David W. Saxey

Correlated ion analysis and the interpretation of atom probe mass spectra

Several techniques are presented for extracting information from atom probe mass spectra by investigating correlations within multiple-ion detector events. Analyses of this kind can provide insights into the origins of noise, the shape of mass peaks, or unexpected anomalies within the spectrum. Data can often be recovered from within the spectrum noise by considering the time-of-flight differences between ions within a multiple event. Correlated ion detection, particularly when associated with shifts in ion energies, may be used to probe the phenomenon of molecular ion dissociation, including the questions of data loss due to ion pile-up or the generation of neutrals in the dissociation process.

Three-dimensional atom probe analysis of green- and blue-emitting InxGa1−xN∕GaN multiple quantum well structures

The three-dimensional atom probe has been used to characterize green- and blue-emitting InxGa1−xN∕GaN multiple quantum well structures with subnanometer resolution over a 100nm field of view. The distribution of indium in InxGa1−xN samples with different compositions is analyzed. No evidence is found wherein the indium distribution deviates from that of a random alloy, which appears to preclude indium clustering as the cause of the reported carrier localization in these structures. The upper interface of each quantum well layer is shown to be rougher and more diffuse than the lower interface, and the existence of monolayer steps in the upper interfaces is revealed. These steps could effectively localize carriers at room temperature. Indium is shown to be present in the GaN barrier layers despite the absence of indium precursor flux during barrier layer growth. A strong evidence is produced to support a mechanism for the presence of indium in these layers, namely, that a layer of indium forms on the surfac...

Some aspects of the field evaporation behaviour of GaSb.

In-depth analysis of pulsed laser atom probe tomography (APT) data on the field evaporation of the III-V semiconductor material GaSb reveals strong variations in charge states, relative abundances of different cluster ions, multiplicity of detector events and spatial correlation of evaporation events, as a function of the effective electric field at the specimen surface. These variations are discussed in comparison with the behaviour of two different metallic specimen materials, an Al-6XXX series alloy and pure W, studied under closely related experimental conditions in the same atom probe instrument. It is proposed that the complex behaviour of GaSb originates from a combination of spatially correlated evaporation events and the subsequent field induced dissociation of cluster ions, the latter contributing to inaccuracies in the overall atom probe composition determination for this material.

Nuclear reactor materials at the atomic scale

With the renewed interest in nuclear energy, developing new materials able to respond to the stringent requirements of the next-generation fission and future fusion reactors has become a priority. An efficient search for such materials requires detailed knowledge of material behaviour under irradiation, high temperatures and corrosive environments. Minimizing the rates of materials degradation will be possible only if the mechanisms by which it occurs are understood. Atomic-scale experimental probing as well as modelling can provide some answers and help predict in-service behaviour. This article illustrates how this approach has already improved our understanding of precipitation under irradiation, corrosion behaviour, and stress corrosion cracking. It is also now beginning to provide guidance for the development of new alloys.

Examinations of oxidation and sulfidation of grain boundaries in alloy 600 exposed to simulated pressurized water reactor primary water

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.

Atom probe tomography assessment of the impact of electron beam exposure on InxGa1−xN/GaN quantum wells

This study addresses the ongoing debate concerning the distribution of indium in InxGa1−xN quantum wells (QWs) using a combination of atom probe tomography (APT) and transmission electron microscopy (TEM). APT analysis of InxGa1−xN QWs, which had been exposed to the electron beam in a TEM, revealed an inhomogeneous indium distribution which was not observed in a control sample which had not been exposed to the electron beam. These data validate the effectiveness of APT in detecting subtle compositional inhomogeneities in the nitrides.

Behavior of molecules and molecular ions near a field emitter

The cold emission of particles from surfaces under intense electric fields is a process which underpins a variety of applications including atom probe tomography (APT), an analytical microscopy technique with near-atomic spatial resolution. Increasingly relying on fast laser pulsing to trigger the emission, APT experiments often incorporate the detection of molecular ions emitted from the specimen, in particular from covalently or ionically bonded materials. Notably, it has been proposed that neutral molecules can also be emitted during this process. However, this remains a contentious issue. To investigate the validity of this hypothesis, a careful review of the literature is combined with the development of new methods to treat experimental APT data, the modelling of ion trajectories, and the application of density-functional theory (DFT) simulations to derive molecular ion energetics. It is shown that the direct thermal emission of neutral molecules is extremely unlikely. However, neutrals can still be formed in the course of an APT experiment by dissociation of metastable molecular ions.

Nanogeochronology of discordant zircon measured by atom probe microscopy of Pb-enriched dislocation loops

Atom probe yields geologically meaningful ages from nanoscale Pb-enriched dislocation loops in discordant zircon. Isotopic discordance is a common feature in zircon that can lead to an erroneous age determination, and it is attributed to the mobilization and escape of radiogenic Pb during its post-crystallization geological evolution. The degree of isotopic discordance measured at analytical scales of ~10 μm often differs among adjacent analysis locations, indicating heterogeneous distributions of Pb at shorter length scales. We use atom probe microscopy to establish the nature of these sites and the mechanisms by which they form. We show that the nanoscale distribution of Pb in a ~2.1 billion year old discordant zircon that was metamorphosed c. 150 million years ago is defined by two distinct Pb reservoirs. Despite overall Pb loss during peak metamorphic conditions, the atom probe data indicate that a component of radiogenic Pb was trapped in 10-nm dislocation loops that formed during the annealing of radiation damage associated with the metamorphic event. A second Pb component, found outside the dislocation loops, represents homogeneous accumulation of radiogenic Pb in the zircon matrix after metamorphism. The 207Pb/206Pb ratios measured from eight dislocation loops are equivalent within uncertainty and yield an age consistent with the original crystallization age of the zircon, as determined by laser ablation spot analysis. Our results provide a specific mechanism for the trapping and retention of radiogenic Pb during metamorphism and confirm that isotopic discordance in this zircon is characterized by discrete nanoscale reservoirs of Pb that record different isotopic compositions and yield age data consistent with distinct geological events. These data may provide a framework for interpreting discordance in zircon as the heterogeneous distribution of discrete radiogenic Pb populations, each yielding geologically meaningful ages.

Atom probe tomography of reactor pressure vessel steels: an analysis of data integrity.

In this work, the importance of optimising experimental conditions for the analysis of reactor pressure vessel (RPV) steels using atom probe tomography is explored. The quality of the resultant atom probe data is assessed in terms of detection efficiency, noise levels and mass resolution. It is demonstrated that artefacts can exist even when experimental conditions have been optimised. In particular, it is shown that surface diffusion of some minority species, including P and Si, to major poles prior to field evaporation can be an issue. The effects were most noticeable during laser pulsing. The impact of surface migration on the characterisation of dislocations and grain boundaries is assessed. The importance of selecting appropriate regions of the reconstructed data for subsequent re-analysis is emphasised.

Nanoscale gold clusters in arsenopyrite controlled by growth rate not concentration: Evidence from atom probe microscopy

Abstract Auriferous sulfides, most notably pyrite (FeS2) and arsenopyrite (FeAsS), are among the most important economic minerals on Earth because they can host large quantities of gold in many of the world’s major gold deposits. Here we present the first atom probe study of gold distribution in arsenopyrite to characterize the three-dimensional (3D) distribution of gold at the nanoscale and provide data to discriminate among competing models for gold incorporation in refractory ores. In contrast to models that link gold distribution to gold concentration, gold incorporation in arsenopyrite is shown to be controlled by the rate of crystal growth, with slow growth rate promoting the formation of gold clusters and rapid growth rate leading to homogeneous gold distribution. This study yields new information on the controls of gold distribution and incorporation in sulfides that has important implications for ore deposit formation. More broadly this study reveals new information about crystal-fluid interface dynamics that determine trace element incorporation into growing mineral phases.