Direct Observation of Trace Elements in Barium Titanate of Multilayer Ceramic Capacitors Using Atom Probe Tomography.

Accurately controlling trace additives in dielectric barium titanate (BaTiO3) layers is important for optimizing the performance of multilayer ceramic capacitors (MLCCs). However, characterizing the spatial distribution and local concentration of the additives, which strongly influence the MLCC performance, poses a significant challenge. Atom probe tomography (APT) is an ideal technique for obtaining this information, but the extremely low electrical conductivity and piezoelectricity of BaTiO3 render its analysis with existing sample preparation approaches difficult. In this study, we developed a new APT sample preparation method involving W coating and heat treatment to investigate the trace additives in the BaTiO3 layer of MLCCs. This method enables determination of the local concentration and distribution of all trace elements in the BaTiO3 layer, including additives and undesired impurities. The developed method is expected to pave the way for the further optimization and advancement of MLCC technology.

Exploring the Effects of the Photochromic Response and Crystallization on the Local Structure of Noncrystalline Niobium Oxide.

Niobium oxide (Nb2O5) is a versatile semiconductor material with photochromic properties. This study investigates the local structure of noncrystalline, short-range-ordered niobium oxide synthesized via a sol-gel method. X-ray atomic pair distribution function analysis unravels the structural arrangements within the noncrystalline materials at a local scale. In the following, in situ scattering and diffraction experiments elucidate the heat-induced structure transformation of the amorphous material into crystalline TT-Nb2O5 at 550 °C. In addition, the effect of photocatalytic conditions on the structure of the material was investigated by exposing the short-range-ordered and crystalline materials to ultraviolet light, resulting in a reversible color change from white to dark brown or blue. This photochromic response is due to the reversible elongation of the nearest Nb-O neighbors, as shown by local structure analysis based on in situ PDF analyses. Optical band gap calculations based on the ultraviolet-visible spectra collected for both the short-range-ordered and crystalline materials show that the band gap values reduced for the darkened materials return to their initial state after bleaching. Furthermore, electron energy loss spectroscopy reveals the reduction of Nb5+ to Nb4+ centers as a persistent effect. The study establishes a correlation between the band gap and the structure of niobium oxide, providing insights into the structure-performance relation at the atomic level.

Unraveling the Evolution of Dynamic Active Sites of LaNixFe1-xO3 Catalysts During OER.

Perovskites have attracted tremendous attention as potential catalysts for the oxygen evolution reaction (OER). It is well-known that the introduction of Fe into rare earth perovskites such as LaNiO3 enhances the intrinsic OER activity. Despite numerous studies on structure-property relationships, the origin of the activity and the nature of the active species are still elusive and unclear. In this work, we study a series of LaNixFe1-xO3 perovskites using in situ electrochemical surface-enhanced Raman spectroscopy and electron energy loss spectroscopy to decipher the surface evolution and formation of active species during OER. While the origin of the activity arises from NiOOH species formed from the active Ni centers in LaNiO3, our work shows that Fe serves as the active center in LaNi0.5Fe0.5O3 and forms Fe-O-Ni and FeOOH species during OER. The OER activity of LaFeO3 originates from FeOOH species, which interact with the soluble Ni species in the electrolyte forming an active electrode-electrolyte interface with high-valent stable surface iron species (Fe4+) and thereby improving the performance. Our work provides deeper insights into the synergistic effects of Ni and Fe on the catalytic activity, which in turn provides new design principles for perovskite catalysts for the OER.

Compositional defects in a MoAlB MAB phase thin film grown by high-power pulsed magnetron sputtering.

Various compositional defects such as Mo3Al2B4, Mo4Al3B4, Mo6Al5B6 and Al3Mo, together with MoB MBene, are observed to be coexisting in a MoAlB MAB phase thin film grown at 800 °C by high-power pulsed magnetron sputtering. An overall film composition of Mo0.29Al0.33B0.38 is measured by time-of-flight elastic recoil detection analysis. The concurrent formation of these compositional defects in the MoAlB matrix occurs during the synthesis without using any chemical reagent, and their coexistence with the MAB phase is thermodynamically possible, as elucidated by density functional theory simulations. These defect phases are imaged at the atomic scale by aberration-corrected scanning transmission electron microscopy. A rough estimation of defect populations of 0.073, 0.037, 0.042 and 0.039 nm-1 for Mo3Al2B4, Mo4Al3B4, Mo6Al5B6 and Al3Mo compositional defects, respectively, is performed within the MoAlB matrix. The calculated energies of formation reveal that the Mo4Al3B4 and Mo6Al5B6 defect phases form spontaneously in the MoAlB host matrix, while the energy barrier towards the formation of the metastable Mo3Al2B4 phase is approx. 20 meV per atom. The small magnitude of this barrier is easily overcome during vapor phase condensation, and the surface diffusion of adatoms during deposition leads to local compositional variations and the coexistence of the defect phases in the host matrix. Additionally, at grain boundaries, the presence of MoB MBene is observed, with an interlayer spacing between two Mo2B2 units increasing up to ∼50% compared to the pristine MoAlB phase.

Effect of Heat Treatment Temperature on the Crystallization Behavior and Microstructural Evolution of Amorphous NbCo1.1Sn.

Heat treatment-induced nanocrystallization of amorphous precursors is a promising method for nanostructuring half-Heusler compounds as it holds significant potential in the fabrication of intricate and customizable nanostructured materials. To fully exploit these advantages, a comprehensive understanding of the crystallization behavior of amorphous precursors under different crystallization conditions is crucial. In this study, we investigated the crystallization behavior of the amorphous NbCo1.1Sn alloy at elevated temperatures (783 and 893 K) using transmission electron microscopy and atom probe tomography. As a result, heat treatment at 893 K resulted in a significantly finer grain structure than heat treatment at 783 K owing to the higher nucleation rate at 893 K. At both temperatures, the predominant phase was a half-Heusler phase, whereas the Heusler phase, associated with Co diffusion, was exclusively observed at the specimen annealed at 893 K. The Debye-Callaway model supports that the lower lattice thermal conductivity of NbCo1.1Sn annealed at 893 K is primarily attributed to the formation of Heusler nanoprecipitates rather than a finer grain size. The experimental findings of this study provide valuable insights into the nanocrystallization of amorphous alloys for enhancing thermoelectric properties.

Expanding the Potential of Identical Location Scanning Transmission Electron Microscopy for Gas Evolving Reactions: Stability of Rhenium Molybdenum Disulfide Nanocatalysts for Hydrogen Evolution Reaction.

Identical location (scanning) transmission electron microscopy provides valuable insights into the mechanisms of the activity and degradation of nanocatalysts during electrochemical reactions. However, the technique suffers from limitations that hinder its widespread use for nanocatalysts of gas evolving reactions, e.g., the hydrogen evolution reaction (HER). The main issue is the production of bubbles that cause the loss of electric contact in identical location measurements, which is critical for the correct cycling of the nanocatalysts and interpretation of the electron microscopy results. Herein, we systematically evaluate different set-ups, materials, and tools to allow the facile and reliable study of the stability of HER nanocatalysts. The optimized conditions are applied for the study of layered rhenium molybdenum disulfide (Re0.2Mo0.8S2) nanocatalysts, a relevant alternative to Pt catalysts for the HER. With our approach, we demonstrate that although the morphology of the Re0.2Mo0.8S2 catalyst is maintained during HER, chemical composition changes could be correlated to the electrochemical reaction. This study expands the potential of the IL(S)TEM technique for the construction of structure-property relationships of nanocatalysts of gas evolving reactions.

Electrochemical Stability of Rhodium-Platinum Core-Shell Nanoparticles: An Identical Location Scanning Transmission Electron Microscopy Study.

Rhodium-platinum core-shell nanoparticles on a carbon support (Rh@Pt/C NPs) are promising candidates as anode catalysts for polymer electrolyte membrane fuel cells. However, their electrochemical stability needs to be further explored for successful application in commercial fuel cells. Here we employ identical location scanning transmission electron microscopy to track the morphological and compositional changes of Rh@Pt/C NPs during potential cycling (10 000 cycles, 0.06-0.8 VRHE, 0.5 H2SO4) down to the atomic level, which are then used for understanding the current evolution occurring during the potential cycles. Our results reveal a high stability of the Rh@Pt/C system and point toward particle detachment from the carbon support as the main degradation mechanism.

Chemistry and microstructure of C-supported Ru catalyst nanoparticles: A correlative study.

Ru@Pt core shell nanoparticles possess optimal catalytic properties that facilitate the anodic oxidation reaction of H2 with decreased Pt loading in hydrogen fuel cells. Moreover, since they preferentially oxidize CO, Pt poisoning is considerably reduced, which significantly improves the stability of the cell. The Ru cores used in this system are usually synthesized by dissolving a RuCl3*H2O precursor in an ethylene glycol-carbon black-NaOH mixture. However, the possibility that remnant Cl and Na from the synthesis process are present in the Ru nanoparticles has not been extensively studied. Therefore, due to the challenges in detecting impurities with traditional characterization methods, here correlative atom probe tomography (APT) with scanning transmission electron microscopy ((S)TEM) techniques were implemented. The capabilities of APT to obtain chemical information with high sensitivity at the nanoscale, in combination with the high spatial resolving power of (S)TEM, provide the necessary resolution to fully characterize the structure and chemical makeup of Ru nanoparticles.

Combined structural analysis and cathodoluminescence investigations of single Pr3+-doped Ca2Nb3O10 nanosheets.

Due to the novel properties of both 2D materials and rare-earth elements, developing 2D rare-earth nanomaterials has a growing interest in research. To produce the most efficient rare-earth nanosheets, it is essential to find out the correlation between chemical composition, atomic structure and luminescent properties of individual sheets. In this study, 2D nanosheets exfoliated from Pr3+-doped KCa2Nb3O10 particles with different Pr concentrations were investigated. Energy dispersive X-ray spectroscopy analysis indicates that the nanosheets contain Ca, Nb and O and a varying Pr content between 0.9 and 1.8 at%. K was completely removed after exfoliation. The crystal structure is monoclinic as in the bulk. The thinnest nanosheets are 3 nm corresponding to one triple perovskite-type layer with Nb on the B sites and Ca on the A sites, surrounded by charge compensating TBA+ molecules. Thicker nanosheets of 12 nm thickness (and above) were observed too by transmission electron microscopy with the same chemical composition. This indicates that several perovskite-type triple layers remain stacked similar to the bulk. Luminescent properties of individual 2D nanosheets were studied using a cathodoluminescence spectrometer revealing additional transitions in the visible region in comparison to the spectra of different bulk phases.

Tailoring the Plasticity of Topologically Close-Packed Phases via the Crystals' Fundamental Building Blocks.

Brittle topologically close-packed precipitates form in many advanced alloys. Due to their complex structures, little is known about their plasticity. Here, a strategy is presented to understand and tailor the deformability of these complex phases by considering the Nb-Co µ-phase as an archetypal material. The plasticity of the Nb-Co µ-phase is controlled by the Laves phase building block that forms parts of its unit cell. It is found that between the bulk C15-NbCo2 Laves and Nb-Co µ-phases, the interplanar spacing and local stiffness of the Laves phase building block change, leading to a strong reduction in hardness and stiffness, as well as a transition from synchroshear to crystallographic slip. Furthermore, as the composition changes from Nb6 Co7 to Nb7 Co6 , the Co atoms in the triple layer are substituted such that the triple layer of the Laves phase building block becomes a slab of pure Nb, resulting in inhomogeneous changes in elasticity and a transition from crystallographic slip to a glide-and-shuffle mechanism. These findings open opportunities to purposefully tailor the plasticity of these topologically close-packed phases in the bulk by manipulating the interplanar spacing and local shear modulus of the fundamental crystal building blocks at the atomic scale.

Revealing the Formation Mechanism and Optimizing the Synthesis Conditions of Layered Double Hydroxides for the Oxygen Evolution Reaction.

Layered double hydroxides (LDHs), whose formation is strongly related to OH- concentration, have attracted significant interest in various fields. However, the effect of the real-time change of OH- concentration on LDHs' formation has not been fully explored due to the unsuitability of the existing synthesis methods for in situ characterization. Here, the deliberately designed combination of NH3 gas diffusion and in situ pH measurement provides a solution to the above problem. The obtained results revealed the formation mechanism and also guided us to synthesize a library of LDHs with the desired attributes in water at room temperature without using any additives. After evaluating their oxygen evolution reaction performance, we found that FeNi-LDH with a Fe/Ni ratio of 25/75 exhibits one of the best performances so far reported.

Atomistic structures of 〈0001〉 tilt grain boundaries in a textured Mg thin film.

Nanocrystalline Mg was sputter deposited onto an Ar ion etched Si {100} substrate. Despite an ∼6 nm amorphous layer found at the interface, the Mg thin film exhibits a sharp basal-plane texture enabled by surface energy minimization. The columnar grains have abundant 〈0001〉 tilt grain boundaries in between, most of which are symmetric with various misorientation angles. Up to ∼20° tilt angle, they are composed of arrays of equally-spaced edge dislocations. Ga atoms were introduced from focused ion beam milling and found to segregate at grain boundaries and preferentially decorate the dislocation cores. Most symmetric grain boundaries are type-1, whose boundary planes have smaller dihedral angles with {21̄1̄0} rather than {101̄0}. Atomistic simulations further demonstrate that type-2 grain boundaries, having boundary planes at smaller dihedral angles with {101̄0}, are composed of denser dislocation arrays and hence have higher formation energy than their type-1 counterparts. The finding correlates well with the dominance of type-1 grain boundaries observed in the Mg thin film.

Insights into the performance and degradation of Ru@Pt core-shell catalysts for fuel cells by advanced (scanning) transmission electron microscopy.

Ru@Pt core-shell nanoparticles are currently being explored as carbon monoxide tolerant anode catalysts for proton exchange membrane fuel cells. However, little is known about their degradation under fuel cell conditions. In the present work, two types of Ru@Pt nanoparticles with nominal shell thicknesses of 1 (Ru@1Pt) and 2 (Ru@2Pt) Pt monolayers are studied as synthesized and after accelerated stress tests. These stress tests were designed to imitate the degradation occurring under fuel cell operating conditions. Our advanced (scanning) transmission electron microscopy characterization explains the superior initial electrochemical performance of Ru@1Pt. Moreover, the 3D reconstruction of the Pt shell by electron tomography reveals an incomplete shell for both samples, which results in a less stable Ru metal being exposed to an electrolyte. The degree of coverage of the Ru cores provides insights into the higher stability of Ru@2Pt during the accelerated stress tests. Our results explain how to maximize the initial performance of Ru@Pt-type catalysts, without compromising their stability under fuel cell conditions.

Elemental (im-)miscibility determines phase formation of multinary nanoparticles co-sputtered in ionic liquids.

Non-equilibrium synthesis methods allow the alloying of bulk-immiscible elements into multinary nanoparticles, which broadens the design space for new materials. Whereas sputtering onto solid substrates can combine immiscible elements into thin film solid solutions, this is not clear for sputtering of nanoparticles in ionic liquids. Thus, the suitability of sputtering in ionic liquids for producing nanoparticles of immiscible elements is investigated by co-sputtering the systems Au-Cu (miscible), Au-Ru and Cu-Ru (both immiscible), and Au-Cu-Ru on the surface of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][(Tf)2N]. The sputtered nanoparticles were analyzed to obtain (i) knowledge concerning the general formation process of nanoparticles when sputtering onto ionic liquid surfaces and (ii) information, if alloy nanoparticles of immiscible elements can be synthesized as well as (iii) evidence if the Hume-Rothery rules for solid solubility are valid for sputtered nanoparticles. Nanoparticle characteristics were found to depend on elemental miscibility: (1) nanoparticles from immiscible elemental combinations showed bigger mean diameters ranging from (3.3 ± 1.4) nm to (5.0 ± 1.7) nm in contrast to mean diameters of nanoparticles from elemental combinations with at least one miscible element pair ((1.7 ± 0.7) nm to (1.8 ± 0.6) nm). (2) Nanoparticles from immiscible combinations showed compositions with one element strongly dominating the ratio and very narrow differences between the highest and lowest fraction of the dominating element (Cu94Ru6 to Cu100Ru0; Au96Ru4 to Au99Ru1) in contrast to the other compositions (Au64Cu36 to Au81Cu19; Au83Cu13Ru4/Au75Cu22Ru3 to Au87Cu11Ru2). Accompanying atomistic simulations using density-functional theory for clusters of different size and ordering confirm that the miscibility of Au-Cu and the immiscibility of Au-Ru and Cu-Ru govern the thermodynamic stability of the nanoparticles. Based on the matching experimental and theoretical results for the NP/IL-systems concerning NP stability, a formation model of multinary NPs in ILs was developed.

Evaluation of functional layers thinning of high temperature polymer electrolyte membrane fuel cells after long term operation.

The operation related degradation processes of high temperature polymer electrolyte membrane fuel cell operated with hydrogen-rich reformate gas are studied. CO impurities from the reformate gas are strongly adsorbed by the catalyst surface, leading to poisoning and thus, reduction of the overall performance of the cell. Most of the studies are performed in a laboratory set-up by applying accelerated stress tests. In the present work, a high temperature polymer electrolyte membrane fuel cell is operated in a realistic configuration for 12 000 h (500 days). The fuel cell contains as electrocatalyst Pt in the cathode and a Pt-Ru alloy in the anode. The study of the degradation occurring in the functional layers, i.e. in different regions of cathode, anode and membrane layer, is carried out by scanning electron microscopy, (scanning) transmission electron microscopy and energy dispersive X-ray spectroscopy. We observed a thinning of the functional layers and a redistribution of catalyst material. The thinning of the cathode side is larger compared to the anode side due to harsher operation conditions likely causing a degradation of the support material via C corrosion and/or due to a degradation of the catalyst via oxidation of Pt and Ru. A thinning of the membrane caused by oxidation agents is also detected. Moreover, during operation, catalyst material is dissolved at the cathode side and redistributed. Our results will help to design and develop fuel cells with higher performance.

Controlled Doping of Electrocatalysts through Engineering Impurities.

Fuel cells recombine water from H2 and O2 thereby can power, for example, cars or houses with no direct carbon emission. In anion-exchange membrane fuel cells (AEMFCs), to reach high power densities, operating at high pH is an alternative to using large volumes of noble metals catalysts at the cathode, where the oxygen-reduction reaction occurs. However, the sluggish kinetics of the hydrogen-oxidation reaction (HOR) hinders upscaling despite promising catalysts. Here, the authors observe an unexpected ingress of B into Pd nanocatalysts synthesized by wet-chemistry, gaining control over this B-doping, and report on its influence on the HOR activity in alkaline conditions. They rationalize their findings using ab initio calculations of both H- and OH-adsorption on B-doped Pd. Using this "impurity engineering" approach, they thus design Pt-free catalysts as required in electrochemical energy conversion devices, for example, next generations of AEMFCs, that satisfy the economic and environmental constraints, that is, reasonable operating costs and long-term stability, to enable the "hydrogen economy."

Defects in an orthorhombic MoAlB MAB phase thin film grown at moderate synthesis temperature.

Here, we report on atomic scale characterization of various defects in a MoAlB (MAB) phase thin film grown by DC sputtering at a synthesis temperature of 700 °C. Aberration-corrected scanning transmission electron microscopy reveals the formation of an intergrown metastable Mo3Al2B4 phase accompanied by thermally stable 90° twist boundaries, coexisting within the pristine MoAlB matrix. The concurrent formation of these structural defects in the MoAlB matrix can be rationalized based on minute differences in formation enthalpies as shown via density functional theory calculations. The specific structural nature of both the twist boundary and compositional defect (Mo3Al2B4) in a MoAlB matrix is hitherto unreported in literature. Apart from these defects, faceted grain boundaries are observed. In the vicinity of amorphous AlOx regions, Al is deintercalated and a 2D MoB MBene phase is formed as reported before. Besides these amorphous AlOx regions, a few nanometer-sized 3D MoB clusters are found. The advancement of aberration-corrected scanning transmission electron microscopy significantly improves characterization from 1D to 3D defects which is important for thin film materials design for the moderate synthesis temperature range. The reported defects might play an important role in the formation of 2D MoB MBenes.

Understanding Alkali Contamination in Colloidal Nanomaterials to Unlock Grain Boundary Impurity Engineering.

Metal nanogels combine a large surface area, a high structural stability, and a high catalytic activity toward a variety of chemical reactions. Their performance is underpinned by the atomic-level distribution of their constituents, yet analyzing their subnanoscale structure and composition to guide property optimization remains extremely challenging. Here, we synthesized Pd nanogels using a conventional wet chemistry route, and a near-atomic-scale analysis reveals that impurities from the reactants (Na and K) are integrated into the grain boundaries of the poly crystalline gel, typically loci of high catalytic activity. We demonstrate that the level of impurities is controlled by the reaction condition. Based on ab initio calculations, we provide a detailed mechanism to explain how surface-bound impurities become trapped at grain boundaries that form as the particles coalesce during synthesis, possibly facilitating their decohesion. If controlled, impurity integration into grain boundaries may offer opportunities for designing new nanogels.

Direct MoB MBene domain formation in magnetron sputtered MoAlB thin films.

Two-dimensional (2D) inorganic transition metal boride nanosheets are emerging as promising post-graphene materials in energy research due to their unique properties. State-of-the-art processing strategies are based on chemical etching of bulk material synthesized via solid-state reaction at temperatures above 1000 °C. Here, we report the direct formation of MoB MBene domains in a MoAlB thin film by Al deintercalation from MoAlB in the vicinity of AlOx regions. Hence, based on these results a straightforward processing pathway for the direct formation of MoB MBene-AlOx heterostructures without employing chemical etching is proposed here.

Monitoring the Structure Evolution of Titanium Oxide Photocatalysts: From the Molecular Form via the Amorphous State to the Crystalline Phase.

Amorphous Tix Oy with high surface area has attracted significant interest as photocatalyst with higher activity in ultraviolet (UV) light-induced water splitting applications compared to commercial nanocrystalline TiO2 . Under photocatalytic operation conditions, the structure of the molecular titanium alkoxide precursor rearranges upon hydrolysis and leads to higher connectivity of the structure-building units. Structurally ordered domains with sizes smaller than 7 Šform larger aggregates. The experimental scattering data can be explained best with a structure model consisting of an anatase-like core and a distorted shell. Upon exposure to UV light, the white Tix Oy suspension turns dark corresponding to the reduction of Ti4+ to Ti3+ as confirmed by electron energy loss spectroscopy (EELS). Heat-induced crystallisation was followed by in situ temperature-dependent total scattering experiments. First, ordering in the Ti-O environment takes place upon to 350 °C. Above this temperature, the distorted anatase core starts to grow but the structure obtained at 400 °C is still not fully ordered.