Daniel Schreiber

Atom probe tomography (APT) provides a unique, three-dimensional map of elemental and isotopic distributions over a wide range of materials with near-atomic scale resolution and is particularly strong at analyzing buried interfaces within materials. However, it is much more difficult to apply atom probe to the analysis of nanoscale surface films, such as those formed during alloy passivation, where unique challenges persist for sample preparation and data collection. Here, we present sample preparation strategies involving the deposition of a <100 nm capping layer that enables reliable characterization of thin passive films ∼2–5 nm thick formed on binary and multiprincipal element alloys via APT. Several capping layer materials (Pt, Ti, and Ni/Cr bilayer) and deposition methods are contrasted. Our results indicate a sputtered Ni/Cr bilayer enables the characterization of the entire passive film and concentration profiles that can easily be interpreted to clearly distinguish base alloy/passive film/capping layer interfaces. Lastly, we highlight ongoing challenges and opportunities for this experimental approach.

Surface passivation, a desirable natural consequence during initial oxidation of alloys, is the foundation for functioning of corrosion and oxidation resistant alloys ranging from industrial stainless steel to kitchen utensils. This initial oxidation has been long perceived to vary with crystal facet, however, the underlying mechanism remains elusive. Here, using in situ environmental transmission electron microscopy, we gain atomic details on crystal facet dependent initial oxidation behavior in a model Ni-5Cr alloy. We find the (001) surface shows higher initial oxidation resistance as compared to the (111) surface. We reveal the crystal facet dependent oxidation is related to an interfacial atomic sieving effect, wherein the oxide/metal interface selectively promotes diffusion of certain atomic species. Density functional theory calculations rationalize the oxygen diffusion across Ni(111)/NiO(111) interface, as contrasted with Ni(001)/NiO(111), is enhanced. We unveil that crystal facet with initial fast oxidation rate could conversely switch to a slow steady state oxidation.

High-resolution transmission electron microscopy and atom probe tomography are used to characterize the initial passivation and subsequent intergranular corrosion of degraded grain boundaries in a model Ni-30Cr alloy exposed to 360 °C hydrogenated water. Upon initial exposure for 1000 h, the alloy surface directly above the grain boundary forms a thin passivating film of Cr₂O₃, protecting the underlying grain boundary from intergranular corrosion. However, the metal grain boundary experiences severe Cr depletion and grain boundary migration during this initial exposure. To understand how Cr depletion affects further corrosion, the local protective film was sputtered away using a glancing angle focused ion beam. Upon further exposure, the surface fails to repassivate, and intergranular corrosion is observed through the Cr-depleted region. Through this combination of high-resolution microscopy and localized passive film removal, we show that, although high-Cr alloys are resistant to intergranular attack and stress corrosion cracking, degradation-induced changes in the underlying metal at grain boundaries make the material more susceptible once the initial passive film is breached.

The transport paths of O during intergranular oxidation in binary Ni-Cr were investigated. To isolate the selective oxidation of Cr, oxidation was performed with a CO/CO₂ gas mixture in which the oxygen partial pressure was kept under the NiO dissociation pressure. A combination of electron microscopy and atom probe tomography (APT) was used to study the nanometer-scale details of the passivation and penetrative intergranular oxidation processes at high-energy grain boundaries. Oxygen transport towards the terminating oxidation front is elucidated with dedicated usage of oxygen tracer exchange experiments. Secondary ion mass spectroscopy and APT support classical theories of internal oxidation, revealing preferred transport paths at the oxide/alloy interface with sub-nanometer resolution.

Perovskite structured transition metal oxides are important technological materials for catalysis and solid oxide fuel cell applications. Their functionality often depends on oxygen diffusivity and mobility through complex oxide heterostructures, which can be significantly impacted by structural and chemical modifications, such as doping. Further, when utilized within electrochemical cells, interfacial reactions with other components (e.g., Ni‐ and Cr‐based alloy electrodes and interconnects) can influence the perovskite's reactivity and ion transport, leading to complex dependencies that are difficult to control in real‐world environments. Here, this work uses isotopic tracers and atom probe tomography to directly visualize oxygen diffusion and transport pathways across perovskite and metal‐perovskite heterostructures, that is, (Ni‐Cr coated) Sr‐doped lanthanum ferrite (La_0.5Sr_0.5FeO₃; LSFO). Annealing in ¹⁸O_2(g) results in elemental and isotopic redistributions through oxygen exchange (OE) in the LSFO while Ni‐Cr undergoes oxidation via multiple mechanisms and transport pathways. Complementary density functional theory calculations at experimental conditions provide rationale for OE reaction mechanisms and reveal a complex interplay of different thermodynamic and kinetic drivers. These results shed light on the fundamental coupling of defects and oxygen transport in an important class of catalytic materials.

Mass transport along grain boundaries in alloys depends not only on the atomic structure of the boundary, but also its chemical make-up. In this work, we use molecular dynamics to examine the effect of Cr alloying on interstitial and vacancy-mediated transport at a variety of grain boundaries in Ni. We find that, in general, Cr tends to reduce the rate of mass transport, an effect which is greatest for interstitials at pure tilt boundaries. However, there are special scenarios in which it can greatly enhance atomic mobility. Cr tends to migrate faster than Ni, though again this depends on the structure of the grain boundary. Further, grain boundary mobility, which is sometimes pronounced for pure Ni grain boundaries, is eliminated on the time scales of our simulations when Cr is present. We conclude that the enhanced transport and grain boundary mobility often seen in this system in experimental studies is the result of non-equilibrium effects and is not intrinsic to the alloyed grain boundary. These results provide new insight into the role of grain boundary alloying on transport that can help in the interpretation of experimental results and the development of predictive models of materials evolution.

Atom probe results of the NMC811 sample from an ultra-high vacuum vs. air transferring.

Atom probe tomography, and related methods, probe the composition and the three-dimensional architecture of materials. The software tools which microscopists use, and how these tools are connected into workflows, make a substantial contribution to the accuracy and precision of such material characterization experiments. Typically, we adapt methods from other communities like mathematics, data science, computational geometry, artificial intelligence, or scientific computing. We also realize that improving on research data management is a challenge when it comes to align with the FAIR data stewardship principles. Faced with this global challenge, we are convinced it is useful to join forces. Here, we report the results and challenges with an inter-laboratory call for developing test cases for several types of atom probe microscopy software tools. The results support why defining detailed recipes of software workflows and sharing these recipes is necessary and rewarding: Open source tools and (meta)data exchange can help to make our day-to-day data processing tasks become more efficient, the training of new users and knowledge transfer become easier, and assist us with automated quantification of uncertainties to gain access to substantiated results.

Irradiation induced non-equilibrium point defect populations influence mass transport in oxides, which in turn affects their stability and performance in hostile environments. In this study a strong dose rate dependence is observed.

Fe–Cr alloys are at the forefront for high radiation tolerant materials with long-standing validated performance. Yet, the detailed mechanism behind their high radiation resistance is in question and understanding the effect of varying Cr percentage is a grand challenge limiting further improvements. Here, we applied depth-resolved positron annihilation lifetime spectroscopy and Doppler broadening spectroscopy to study the effect of Cr alloying on the formation and evolution of atomic size clusters induced by ion-irradiation in Fe. We also used atom probe tomography to investigate the possible presence of Cr clusters or α′ phase precipitates with high Cr composition. The study reveals that the well-known resistance to radiation in Fe–Cr alloys may arise from the stabilization of vacancy clusters around Cr atoms, which act as sinks for radiation-induced defects. This implies that Cr atoms do not provide a direct sink for interstitials; rather defect complexes that consist of Cr atoms and vacancies, in turn, act as sinks for irradiation-induced vacancies and interstitials. we also find that lower amounts of Cr create smaller defect clusters that act as efficient sinks for radiation damage, but larger quantities of Cr form a defect structure that is less homogenous and larger in size, resulting in less efficient damage recombination. No evidence of α′ was found before or after irradiation, which indicates that it does not contribute to the observed radiation tolerance.

Self‐diffusion is a fundamental physical process that, in solid materials, is intimately correlated with both microstructure and functional properties. Local transport behavior is critical to the performance of functional ionic materials for energy generation and storage, and drives fundamental oxidation, corrosion, and segregation phenomena in materials science, geosciences, and nuclear science. Here, an adaptable approach is presented to precisely characterize self‐diffusion in solids by isotopically enriching component elements at specific locations within an epitaxial film stack, and measuring their redistribution at high spatial resolution in 3D with atom probe tomography. Nanoscale anion diffusivity is quantified in a‐Fe₂O₃ thin films deposited by molecular beam epitaxy with a thin (10 nm) buried tracer layer highly enriched in ¹⁸O. The isotopic sensitivity of the atom probe allows precise measurement of the initial sharp layer interfaces and subsequent redistribution of ¹⁸O after annealing. Short‐circuit anion diffusion through 1D and 2D structural defects in Fe₂O₃ is also directly visualized in 3D. This versatile approach to study precisely tailored thin film samples at high spatial and mass fidelity will facilitate a deeper understanding of atomic‐scale diffusion phenomena.

The next generation of nuclear reactors will expose materials to conditions that, in some cases, are even more extreme than those in current fission reactors, inevitably leading to new materials science challenges. Radiation-induced damage and corrosion are two key phenomena that must be understood both independently and synergistically, but their interactions are often convoluted. In the light water reactor community, a tremendous amount of work has been done to illuminate irradiation-corrosion effects, and similar efforts are under way for heavy liquid metal and molten salt environments. While certain effects, such as radiolysis and irradiation-assisted stress corrosion cracking, are reasonably well established, the basic science of how irradiation-induced defects in the base material and the corrosion layer influence the corrosion process still presents many unanswered questions. In this review, we summarize the work that has been done to understand these coupled extremes, highlight the complex nature of this problem, and identify key knowledge gaps.

A multimodal chemical imaging approach has been developed and applied to detail the dynamic, atomic-scale changes associated with oxidation of a zirconium alloy (Zircaloy-4). Scanning transmission electron microscopy, a gas-phase reactor chamber attached to an atom probe tomography instrument, and synchrotron-based X-ray absorption near-edge spectroscopy were employed to reveal morphology, composition, crystal, and electronic structure changes that occur during initial stages of oxidation at 300 °C. Oxidation was carried out in 10 mbar O₂gas for short exposure times of 1 and 5 min. A multilayered oxide film with a cubic ZrO adjacent to the oxide/metal interface, a nanoscopic transition region with a graded composition of ZrO_2−x(where 0 < x < 1), and tetragonal ZrO₂in the outermost oxide were formed. Partitioning of the major alloying element (tin) to the oxide/metal interface and heterogeneously within the oxide accompanied the development of the layered oxide. Our work provides a rapid, high-throughput approach for detailed characterisation of initial stages of zirconium alloy oxidation at an accelerated time scale, with implications for several other alloy systems.

Distinct atomic-scale surface oxidation processes of alloy in O ₂ and water vapor have been revealed by environmental TEM.

Cryo-based atom probe tomography has been applied to directly reveal the water-solid interface and hydrated corrosion layers making up the nanoscale porous structure of a corroded borosilicate glass in its native aqueous environment. The analysis includes morphology and compositional mapping of the inner gel/glass interface, isolation of a tomographic sub-volume of the tortuous water-filled gel, and comparison of the gel structure with simulations. The nanoscale porous structure is qualitatively consistent with that of the molecular dynamics simulation, enabling in greater confidence in both interrogations. Comparison of the gel/glass interface between desiccated and cryogenically preserved samples reveals consistently abrupt B dissolution behavior and quantitative differences in the apparent H ingress into the glass. These comparisons give some guidance to future experimental approaches to understanding glass corrosion behavior. More broadly, the cryogenic preservation and 3D visualization of the native water/solid structure in 3D at the nanoscale has direct relevance to a wide range of materials systems beyond glass science.

While various glass alteration layer formation mechanisms have been debated in recent years, the glass alteration community generally agrees that more information on physical properties of the alteration layers is needed to further the understanding of their impacts on overall glass alteration. In this work, pore volumes and solid structures of glass (International Simple Glass, ISG) alteration layers formed in solutions of various pH conditions in initially dilute conditions at 90 °C are evaluated with positron annihilation spectroscopy, small-angle X-ray scattering, and scanning transmission electron microscopy. Pore volumes of alteration layers formed at pH 9 were found to be at their lowest near the surfaces of the alteration layers. Solid structures of alteration layers are compared with those of synthetic aerogels of comparable compositions produced under various pH conditions. Alteration layers formed at pH 11 on ISG were shown to contain large structures (>10 nm) similar to synthetic aerogels created under neutral and basic conditions whereas alteration layers formed at pH 9 did not. Available dissolved silica species defined by silica solubility were proposed to have the greatest impact on alteration layer structure.

We summarize the findings from an interlaboratory study conducted between ten international research groups and investigate the use of the commonly used maximum separation distance and local concentration thresholding methods for solute clustering quantification. The study objectives are: to bring clarity to the range of applicability of the methods; identify existing and/or needed modifications; and interpretation of past published data. Participants collected experimental data from a proton-irradiated 304 stainless steel and analyzed Cu-rich and Ni–Si rich clusters. The datasets were also analyzed by one researcher to clarify variability originating from different operators. The Cu distribution fulfills the ideal requirements of the maximum separation method (MSM), namely a dilute matrix Cu concentration and concentrated Cu clusters. This enabled a relatively tight distribution of the cluster number density among the participants. By contrast, the group analysis of the Ni–Si rich clusters by the MSM was complicated by a high Ni matrix concentration and by the presence of Si-decorated dislocations, leading to larger variability among researchers. While local concentration filtering could, in principle, tighten the results, the cluster identification step inevitably maintained a high scatter. Recommendations regarding reporting, selection of analysis method, and expected variability when interpreting published data are discussed.

Although highly cold-worked UNS N06690 has been shown to be susceptible to stress corrosion crack growth in pressurized water reactor primary water, it is unclear whether cold-work promotes stress corrosion crack initiation under constant load test conditions. To evaluate the stress corrosion cracking initiation response, constant load tensile and blunt notch compact tension testing were performed on 21% and 31% cold-worked samples from two thermally treated UNS N06690 materials in 360°C simulated pressurized water reactor primary water. High-resolution examinations were conducted mid- and post-test to record the evolution of grain boundary precursor damage and intergranular crack nucleation by focused ion beam milling combined with scanning electron microscopy and by transmission electron microscopy. The surface and subsurface morphology of intergranular cavities, local corrosion, and shallow cracks were documented. Nanometer-sized cavities were observed associated with grain boundary carbides in all specimens. The 31% cold-work specimens consistently exhibited shallow intergranular cracks with oxidized crack flanks and a high density of cavities ahead of the oxide front. Three-dimensional distribution of carbides and cavities ahead of the cracked grain boundaries was analyzed to gain mechanistic insights into the processes that lead to crack initiation in highly cold-worked UNS N06690.

Atom probe tomography (APT) is a powerful technique to characterize buried three-dimensional nanostructures in a variety of materials. Accurate characterization of those nanometer-scale clusters and precipitates is of great scientific significance to understand the structure–property relationships and the microstructural evolution. The current widely used cluster analysis method, a variant of the density-based spatial clustering of applications with noise algorithm, can only accurately extract clusters of the same atomic density, neglecting several experimental realities, such as density variations within and between clusters and the nonuniformity of the atomic density in the APT reconstruction itself (e.g., crystallographic poles and other field evaporation artifacts). This clustering method relies heavily on multiple input parameters, but ideal selection of those parameters is challenging and oftentimes ambiguous. In this study, we utilize a well-known cluster analysis algorithm, called ordering points to identify the clustering structures, and an automatic cluster extraction algorithm to analyze clusters of varying atomic density in APT data. This approach requires only one free parameter, and other inputs can be estimated or bounded based on physical parameters, such as the lattice parameter and solute concentration. The effectiveness of this method is demonstrated by application to several small-scale model datasets and a real APT dataset obtained from an oxide-dispersion strengthened ferritic alloy specimen.

The bioavailability of iron in the environment, and coupled metals, nutrients, and contaminants, depends on the stability of common Fe(III) minerals such as goethite (FeOOH) and hematite (Fe ₂ O ₃ ). At redox boundaries, iron isotopic tracer studies suggest that interaction with aqueous Fe(II) creates dynamic conditions of atom exchange (AE). However, mechanistic models have not advanced beyond speculation, because of the challenges of mapping AE fronts recorded in isotopic distributions in individual nanoscale crystallites. Here we demonstrate successful use of 3D atom probe tomography for this purpose. The penetration depth, spatial heterogeneity, and ties to mineral defects are visualized, helping constrain mechanistic models and setting a precedent for detailed interrogation of iron redox cycling in the environment.

Accelerator-based ion beam irradiation techniques have been used to study radiation effects in materials for decades. Although carbon contamination induced by ion beams in target materials is a well-known issue in some material systems, it has not been fully characterized nor quantified for studies in ferritic/martensitic (F/M) steels that are candidate materials for applications such as core structural components in advanced nuclear reactors. It is an especially important issue for this class of material because of the strong effect of carbon level on precipitate formation. In this paper, the ability to quantify carbon contamination using three common techniques, namely time-of-flight secondary ion mass spectroscopy (ToF-SIMS), atom probe tomography (APT), and transmission electron microscopy (TEM) is compared. Their effectiveness and shortcomings in determining carbon contamination are presented and discussed. The corresponding microstructural changes related to carbon contamination in ion irradiated F/M steels are also presented and briefly discussed.

Microstructures of magnetic materials, including defects and crystallographic orientations, are known to strongly influence magnetic domain structures. Measurement techniques such as magnetic force microscopy (MFM) thus allow study of correlations between microstructural and magnetic properties. The present work probes effects of anisotropy and artificial defects on the evolution of domain structure with applied field. Single crystal iron thin films on MgO substrates were milled by Focused Ion Beam (FIB) to create different magnetically isolated squares and rectangles in [110] crystallographic orientations, having their easy axis 45° from the sample edge. To investigate domain wall response on encountering non-magnetic defects, a 150 nm diameter hole was created in the center of some samples. By simultaneously varying crystal orientation and shape, both magnetocrystalline anisotropy and shape anisotropy, as well as their interaction, could be studied. Shape anisotropy was found to be important primarily for the longer edge of rectangular samples, which exaggerated the FIB edge effects and provided nucleation sites for spike domains in non-easy axis oriented samples. Center holes acted as pinning sites for domain walls until large applied magnetic fields. The present studies are aimed at deepening the understanding of the propagation of different types of domain walls in the presence of defects and different crystal orientations.

Atom probe tomography (APT) is a novel analytical microscopy method that provides three dimensional elemental mapping with sub‐nanometer spatial resolution and has only recently been applied to insulating glass and ceramic samples. In this paper, we have studied the influence of the optical absorption in glass samples on APT characterization by introducing different transition metal optical dopants to a model borosilicate nuclear waste glass. A systematic comparison is presented of the glass optical properties and the resulting APT data quality in terms of compositional accuracy and the mass spectra quality for two APT systems: one with a green laser (532 nm, LEAP 3000X HR) and one with a UV laser (355 nm, LEAP 4000X HR). These data were also compared to the study of a more complex borosilicate glass (SON68). The results show that the analysis data quality, particularly the compositional accuracy and sample yield, was clearly linked to optical absorption when using a green laser, while for the UV laser optical doping aided in improving data yield but did not have a significant effect on compositional accuracy. Comparisons of data between the LEAP systems suggest that the smaller laser spot size of the LEAP 4000X HR played a more critical role for optimum performance than the optical dopants themselves. The smaller spot size resulted in more accurate composition measurements due to a reduced background level independent of the material's optical properties.

Calculated frequency distributions of atom probe tomography reconstructions (∼80 nm field of view) of very thin AlxGa1−xN (0.18 ≤ x ≤ 0.51) films grown via metalorganic vapor phase epitaxy on both (0001) GaN/AlN/SiC and (0001) GaN/sapphire heterostructures revealed homogeneous concentrations of Al and chemically abrupt AlxGa1−xN/GaN interfaces. The results of scanning transmission electron microscopy and selected area diffraction corroborated these results and revealed that neither superlattice ordering nor phase separation was present at nanometer length scales.

We report the in situ atomic-scale visualization of the dynamic three-dimensional growth of NiO during the initial oxidation of Ni–10at%Cr using environmental transmission electron microscopy.

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides. The simulations further demonstrate that the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr2O3. This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl2O4. Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3–10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr2O3 has a plate-like structure with 1.2–1.7 nm wide pores running along the grain boundary, while NiAl2O4 has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional pathway for oxygen diffusion through the oxide. The proposed theoretical methodology provides a framework for modeling metal alloy oxidation processes from first principles and on the experimentally relevant length scales.

Analysis of the detected Fe ion charge states from laser-assisted field evaporation of magnetite (Fe3O4) reveals unexpected trends as a function of laser pulse energy that break from conventional post-ionization theory for metals. For Fe ions evaporated from magnetite, the effects of post-ionization are partially offset by the increased prevalence of direct evaporation into higher charge states with increasing laser pulse energy. Therefore, the final charge state is related to both the field strength and the laser pulse energy, despite those variables themselves being intertwined when analyzing at a constant detection rate. Comparison of data collected at different base temperatures also shows that the increased prevalence of Fe2+ at higher laser energies is possibly not a direct thermal effect. Conversely, the ratio of 16O+:(16O2+ + 16O+) is well correlated with field strength and unaffected by laser pulse energy on its own, making it a better overall indicator of the field evaporation conditions. Plotting the normalized field strength versus laser pulse energy also elucidates a non-linear dependence, in agreement with the previous observations on semiconductors, which suggests field-dependent laser absorption efficiency. Together these observations demonstrate that the field evaporation process for laser-pulsed oxides exhibits fundamental differences from metallic specimens that cannot be completely explained by post-ionization theory. Further theoretical studies, combined with detailed analytical observations, are required to understand fully the field evaporation process of non-metallic samples.

In0.20Ga0.80N/GaN multiquantum wells (MQWs) grown on [0001]-oriented GaN substrates with and without an InGaN buffer layer were characterized using three-dimensional atom probe tomography. In all samples, the upper interfaces of the QWs were slightly more diffuse than the lower interfaces. The buffer layers did not affect the roughness of the interfaces within the quantum well structure, a result attributed to planarization of the surface of the first GaN barrier layer, which had an average root-mean-square roughness of 0.18 nm. The In and Ga distributions within the MQWs followed the expected distributions for a random alloy with no indications of In clustering. High resolution Rutherford backscattering characterizations showed the ability to resolve the MQWs, and the resulting compositions and widths corroborated those determined from the atom probe analyses.

Currently, nuclear wastes are commonly immobilized into glasses because of their long‐term durability. Exposure to water for long periods, however, will eventually corrode the waste form and is the leading potential avenue for radionuclide release into the environment. Because such slow processes cannot be experimentally tested, the prediction of release requires a thorough understanding of the mechanisms governing glass corrosion. In addition, because of the exceptional durability of glass, much of the testing must be performed on high‐surface area powders. A technique that can provide accurate compositional profiles with nanometer scale depth resolution for non‐flat samples would be a major benefit to the field. In this study, NanoSIMS was used to image the cross section of the corrosion layers of a leached SON68 glass sample. A wedged crater was prepared by a focused ion beam instrument to obtain a five‐fold improvement in depth information for NanoSIMS measurements. This improvement allowed us to confirm that the breakdown of the silica glass network is further from the pristine glass than a second dissolution front for boron, another glass former, despite only ~50 nm distance between them. More importantly, NanoSIMS images show that the roughness majorly exists in Si corrosion layer. This novel sample geometry will be a major benefit to efficient NanoSIMS sampling of irregular interfaces at the nanometer scale that would otherwise be obscured within time‐of‐flight secondary ion mass spectroscopy depth profiles. Copyright © 2014 John Wiley & Sons, Ltd.

High-resolution characterizations of intergranular attack in alloy 600 (Ni-17Cr-9Fe) exposed to 325°C simulated pressurized water reactor primary water have been conducted using a combination of scanning electron microscopy, NanoSIMS, analytical transmission electron microscopy, and atom probe tomography. The intergranular attack exhibited a two-stage microstructure that consisted of continuous corrosion/oxidation to a depth of ~200 nm from the surface followed by discrete Cr-rich sulfides to a further depth of ~500 nm. The continuous oxidation region contained primarily nanocrystalline MO-structure oxide particles and ended at Ni-rich, Cr-depleted grain boundaries with spaced CrS precipitates. Three-dimensional characterization of the sulfidized region using site-specific atom probe tomography revealed extraordinary grain boundary composition changes, including total depletion of Cr across a several nm wide dealloyed zone as a result of grain boundary migration.

A sample preparation method is described for enabling direct correlation of site-specific plan-view and cross-sectional transmission electron microscopy (TEM) analysis of individual nanostructures by employing a dual-beam focused-ion beam (FIB) microscope. This technique is demonstrated using Si nanowires dispersed on a TEM sample support (lacey carbon or Si-nitride). Individual nanowires are first imaged in the plan-view orientation to identify a region of interest; in this case, impurity atoms distributed at crystalline defects that require further investigation in the cross-sectional orientation. Subsequently, the region of interest is capped with a series of ex situ and in situ deposited layers to protect the nanowire and facilitate site-specific lift-out and cross-sectioning using a dual-beam FIB microscope. The lift-out specimen is thinned to electron transparency with site-specific positioning to within ∼200 nm of a target position along the length of the nanowire. Using the described technique, it is possible to produce correlated plan-view and cross-sectional view lattice-resolved TEM images that enable a quasi-3D analysis of crystalline defect structures in a specific nanowire. While the current study is focused on nanowires, the procedure described herein is general for any electron-transparent sample and is broadly applicable for many nanostructures, such as nanowires, nanoparticles, patterned thin films, and devices.

Correlated transmission electron microscopy imaging, electron diffraction, and Raman spectroscopy are used to investigate the structure of Si nanowires with planar defects. In addition to plan‐view imaging, individual defective nanowires are imaged in axial cross‐section at specific locations selected in plan‐view imaging. This correlated characterization approach enables definitive identification of complex defect structures that give rise to diffraction patterns that have been misinterpreted in the literature. Conclusive evidence for the 9R Si polytype is presented, and the atomic structure of this phase is correlated with kinematically‐forbidden reflections in Si diffraction patterns. Despite striking similarities between imaging and diffraction data from twinned nanowires and the 9R polytype, clear distinctions between the structures can be made. Finally, the structural origins of ⅓{422} reflections in Si [111] diffraction patterns are identified.

Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 – August 2, 2012.

The protocol to calculate the chemical roughness from three-dimensional (3-D) data cube acquired by energy-filtered electron tomography has been developed and applied to analyze the 3-D Zr distribution at the arbitrarily shaped interfaces in the ZrO2/In2O3 multilayer films. The calculated root-mean-square roughness quantitatively revealed the chemical roughness at the buried ZrO2/In2O3 interfaces, which is the deviation of Zr distribution from the ideal flat interface. Knowledge of the chemistry and structure of oxide interfaces in 3-D provides information useful for understanding changes in the behavior of a model ZrO2/In2O3 heterostructure that has potential to exhibit mixed conduction behavior.

Three-dimensional atom-probe tomography and transmission electron microscopy have been utilized to study the effects of Ta getter presputtering and either a Mg or Ru free-layer cap on the elemental distributions and properties of MgO-based magnetic tunnel junctions after annealing. Annealing the samples resulted in crystallization of the amorphous CoFeB layer and diffusion of the majority of the boron away from the crystallized CoFeB layers. The Ta getter presputter is found to reduce the segregation of boron at the MgO/CoFeB interface after annealing, improving the tunneling magnetoresistance of the tunnel junction. This effect is observed for samples with either a Ru free-layer cap or a Mg free-layer cap and is thought to be a result of a reduced oxygen concentration within the MgO due to the effect of Ta getter presputtering. A Ru free-layer cap provides superior magnetic and magnetotransport properties compared to a Mg free-layer cap. Mg from the Mg free-layer cap is observed to diffuse toward the MgO tunnel barrier upon annealing, degrading both the crystalline quality of the CoFeB and magnetic isolation of the CoFeB free-layer from the CoFeB reference-layer. Lateral variations in the B distribution within the CoFeB free-layer are observed in the samples with a Ru free-layer cap, which are associated with crystalline and amorphous grains. The B-rich, amorphous grains are found to be depleted in Fe, while the B-poor crystalline grains are slightly enriched in Fe.

Three-dimensional elemental distributions in magnetic tunnel junctions containing naturally oxidized MgO tunnel barriers are characterized using atom-probe tomography. Replacing the CoFeB free layer (reference layer) with a CoFe/CoFeB (CoFeB/CoFe) bilayer increases the magnetoresistance from 105% to 192% and decreases the resistance-area product from 14.5 to 3.4 Ω μm2. The CoFe/CoFeB bilayer improves the compositional uniformity within the free layer by nucleating CoFeB crystals across the entire layer, resulting in a homogeneous barrier/free layer interface. In contrast, the simple CoFeB free layer partially crystallizes with composition differences from grain to grain (5–30 nm), degrading the tunnel junction performance.

Large nonlocal spin valve signals are reported in mesoscopic Ni80Fe20/Ag lateral spin valves upon exposing them to air. Magnetotransport measurements combined with transmission electron microscopy show that the formation of a native oxide layer at the Ni80Fe20/Ag interface is responsible for the large signals. The results indicate that lateral spin valves with superior performance to those based on high-resistance tunnel barriers can be achieved via controllable growth of native permalloy oxides.

Extended abstract of a paper presented at Microscopy and Microanalysis 2009 in Richmond, Virginia, USA, July 26 – July 30, 2009

Extended abstract of a paper presented at Microscopy and Microanalysis 2009 in Richmond, Virginia, USA, July 26 – July 30, 2009

The effects of annealing on the electrical transport behavior of CoFe/MgO/CoFe magnetic tunnel junctions have been studied using a combination of site-specific in situ transmission electron microscopy and three-dimensional atom-probe tomography. Annealing leads to an increase in the resistance of the junctions. A shift in the conductance curve (dI/dV) minimum from 0 V for the as-grown specimen correlates with a sharply defined layer of CoFe oxide at the lower ferromagnetic interface. Annealing decreases the asymmetry in the conductance by making the interfaces more diffuse and the tunnel barrier more chemically homogeneous.