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Defect engineering is a promising approach to address the inherently low conductivity and limited number of reaction sites of manganese-based spinel oxides as electrocatalysts. However, high formation energies make it challenging to controllably generate cation defects in such spinel oxides. Herein, we report a heterogeneous core–shell electrocatalyst [Mn3O4@MnxCo3−xO4–Co2(OH)3Cl, MCIL] based on a facile cation-deficiency strategy. The addition of ionic liquid (1-butyl-3-methylimidazole hexafluorophosphate) to the reaction system can simply and quickly control the octahedral field defects in spinel MnCo2O4. The results show that the selective generation of defects in the Co(Oh) octahedral field can accelerate the OER reaction kinetics and provide excellent OER electrocatalytic performance. Specifically, the MCIL series catalysts can exhibit the lowest overpotential of 332 mV at 10 mA cm−2 and Tafel slope of 50 mV dec−1, compared with that of pristine samples [i.e., Mn3O4 (890 and 343 mV dec−1) and Mn3O4@MnCo2O4 (357 and 56 mV dec−1)]. This work highlights the importance of cation defect engineering to enhance the catalytic activity of materials. [ABSTRACT FROM AUTHOR]

Two major challenges hinder the advance of aqueous zinc metal batteries for sustainable stationary storage: (1) achieving predominant Zn-ion (de)intercalation at the oxide cathode by suppressing adventitious proton co-intercalation and dissolution, and (2) simultaneously overcoming Zn dendrite growth at the anode that triggers parasitic electrolyte reactions. Here, we reveal the competition between Zn2+vs proton intercalation chemistry of a typical oxide cathode using ex-situ/operando techniques, and alleviate side reactions by developing a cost-effective and non-flammable hybrid eutectic electrolyte. A fully hydrated Zn2+ solvation structure facilitates fast charge transfer at the solid/electrolyte interface, enabling dendrite-free Zn plating/stripping with a remarkably high average coulombic efficiency of 99.8% at commercially relevant areal capacities of 4 mAh cm−2 and function up to 1600 h at 8 mAh cm−2. By concurrently stabilizing Zn redox at both electrodes, we achieve a new benchmark in Zn-ion battery performance of 4 mAh cm−2 anode-free cells that retain 85% capacity over 100 cycles at 25 °C. Using this eutectic-design electrolyte, Zn | |Iodine full cells are further realized with 86% capacity retention over 2500 cycles. The approach represents a new avenue for long-duration energy storage. Achieving high-performance aqueous Zn-metal batteries is a challenge. Here, authors report a eutectic electrolyte that concurrently enables selective Zn2+ intercalation at the cathode and highly reversible Zn metal plating/stripping, resulting in a benchmark high-areal capacity Zn anode-free cell. [ABSTRACT FROM AUTHOR]

Lithium‐ion batteries (LIBs) have been the focus of research for decades owing to their superior energy storage potential and wide range of applications. However, long‐term stability issues still persist in LIB cathodes as the result of the formation of a solid electrolyte interface (SEI), structural transformations, or the loss of active cathode materials. In nanoscale cathodes, it is often impossible to isolate, let alone mitigate the causes of the observed capacity loss. Herein, a novel approach is presented to synthesizing LIB cathode model systems using thin‐film molecular beam epitaxy (MBE). Specifically, 100 nm thick LiMn2O4 (LMO) thin‐film cathodes are grown on SrRuO3/SrTiO3 (100) single‐crystal substrates and characterized in their pristine and cycled states. The pristine thin films exhibit the electro‐chemical cycling behavior and structural evolution previously seen in bulk LMO cathodes. The formation of surface‐layer rocksalt MnO and spinel Mn3O4 along with the mass‐loss associated with the corrosion of active Mn ions is also reported. It is, therefore, demonstrated that these MBE‐grown model systems can be used for detailed studies of their surface structures and the electrode/electrolyte interfacial evolution in LIB cathodes, leading to the development of materials for rechargeable batteries with higher capacity and better stability. [ABSTRACT FROM AUTHOR]

The growth of high quality epitaxial beta-gallium oxide (β-Ga2O3) using a compound source by molecular beam epitaxy has been demonstrated on c-plane sapphire (Al2O3) substrates. The compound source provides oxidized gallium molecules in addition to oxygen when heated from an iridium crucible in a high temperature effusion cell enabling a lower heat of formation for the growth of Ga2O3, resulting in a more efficient growth process. This source also enabled the growth of crystalline β-Ga2O3 without the need for additional oxygen. The influence of the substrate temperatures on the crystal structure and quality, chemical bonding, surface morphology, and optical properties has been systematically evaluated by x-ray diffraction, scanning transmission electron microscopy, x-ray photoelectron spectroscopy, atomic force microscopy, spectroscopic ellipsometry, and UV-vis spectroscopy. Under optimized growth conditions, all films exhibited pure (201) oriented β-Ga2O3 thin films with six-fold rotational symmetry when grown on a sapphire substrate. The thin films demonstrated significant absorption in the deep-ultraviolet (UV) region with an optical bandgap around 5.0 eV and a refractive index of 1.9. A deep-UV photodetector fabricated on the high quality β-Ga2O3 thin film exhibits high resistance and small dark current (4.25 nA) with expected photoresponse for 254 nm UV light irradiation suggesting that the material grown using the compound source is a potential candidate for deep-ultraviolet photodetectors. [ABSTRACT FROM AUTHOR]

We examine the role of Ti doping in the incommensurately layered thermoelectric oxide material Ca3Co4O9 (CCO). The measured Seebeck coefficient of S=135 lV/K in Ti-doped CCO thin films of composition Ca3Co3.8Ti0.2O9 indicates no significant enhancement of S compared to pristine CCO, thus confirming prior experimental results. Using a combination of aberration-corrected scanning transmission electron microscopy, electron energy-loss spectroscopy and first-principles computations, we determine the atomic and electronic structures of Ti-doped CCO, including the preferred location of Ti dopants and valence states of Ti and Co atoms. Our findings on the structural, electronic, and transport properties of the Ti-doped CCO are discussed in light of the previously published results. [ABSTRACT FROM AUTHOR]

Thin films consisting of 17 groups of Hf/In/C multilayers cyclically alternating layers of Hf, In and C each with a thickness of 4–5 nm were synthesized by ion sputtering using a 25 keV Ar+ ion beam with 400 µA current and targets made of pure hafnium, indium and carbon. The films were subsequently annealed in vacuum at 120°C for 24 hours to induce intermixing of elements phases, their interaction, and formation of the Hf-In-C nanostructures (including the Hf2InC MAX phase). After fabrication, a part of the pristine (as deposited) samples was irradiated by 200 keV Ar+ ions at high fluences 1015 and 1017 cm−2. Both samples (as prepared and irradiated) were analyzed by IBA nuclear analytical methods, as well as by AFM and TEM microscopic techniques, and by XPS and profilometry to understand the microstructural evolution. Moreover, nanoindentation analysis was performed to assess the effects of ion irradiation on the microstructure and mechanical properties of the films. The experimental results showed that thin Hf-In-C nanostructured films can be formed by ion sputtering with promising mechanical parameters. The irradiated Hf-In-C films were found to be resistant only up to a fluence of about 1015 Ar cm−2. At higher fluences it degrades, and Hf2InC transforms to the binary HfC0.95 phase due to sublimation of In. At 1017 cm−2 the original matrix (including M2AX) is destroyed, and instead, a mixture of MX binary phases (e.g. HfC0.95) and crystalline oxides (e.g. HfO2 and In2O3) are formed. [ABSTRACT FROM AUTHOR]

Liquid cell electron microscopy is an imaging technique allowing for the investigation of the interaction of liquids and solids at nanoscopic length scales. Such in situ observations 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− Ĺ−2 s−1. With the measured threshold dose for the bubble formation in pure water equaling 9 e− Ĺ−2 s−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. [ABSTRACT FROM AUTHOR]

Nanoscale thermometry, an approach based on non-invasive, yet precise measurements of temperature with nanometer spatial resolution, has emerged as a very active field of research over the last few years. In transmission electron microscopy, nanoscale thermometry is particularly important during in situ experiments or to assess the effects of beam induced heating. In this article, we present a nanoscale thermometry approach based on electron energy-loss spectroscopy in a transmission electron microscope to measure locally the temperature of silicon nanoparticles using the energy shift of the plasmon resonance peak with respect to the zero-loss peak as a function of temperature. We demonstrate that using non-negative matrix factorization and curve fitting of stacked spectra, the temperature accuracy can be improved significantly over previously reported manual fitting approaches. We will discuss the necessary acquisition parameters to achieve a precision of 6 meV to determine the plasmon peak position. [ABSTRACT FROM AUTHOR]

The development and implementation of high-stability monochromators in state-of-the-art aberration-corrected scanning transmission electron microscopes has enabled materials characterization with an energy resolution as good as 3 meV. This allows the vibrational modes, which would otherwise be obscured by the energy spread of the electron beam, to be probed with very high precision in molecular materials. Since the vibrational energies depend on the weight of the atomic nuclei, vibrational spectroscopy can distinguish isotopes whose only difference lies in their neutron content. This opens up isotopic analysis and mapping in transmission electron microscopy as two important new research areas. Here, we review the monochromated electron energy loss spectroscopy (EELS) instrumentation, discuss optimal methods for probing beam-sensitive materials without destroying them, and review key nanoscale isotope-resolved results. [ABSTRACT FROM AUTHOR]

Bandgap engineering plays a critical role in optimizing the electrical, optical and (photo)‐electrochemical applications of semiconductors. Alloying has been a historically successful way of tuning bandgaps by making solid solutions of two isovalent semiconductors. In this work, a novel form of bandgap engineering involving alloying non‐isovalent cations in a 2D transition metal dichalcogenide (TMDC) is presented. By alloying semiconducting MoSe2 with metallic NbSe2, two structural phases of Mo0.5Nb0.5Se2, the 1T and 2H phases, are produced each with emergent electronic structure. At room temperature, it is observed that the 1T and 2H phases are semiconducting and metallic, respectively. For the 1T structure, scanning tunneling microscopy/spectroscopy (STM/STS) is used to measure band gaps in the range of 0.42–0.58 at 77 K. Electron diffraction patterns of the 1T structure obtained at room temperature show the presence of a nearly commensurate charge density wave (NCCDW) phase with periodic lattice distortions that result in an uncommon 4 × 4 supercell, rotated approximately 4° from the lattice. Density‐functional‐theory calculations confirm that local distortions, such as those in a NCCDW, can open up a band gap in 1T‐Mo0.5Nb0.5Se2, but not in the 2H phase. This work expands the boundaries of alloy‐based bandgap engineering by introducing a novel technique that facilitates CDW phases through alloying. [ABSTRACT FROM AUTHOR]

The ability to predict the likelihood of impurity incorporation and their electronic energy levels in semiconductors is crucial for controlling its conductivity, and thus the semiconductor's performance in solar cells, photodiodes, and optoelectronics. The difficulty and expense of experimental and computational determination of impurity levels makes a data-driven machine learning approach appropriate. In this work, we show that a density functional theory-generated dataset of impurities in Cd-based chalcogenides CdTe, CdSe, and CdS can lead to accurate and generalizable predictive models of defect properties. By converting any semiconductor + impurity system into a set of numerical descriptors, regression models are developed for the impurity formation enthalpy and charge transition levels. These regression models can subsequently predict impurity properties in mixed anion CdX compounds (where X is a combination of Te, Se and S) fairly accurately, proving that although trained only on the end points, they are applicable to intermediate compositions. We make machine-learned predictions of the Fermi-level-dependent formation energies of hundreds of possible impurities in 5 chalcogenide compounds, and we suggest a list of impurities which can shift the equilibrium Fermi level in the semiconductor as determined by the dominant intrinsic defects. Machine learning predictions for the dominating impurities compare well with DFT predictions, revealing the power of machine-learned models in the quick screening of impurities likely to affect the optoelectronic behavior of semiconductors. [ABSTRACT FROM AUTHOR]

We present a series of electron energy-loss spectroscopy (EELS) studies on niobium (Nb) and its oxides (NbO, NbO2, and Nb2O5) to develop a reliable method for quantifying the oxidation state in mixed niobium oxide thin films. Our approach utilizes a combination of transmission electron microscopy and EELS experiments with density functional theory calculations to distinguish between metallic niobium and the different niobium oxides. More specifically, the differences in the near-edge fine-structure of the Nb M-edge and O K-edge provide sufficient information to determine the valence state of niobium. Based on these observed changes in the core-loss edges, we propose a linear relationship that correlates the peak positions in the Nb M- and O K-edges with the Nb valence state. The methods developed in this paper are also applied to ultrathin niobium oxide films to examine the effects of low-temperature baking on the films' oxidation states. [ABSTRACT FROM AUTHOR]

Temperature dependent photoluminescence (PL) spectroscopy along with structural investigations of luminescent porous Si enable us to experimentally distinguish between the relative contributions of band-to-band and oxide interface mediated electronic transitions responsible for light emission from these nanostructures. Porous Si samples formed using high current densities (J ≥ 80 mA/cm2) have large porosities (P ≥ 85%) and consequently smaller (∼1-6 nm) average crystallite sizes. The PL spectra of these high porosity samples are characterized by multiple peaks. Two dominant peaks-one in the blue regime and one in the yellow/orange regime, along with a very low intensity red/NIR peak, are observed for these samples. The high energy peak position is nearly independent of temperature, whereas the yellow/orange peak red-shifts with increasing temperature. Both the peaks blue shift with ageing and with increasing porosity. The intensity of the blue peak increases whereas the yellow/orange peak decreases with increasing temperature, while the intensity and peak position of the very low intensity red/NIR peak appears to be unaffected by temperature, porosity, and ageing. The low porosity samples (P ≤ 60%) on the other hand exhibit a single PL peak whose intensity decreases and exhibits a very small red spectral shift with increase in temperature. From the variation of intensity and PL peak positions, it is established that both quantum confinement of excitons and oxide related interfacial defect states play dominant role in light emission from porous Si and it is possible to qualitatively distinguish and assign their individual contributions. [ABSTRACT FROM AUTHOR]

Determining the Co valence, particularly in Co-based nanocatalysts is a longstanding experimental challenge. In this paper, we utilize in situ electron energy-loss spectroscopy and first-principles density functional theory calculations to distinguish between metallic Co, Co3O4, as well as CoO. More specifically, differences in the O K- and Co L-edges are utilized to determine the Co valence in different Co-oxide particles. We will further demonstrate that while the metallic Co L3/L2-ratio equals that of partially reduced Co3O4, the near-edge fine-structure of the metallic Co L-edge exhibits additional features not present in any Co-oxide. The origin of these features will be discussed. Based on our experimental and theoretical results, we will propose a fitting method to distinguish metallic Co from Co-oxides. [ABSTRACT FROM AUTHOR]

We report synthesis and luminescent characteristics of core-shell nanostructures of silicon and silicon oxide having two different morphologies—spherical (nanodot) and rodlike (nanorod), prepared by controlled oxidation of mechanically milled crystalline silicon and by exfoliation of the affected layer of porous silicon. Colloidal suspensions of these nanostructures exhibit intense room temperature photoluminescence (PL), detectable with the unaided eye. PL band peak energies of the colloidal suspensions formed from porous silicon are blue shifted by ∼1 eV compared to the as-prepared films on silicon substrate. In addition, PL spectra of all the colloidal suspensions blueshift with increase in excitation energy but the PL peaks of as-prepared porous silicon are independent of excitation. However, shape of the nanocrystals (spherical or rodlike) is found to have little effect on the emission spectra. These observations are explained in terms discretization of phonon density of states and electronic transitions involving surface defect states and quantum confinement induced widened band states. [ABSTRACT FROM AUTHOR]

Layered perovskite La2CuO4+δ (LCO) thin films were epitaxially grown on SrTiO3 (STO) and LaSrAlO4 substrates by atomic-layer-by-layer molecular beam epitaxy. The lattice defects and residual strain in these films were investigated by means of transmission electron microscopy and electron energy loss spectroscopy. The LCO films showed a high epitaxial quality with flat interfaces and top surfaces. Misfit dislocations with Burgers vector a<010> and shear defects were frequently observed at or near the film/substrate interfaces and in the films, respectively. In one LCO film, grown on STO at the highest temperature, 700 °C, we observed a two layered structure with the top layer being rhombohedral CuLaO2. In addition, stacking faults were observed in the plane views of one LCO film grown on the STO substrate. The residual strains were evaluated from the associated splitting of Bragg reflection. Possible mechanisms of strain relaxations are discussed based on the observed defects. [ABSTRACT FROM AUTHOR]

Electrochemically driven chemical transformations play the key role in controlling storage of energy in chemical bonds and subsequent conversion to power electric vehicles and consumer electronics. The promise of coupling anionic oxygen redox with cationic redox to achieve a substantial increase in capacities has inspired research in a wide range of electrode materials. A key challenge is that these studies have focused on polycrystalline materials, where it is hard to perform precise structural determinations, especially related to the location of light atoms. Here a different approach is utilized and a highly ordered single crystal, Na2−xIrO3 is harnessed, to explore the role of defects and structural transformations in layered transition metal oxide materials on redox‐activity, capacity, reversibility, and stability. Within a combined experimental and theoretical framework, it is demonstrated that 1) it is possible to cycle Na2−xIrO3, offering proof of principle for single‐crystal based batteries 2) structural phase transitions coincide with Ir 4+/Ir 5+ redox couple with no evident contribution from anionic redox 3) strong irreversibility and capacity fade observed during cycling correlates with the Na + migration resulting in progressive growth of an electrochemically inert O3‐type NaIrO3 phase. [ABSTRACT FROM AUTHOR]

CdTe-based solar cell efficiency has rapidly improved over the last few years. Some of the reasons have been a change to the absorber composition including the incorporation of selenium, and better front contact and emitter materials in CdTe photovoltaic devices. In addition to the increase in short-circuit current by reducing the bandgap, Se plays other important roles in passivation of defects thus improving the conversion efficiency of CdSeTe/CdTe graded absorber photovoltaic devices. Here, we combine structural and optical characterizations with first principles calculations to investigate the role of Se and Cl segregation in CdSeTe devices. We find that in the presence of Se and Cl, the minority carrier lifetime improves due to a reduction of midgap defect states. We also correlate this effect with defect passivation in CdSeTe devices and suggest innovative ways to further improve CdTe-based photovoltaic efficiency. [ABSTRACT FROM AUTHOR]

The presence and potential ordering of oxygen vacancies play an important role in determining the electronic, ionic, and thermal transport properties of many transition metal oxide materials. Controlling the concentration of oxygen vacancies, as well as the structures of ordered oxygen vacancy domains, has been the subject of many experimental and theoretical studies. In epitaxial thin films, the concentration of oxygen vacancies and the type of ordering depend on the structure of the substrate as well as the lattice mismatch between the thin films and the substrate. However, the role of temperature or structural phase transitions in either the substrate or the epitaxial thin films in the oxygen vacancy ordering has remained largely unexplored. In particular, atomic-resolution imaging and spectroscopy analysis of oxygen vacancy ordering in thin films at temperatures below 300 K have not yet been reported. Here, we use aberration-corrected scanning transmission electron microscopy combined with in-situ cooling experiments to characterize the atomic/electronic structures of oxygen-deficient La0.5Sr0.5CoO3−δ thin films grown on SrTiO3 across its antiferrodistortive phase transition at 105 K. We demonstrate that atomic-resolution imaging and electron energy-loss spectroscopy can be used to examine variations in the local density of states as a function of sample temperature. [ABSTRACT FROM AUTHOR]