Polymorphism in the Ruddlesden-Popper Nickelate La3Ni2O7: Discovery of a Hidden Phase with Distinctive Layer Stacking.

We report the discovery of a novel form of Ruddlesden-Popper (RP) nickelate that stands as the first example of long-range, coherent polymorphism in this class of inorganic solids. Rather than the well-known, uniform stacking of perovskite blocks ubiquitously found in RP phases, this newly discovered polymorph of the bilayer RP phase La3Ni2O7 adopts a novel stacking sequence in which single-layer and trilayer blocks of NiO6 octahedra alternate in a "1313" sequence. Crystals of this new polymorph are described in space group Cmmm, although we note evidence for a competing Imam variant. Transport measurements at ambient pressure reveal metallic character with evidence of a charge density wave transition with an onset at T ≈ 134 K. The discovery of such polymorphism could reverberate to the expansive range of science and applications that rely on RP materials, particularly the recently reported signatures of superconductivity in bilayer La3Ni2O7 with Tc as high as 80 K above 14 GPa.

A lithium-oxygen battery with a long cycle life in an air-like atmosphere.

Lithium-air batteries are considered to be a potential alternative to lithium-ion batteries for transportation applications, owing to their high theoretical specific energy. So far, however, such systems have been largely restricted to pure oxygen environments (lithium-oxygen batteries) and have a limited cycle life owing to side reactions involving the cathode, anode and electrolyte. In the presence of nitrogen, carbon dioxide and water vapour, these side reactions can become even more complex. Moreover, because of the need to store oxygen, the volumetric energy densities of lithium-oxygen systems may be too small for practical applications. Here we report a system comprising a lithium carbonate-based protected anode, a molybdenum disulfide cathode and an ionic liquid/dimethyl sulfoxide electrolyte that operates as a lithium-air battery in a simulated air atmosphere with a long cycle life of up to 700 cycles. We perform computational studies to provide insight into the operation of the system in this environment. This demonstration of a lithium-oxygen battery with a long cycle life in an air-like atmosphere is an important step towards the development of this field beyond lithium-ion technology, with a possibility to obtain much higher specific energy densities than for conventional lithium-ion batteries.

Variational Convolutional Autoencoders for Anomaly Detection in Scanning Transmission Electron Microscopy.

Identifying point defects and other structural anomalies using scanning transmission electron microscopy (STEM) is important to understand a material's properties caused by the disruption of the regular pattern of crystal lattice. Due to improvements in instrumentation stability and electron optics, atomic-resolution images with a field of view of several hundred nanometers can now be routinely acquired at 1-10 Hz frame rates and such data, which often contain thousands of atomic columns, need to be analyzed. To date, image analysis is performed largely manually, but recent developments in computer vision (CV) and machine learning (ML) now enable automated analysis of atomic structures and associated defects. Here, the authors report on how a Convolutional Variational Autoencoder (CVAE) can be utilized to detect structural anomalies in atomic-resolution STEM images. Specifically, the training set is limited to perfect crystal images , and the performance of a CVAE in differentiating between single-crystal bulk data or point defects is demonstrated. It is found that the CVAE can reproduce the perfect crystal data but not the defect input data. The disagreesments between the CVAE-predicted data for defects allows for a clear and automatic distinction and differentiation of several point defect types.

Investigation of Ca Insertion into α-MoO3 Nanoparticles for High Capacity Ca-Ion Cathodes.

Calcium-ion batteries (CIBs) are a promising alternative to lithium-ion batteries (LIBs) due to the low redox potential of calcium metal and high abundance of calcium compounds. Due to its layered structure, α-MoO3 is regarded as a promising cathode host lattice. While studies have reported that α-MoO3 can reversibly intercalate Ca ions, limited electrochemical activity has been noted, and its reaction mechanism remains unclear. Here, we re-examine Ca insertion into α-MoO3 nanoparticles with a goal to improve reaction kinetics and clarify the storage mechanism. The α-MoO3 electrodes demonstrated a specific capacity of 165 mA h g-1 centered near 2.7 V vs Ca2+/Ca, stable long-term cycling, and good rate performance at room temperature. This work demonstrates that, under the correct conditions, layered oxides can be a promising host material for CIBs and renews prospects for CIBs.

Parabolic Potential Surfaces Localize Charge Carriers in Nonblinking Long-Lifetime "Giant" Colloidal Quantum Dots.

Materials for studying biological interactions and for alternative energy applications are continuously under development. Semiconductor quantum dots are a major part of this landscape due to their tunable optoelectronic properties. Size-dependent quantum confinement effects have been utilized to create materials with tunable bandgaps and Auger recombination rates. Other mechanisms of electronic structural control are under investigation as not all of a material's characteristics are affected by quantum confinement. Demonstrated here is a new structure-property concept that imparts the ability to spatially localize electrons or holes within a core/shell heterostructure by tuning the charge carrier's kinetic energy on a parabolic potential energy surface. This charge carrier separation results in extended radiative lifetimes and in continuous emission at the single-nanoparticle level. These properties enable new applications for optics, facilitate novel approaches such as time-gated single-particle imaging, and create inroads for the development of other new advanced materials.

Ingrained: An Automated Framework for Fusing Atomic-Scale Image Simulations into Experiments.

To fully leverage the power of image simulation to corroborate and explain patterns and structures in atomic resolution microscopy, an initial correspondence between the simulation and experimental image must be established at the outset of further high accuracy simulations or calculations. Furthermore, if simulation is to be used in context of highly automated processes or high-throughput optimization, the process of finding this correspondence itself must be automated. In this work, "ingrained," an open-source automation framework which solves for this correspondence and fuses atomic resolution image simulations into the experimental images to which they correspond, is introduced. Herein, the overall "ingrained" workflow, focusing on its application to interface structure approximations, and the development of an experimentally rationalized forward model for scanning tunneling microscopy simulation are described.

Dynamically Stable Active Sites from Surface Evolution of Perovskite Materials during the Oxygen Evolution Reaction.

Perovskite oxides are an important class of oxygen evolution reaction (OER) catalysts in alkaline media, despite the elusive nature of their active sites. Here, we demonstrate that the origin of the OER activity in a La1-xSrxCoO3 model perovskite arises from a thin surface layer of Co hydr(oxy)oxide (CoOxHy) that interacts with trace-level Fe species present in the electrolyte, creating dynamically stable active sites. Generation of the hydr(oxy)oxide layer is a consequence of a surface evolution process driven by the A-site dissolution and O-vacancy creation. In turn, this imparts a 10-fold improvement in stability against Co dissolution and a 3-fold increase in the activity-stability factor for CoOxHy/LSCO when compared to nanoscale Co-hydr(oxy)oxides clusters. Our results suggest new design rules for active and stable perovskite oxide-based OER materials.

Hydroxyapatite as a scavenger of reactive radiolysis species in graphene liquid cells forin situelectron microscopy.

Liquid cell electron microscopy is an imaging technique allowing for the investigation of the interaction of liquids and solids at nanoscopic length scales. Suchin situobservations are increasingly in-demand in an array of fields, from biological sciences to medicine to batteries. Graphene liquid cells (GLCs), in particular, have generated a great interest as a low-scattering window material with the potential for increasing the quality of both imaging and spectroscopy. However, preserving the stability of the liquid and of the sample in the GLC remains a considerable challenge. In the present work we encapsulate water and hydroxyapatite (HAP), a pH-sensitive biological material, in GLCs to observe the interactions between the graphene, HAP, and the electron beam. HAP was chosen for several reasons. One is its ubiquity in biological specimens such as bones and teeth, and the second is the presence of phosphate ions in common buffer solutions. Finally, there is its sensitivity to changes in pH, which result from beam-induced hydrolysis in liquid cells. A dynamic process of dissolution and recrystallization of HAP was observed, which correlated with the production of H+ions by the beam during imaging. In addition, a large increase in the stability of the GLC under irradiation was noted. Specifically, no stable hydrogen bubbles were detected under the electron fluxes routinely exceeding 170 e-Å-2s-1. With the measured threshold dose for the bubble formation in pure water equaling 9 e-Å-2s-1, it was concluded that the presence of HAP increases the resistance of water against radiolysis in the GLC by more than an order of magnitude. These results confirm the possibility of using biological materials, such as HAP, as stabilizers in liquid cell electron microscopy. They outline a potential route for stabilization of specimens in liquid cells through the addition of a scavenger of reactive species generated by the beam-induced hydrolysis of water. These improvements are essential for enhancing both the resolution of imaging and the available imaging time, as well as avoiding the beam-induced artifacts.

Controlling Nanoscale Thermal Expansion of Monolayer Transition Metal Dichalcogenides by Alloy Engineering.

2D materials, such as transition metal dichalcogenides (TMDs), graphene, and boron nitride, are seen as promising materials for future high power/high frequency electronics. However, the large difference in the thermal expansion coefficient (TEC) between many of these 2D materials could impose a serious challenge for the design of monolayer-material-based nanodevices. To address this challenge, alloy engineering of TMDs is used to tailor their TECs. Here, in situ heating experiments in a scanning transmission electron microscope are combined with electron energy-loss spectroscopy and first-principles modeling of monolayer Mo1- x Wx S2 with different alloying concentrations to determine the TEC. Significant changes in the TEC are seen as a function of chemical composition in Mo1- x Wx S2 , with the smallest TEC being reported for a configuration with the highest entropy. This study provides key insights into understanding the nanoscale phenomena that control TEC values of 2D materials.

Probing Mg Intercalation in the Tetragonal Tungsten Bronze Framework V4Nb18O55.

While commercial Li-ion batteries offer the highest energy densities of current rechargeable battery technologies, their energy storage limit has almost been achieved. Therefore, there is considerable interest in Mg batteries, which could offer increased energy densities in comparison to Li-ion batteries if a high-voltage electrode material, such as a transition-metal oxide, can be developed. However, there are currently very few oxide materials which have demonstrated reversible and efficient Mg2+ insertion and extraction at high voltages; this is thought to be due to poor Mg2+ diffusion kinetics within the oxide structural framework. Herein, the authors provide conclusive evidence of electrochemical insertion of Mg2+ into the tetragonal tungsten bronze V4Nb18O55, with a maximum reversible electrochemical capacity of 75 mA h g-1, which corresponds to a magnesiated composition of Mg4V4Nb18O55. Experimental electrochemical magnesiation/demagnesiation revealed a large voltage hysteresis with charge/discharge (1.12 V vs Mg/Mg2+); when magnesiation is limited to a composition of Mg2V4Nb18O55, this hysteresis can be reduced to only 0.5 V. Hybrid-exchange density functional theory (DFT) calculations suggest that a limited number of Mg sites are accessible via low-energy diffusion pathways, but that larger kinetic barriers need to be overcome to access the entire structure. The reversible Mg2+ intercalation involved concurrent V and Nb redox activity and changes in crystal structure, as confirmed by an array of complementary methods, including powder X-ray diffraction, X-ray absorption spectroscopy, and energy-dispersive X-ray spectroscopy. Consequently, it can be concluded that the tetragonal tungsten bronzes show promise as intercalation electrode materials for Mg batteries.

Synthesis of Type I PbSe/CdSe Dot-on-Plate Heterostructures with Near-Infrared Emission.

Zero-dimensional PbSe quantum dots are heterogeneously nucleated and grown onto two-dimensional zincblende CdSe nanoplatelets. Electron microscopy shows ad-grown dots predominantly decorate edges and corners of the nanoplatelets. Spectroscopic characterizations relate type I electronic alignment as demonstrated via photoluminescence excitation spectroscopy enhancement of near-infrared emission. Transient photoluminescence and absorption convey ultrafast transfer of excitons to the lower energy semiconductor dots. These structures combine benefits of large absorption cross sections of nanoplatelets and efficient near-infrared emission of PbSe with quantum confinement tuning of energy gap.

Colloidal Atomic Layer Deposition with Stationary Reactant Phases Enables Precise Synthesis of "Digital" II-VI Nano-heterostructures with Exquisite Control of Confinement and Strain.

In contrast to molecular systems, which are defined with atomic precision, nanomaterials generally show some heterogeneity in size, shape, and composition. The sample inhomogeneity translates into a distribution of energy levels, band gaps, work functions, and other characteristics, which detrimentally affect practically every property of functional nanomaterials. We discuss a novel synthetic strategy, colloidal atomic layer deposition (c-ALD) with stationary reactant phases, which largely circumvents the limitations of traditional colloidal syntheses of nano-heterostructures with atomic precision. This approach allows for significant reduction of inhomogeneity in nanomaterials in complex nanostructures without compromising their structural perfection and enables the synthesis of epitaxial nano-heterostructures of unprecedented complexity. The improved synthetic control ultimately enables bandgap and strain engineering in colloidal nanomaterials with close to atomic accuracy. To demonstrate the power of the new c-ALD method, we synthesize a library of complex II-VI semiconductor nanoplatelet heterostructures. By combining spectroscopic and computational studies, we elucidate the subtle interplay between quantum confinement and strain effects on the optical properties of semiconductor nanostructures.

Colloidal Chemistry in Molten Salts: Synthesis of Luminescent In1- xGa xP and In1- xGa xAs Quantum Dots.

Control of composition, stoichiometry, and defects in colloidal quantum dots (QDs) of III-V semiconductors has proven to be difficult due to their covalent character. Whereas the synthesis of colloidal indium pnictides such as InP, InAs, and InSb has made significant progress, gallium-containing colloidal III-V QDs still remain largely elusive. Gallium pnictides represent an important class of semiconductors due to their excellent optoelectronic properties in the bulk; however, the difficulty with the synthesis of gallium-containing colloidal III-V QDs has largely prohibited their exploration as solution-processed semiconductors. Here we introduce molten inorganic salts as high-temperature solvents for the synthesis and manipulation of III-V QDs. We demonstrate cation exchange reactions on presynthesized InP and InAs QDs to form In1- xGa xP and In1- xGa xAs QDs at temperatures above 380 °C. This approach produces novel ternary alloy QDs with controllable compositions that show size- and composition-dependent absorption and emission features. Emission quantum yields of up to ∼50% can be obtained for In1- xGa xP/ZnS core-shell QDs. A comparison of the optical properties of InP/ZnS core-shells with In1- xGa xP/ZnS core-shells reveals that Ga incorporation leads to significant improvement in the optical properties of III-V/II-VI core-shell emitters which is of great importance for quantum dot-based lighting and display applications. This work also demonstrates the potential of molten inorganic salts as versatile solvents for the synthesis and processing of colloidal nanomaterials at temperatures inaccessible for traditional solvents.

Mapping Thermal Expansion Coefficients in Freestanding 2D Materials at the Nanometer Scale.

Two-dimensional materials, including graphene, transition metal dichalcogenides and their heterostructures, exhibit great potential for a variety of applications, such as transistors, spintronics, and photovoltaics. While the miniaturization offers remarkable improvements in electrical performance, heat dissipation and thermal mismatch can be a problem in designing electronic devices based on two-dimensional materials. Quantifying the thermal expansion coefficient of 2D materials requires temperature measurements at nanometer scale. Here, we introduce a novel nanometer-scale thermometry approach to measure temperature and quantify the thermal expansion coefficients in 2D materials based on scanning transmission electron microscopy combined with electron energy-loss spectroscopy to determine the energy shift of the plasmon resonance peak of 2D materials as a function of sample temperature. By combining these measurements with first-principles modeling, the thermal expansion coefficients (TECs) of single-layer and freestanding graphene and bulk, as well as monolayer MoS_{2}, MoSe_{2}, WS_{2}, or WSe_{2}, are directly determined and mapped.

Synthesis and Characterization of MgCr2S4 Thiospinel as a Potential Magnesium Cathode.

Magnesium-ion batteries are a promising energy storage technology because of their higher theoretical energy density and lower cost of raw materials. Among the major challenges has been the identification of cathode materials that demonstrate capacities and voltages similar to lithium-ion systems. Thiospinels represent an attractive choice for new Mg-ion cathode materials owing to their interconnected diffusion pathways and demonstrated high cation mobility in numerous systems. Reported magnesium thiospinels, however, contain redox inactive metals such as scandium or indium, or have low voltages, such as MgTi2S4. This article describes the direct synthesis and structural and electrochemical characterization of MgCr2S4, a new thiospinel containing the redox active metal chromium and discusses its physical properties and potential as a magnesium battery cathode. However, as chromium(III) is quite stable against oxidation in sulfides, removing magnesium from the material remains a significant challenge. Early attempts at both chemical and electrochemical demagnesiation are discussed.