arXiv subjects

Christina Scheu

Publications and source records attributed to Christina Scheu.

At least 19 recordsLinked to original sources

arXiv2026

EBSD and Subtle Crystallographic Differences - A Study of Resolving Interlayer Spacings in Nb-Ni and Nb-Co mu-phases

In ordered intermetallics, slight variations in lattice site occupancy and specific interlayer spacings have been identified as the sources of significant changes in critical resolved shear stress and therefore how a given phase may affect alloy properties. So far, atom positions and lattice site occupancies have traditionally been characterised by high-resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD), which are methods that offer either local detail or high statistical significance but not both. Electron backscatter diffraction (EBSD), by contrast, provides high spatial resolution across large sample areas and therefore, has the potential to enable the local investigation of interlayer spacing and site lattice occupancy with improved statistical reliability. The objectives of the study are to benchmark EBSDs capability for resolving these subtle features and to correlate them with compositional and mechanical properties. In this case study, we therefore show that EBSD can resolve key crystallographic features of mu-phase intermetallics, specifically interlayer spacings. We combine pattern matching with large-scale dynamical simulations of template libraries guided by XRD based information on lattice parameters. For this, we generate structures that vary in the spacing between triple-layer and Kagome layer and in the site lattice occupancy of the 3a site. This approach successfully predicts the change of interlayer spacing between Kagome and triple layers in Nb-Co and Nb-Ni mu-phases, in good agreement with XRD and HR-TEM.

cond-mat.mtrl-sci↗

arXiv2026

Epitaxial Films as Model Platform for Understanding Compositionally Complex Electrocatalysts

Compositionally complex solid solutions provide a unique route for engineering high-performance electrocatalysts, where the polyelemental surface composition can be seamlessly tuned to optimize activity, selectivity, and stability. However, the mechanistic understanding of these electrocatalysts remains limited by the lack of a model system with a crystallographically-defined surface that is compatible with correlative, multi-scale characterization. Here, we present epitaxial films as a model platform for studying compositionally complex electrocatalysts. Using magnetron sputtering, we realize (111) epitaxial Ir-Pd-Pt-Rh-Ru films on (0001) sapphire substrate via a (111) Pt buffer layer, confirmed by X-ray diffraction and transmission electron microscopy. The growth approach is applicable across a broad composition range and produces smooth surfaces (root mean square roughness < 1 nm) with micrometer-sized grains in the nanoscale films. With these films, we demonstrate direct structure-activity mapping at the nanoscale through precise co-localization using micro-indents and performing correlative atomic force microscopy, electron backscatter diffraction, and scanning electrochemical cell microscopy. Our work establishes a model platform for fundamental scalebridging characterization and paves the way for rational design of compositionally complex electrocatalysts.

cond-mat.mtrl-sci↗

arXiv2026

Influence of Ru content on electrocatalytic activity and defect formation of Au-Pd-Pt-Ru compositionally complex solid solution thin films

Compositionally complex solid solutions (CCSSs) consist of a randomly mixed single phase with the potential to enhance electrocatalytic activity through their polyelemental surface atom arrangements. However, microstructural complexity originating from multiple principal elements influences local structure, chemistry, and lattice strain, which might also affect electrocatalytic activity. Here, we investigate the effect of Ru content on electrochemistry and defect formation in Au-Pd-Pt-Ru CCSS thin films. Such defects could provide active sites when terminating at the CCSS surface or modify surface composition through preferential segregation. A thin-film material library covering a wide composition range was fabricated by room-temperature combinatorial co-sputtering. High-throughput compositional, structural and functional characterization, including electron microscopy equipped with energy dispersive X-ray spectroscopy, X-ray diffraction, and electrochemical screening, were used to correlate composition and microstructural features with catalytic activity. Three representative compositions selected from the library - Au68Pd13Pt15Ru4, Au27Pd24Pt23Ru26, and Au9Pd21Pt18Ru52 - were examined in detail. The three samples exhibit face-centered cubic structures, with lattice contraction occurring with increasing Ru content. In addition, with increasing Ru content, a transition from a high density of nanotwins to high-density, atomic-layer stacking faults was observed. Moreover, the hydrogen evolution reaction activity improves with higher Ru content. Atom probe tomography reveals local compositional fluctuations, including element-specific enrichment and depletion at grain boundaries. The findings provide a new insight into surface atom arrangement design in the CCSS electrocatalysts with enhanced performance.

cond-mat.mtrl-sci↗

arXiv2025

Chemically tailored planar defect phases in the Ta-Fe {\mu}-phase

Intermetallics often exhibit complex crystal structures, which give rise to intricate defect structures that critically influence their mechanical and functional properties. Despite studies on individual defect types, a comprehensive understanding of the defect landscape in {\mu}-phases, a class of topologically close-packed phases, remains elusive. In this study, we investigated the planar defect structures in the Ta-Fe {\mu}-phase across a compositional range of 46 to 58 at.% Ta using electron microscopy and density functional theory calculations. Electron backscatter diffraction and high-resolution scanning transmission electron microscopy reveal a transition from basal twin boundaries and planar faults containing C14 TaFe2 Laves phase layers at a low Ta content to pyramidal {1\bar{1}02} twins at a higher Ta content. Density functional theory calculations of defect formation energies confirm a chemical potential-driven stabilisation of Laves phase lamellae. The prevalence of pyramidal twins in Ta-rich {\mu}-phase samples is attributed to the competitive nature of different planar defects during solidification. A defect landscape for {\mu}-phases is proposed, illustrating the interplay between site occupancy, dislocation types and planar faults across the chemical potential space. These findings provide fundamental insights into defect engineering in structurally complex intermetallics and open pathways for optimising material properties through chemical tuning.

cond-mat.mtrl-sci↗

arXiv2025

Kinetics and direct imaging of electrochemically formed palladium hydride for efficient hydrogen evolution reaction

Active and reliable electrocatalysts are fundamental to renewable energy technologies. PdCoO2 has recently been recognized as a promising catalyst template for the hydrogen evolution reaction (HER) in acidic media thanks to the formation of active PdHx. In this article, we monitor the transformation of single PdCoO2 particles during HER, and confirm their almost complete transformation to PdHx with sub-millimeter depths and cracks throughout the particles. Using operando mass spectrometry, Co dissolution is observed under reductive potentials, leading to PdHx formation, whereas the dissolution partial current is found to be 0.1 % of the HER current. The formation of PdHx is confirmed through secondary ion mass spectrometry and quantitatively analyzed by atom probe tomography, enabled by isotope labelling of hydrogen using heavy water. Despite dry storage and high vacuum during sample preparations, an overall composition of PdD0.28 is measured for the PdHx sample, with separation between alpha- (D-poor) and beta- (D-rich) PdHx phases. The PdHx phase formed on PdCoO2 particles is stable for a wide electrochemical potential window, until Pd dissolution is observed at open circuit potentials. Our findings highlight the critical role of a templated growth method in obtaining stabilized PdHx, enabling efficient HER without the commonly slow activation processes observed in Pd. This offers insights into the design of more efficient electrocatalysts for renewable energy technologies.

physics.chem-ph↗

arXiv2024

Grain boundaries control lithiation of solid solution substrates in lithium metal batteries

The development of sustainable transportation and communication systems requires an increase in both energy density and capacity retention of Li-batteries. Using substrates forming a solid solution with body centered cubic Li enhances the cycle stability of anode-less batteries. However, it remains unclear how the substrate microstructure affects the lithiation behavior. Here, we deploy a correlative, near-atomic scale probing approach through combined ion- and electron-microscopy to examine the distribution of Li in Li-Ag diffusion couples as model system. We reveal that Li regions with over 93.8% at.% nucleate within Ag at random high angle grain boundaries, whereas grain interiors are not lithiated. We evidence the role of kinetics and mechanical constraint from the microstructure over equilibrium thermodynamics in dictating the lithiation process. The findings suggest that grain size and grain boundary character are critical to enhance the electrochemical performance of interlayers/electrodes, particularly for improving lithiation kinetics and hence reducing dendrite formation.

cond-mat.mtrl-sci↗

arXiv2023

Operando Insights on the Degradation Mechanisms of Rhenium-doped and Undoped Molybdenum Disulfide Nanocatalysts for Electrolyzer Applications

MoS2 nanostructures are promising catalysts for proton-exchange-membrane (PEM) electrolyzers to replace expensive noble metals. Their broadscale application demands high activity for the hydrogen evolution reaction (HER) as well as robust durability. Doping is commonly applied to enhance the HER activity of MoS2-based nanocatalysts, but the effect of dopants in the electrochemical and structural stability is yet to be discussed. Herein, we correlate operando electrochemical measurements to the structural evolution of the materials down to the nanometric scale by identical location electron microscopy and spectroscopy. The range of stable operation for MoS2 nanocatalysts with and without rhenium doping is experimentally defined. The responsible degradation mechanisms at first electrolyte contact, open circuit stabilization and HER conditions are experimentally identified and confirmed with the calculated Pourbaix diagram of Re-doped MoS2. Doping MoS2-based nanocatalysts is validated as a promising strategy for the continuous improvement of high performance and durable PEM electrolyzers.

physics.app-ph↗

arXiv2023

Contribution of the oxygen reduction reaction to the electrochemical cathodic partial reaction for Mg-Al-Ca solid solutions

The electrochemical corrosion rate of Magnesium (Mg) and Mg alloys depends on the stability of the formed surface layer. Based on the Mg substrate, the oxide structure comprises a dense MgO/Mg(OH)2 mixture underneath a porous plate-like Mg(OH)2 layer. While the kinetics of the anodic partial reaction has been mainly attributed to MgO, recent studies showed an effect of the Mg(OH)2 layer thickness on the cathodic partial reaction. A thinner Mg(OH)2 layer has been associated with a higher kinetics of the oxygen reduction rate. In the present study, the proposed mechanism has been further investigated via in situ respirometric measurements with Mg-Al-Ca solid solution in electrolytes with different pH values (pH = 8-13). The results indicate an additional effect based on the structure of the surface layer in the passive state of Mg corrosion. Furthermore, two different Al enriched interlayers at the Mg/MgO- and MgO/Mg(OH)2 interfaces were observed and discussed in terms of their thermodynamic stability under alkaline immersion conditions.

physics.chem-ph↗

arXiv2023

Constructing phase diagrams for defects by correlated atomic-scale characterization

Phase transformations and crystallographic defects are two essential tools to drive innovations in materials. Bulk materials design via tuning chemical compositions has been systematized using phase diagrams. We show here that the same thermodynamic concept can be applied to understand the chemistry at defects. We present a combined experimental and modelling approach to scope and build phase diagrams for defects. The discovery was enabled by triggering phase transformations of individual defects through local alloying, and sequentially imaging the structural and chemical changes using atomic-resolution scanning transmission electron microscopy. By observing atomic-scale phase transformations of a Mg grain boundary through Ga alloying, we exemplified the method to construct a grain boundary phase diagram using ab initio simulations and thermodynamic principles. The methodology enables a systematic development of defect phase diagrams to propel a new paradigm for materials design utilizing chemical complexity and phase transformations at defects.

cond-mat.mtrl-sci↗

arXiv2023

Chemical and structural characterization of the native oxide scale on a Mg-based alloy

In this study, the structure and composition of the native oxide forming on the basal plane (0001) of Mg-2Al-0.1Ca is investigated by a correlative approach, combining scanning transmission electron microscopy (STEM) and atom probe tomography (APT). Atom probe specimens were prepared conventionally in a Ga focused ion beam (FIB) as well as a Xe plasma FIB in a cryogenic setup and subsequently cleaned in the atom probe to remove surface contamination before oxidation. While thermal energy input from the laser and longer atmospheric exposure time increased the measured hydrogen content in the specimen's apex region, cryo preparation revealed, that the hydrogen uptake in magnesium is independent of the employment of conventional or cryogenic FIB preparation. TEM measurements demonstrated the growth of a (111) MgO oxide layer with 3-4 nm thickness on the basal (0001) plane of the Mg atom probe specimen. APT data further revealed the formation of an aluminum-rich region between bulk Mg and the native oxide. The aluminum enrichment of up to ~20 at.% at the interface is consistent with an inward growth of the oxide scale.

cond-mat.mtrl-sci↗

arXiv2023

Atomic cluster expansion for Pt-Rh catalysts: From ab initio to the simulation of nanoclusters in few steps

Insight into structural and thermodynamic properties of nanoparticles is crucial for designing optimal catalysts with enhanced activity and stability. We present a semi-automated workflow for parameterizing the atomic cluster expansion (ACE) from ab initio data. The main steps of the workflow are the generation of training data from accurate electronic structure calculations, an efficient fitting procedure supported by active learning and uncertainty indication, and a thorough validation. We apply the workflow to the simulation of binary Pt-Rh nanoparticles that are important for catalytic applications. We demonstrate that the Pt-Rh ACE is able to reproduce accurately a broad range of fundamental properties of the elemental metals as well as their compounds while retaining an outstanding computational efficiency. This enables a direct comparison of simulations to high resolution experiments.

cond-mat.mtrl-sci↗

arXiv2023

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, we present a strategy to understand and tailor the deformability of these complex phases by considering the Nb-Co {\mu}-phase as an archetypal material. The plasticity of the Nb-Co {\mu}-phase is controlled by the Laves phase building block that forms parts of its unit cell. We find that between the bulk C15-NbCo$_2$ Laves and Nb-Co {\mu}-phase, the interplanar spacing and local elastic modulus of the Laves phase building block change, leading to a strong reduction in hardness and elastic modulus, as well as a transition from synchroshear to crystallographic slip. Furthermore, as the composition changes from Nb$_6$Co$_7$ to Nb$_7$Co$_6$, 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 bulk, but at the atomic scale of interplanar spacing and local shear modulus of the fundamental crystal building blocks in their large unit cells.

cond-mat.mtrl-sci↗

arXiv2022

Preferred corrosion pathways for oxygen in Al2Ca-twin boundaries and dislocations

With an ongoing discussion on the oxygen diffusion along crystal defects remaining, it is difficult to study this phenomenon in Al containing intermetallic materials due to its rapid and passivating oxide formation. We report here the observation of enhanced oxygen diffusion along crystal defects, i.e. dislocations and twin boundaries, in the C15 Al 2 Ca Laves phase and how the presence of oxygen induces structural changes at these defects. Three main phases were identified and characterized structurally by aberration-corrected, atomic resolution scanning transmission electron microscopy, analytically by energy dispersive X-ray spectroscopy and electron energy loss spectroscopy. Unlike the C15 bulk phase, the twin boundary and dislocation transformed into a few nanometer wide amorphous phase, which depletes in Al and Ca but is highly enriched in oxygen. The dislocation even shows coexistence of the amorphous phase with a simple Al-rich A1 fcc phase. This A1 phase only depletes in Ca, not in Al (Al remains at bulk concentration), and is also enriched in oxygen. The Al-rich A1 phase is coherent with the C15 matrix. Electron energy loss spectroscopy revealed the amorphous phase to be Al 2 O 3 . We thereby show as one of the first studies that oxygen diffusion along crystal defects, especially also at the twin boundary can induce the formation of an amorphous oxide along themselves. The identification of oxygen-induced transformation at strained defects has to be considered when the material is exposed to air during plastic deformation at elevated temperatures.

cond-mat.mtrl-sci↗

arXiv2022

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

Non-equilibrium synthesis methods allow to alloy 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. 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.

cond-mat.mtrl-sci↗

arXiv2022

Correlating atom probe tomography with X-Ray and electron spectroscopies to understand microstructure-activity relationships in electrocatalysts

The search for a new energy paradigm with net-zero carbon emissions requires new technologies for energy generation and storage that are at the crossroad between engineering, chemistry, physics, surface and materials sciences. To keep pushing the inherent boundaries of device performance and lifetime, we need to step away from a cook-and-look approach and aim to establish the scientific ground to guide the design of new materials. This requires strong efforts in establishing bridges between microscopy and spectroscopy techniques, across multiple scales. Here, we discuss how the complementarities of X-ray- and electron-based spectroscopies and atom probe tomography can be exploited in the study of surfaces and sub-surfaces to understand structure-property relationships in electrocatalysts.

cond-mat.mtrl-sci↗

arXiv2022

Dynamic doping and Cottrell atmosphere optimize the thermoelectric performance of n-type PbTe

High thermoelectric energy conversion efficiency requires a large figure-of-merit, zT, over a broad temperature range. To achieve this, we optimize the carrier concentrations of n-type PbTe from room up to hot-end temperatures by co-doping Bi and Ag. Bi is an efficient n-type dopant in PbTe, often leading to excessive carrier concentration at room temperature. As revealed by density functional theory calculations, the formation of Bi and Ag defect complexes is exploited to optimize the room temperature carrier concentration. At elevated temperatures, we demonstrate the dynamic dissolution of Ag2Te precipitates in PbTe in situ by heating in a scanning transmission electron microscope. The release of n-type Ag interstitials with increasing temperature fulfills the requirement of higher carrier concentrations at the hot end. Moreover, as characterized by atom probe tomography, Ag atoms aggregate along parallel dislocation arrays to form Cottrell atmospheres. This results in enhanced phonon scattering and leads to a low lattice thermal conductivity. As a result of the synergy of dynamic doping and phonon scattering at decorated dislocations, an average zT of 1.0 is achieved in n-type Bi/Ag-codoped PbTe between 400 and 825 K. Introducing dopants with temperature-dependent solubility and strong interaction with dislocation cores enables simultaneous optimization of the average power factor and thermal conductivity, providing a new concept to exploit in the field of thermoelectrics.

cond-mat.mtrl-sci↗

arXiv2022

In-situ nitriding of Fe2VAl during laser surface remelting to manipulate microstructure and crystalline defects

Tailoring the physical properties of complex materials for targeted applications requires optimizing the microstructure and crystalline defects that influence electrical and thermal transport, and mechanical properties. Laser surface remelting can be used to modify the sub-surface microstructure of bulk materials and hence manipulate their properties locally. Here, we introduce an approach to perform remelting in a reactive nitrogen atmosphere, in order to form nitrides and induce segregation of nitrogen to structural defects. These defects arise from the fast solidification of the full-Heusler Fe2VAl compound that is a promising thermoelectric material. Advanced scanning electron microscopy, including electron channelling contrast imaging and three-dimensional electron backscatter diffraction, is complemented by atom probe tomography to study the distribution of crystalline defects and their local chemical composition. We reveal a high density of dislocations, which are stable due to their character as geometrically necessary dislocations. At these dislocations and low-angle grain boundaries, we observe segregation of nitrogen and vanadium, which can be enhanced by repeated remelting in nitrogen atmosphere. We propose that this approach can be generalized to other additive manufacturing processes to promote local segregation and precipitation states, thereby manipulating physical properties.

cond-mat.mtrl-sci↗

arXiv2022

Controlled doping of electrocatalysts through engineering impurities

Fuel cells recombine water from H2 and O2 thereby powering e.g. 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, we observe an unexpected ingress of B into Pd nano-catalysts synthesised by wet-chemistry, gain control over this B-doping, and report on its influence on the HOR activity in alkaline conditions. We rationalize our findings using ab-initio calculations of both H- and OH-adsorption on B-doped Pd. Using this "impurity engineering" approach, we thus design Pt-free catalysts as required in electrochemical energy conversion devices, e.g. next generations of AEMFCs, that satisfy the economic and environmental constraints, i.e. reasonable operating costs and long-term stability, to enable the hydrogen economy.

cond-mat.mtrl-sci↗