A rechargeable Mg battery where the capacity mainly originates from reversible reactions occurring at the electrode/electrolyte interface efficiently avoids the challenge of sluggish Mg intercalation encountered in conventional Mg batteries. The interfacial reactions in a cell based on microwave-exfoliated graphite oxide (MEGO) as the cathode and all phenyl complex (APC) as electrolyte are identified by quantitative kinetics analysis as a combination of diffusion-controlled reactions involving ether solvents ( esols) and capacitive processes. During magnesiation, esols in APC electrolytes can significantly affect the electrochemical reactions and charge transfer resistances at the electrode/electrolyte interface and thus govern the charge storage properties of the MEGO cathode. In APC-tetrahydrofuran (THF) electrolyte, MEGO exhibits a reversible capacity of ∼220 mAh g-1 at 10 mA g-1, while a reversible capacity of ∼750 mAh g-1 at 10 mA g-1 was obtained in APC-1,2-dimethoxyethane (DME) electrolyte. The high capacity improvement not only points to the important role of the esols in the APC electrolytes but also presents a Mg battery with high interfacial charge storage capability as a very promising and viable competitor to the conventional intercalation-based batteries.

Solvent-Controlled Charge Storage Mechanisms of Spinel Oxide Electrodes in Mg Organohaloaluminate Electrolytes.

Considering the improved safety, reduced cost, and high volumetric energy density associated with Mg batteries, this technology has distinct advantages for large-scale energy storage compared to other existing battery technologies. However, the divalency of the Mg2+ cation cause sluggish magnesiation kinetics in crystalline host materials, resulting in poor performance with regards to capacity and cycling stability for intercalation based electrodes. Here, we present a Mg battery using Mn3O4 as the electrode material and Mg metal as the counter electrode in a Mg organohaloaluminate electrolyte. The reversible capacity when Mn3O4 was used as cathode reached ∼580 mAh g-1 at a current density of 15.4 mA g-1, whereas a reversible capacity of ∼1800 mAh g-1 was obtained in an anode configuration. The Mn3O4 in a cathode configuration shows excellent cycling stability with no loss of capacity after 500 cycles at a current density of 770 mA g-1. As an anode, Mn3O4 retained 86% of its initial capacity after 200 cycles. These exceptional charge storage properties and high cycling stability are attributed to highly reversible interfacial reactions involving the electrolyte solvents. Our conclusions are supported by density functional theory calculations in addition to quantitative kinetics analysis and scanning transmission electron microscopy combined with energy dispersive spectroscopy and electron energy loss spectroscopy.

Bandgap measurement of high refractive index materials by off-axis EELS.

In the present work Cs aberration corrected and monochromated scanning transmission electron microscopy electron energy loss spectroscopy (STEM-EELS) has been used to explore experimental set-ups that allow bandgaps of high refractive index materials to be determined. Semi-convergence and -collection angles in the µrad range were combined with off-axis or dark field EELS to avoid relativistic losses and guided light modes in the low loss range to contribute to the acquired EEL spectra. Off-axis EELS further supressed the zero loss peak and the tail of the zero loss peak. The bandgap of several GaAs-based materials were successfully determined by simple regression analyses of the background subtracted EEL spectra. The presented set-up does not require that the acceleration voltage is set to below the Cerenkov limit and can be applied over the entire acceleration voltage range of modern TEMs and for a wide range of specimen thicknesses.