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Here, we present a comprehensive study on atomic-scale in-situ biasing/heating scanning transmission electron microscopy ((S)TEM) of Al-amorphous SiO2–SiC interface. The investigation includes electrical, chemical, and structural analysis of the interface at different temperatures (25–600 °C). The results show that at ~ 500 °C the electrical (three-orders of magnitude resistivity drop), chemical (dissolution of SiO2 amorphous layer), and microstructural features (e.g. formation of Al2O3, Si and Al4C3) of the interface start to change. According to the results, amorphous SiO2 dissolves in Al, leading to formation of α-Al2O3 and Si within the Al. In contrast, elemental interdiffusion (Al3+ ⇄ Si4+) between Al and SiC occurs resulting in formation of Al4C3. From the results, we can infer that reaction mechanism between Al and crystalline SiC is different with that between Al and SiO2 amorphous phase. It is believed that structural similarities between SiC and Al4C3 play an important role in paving the way for elemental interdiffusion.

Permanent magnets draw their properties from a complex interplay, across multiple length scales, of the composition and distribution of their constituting phases, that act as building blocks, each with their associated intrinsic properties 1. Gaining a fundamental understanding of these interactions is hence key to decipher the origins of their magnetic performance2 and facilitate the engineering of better-performing magnets, through unlocking the design of the “perfect defects” for ultimate pinning of magnetic domains3. Here, we deployed advanced multiscale microscopy and microanalysis on a bulk Sm2(CoFeCuZr)17 pinning-type high-performance magnet with outstanding thermal and chemical stability 4. Making use of regions with different chemical compositions, we showcase how both a change in the composition and distribution of copper, along with the atomic arrangements enforce the pinning of magnetic domains, as imaged by nanoscale magnetic induction mapping. Micromagnetic simulations bridge the scales to provide an understanding of how these peculiarities of micro- and nanostructure change the hard magnetic behaviour of Sm2(CoFeCuZr)17 magnets. Unveiling the origins of the reduced coercivity allows us to propose an atomic-scale defect and chemistry manipulation strategy to define ways toward future hard magnets.

Powder bed fusion of metals using a laser beam (PBF-LB/M) is an established additive manufacturing (AM) method that can be used to fabricate geometrically complex NdFe-B magnets. However, the magnetic properties of Nd-Fe-B magnets manufactured by PBF-LB/M are typically inferior to conventionally produced magnets. To overcome this drawback, we modified the surface of the permanent magnet feedstock powder with 1 wt.% surfactant-free Ag nanoparticles (NPs) supporting the formation of relevant phases required for permanent magnetic performance to achieve a suitable micro- and nanostructure after AM. Our study is accompanied by finite element simulations, revealing the impact and dependency of process parameters during PBF-LB/M: a wide temperature field with a high-gradient profile in the front and on the bottom of an overheated region, implying a vast local heating/cooling rate and in-process high thermal stress. We found experimentally that the as-built part density can be affected by both the laser power and scan speed, causing a reduction in density as both parameters increase. The functionality and microstructural properties are also investigated via VSM, HR-SEM, EDX, EBSD, and exemplarily with HR-TEM-EDX and APT. Our study found that modifying MQP-S with Ag NPs increases the coercivity by approximately 20%, which we correlate to a decreased grain size. Additionally, we identified three distinct phases in the modified and unmodified samples, where Ag is primarily found in the intergranular and Nd-rich phases of the as-built parts. Overall, the study's findings contribute to the understanding of the factors that affect the quality and magnetic properties of Nd-Fe-B magnets fabricated through PBF-LB/M and provide valuable insights for further research in this area.

SiBN ceramics are widely considered to be the most promising material for microwave-transparent applications in harsh environments owing to its excellent thermal stability and low dielectric constant. This work focuses on the synthesis and ceramization of single-source precursors for the preparation of SiBN ceramics as well as the investigation of the corresponding microstructural evolution at high temperatures including molecular dynamic simulations. Carbon- and chlorine-free perhydropolysilazanes were reacted with borane dimethyl sulfide complex at different molar ratios to synthesize single-source precursors, which were subsequently pyrolyzed and annealed under N2 atmosphere (without ammonolysis) to prepare SiBN ceramics at 1100, 1200, and 1300 °C with high ceramic yield in contrast to previously widely-used ammonolysis synthesis process. The obtained amorphous SiBN ceramics were shown to have remarkably improved thermal stability and oxidation resistance compared to amorphous silicon nitride. Particularly, the experimental results have been combined with molecular dynamics simulation to further study the amorphous structure of SiBN and the atomic-scale diffusion behavior of Si, B, and N at 1300 °C. Incorporation of boron into the Si—N network is found to suppress the crystallization of the formed amorphous silicon nitride and hence improves its thermal stability in N2 atmosphere.

Hafnium oxide plays an important role as a dielectric material in various thin-film electronic devices such as transistors and resistive or ferroelectric memory. The crystallographic and electronic structure of the hafnia layer often depends critically on its composition and defect structure. Here, we report two novel defect-stabilized polymorphs of substoichiometric HfO

Utilizing the molecular beam epitaxy technique, a nanoscale thin-film magnet of c-axis-oriented Sm2Co17 and SmCo5 phases is stabilized. While typically in the prototype Sm(Co, Fe, Cu, Zr)7.5-8 pinning-type magnets, an ordered nanocomposite is formed by complex thermal treatments, here, a one-step approach to induce controlled phase separation in a binary Sm-Co system is shown. A detailed analysis of the extended X-ray absorption fine structure confirmed the coexistence of Sm2Co17 and SmCo5 phases with 65% Sm2Co17 and 35% SmCo5. The SmCo5 phase is stabilized directly on an Al2O3 substrate up to a thickness of 4 nm followed by a matrix of Sm2Co17 intermixed with SmCo5. This structural transition takes place through coherent atomic layers, as revealed by scanning transmission electron microscopy. Highly crystalline growth of well-aligned Sm2Co17 and SmCo5 phases with coherent interfaces result in strong exchange interaction, leading to enhanced magnetization and magnetic coupling. The arrangement of Sm2Co17 and SmCo5 phases at the nanoscale is reflected in the observed magnetocrystalline anisotropy and coercivity. As next-generation permanent magnets require designing of materials at an atomic level, this work enhances our understanding of self-assembling and functioning of nanophased magnets and contributes to establishing new concepts to engineer the microstructure for beyond state-of-the-art magnets.

Reversible antiferroelectric-ferroelectric phase transitions were recently observed in a series of SrSnO3-modified NaNbO3 lead-free antiferroelectric materials, exhibiting well-defined double polarization hysteresis loops at ambient conditions. Here, transmission electron microscopy was employed to investigate the crystallographyand domain configuration of this newly designed system via electron diffraction and centered dark-field imaging. It was confirmed that antiferroelectricity is maintained in all compositions, manifested by the characteristic ¼ superlattice reflections in the electron-diffraction patterns. By investigating the antiferroelectric domains and domain boundaries in NaNbO3, we demonstrate that antiphase boundaries are present and their irregular periodicity is responsible for the streaking features along the ¼ superlattice reflections in the electron-diffraction patterns. The signature domain blocks observed in pure NaNbO3 are maintained in the SrSnO3-modified ceramics, but disappear when the amount of SrSnO3 reaches 7 mol.%. In particular, a well-defined and distinct domain configuration is observed in the NaNbO3 sample modified with 5 mol.% SrSnO3, which presents a parallelogram domain morphology.

Ni-Mn-based Heusler alloys, in particular all-d-metal Ni(-Co)-Mn-Ti, are highly promising materials for energy-efficient solid-state refrigeration as large multicaloric effects can be achieved across their magnetostructural martensitic transformation. However, no comprehensive study on the crucially important transition entropy change Δs exists so far for Ni(-Co)-Mn-Ti. Here, we present a systematic study analyzing the composition and temperature dependence of Δst. Our results reveal a substantial structural entropy change contribution of approximately 65 J(kgK)-1, which is compensated at lower temperatures by an increasingly negative entropy change associated with the magnetic subsystem. This leads to compensation temperatures Tcomp of 75 K and 300 K in Ni35Co15Mn50-yTiy and Ni33Co17Mn50-yTiy, respectively, below which the martensitic transformations are arrested. In addition, we simultaneously measured the responses of the magnetic, structural and electronic subsystems to the temperature- and field-induced martensitic transformation near Tcomp, showing an abnormal increase of hysteresis and consequently dissipation energy at cryogenic temperatures. Simultaneous measurements of magnetization and adiabatic temperature change ΔTad in pulsed magnetic fields reveal a change in sign of ΔTad and a substantial positive and irreversible ΔTad up to 15 K at 15 K as a consequence of increased dissipation losses and decreased heat capacity. Most importantly, this phenomenon is universal, it applies to any first-order material with non-negligible hysteresis and any stimulus, effectively limiting the utilization of their caloric effects for gas liquefaction at cryogenic temperatures.

Electric-field-induced phase transitions are the most important characteristics of antiferroelectric materials. However, in several prototype antiferroelectrics, these transitions are irreversible and the origin of this behavior is poorly understood. This prevents their widespread use, for example, in energy storage and memory applications. Here, we investigated the antiferroelectric-ferroelectric phase transitions in polycrystalline NaNbO3, a material recently suggested as the basis for lead-free antiferroelectrics with high energy storage densities. An irreversible transition from the antiferroelectric state to a new state showing macroscopic piezoelectricity (d33=35 pC/N) was induced at 11.6 kV/mm (room temperature, 1 Hz), accompanied by a 33% drop in permittivity. Microscopically, a change from a translational antiferroelectric domain structure to a wedge-shaped ferroelectric domain structure was observed using transmission electron microscopy. 23Na solid-state nuclear magnetic resonance allowed for a detailed study of the local structure and revealed pure antiferroelectric and coexisting antiferroelectric/ferroelectric nature of the samples before and after the application of an electric field, respectively. Interestingly, despite the large electric fields applied, only 50±5% of the material underwent the antiferroelectric-ferroelectric phase transition, which was related to the material´s microstructure. The temperature- and frequency-dependence of the phase transition was studied and compared to the behavior observed in lead-based antiferroelectric systems.

In this work, the reduction of iron oxide γ-Fe2O3 nanoparticles by hydrogen at high pressures is studied. Increasing the hydrogen pressure enables reduction of γ-Fe2O3 to α-Fe at significantly lower temperatures. At low pressures, a temperature of 390 °C is necessary whereas at 530 bar complete reduction can be realized at temperatures as low as 210 °C. This leads to significant improvement in the final particle morphology, maintaining high surface-to-volume ratio of the nanoparticles with an average size of 47 ± 5 nm which is close to that of the precursor γ-Fe2O3. Neck formation, coalescence and growth during reduction can be significantly suppressed. Investigations of magnetic properties show that saturation magnetization of the reduced α-Fe nanoparticles decreases with particle size from 209 A m2 kg−1 at 390 °C reduction temperature to 204 A m2 kg−1 at 210 °C. Coercivity for the fine iron particles reaches 0.076 T which exceeds the theoretical anisotropy field. This is attributed to nano-scale surface effects.

Two-dimensional carbides/nitrides, typically called MXenes, are an emerging member of the ever-growing family of two-dimensional materials. The prediction of a ferromagnetic groundstate in chromium-containing MXenes has triggered growing interest in their chemical exfoliation from Cr-based MAX phases. However, the exfoliation poses serious difficulties using standard etching agents such as hydrofluoric acid (HF). Here, we investigate the exfoliability of Cr2GaC particles by chemical etching with aqueous HF both experimentally and theoretically. Structural and microstructural analyses show that the Cr2GaC particles decompose into chromium carbide and oxide without the formation of a Cr-based MXene. A thermodynamic analysis based on ab initio electronic structure calculations reveals that the exfoliation of Cr-based MXene from Cr2GaC by HF-etching is inhibited by more favorable competing reactions. This result confirms the experimental finding and suggests that HF is an unsuitable etching agent for a successful exfoliation of Cr2GaC.

Ferromagnetic Fe3Sn, Fe5Sn3 and Fe3Sn2 single crystals were synthesized using the reactive flux technique. Derived from single crystal x-ray diffraction and Transmission Electron Microscopy (TEM), a new structural model is proposed for the Fe5Sn3 crystals - the threefold twinning of an orthorhombic unit cell with (3 + 1) dimensional space group Pbcm(α00)0s0. The spontaneous magnetization (Ms) and the anisotropy constants K1 and K2 of Fe3Sn, Fe5Sn3 and Fe3Sn2 single crystals were determined in a wide temperature range using M(H) dependencies and a modified Sucksmith-Thompson technique. Ms and K1 were also evaluated in the framework of Density Functional Theory (DFT) and an overall good agreement was observed between the calculated and experimental results. Furthermore, a critical evaluation of different analytical models for the assessment of magnetocrystalline anisotropy was performed, which are restricted to the analysis of uniaxial magnetic domain patterns, and it is shown that such high-throughput techniques can lead to unrealistic results. Finally, a DFT high-throughput screening of the Fe-Sn phase diagram was used to identify Fe-Sn based phases with potential to be stabilized upon alloying, and their magnetization and magnetocrystalline anisotropy were evaluated. The results show that a similar strong anisotropy as observed in Fe3Sn may also be found in other Fe-Sn based phases, having higher potential to be used as hard magnetic material.

Permanent magnets based on neodymium-iron-boron (Nd-Fe-B) alloys provide the highest performance and energy density, finding usage in many high-tech applications. Their magnetic performance relies on the intrinsic properties of the hard-magnetic Nd$_2$Fe$_{14}$B phase combined with control over the microstructure during production. In this study, a novel magnetic hardening mechanism is described in such materials based on a solid-state phase transformation. Using modified Nd-Fe-B alloys of the type Nd$_{16}$Fe$_{bal-x-y-z}$Co$_x$Mo$_y$Cu$_z$B$_7$ for the first time it is revealed how the microstructural transformation from the metastable Nd$_2$Fe$_{17}$B$_x$ phase to the hard-magnetic Nd$_2$Fe$_{14}$B phase can be thermally controlled, leading to an astonishing increase in coercivity from ≈200 kAm$^{−1}$ to almost 700 kAm$^{−1}$. Furthermore, after thermally treating a quenched sample of Nd$_{16}$Fe$_{56}$Co$_{20}$Mo$_2$Cu$_2$B$_7$, the presence of Mo leads to the formation of fine FeMo$_2$B$_2$ precipitates, in the range from micrometers down to a few nanometers. These precipitates are responsible for the refinement of the Nd$_2$Fe$_{14}$B grains and so for the high coercivity. This mechanism can be incorporated into existing manufacturing processes and can prove to be applicable to novel fabrication routes for Nd-Fe-B magnets, such as additive manufacturing

MAX phases are typically prepared by high-temperature (oftentimes high-pressure) solid-state methods. Here, we report a new wet chemistry based synthesis technique starting from an aqueous solution of metal nitrates and citric acid to prepare MAX phase Cr2GaC. This solution-processable precursor mixture has the potential to be easily scaled, painted, printed or fabricated onto supports – an advantage that is demonstrated by the formation of hollow carbon microspheres which are decorated with Cr2GaC particles. A small amount of chromium carbide and oxide remains in the product, however, the amount of the latter can be reduced by a larger excess in citric acid in the precursor gel. The transformation mechanism of the initial amorphous gel into highly crystalline and anisotropic MAX phase particles is investigated by detailed thermal analysis. Transmission electron microscopy studies are conducted to elucidate the microstructure of the sol–gel-prepared particles as well as the decorated hollow microspheres. From magnetic susceptibility measurements, the density of states at the Fermi level is deduced reflecting the quality of the Pauli paramagnet Cr2GaC.

Ni-Mn-based metamagnetic shape-memory alloys exhibit a giant thermal response to magnetic fields and uniaxial stress which can be utilized in single caloric or multicaloric cooling concepts for energy-efficient and sustainable refrigeration. However, during cyclic operation these alloys suffer from structural and functional fatigue as a result of their high intrinsic brittleness. Here, we present based on Fe-doping of Ni-Mn-In a microstructure design strategy which simultaneously improves cyclic stability and maintains the excellent magnetocaloric and elastocaloric properties. Our results reveal that precipitation of a strongly Fe-enriched and In-depleted coherent secondary gamma-phase at grain boundaries can ensure excellent mechanical stability by hindering intergranular fracture during cyclic loading. In this way, a large elastocaloric effect of -4.5 K was achieved for more than 16000 cycles without structural or functional degradation, which corresponds to an increase of the cyclic stability by more than three orders of magnitude as compared to single-phase Ni-Mn-In-(Fe). In addition, we demonstrate that the large magnetocaloric effect of single-phase Ni-Mn-In-(Fe) can be preserved in the dual-phase material when the secondary gamma-phase is exclusively formed at grain boundaries as the martensitic transformation within the Heusler matrix is barely affected. This way, an adiabatic temperature change of -3 K and an isothermal entropy change of 15 $Jkg^{-1}K^{-1}$ was obtained in 2 T for dual-phase Ni-Mn-In-Fe. We expect that this concept can be applied to other single caloric and mutlicaloric materials, therewith paving the way for solid-state caloric cooling applications.

Microstructure design allows to prevent intergranular cracking and premature failure in Co–Ni–Ga shape memory alloys. Favorable grain boundary configurations are established using additive manufacturing techniques, namely, direct energy deposition (DED) and laser powder bed fusion (L-PBF). L-PBF allows to establish a columnar grain structure. In the Co–Ni–Ga alloy processed by DED, a microstructure with strong ⟨001⟩ texture is obtained. In line with optimized microstructures, the general transformation behavior is essential for performance. Transition parameters such as transition temperature and thermal hysteresis depend on chemical composition, homogeneity, and presence of precipitates. However, these parameters are highly dependent on the processing method used. Herein, the first-order magnetostructural transformation and magnetization properties of Co–Ni–Ga processed by DED and L-PBF are compared with single-crystalline and as-cast material. In the alloy processed by L-PBF, Ga evaporation and extensive formation of the ferromagnetic Co-rich γ'-phase are observed, promoting a very wide transformation range and large thermal hysteresis. In comparison, following DED, the material is characterized by minor chemical inhomogeneity and transition and magnetization behavior being similar to that of a single crystal. This clearly renders DED-processed Co–Ni–Ga to become a promising candidate material for future shape memory applications. © 2022 The Authors. Advanced Engineering Materials published by Wiley-VCH GmbH.

Low-frequency noise in Y2O3-based resistive random-access memory devices with analog switching is studied at intermediate resistive states and as a function of dc cycling. A universal 1/f(alpha)-type behavior is found, with a frequency exponent of alpha approximate to 1.2 that is independent of the applied reset voltage or the device resistance and is attributed to the intrinsic abundance of oxygen vacancies unique to the structure of yttria. Remarkably, the noise magnitude in the high resistive state systematically decreases through dc training. This effect is attributed to the stabilization of the conductive filament via the consumption of oxygen vacancies, thus reducing the number of active fluctuators in the vicinity of the filament.

Any dielectric material under a strain gradient presents flexoelectricity. Here, we synthesized 0.75 sodium bismuth titanate −0.25 strontium titanate (NBT-25ST) core–shell nanoparticles via a solid-state chemical reaction directly inside a transmission electron microscope (TEM) and observed domain-like nanoregions (DLNRs) up to an extreme temperature of 800 °C. We attribute this abnormal phenomenon to a chemically induced lattice strain gradient present in the core–shell nanoparticle. The strain gradient was generated by controlling the diffusion of strontium cations. By combining electrical biasing and temperature-dependent in situ TEM with phase field simulations, we analyzed the resulting strain gradient and local polarization distribution within a single nanoparticle. The analysis confirms that a local symmetry breaking, occurring due to a strain gradient (i.e. flexoelectricity), accounts for switchable polarization beyond the conventional temperature range of existing polar materials. We demonstrate that polar nanomaterials can be obtained through flexoelectricity at extreme temperature by tuning the cation diffusion., The limited number of materials with a switchable electrical polarization available for applications can be increased by exploiting the flexoelectric effect. Here, switchable polarization in nanoparticles induced by an elemental distribution dependent strain gradient up to 800 °C is demonstrated.

Point defects largely determine the properties of functional oxides. So far, limited knowledge exists on the impact of cation vacancies on electroceramics, especially in (Na1/2Bi1/2)TiO3 (NBT)-based materials. Here, we report on the drastic effect of A-site non-stoichiometry on the cation diffusion and functional properties in the representative ferroelectric (Na1/2Bi1/2)TiO3–SrTiO3 (NBT–ST). Experiments on NBT/ST bilayers and NBT–ST with Bi non-stoichiometry reveal that Sr2+-diffusion is enhanced by up to six orders of magnitude along the grain boundaries in Bi-deficient material as compared to Bi-excess material with values of grain boundary diffusion ∼10−8 cm2 s−1 and ∼10−13 cm2 s−1 in the bulk. This also means a nine orders of magnitude higher diffusion coefficient compared to reports from other Sr-diffusion coefficients in ceramics. Bi-excess leads to the formation of a material with a core–shell microstructure. This results in 38% higher strain and one order of magnitude lower remanent polarization. In contrast, Bi-deficiency leads to a ceramic with a grain size six times larger than in the Bi-excess material and homogeneous distribution of compounds. Thus, the work sheds light on the rich opportunities that A-site stoichiometry offers to tailor NBT-based materials microstructure, transport properties, and electromechanical properties.

A molecular dynamics simulation approach is applied to investigate thermal expansion of the lattice parameters and heat capacities of SrMoO3 and BaMoO3 perovskite-type molybdates in the temperature range between 300 and 1000 K. The meaningful shape of the pairwise potential for SrMoO3 and BaMoO3 is achieved by fitting their lattice parameters to those of the high-purity polycrystalline powders synthesized via reduction of their respective scheelite precursors in hydrogen atmosphere at high pressure. The approach is validated by the simulated temperature dependences of the heat capacity, which follow the reported experimental data near and above the Debye temperature.

A higher saturation magnetization obtained by an increased iron content is essential for yielding larger energy products in rare-earth Sm2Co17-type pinning-controlled permanent magnets. These are of importance for high-temperature industrial applications due to their intrinsic corrosion resistance and temperature stability. Here we present model magnets with an increased iron content based on a unique nanostructure and -chemical modification route using Fe, Cu, and Zr as dopants. The iron content controls the formation of a diamond-shaped cellular structure that dominates the density and strength of the domain wall pinning sites and thus the coercivity. Using ultra-high-resolution experimental and theoretical methods, we revealed the atomic structure of the single phases present and established a direct correlation to the macroscopic magnetic properties. With further development, this knowledge can be applied to produce samarium cobalt permanent magnets with improved magnetic performance., Understanding the factors that determine the properties of permanent magnets, which play a central role in many industrial applications, can help in improving their performance. Here, the authors study how changes in the iron content affect the microstructure of samarium cobalt magnets.

The crystal structure and disorder phenomena of Al4B2O9, an aluminum borate from the mullite-type family, were studied using automated diffraction tomography (ADT), a recently established method for collection and analysis of electron diffraction data. Al4B2O9, prepared by sol-gel approach, crystallizes in the monoclinic space group C2/m. The ab initio structure determination based on three-dimensional electron diffraction data from single ordered crystals reveals that edge-connected AlO6 octahedra expanding along the b axis constitute the backbone. The ordered structure (A) was confirmed by TEM and HAADF-STEM images. Furthermore, disordered crystals with diffuse scattering along the b axis are observed. Analysis of the modulation pattern implies a mean superstructure (AAB) with a threefold b axis, where B corresponds to an A layer shifted by ½a and ½c. Diffraction patterns simulated for the AAB sequence including additional stacking disorder are in good agreement with experimental electron diffraction patterns.

In this study lead-free 2-2 and 0-3 ceramic/ceramic composites comprised of the non-ergodic relaxor 0.93(Bi1/2Na1/2)TiO3–0.07BaTiO3 and ergodic relaxor 0.94Bi0.5(Na0.75K0.25)0.5TiO3–0.06BiAlO3 were investigated. The macroscopic electromechanical behavior was characterized as a function of continuent content,revealing an enhancement in the unipolar strain from the multilayer composite structure. Systematic evaluation of the effects of co-sintering on microstructural properties, such as grain size and porosity, revealed potential mechanisms by which the increase in unipolar strain was achieved. In addition, interdiffusion between the constituents was observed, providing evidence for the formation of a functionally graded ceramic by co-sintering. These data are contrasted with highresolution energy dispersive X-ray microanalysis for measurement of chemical composition across the interface of 2-2 ceramics. These findings provide insight into how synthesis routes can be optimized for tailoring the enhancement of electromechanical properties of lead-free electroceramic composite systems.

e-Fe3N shows interesting magnetism but is difficult to obtain as a pure and single-phase sample. We report a new preparation method using the reduction of iron(II) bromide with elemental sodium in liquid ammonia at −78 °C, followed by annealing at 573 K. Nanostructured and monophasic oxygen-free iron nitride, e-Fe3N, is produced according to X-ray diffraction and transmission electron microscopy experiments. The magnetic properties between 2 and 625 K were characterized using a vibrating sample magnetometer, revealing soft ferromagnetic behavior with a low-temperature average moment of 1.5 μB/Fe and a Curie temperature of 500 K. TC is lower than that of bulk e-Fe3N (575 K) [Chem. Phys. Lett 2010, 493, 299], which corresponds well with the small particle size within the agglomerates (15.4 (±4.1) nm according to TEM, 15.8(1) according to XRD). Samples were analyzed before and after partial oxidation (Fe3N–FexOy core–shell nanoparticles with a 2–3 nm thick shell) by X-ray diffraction, transmission electron m...

Rapid dielectric characterization and modeling play an essential role in developing new technologies and materials for RF systems. In RF frontends, flexible impedance matching and frequency tuning can be introduced by deploying tunable capacitors (varactors), e.g., in metal-insulator–metal (MIM) configuration. On the physical side, test structures are available that only require patterning of the top layer and allow a fast characterization. On the modeling side, still, time-consuming 3-D EM simulations are necessary to extract the corresponding material properties. While analytic/schematic modeling would be fast, no accurate models that closely fit the dispersive characteristic are available up to now. In this article, we present a novel analytic model derived from the common $RLC$ model, which splits the electrode’s contribution into two parts and adds a parallel substrate impedance. Other than the common $RLC$ model, it is consistent for varying thickness of the dielectric and electrode, electrode conductivity, and dielectric properties. This model is verified by systematic, multivariate simulations and a large set of measured test structures. The analysis shows that the root mean squared error (RMSE) can be decreased by orders with our model.

In this work, analysis and simulation of all experimentally observed switching modes in hafnium oxide based resistive random access memories are carried out using a simplified electrical conduction model. To achieve switching mode variation, two metal-insulator-metal cells with identical stack combination, but varying oxygen stoichiometry of the hafnia layer, namely, stoichiometric vs highly deficient, are considered. To access the individual switching modes, the devices were subjected to a variety of cycling conditions comprising different voltage and current ranges. For modeling the device behavior, a single or two antiserially connected memdiodes (diode with memory) were utilized. In this way, successful compact simulation of unipolar, bipolar, threshold, and complementary resistive switching modes is accomplished confirming the coexistence of two switching mechanisms of opposite polarity as the basis for all observable switching phenomena in this material. We show that only calibration of the outer current-voltage loops with the memdiode model is necessary for predicting the device behavior in the defined region revealing additional information on the switching process. The correspondence of each memdiode device with the conduction characteristics of the individual top and bottom metal-oxide contacts allows one to assess the role played by each interface in the switching process separately. This identification paves the path for a future improvement of the device performance and functionality by means of appropriate interface engineering.

Grid applications require high power density (for frequency regulation, load leveling, and renewable energy integration), achievable by combining multiple batteries in a system without strict high capacity requirements. For these applications however, safety, cost efficiency, and the lifespan of electrode materials are crucial. Titanates, safe and longevous anode materials providing much lower energy density than graphite, are excellent candidates for this application. The innovative molten salt synthesis approach proposed in this work provides exceptionally pure Na2Ti6O13 nanorods generated at 900–1100 °C in a yield ≥80 wt%. It is fast, cost‐efficient, and suitable for industrial upscaling. Electrochemical tests reveal stable performance providing capacities of ≈100 mA h g−1 (Li) and 40 mA h g−1 (Na). Increasing the synthesis temperature to 1100 °C leads to a capacity decrease, most likely resulting from 1) the morphology/volume change with the synthesis temperature and 2) distortion of the Na2Ti6O13 tunnel structure indicated by electron energy‐loss and Raman spectroscopy. The suitability of pristine Na2Ti6O13 as the anode for grid‐level energy storage systems has been proven a priori, without any performance‐boosting treatment, indicating considerable application potential especially due to the high yield and low cost of the synthesis route., Highly pure Na2Ti6O13 is reliably obtained via molten salt synthesis (MSS). Its suitability as an anode for Li‐ion and Na‐ion batteries has been proven a priori, without any performance‐boosting treatment (e.g., carbon coating and activation process), indicating considerable application potential, especially for grid‐scale energy storage devices. MSS has also proven to be suitable for industrial upscaling.© 2020 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim

The aim of this work is to investigate the effect of very fine grain sizes on the spinodal decomposition in the Alnico system. Commercial Alnico 5 was melted and melt-spun with varying copper wheel speeds, which led to a grain size of 1–2 µm. This value was further reduced to sub-micrometer size by a small addition of Boron (1 at%). The spinodal decomposition was induced through a two-step annealing treatment under magnetic field in the range of 600–900 °C. It was found that the size of the spinodal structures is not influenced much by increased wheel speeds but becomes smaller with the addition of Boron. However, the difference in coercivity between the samples with and without Boron is only 50 Oe (4 kA/m). To study the influence of the annealing treatment two sets of samples are compared, one with the highest coercivity (366 Oe/29 kA/m) and the other one with lower coercivity (180 Oe/14.5 kA/m). We found with Scanning transmission electron microscopy Energy-dispersive X-ray spectroscopy (STEM EDX) a much sharper chemical interface between the α1 and α2 precipitates in the former sample, which we attribute to be the main reason for the higher coercivity.

Electroless deposition of anisotropic catalyst layers is introduced as an efficient approach to fabricate high-performing multiscale electrode architectures. In the present study, a biomass-derived, solidified foam is coated with nickel nano-spikes. This results in an amplification of the surface area and an introduction of catalytic functionality, while the favorable mass transfer properties of the porous support are retained. Both the substrate and the metal film are produced using simple, readily scalable processes. The support is prepared from liquefied sawdust by self-foaming, and nickel deposition is performed by immersion in a hydrazine-based plating bath. The favorable functional properties of the nickel-coated foam are demonstrated in enzyme-free glucose sensing. Due to the large surface area and the high activity of the nickel nanofilm, an outstanding sensitivity of 8.1 mA mM−1 cm−2 and a low detection limit of 60 nM were achieved. Keywords: Anisotropic nanoparticles, Electrode nanostructuring, Electroless plating, Biomass conversion, Enzyme-free glucose sensing

This work investigates the transition from digital to gradual or analog resistive switching in yttrium oxide-based resistive random-access memory devices. It is shown that this transition is determined by the amount of oxygen in the functional layer. A homogeneous reduction of the oxygen content not only reduces the electroforming voltage, allowing for forming-free devices, but also decreases the voltage operation window of switching, thereby reducing intra-device variability. The most important effect as the dielectric becomes substoichiometric by oxygen engineering is that more intermediate (quantized) conduction states are accessible. A key factor for this reproducibly controllable behavior is the reduced local heat dissipation in the filament region due to the increased thermal conductivity of the oxygen depleted layer. The improved accessibility of quantized resistance states results in a semi-gradual switching both for the set and reset processes, as strongly desired for multi-bit storage and for an accurate definition of the synaptic weights in neuromorphic systems. A theoretical model based on the physics of mesoscopic structures describing current transport through a nano-constriction including asymmetric potential drops at the electrodes and non-linear conductance quantization is provided. The results contribute to a deeper understanding on how to tailor materials properties for novel memristive functionalities.

International audience; (K,Na)NbO 3 -based ferroelectric single crystals have recently undergone a substantial development, resulting in improved crystal quality and large piezoelectric coefficients, exceeding 700 pC/N, over a broad temperature range. However, further development necessitates a detailed understanding of the mechanisms defining the domain structure and its temperature evolution. This paper presents the investigation into the crystallographic structure and domain configurations of a (K,Na,Li)(Ta,Nb)O 3 single crystal over a broad temperature range. The crystal was grown by the submerged-seed solution growth technique and investigated using in situ transmission electron microscopy, X-ray diffraction, dielectric measurements, and polarized light microscopy. The lattice distortion, structural phase transitions, and domain configurations are reported. A transition from the lamellar orthorhombic to the rectangular tetragonal domain structure is observed upon heating. Moreover, the milky optical appearance of the crystal was investigated and found to result from the presence of regions with different domain configurations and domain sizes. The formation of these regions is related to the growth defects, which govern the domain formation when cooling below the Curie temperature.

The design of core–shell materials affords additional degrees of freedom to tailor functional properties as compared to solid solution counterparts. Although to date most of the work in core–shell materials has focused on dielectrics, piezoelectric core–shell ceramics may gain similar interest. Generalities of core–shell functional ceramics features are addressed in this work. A model system, Bi1/2Na1/2TiO3–SrTiO3, is introduced to discuss structure–property relationships. We demonstrate that this system features a core–shell microstructure for the composition corresponding to 25 at.% Sr. The material is studied by means of macroscopic functional properties and in situ structural characterization techniques at different length scales, such as X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. The evolution of the core–shell with field and temperature determines its functional properties. The high strain of the system, ~0.3% at 4 kV/mm, is due to an electric-field-induced phase transition of the core and shell. Upon field removal the core remains in a poled state, whereas the shell is characterized by a reversible transformation. The reversibility of the phase transition of shells and associated switching are key features in the observed giant strain. Dielectric anomalies are found to be related to changes in oxygen octahedral tilting angles within the core and shell.

The temperature-dependent crack growth resistance behavior of the lead-free (1 − x)Ba(Zr0.2Ti0.8)O3–x(Ba0.7Ca0.3)TiO3 (x = 0.385) ceramic was characterized using compact-tension specimens from 25 °C to 60 °C. The observed plateau fracture toughness at 25 °C was found to be approximately 37% lower than commercial Pb(Zr,Ti)O3. At elevated temperature, the maximum fracture toughness displayed a decrease, which was found to be related to the temperature-dependent elastic and ferroelastic properties. Mechanical measurements are presented that demonstrate decreasing effective switching strain, coercive stress and Young’s modulus with increasing temperature.