The nitrogen deficiency in steels measured by atom probe tomography (APT) is considered to arise from the obscurement of singly charged dimer nitrogen ions (N2+) by the iron-dominant peak (56Fe2+) at 28 Da. To verify this by quantifying the amount of N2+ ions, γ′-Fe4N consisting of the 15N isotope was prepared on iron substrates by plasma nitriding using a nitrogen isotopic gas (15N2). Although considerable amounts of 15N2+ were observed at 30 Da without overlap with any iron peak, the observed nitrogen concentrations of γ′-Fe4N were clearly lower than the stoichiometric composition (19–20 at%), using both pulsed voltage and pulsed laser atom probes. The origin of the missing nitrogen, excluding nitrogen obscured by other ion species, was predicted to be the occurrence of neutral nitrogen or nitrogen gas molecules in field evaporation. The generation rate of iron nitride ions (FeN2+) for 15N was significantly lower than that for 14N in γ′-Fe4N, which affected the amount of the missing nitrogen. The isotope effect suggests that the isotopic ratio cannot always be determined from only one ion species among the multiple species observed in the APT analysis. We discuss the mechanism of the isotope effect in FeN2+ formation by field evaporation.

Atom probe tomography (APT) is particularly suited for the analysis of nanoscale microstructural features in metallic alloys. APT has become important in the quantitative assessment at high spatial resolution of light elements, which are notoriously difficult to analyze by electron- or X-ray-based techniques. These control the physical properties of high-strength materials and semiconductors. However, the mass spectrometer of state-of-the-art commercial atom probes with the highest spatial precision and detection efficiency are optimized for elements with mass-to-charge ratios corresponding to Fe and neighboring elements. Little is known on the theoretical performances for light elements. Here, we discuss the theoretical instrumental performance of one such instrument using accurate three-dimensional transient electrostatic simulations in a time-varying field approach. We compare the simulations to experimental measurements obtained on an FeBSi bulk-metallic glass. Dynamics effects during the ion's flight are revealed when examining multi-hit mass-to-charge correlations, and we demonstrate their influence on the mass resolution. The model reveals significant differences in ion projection as a function of the mass. We discuss how these chromatic aberrations affect the spatial precision. This approach shows that by tuning the shape of the voltage pulses used to trigger field evaporation, minimizing the influence of these detrimental dynamic effects is possible.

We report the sputter deposition of Cu-7V and Cu-27V (at.%) alloy films in an attempt to yield a “clean” alloy to investigate nanocrystalline stability. Films grown in high vacuum chambers can mitigate processing contaminates which convolute the identification of nanocrystalline stability mechanism(s). The initial films were very clean with carbon and oxygen contents ranging between ~0.01 and 0.38 at.%. Annealing at 400 °C/1 h facilitated the clustering of vanadium at high-angle grain boundary triple junctions. At 800 °C/1 h annealing, the Cu-7V film lost its nanocrystalline grain sizes with the vanadium partitioned to the free surface; the Cu-27V retained its nanocrystalline grains with vanadium clusters in the matrix, but surface solute segregation was present. Though the initial alloy and vacuum annealing retained the low contamination levels sought, the high surface area-to-volume ratio of the film, coupled with high segregation tendencies, enabled this system to phase separate in such a manner that the stability mechanisms that were to be studied were lost at high temperatures. This illustrates obstacles in using thin films to address nanocrystalline stability.

The quantitative analysis performance of carbon and nitrogen was investigated using stoichiometric θ-Fe3C (25 at% C) and γ′-Fe4N (~20 at% N) precipitates in pulsed voltage and pulsed laser atom probes. The dependencies of specimen temperature, pulse fraction, and laser pulse energy on the apparent concentrations of carbon and nitrogen were measured. Good coincidence with 25 at% carbon concentration in θ-Fe3C was obtained for the pulsed voltage atom probe by considering the mean number of carbon atoms per ion at 24 Da and the detection loss of iron, while better coincidence was obtained for the pulsed laser atom probe by considering only the mean number of carbon at 24 Da. On the other hand, a lack of nitrogen concentration in γ′-Fe4N was observed for the two atom probes. In particular, the pulsed laser atom probe showed a significant lack of nitrogen concentration. This implies that a large amount of 14N2+ was obscured by the main iron peak of 56Fe2+ at 28 Da in the mass-to-charge spectrum. Regarding preferential evaporation or retention, carbon in θ-Fe3C exhibited little of either, but nitrogen in γ′-Fe4N exhibited definite preferential retention. This result can be explained by the large difference in ionization energy between carbon and nitrogen.

The atom-probe field ion microscope was introduced in 1967 at the 14th Field Emission Symposium held at the National Bureau of Standards (now, NIST) in Gaithersburg, Maryland. The atom-probe field ion microscope was, and remains, the only instrument capable of determining “the nature of one single atom seen on a metal surface and selected from neighboring atoms at the discretion of the observer”. The development of the atom-probe is a story of an instrument that one National Science Foundation (NSF) reviewer called “impossible because single atoms could not be detected”. It is also a story of my life with Erwin Wilhelm Müller as his graduate student in the Field Emission Laboratory at the Pennsylvania State University in the late 1960s and his strong and volatile personality, perhaps fostered by his pedigree as Gustav Hertz’s student in the Berlin of the 1930s. It is the story that has defined by scientific career.

Surface sulfurization of Cu(In,Ga)Se2 (CIGSe) absorbers is a commonly applied technique to improve the conversion efficiency of the corresponding solar cells, via increasing the bandgap towards the heterojunction. However, the resulting device performance is understood to be highly dependent on the thermodynamic stability of the chalcogenide structure at the upper region of the absorber. The present investigation provides a high-resolution chemical analysis, using energy dispersive X-ray spectrometry and laser-pulsed atom probe tomography, to determine the sulfur incorporation and chemical re-distribution in the absorber material. The post-sulfurization treatment was performed by exposing the CIGSe surface to elemental sulfur vapor for 20 min at 500°C. Two distinct sulfur-rich phases were found at the surface of the absorber exhibiting a layered structure showing In-rich and Ga-rich zones, respectively. Furthermore, sulfur atoms were found to segregate at the absorber grain boundaries showing concentrations up to ~7 at% with traces of diffusion outwards into the grain interior.

We report on a new algorithm for the detection of crystallographic information in three-dimensional, as retained in atom probe tomography (APT), with improved robustness and signal detection performance. The algorithm is underpinned by one-dimensional distribution functions (DFs), as per existing algorithms, but eliminates an unnecessary parameter as compared to current methods.

By examining traditional DFs in an automated fashion in real space, rather than using Fourier transform approaches, we utilize an error metric based upon the expected value for a spatially random distribution for detecting crystallography. We show cases where the metric is able to successfully obtain orientation information, and show that it can function with high levels of additive and displacive background noise. We additionally compare this metric to Fourier transform methods, showing fewer artifacts when examining simulated datasets. An extension of the approach is used to aid the automatic detection of high-quality data regions within an entire dataset, albeit with a large increase in computational cost.

This extension is demonstrated on acquired aluminum and tungsten APT datasets, and shown to be able to discern regions of the data which have relatively improved spatial data quality. Finally, this program has been made available for use in other laboratories undertaking their own analyses.

We study the effects of Dy, Nb, and Ga additions on the microstructure and magnetic properties of Nd2Fe14B/α-Fe nanocomposites. Dy, Nb, and Ga additions inhibit the growth of the soft magnetic α-Fe phase. Dy and Nb additions are able to refine the microstructure, whereas Ga addition plays only a minor role in prohibiting crystal growth. The magnetic properties are sensitive to Dy, Nb, and Ga additions. The Dy-containing alloy enhances the intrinsic coercivity of 872 kA/m because Dy partially replaces Nd, forming (Nd, Dy)2Fe14B. Nb addition refines the microstructure, and consequently increases the exchange coupling between magnetic grains. The Nd9.5Fe75.4Co5Zr3B6.5Ga0.6 alloy exhibits the highest remanence (0.92 T) due to Ga addition.

Atom probe has been developed for investigating materials at the atomic scale and in three dimensions by using either high-voltage (HV) pulses or laser pulses to trigger the field evaporation of surface atoms. In this paper, we propose an atom probe setup with pulsed evaporation achieved by simultaneous application of both methods. This provides a simple way to improve mass resolution without degrading the intrinsic spatial resolution of the instrument. The basic principle of this setup is the combination of both modes, but with a precise control of the delay (at a femtosecond timescale) between voltage and laser pulses. A home-made voltage pulse generator and an air-to-vacuum transmission system are discussed. The shape of the HV pulse presented at the sample apex is experimentally measured. Optimizing the delay between the voltage and the laser pulse improves the mass spectrum quality.

Atom probe tomography is routinely used for the characterization of materials microstructures, usually assuming that the microstructure is unaltered by the analysis. When analyzing ionic conductors, however, gradients in the chemical potential and the electric field penetrating dielectric atom probe specimens can cause significant ionic mobility. Although ionic mobility is undesirable when aiming for materials characterization, it offers a strategy to manipulate materials directly in situ in the atom probe. Here, we present experimental results on the analysis of the ionic conductor lithium-manganese-oxide with different atom probe techniques. We demonstrate that, at a temperature of 30 K, characterization of the materials microstructure is possible without measurable Li mobility. Also, we show that at 298 K the material can be deintercalated, in situ in the atom probe, without changing the manganese-oxide host structure. Combining in situ atom probe deintercalation and subsequent conventional characterization, we demonstrate a new methodological approach to study ionic conductors even in early stages of deintercalation.

In this work, we report on the atom probe tomography analysis of two metallic hydrides formed by pressurized charging using an ex situ hydrogen charging cell, in the pressure range of 200–500 kPa (2–5 bar). Specifically we report on the deuterium charging of Pd/Rh and V systems. Using this ex situ system, we demonstrate the successful loading and subsequent atom probe analysis of deuterium within a Pd/Rh alloy, and demonstrate that deuterium is likely present within the oxide–metal interface of a native oxide formed on vanadium. Through these experiments, we demonstrate the feasibility of ex situ hydrogen analysis for hydrides via atom probe tomography, and thus a practical route to three-dimensional imaging of hydrogen in hydrides at the atomic scale.

The damage and ion distribution induced in Si by an inductively coupled plasma Xe focused ion beam was investigated by atom probe tomography. By using predefined patterns it was possible to prepare the atom probe tips with a sub 50 nm end radius in the ion beam microscope. The atom probe reconstruction shows good agreement with simulated implantation profiles and interplanar distances extracted from spatial distribution maps. The elemental profiles of O and C indicate co-implantation during the milling process. The presence of small disc-shaped Xe clusters are also found in the three-dimensional reconstruction. These are attributed to the presence of Xe nanocrystals or bubbles that open during the evaporation process. The expected accumulated dose points to a loss of >95% of the Xe during analysis, which escapes undetected.

Atom probe is a nanoscale technique for creating three-dimensional spatially and chemically resolved point datasets, primarily of metallic or semiconductor materials. While atom probe can achieve local high-level resolution, the spatial coherence of the technique is highly dependent upon the evaporative physics in the material and can often result in large geometric distortions in experimental results. The distortions originate from uncertainties in the projection function between the field evaporating specimen and the ion detector. Here we explore the possibility of continuum numerical approximations to the evaporative behavior during an atom probe experiment, and the subsequent propagation of ions to the detector, with particular emphasis placed on the solution of axisymmetric systems, such as isolated particles and multilayer systems. Ultimately, this method may prove critical in rapid modeling of tip shape evolution in atom probe tomography, which itself is a key factor in the rapid generation of spatially accurate reconstructions in atom probe datasets.

In this paper, we have observed an atomic-scale structure and compositional variation at the interface of the InGaN/GaN multi-quantum wells (MQW) by both scanning transmission electron microscopy (STEM) using high-angle annular dark-field mode and atom probe tomography (APT). The iso-concentration analysis of APT results revealed that the roughness of InGaN/GaN interface increased as the MQW layers were filled up, and that the upper interface of MQW (GaN/InGaN to the p-GaN side) was much rougher than that of the lower interface (InGaN/GaN tot he n-GaN side). On the basis of experimental results, it is suggested that the formation of interface roughness can affect the quantum efficiency of InGaN-based light-emitting diodes.

An Fe–1 at.% Cu model alloy was examined by atom probe (3DAP) and small-angle neutron scattering (SANS) to verify the accordance of the gained results. The Fe-Cu alloy was heat-treated for various times at 500°C, forming Cu-rich precipitates within the Fe matrix. The chemical compositions of the precipitates and matrix found by 3DAP were used to calculate the magnetic scattering contrast. Additionally, a magnetic moment of the precipitates that contain a significant amount of Fe was taken into account for the calculation of magnetic scattering contrast. This in turn is used for the evaluation of the magnetic scattering curves gained by SANS. Both the 3DAP data as well as the scattering curves were analyzed with regard to radius, number density, and volume fraction of the precipitates as a function of aging time. The results yielded by both techniques are in good agreement and correspond to the development of the hardness of the alloy. Minor differences can be related to the cluster search algorithm used for the analysis of the 3DAP data as well as Fe overestimation based on different field phases.

As a major improvement in three-dimensional (3D) atom probe, the range of applicable material classes has recently been broadened by the establishment of laser-assisted atom probes (LA-3DAP). Meanwhile, measurements of materials of low conductivity, such as dielectrics, ceramics, and semiconductors, have widely been demonstrated. However, besides different evaporation probabilities, heterogeneous dielectric properties are expected to give rise to additional artifacts in the 3D volume reconstruction on which the method is based. In this article, these conceivable artifacts are discussed based on a numeric simulation of the field evaporation. Sample tips of layer- or precipitate-type geometry are considered. It is demonstrated that dielectric materials tend to behave similarly to metals of reduced critical evaporation field.

Over the last few years there have been significant developments in the field of three-dimensional atom probe (3DAP) analysis. This article reviews some of the technical compromises that have led to different instrument designs and the recent improvements in performance. An instrument has now been developed, based around a novel reflectron configuration combining both energy compensation and focusing elements, that yields a large field of view and very high mass resolution. The use of laser pulsing in the 3DAP, together with developments in specimen preparation methods using a focused ion-beam instrument, have led to a significant widening in the range of materials science problems that can be addressed with the 3DAP. Recent studies of semiconductor materials and devices are described.

The applicability of atom probe to the characterization of photovoltaic devices is presented with special emphasis on high efficiency III–V and low cost ITO/a-Si:H heterojunction cells. Laser pulsed atom probe is shown to enable subnanometer chemical and structural depth profiling of interfaces in III–V heterojunction cells. Hydrogen, oxygen, and phosphorus chemical profiling in 5-nm-thick a-Si heterojunction cells is also illustrated, along with compositional analysis of the ITO/a-Si interface. Detection limits of atom probe tomography useful to semiconductor devices are also discussed. Gaining information about interfacial abruptness, roughness, and dopant profiles will allow for the determination of semiconductor conductivity, junction depletion widths, and ultimately photocurrent collection efficiencies and fill factors.

Nanostructural features of nickel-base superalloys as revealed by atom probe field ion microscopy (APFIM) and atom probe tomography (APT) are reviewed. The more salient information provided by these techniques is discussed through an almost exhaustive analysis of literature over the last 30 years. Atom probe techniques are shown to be able to measure the composition of tiny γ′ precipitates, a few nanometers in size, and to reveal chemical order within these precipitates. Phase separation kinetics in model NiCrAl alloys was investigated with both 3DAP and Monte-Carlo simulation. Results are shown to be in good agreement. Plane by plane analysis of {001} planes of Ni3Al-type γ′ phase makes it possible to estimate the degree of order as well as the preferential sites of various addition elements (Ti, Cr, Co, W, Ta, Re, Ru, etc.) included in superalloys. Clustering effects of Re in the γ solid solution were also exhibited. Due to its ultrahigh depth resolution, the microchemistry of interfaces and grain boundaries can be characterized on an atomic scale. Grain boundaries in Astroloy or N18 superalloys were found to be enriched in B, Mo, and Cr and Al depleted.

A numerical model has been developed to simulate images obtained from the three-dimensional atom probe. This model was used to simulate the artefacts commonly observed in two-phase materials. This model takes into account the dynamic evolution of the atomic-scale shape of the specimen during field evaporation. This article reviews the model and its applications to some specific cases. Local magnification effects were studied as a function of the size, the shape, and the orientation of precipitated phases embedded in the matrix. Small precipitates produce large aberrations in good agreement with experiments. The magnification from such precipitates, as measured from the simulation, is only found to match the theoretical value for mesoscopic scale precipitates (size similar to the specimen size). Orientation effects are also observed in excellent agreement with experiments. The measured thickness of a grain-boundary-segregated film in the simulation is found to decrease with the angle between the normal to the grain boundary and the tip axis. Depth scaling artefacts caused by variation in the evaporation field of atoms in multilayer structures were successfully simulated and again showed good agreement with effects observed experimentally.