Compensating Image Distortions in a Commercial Reflectron-Type Atom Probe.

In atom probe tomography, the spatial resolution and accuracy of the data critically depend on the 3D reconstruction of the 2D detector data. Atom probes with a reflectron have an improved mass resolving power and must include a model of the imaging properties of the reflectron. However, for modern wide-angle reflectron instruments, these imaging properties are not trivial and need to be determined for the reflectron used. This is typically done by the instrument manufacturer, and due to the proprietary nature of the instrument design, the imaging properties are opaque to the user. In this paper, we provide a method to determine the imaging properties of a reflectron that can easily be carried out on commercial instrumentation. This method is used to provide the user with a transformation function from the provided detector data, which can already contain some corrections applied, to a virtual detector placed before the reflectron. From there on, 3D reconstructions can be carried out analogous to straight flight path instruments. Correction algorithms and reference data for Imago/CAMECA LEAP 3000, 4000, 5000, and 6000 series instruments are also provided.

A MATLAB Toolbox for Findable, Accessible, Interoperable, and Reusable Atom Probe Data Science.

Atom probe tomography (APT) data analytics have traditionally been based on manual analytics by researchers. As newer atom probes together with focused ion beam-based specimen preparation have opened APT to many more materials, yielding much more complex mass spectra, building up a systematic understanding of the pathway from raw data to final interpretation has increasingly become important. This demands a system in which the data and treatment can be traced, ideally by any interested party. Such an approach of findable, accessible, interoperable, and reusable (FAIR) data and analysis policies is becoming increasingly important, not just in APT. In this paper, we present a toolbox, written in MATLAB, which allows the user to store the raw and processed data in a standardized FAIR format (hierarchical data format 5) and process the data in a largely scriptable environment to minimize manual user input. This allows for the experiment data to be interchanged without owner explanations and the analysis to be reproduced. We have devised a metadata scheme that is extensible to other experiments in the materials science domain. With this toolbox, collective knowledge can be built up, and a large number of data sets can be analyzed in a fully automated fashion.

Miniaturized gas exposure devices for atom probe experiments.

To detect hydrogen in materials at the atomic scale, atom probe tomography is now regularly used. In order to avoid cumbersome cryo-preparation to suppress diffusion, often hydrogen is charged only into the finished specimen. Here, the use of hydrogen gas over electrochemical hydrogen has the advantage that the specimen is not contaminated with an electrolyte. So far, this "charging" has been done in large, expensive systems. Here, we introduce small devices that enable the exposure of atom probe specimens to hydrogen and potentially other gases, using only very small gas volumes. This enables the operation in regular laboratory environments without additional safety measures. These devices can be used to expose the specimen to hydrogen up to 10 bar/90°C. Higher temperatures may be attained with small changes. Validation of the success of charging with these setups is demonstrated through experiments employing deuterium charging of palladium atom probe tips. RESEARCH HIGHLIGHTS: Enabling the exposure of atom probe specimens to hydrogen and potentially other gases, using only very small gas volumes. Built setups can be assembled with little money and from freely available parts, making specimen charging much easier. Validation of the success of charging with these setups is demonstrated through experiments employing deuterium charging of palladium atom probe tips.

Preparation of atom probe tips from (nano)particles in dispersion using (di)electrophoresis and electroplating.

The behavior of catalytic particles depends on their chemical structure and morphology. To reveal this information, the characterization with atom probe tomography has huge potential. Despite progresses and papers proposing various approaches towards the incorporation of particles inside atom probe tips, no single approach has been broadly applicable to date. In this paper, we introduce a workflow that allowed us to prepare atom probe specimens from Ga particles in suspension in the size range of 50 nm up to 2 µm. By combining dielectrophoresis and electrodeposition in a suitable way, we achieve a near-tip shape geometry, without a time-consuming FIB lift-out. This workflow is a simple and quick method to prepare atom probe tips and allows for a high preparation throughput. Also, not using a lift-out allowed us to use a cryo-stage, avoiding melting of the Ga particles, while ensuring a mechanical stable atom probe tip. The specimen prepared by this workflow enable a stable measurement and low fracture rates. RESEARCH HIGHLIGHTS: Enabling cryo-preparation of (nano)particles for the atom probe. Characterization of surface and bulk elemental distribution of GaPt model SCALMS.

Dry reforming of methane over gallium-based supported catalytically active liquid metal solutions.

Gallium-rich supported catalytically active liquid metal solutions (SCALMS) were recently introduced as a new way towards heterogeneous single atom catalysis. SCALMS were demonstrated to exhibit a certain resistance against coking during the dehydrogenation of alkanes using Ga-rich alloys of noble metals. Here, the conceptual catalytic application of SCALMS in dry reforming of methane (DRM) is tested with non-noble metal (Co, Cu, Fe, Ni) atoms in the gallium-rich liquid alloy. This study introduces SCALMS to high-temperature applications and an oxidative reaction environment. Most catalysts were shown to undergo severe oxidation during DRM, while Ga-Ni SCALMS retained a certain level of activity. This observation is explained by a kinetically controlled redox process, namely oxidation to gallium oxide species and re-reduction via H2 activation over Ni. Consequentially, this redox process can be shifted to the metallic side when using increasing concentrations of Ni in Ga, which strongly suppresses coke formation. Density-functional theory (DFT) based ab initio molecular dynamics (AIMD) simulations were performed to confirm the increased availability of Ni at the liquid alloy-gas interface. However, leaching of gallium via the formation of volatile oxidic species during the hypothesised redox cycles was identified indicating a critical instability of Ga-Ni SCALMS for prolonged test durations.

Metal fused filament fabrication of the nickel-base superalloy IN 718.

This study demonstrates metal fused filament fabrication (MF3) as an alternative additive and highly flexible manufacturing method for free-form fabrication of high-performance alloys. This novel processing, which is similar to Metal injection molding (MIM), enables a significant reduction in manufacturing costs for complex geometries, since expensive machining can be avoided. Utilizing existing equipment and reducing material expense, MF3 can pave the way for new and low-cost applications of IN 718, which were previously limited by high manufacturing costs. Iterative process optimization is used to find the most suitable MF3 process parameters. High relative density above 97% after pressureless sintering can be achieved if temperature profiles and atmospheres are well adjusted for thermal debinding and sintering. In this study, the influence of processing parameters on the resulting microstructure of MF3 IN 718 is investigated. Samples sintered in vacuum show coarse-grained microstructure with an area fraction of 0.36% NbC at grain boundaries. Morphology and composition of formed precipitates are analyzed using transmission electron microscopy and atom probe tomography. The γ/γ″/γ' phases' characteristics for IN 718 were identified. Conventional heat treatment is applied for further tailoring of mechanical properties like hardness, toughness and creep behavior. Fabricated samples achieve mechanical properties similar to MIM IN 718 presented in literature.

GaPt Supported Catalytically Active Liquid Metal Solution Catalysis for Propane Dehydrogenation-Support Influence and Coking Studies.

Supported catalytically active liquid metal solutions (SCALMS) of Pt in Ga (2 at.-% Pt) were studied in the temperature range of 500 to 600 °C for propane dehydrogenation. A facile synthesis procedure using ultrasonication was implemented and compared to a previously reported organo-chemical route for gallium deposition. The procedure was applied to synthesize GaPt-SCALMS catalyst on silica (SiO2), alumina (Al2O3), and silicon carbide (SiC) to investigate the effect of the support material on the catalytic performance. The SiC-based SCALMS catalyst showed the highest activity, while SiO2-based SCALMS showed the highest stability and lowest cracking tendency at higher temperatures. The selectivity toward propene for the SiO2-based catalyst remained above 93% at 600 °C. The catalysts were analyzed for coke content after use by temperature-programmed oxidation (TPO) and Raman spectroscopy. While the SiC- and SiO2-supported SCALMS systems showed hardly any coke formation, the Al2O3-supported systems suffered from pronounced coking. SEM-EDX analyses of the catalysts before and after reaction indicated that no perceivable morphological changes occur during reaction. The SCALMS catalysts under investigation are compared with supported Pt and supported GaPt solid-phase catalyst, and possible deactivation pathways are discussed.

Atom Probe Analysis of Nanoparticles Through Pick and Coat Sample Preparation.

The ability to analyze nanoparticles in the atom probe has often been limited by the complexity of the sample preparation. In this work, we present a method to lift­out single nanoparticles in the scanning electron microscope. First, nanoparticles are dispersed on a lacey carbon grid, then positioned on a sharp substrate tip and coated on all sides with a metallic matrix by physical vapor deposition. Compositional and structural insights are provided for spherical gold nanoparticles and a segregation of silver and copper in silver copper oxide nanorods is shown in 3D atom maps. Using the standard atom probe reconstruction algorithm, data quality is limited by typical standard reconstruction artifacts for heterogeneous specimens (trajectory aberrations) and the choice of suitable coatings for the particles. This approach can be applied to various unsupported free-standing nanoparticles, enables preselection of particles via correlative techniques, and reliably produces well-defined structured samples. The only prerequisite is that the nanoparticles must be large enough to be manipulated, which was done for sizes down to ~50 nm.

A versatile cryo-transfer system, connecting cryogenic focused ion beam sample preparation to atom probe microscopy.

Atom probe tomography (APT) is a powerful technique to obtain 3D chemical and structural information, however the 'standard' atom probe experimental workflow involves transfer of specimens at ambient conditions. The ability to transfer air- or thermally-sensitive samples between instruments while maintaining environmental control is critical to prevent chemical or morphological changes prior to analysis for a variety of interesting sample materials. In this article, we describe a versatile transfer system that enables cryogenic- or room-temperature transfer of specimens in vacuum or atmospheric conditions between sample preparation stations, a focused ion beam system (Zeiss Crossbeam 540) and a widely used commercial atom probe system (CAMECA LEAP 4000X HR). As an example for the use of this transfer system, we present atom probe data of gallium- (Ga)-free grain boundaries in an aluminum (Al) alloy specimen prepared with a Ga-based FIB.

Influence of Zn and Sn on the Precipitation Behavior of New Al-Mg-Si Alloys.

In this study, we demonstrate how Zn and Sn influence hardening behavior and cluster formation during pre-aging and paint bake treatment in Al-Mg-Si alloys via hardness tests, tensile tests, and atom probe tomography. Compared to the standard alloy, the Sn-modified variant shows reduced cluster size and yield strength in the pre-aged condition. During the paint bake cycle, the clusters start to grow very fast and the alloy exhibits the highest strength increment. This behavior is attributed to the high vacancy binding energy of Sn. Adding Zn increases the formation kinetics and the size of Mg-Si co-clusters, generating higher yield strength values for both the pre-aged and paint baked conditions. Simultaneous addition of Zn and Sn creates a synergistic effect and produces an alloy that exhibits moderate strength (and good formability) in the pre-aged condition and accelerated hardening behavior during the paint bake cycle.

Interpreting Atom Probe Data from Oxide-Metal Interfaces.

Understanding oxide-metal interfaces is crucial to the advancement of materials and components for many industries, most notably for semiconductor devices and power generation. Atom probe tomography provides three-dimensional, atomic scale information about chemical composition, making it an excellent technique for interface analysis. However, difficulties arise when analyzing interfacial regions due to trajectory aberrations, such as local magnification, and reconstruction artifacts. Correlative microscopy and field simulation techniques have revealed that nonuniform evolution of the tip geometry, caused by heterogeneous field evaporation, is partly responsible for these artifacts. Here we attempt to understand these trajectory artifacts through a study of the local evaporation field conditions. With a better understanding of the local evaporation field, it may be possible to account for some of the local magnification effects during the reconstruction process, eliminating these artifacts before data analysis.

Advanced concentration analysis of atom probe tomography data: Local proximity histograms and pseudo-2D concentration maps.

Analysing the distribution of selected chemical elements with respect to interfaces is one of the most common tasks in data mining in atom probe tomography. This can be represented by 1D concentration profiles, 2D concentration maps or proximity histograms, which represent concentration, density etc. of selected species as a function of the distance from a reference surface/interface. These are some of the most useful tools for the analysis of solute distributions in atom probe data. In this paper, we present extensions to the proximity histogram in the form of 'local' proximity histograms, calculated for selected parts of a surface, and pseudo-2D concentration maps, which are 2D concentration maps calculated on non-flat surfaces. This way, local concentration changes at interfaces or and other structures can be assessed more effectively.

A New Approach to Understand the Adsorption of Thiophene on Different Surfaces: An Atom Probe Investigation of Self-Assembled Monolayers.

Atom probe tomography was used to analyze self-assembled monolayers of thiophene on different surfaces, including tungsten, platinum, and aluminum, where the tungsten was examined in both pristine and oxidized forms. A glovebag with controlled atmospheres was used to alter the level of oxidation for tungsten. It was shown that different substrates lead to substantial changes in the way thiophene adsorbs on the surface. Furthermore, the oxidation of the surface strongly influenced the adsorption behavior of the thiophene molecules, leading to clear differences in the amounts and compositions of field evaporated ions and molecular ions.

A computational geometry framework for the optimisation of atom probe reconstructions.

In this paper, we present pathways for improving the reconstruction of atom probe data on a coarse (>10nm) scale, based on computational geometry. We introduce a way to iteratively improve an atom probe reconstruction by adjusting it, so that certain known shape criteria are fulfilled. This is achieved by creating an implicit approximation of the reconstruction through a barycentric coordinate transform. We demonstrate the application of these techniques to the compensation of trajectory aberrations and the iterative improvement of the reconstruction of a dataset containing a grain boundary. We also present a method for obtaining a hull of the dataset in both detector and reconstruction space. This maximises data utilisation, and can be used to compensate for ion trajectory aberrations caused by residual fields in the ion flight path through a 'master curve' and correct for overall shape deviations in the data.

Linking stress-driven microstructural evolution in nanocrystalline aluminium with grain boundary doping of oxygen.

The large fraction of material residing at grain boundaries in nanocrystalline metals and alloys is responsible for their ultrahigh strength, but also undesirable microstructural instability under thermal and mechanical loads. However, the underlying mechanism of stress-driven microstructural evolution is still poorly understood and precludes rational alloy design. Here we combine quantitative in situ electron microscopy with three-dimensional atom-probe tomography to directly link the mechanics and kinetics of grain boundary migration in nanocrystalline Al films with the excess of O atoms at the boundaries. Site-specific nanoindentation leads to grain growth that is retarded by impurities, and enables quantification of the critical stress for the onset of grain boundary migration. Our results show that a critical excess of impurities is required to stabilize interfaces in nanocrystalline materials against mechanical driving forces, providing new insights to guide control of deformation mechanisms and tailoring of mechanical properties apart from grain size alone.

A simple approach to atom probe sample preparation by using shadow masks.

Here, we present a new method that utilises shadow masks in a broad ion beam system to prepare atom probe samples. It is particularly suited to non-conductors and materials with surface layers such as surface oxides, implanted layers or thin films. This new approach bypasses the focused ion beam (FIB) lift-out step, increasing the sample throughput, dramatically reducing the required FIB beam time and decreasing the complexity of sample preparation.

Mapping interfacial excess in atom probe data.

Using modern wide-angle atom probes, it is possible to acquire atomic scale 3D data containing 1000 s of nm(2) of interfaces. It is therefore possible to probe the distribution of segregated species across these interfaces. Here, we present techniques that allow the production of models for interfacial excess (IE) mapping and discuss the underlying considerations and sampling statistics. We also show, how the same principles can be used to achieve thickness mapping of thin films. We demonstrate the effectiveness on example applications, including the analysis of segregation to a phase boundary in stainless steel, segregation to a metal-ceramic interface and the assessment of thickness variations of the gate oxide in a fin-FET.

The Hidden Pathways in Dense Energy Materials - Oxygen at Defects in Nanocrystalline Metals.

Highly abundant oxygen-rich line defects (blue) can act as fast oxygen transport paths. These defects show similar chemistry and therefore similar catalytic activity to the materials surface. These results provide the opportunity to design and produce simple scalable structures as catalysts, whose functionality derives from internal defects rather than from the materials surfaces.

Mining information from atom probe data.

Whilst atom probe tomography (APT) is a powerful technique with the capacity to gather information containing hundreds of millions of atoms from a single specimen, the ability to effectively use this information creates significant challenges. The main technological bottleneck lies in handling the extremely large amounts of data on spatial-chemical correlations, as well as developing new quantitative computational foundations for image reconstruction that target critical and transformative problems in materials science. The power to explore materials at the atomic scale with the extraordinary level of sensitivity of detection offered by atom probe tomography has not been not fully harnessed due to the challenges of dealing with missing, sparse and often noisy data. Hence there is a profound need to couple the analytical tools to deal with the data challenges with the experimental issues associated with this instrument. In this paper we provide a summary of some key issues associated with the challenges, and solutions to extract or "mine" fundamental materials science information from that data.

Revealing the distribution of the atoms within individual bimetallic catalyst nanoparticles.

To be able to correlate the catalytic properties of nanoparticles with their structure, detailed knowledge about their make-up on the atomic level is required. Herein, we demonstrate how atom-probe tomography (APT) can be used to quantitatively determine the three-dimensional distribution of atoms within a Au@Ag nanoparticle with near-atomic resolution. We reveal that the elements are not evenly distributed across the surface and that this distribution is related to the surface morphology and residues from the particle synthesis.