Trajectory Aberrations Research Articles

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 lift–out 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.

Determination of the Chemical Compositions of Fine titanium Carbide and Niobium Carbide Precipitates in Isothermally Aged Ferritic Steel by Atom Probe Tomography Analysis.

The carbon (C) ratios, namely the atomic ratios of C/(C + M), in nano-sized coherent MC precipitates (M = Ti, Nb) with the NaCl-type (B1) structure in ferritic steels, which had been isothermally aged at 580 °C, were investigated using atom probe tomography (APT). Considering the influences of the trajectory aberration, detection loss, and peak overlap, we determined the C ratios to be ~0.40 and ~0.45 for an equivalent volume diameter of 1.5–5 nm and 1–5 nm for the TiC and NbC precipitates, respectively, suggesting that there is a considerable fraction of C vacancies in both nano-sized precipitates. The apparent C ratios show significant scatter with decreasing particle size, while the apparent mean C ratios of very fine TiC particles, smaller than 1.5 nm, decreased with decreasing particle size. With the use of one of the latest APT instruments with a high detection efficiency, the scattering in the apparent C ratios was reduced because the counting statistics were improved; however, the artificial enrichment of C atoms to particular crystallographic directions of ferrite hindered the determination of the C ratio for very fine TiC particles smaller than 1.5 nm.

Atom Probe Tomography Characterization of Dopant Distributions in Si FinFET: Challenges and Solutions.

Atom probe tomography (APT) has emerged as an important tool in characterizing three-dimensional semiconductor devices. However, the complex structure and hybrid nature of a semiconductor device can pose serious challenges to the accurate measurement of dopants. In particular, local magnification and trajectory aberration observed when analyzing hybrid materials with different evaporation fields can cause severe distortions in reconstructed geometry and uncertainty in local chemistry measurement. To address these challenges, this study systematically investigates the effect of APT sampling directions on the measurement of n-type dopants P and As in an Si fin field-effect transistor (FinFET). We demonstrate that the APT samples made with their Z-axis perpendicular to the center axis of the fin are effective to minimize the negative effects that result from evaporation field differences between the Si fin and SiO2 on reconstruction and achieve improved measurement of dopant distributions. In addition, new insights have been gained regarding the distribution of ion-implanted P and As in the Si FinFET.

Atom probe of GaN/AlGaN heterostructures: The role of electric field, sample crystallography and laser excitation on quantification

Scaling and non-planar architectures are key factors helping to advance the semiconductor field. Accurate 3-dimensional atomic scale information is therefore sought but this presents a significant metrology challenge. Atom probe tomography has emerged as a strong candidate to fulfill this role, but before it can be considered an accurate and precise metrology method, numerous difficulties need to be overcome. In this paper we highlight some of these in respect to the analysis of GaN/AlGaN device heterostructures. Although a significant range of conditions for accurate GaN stoichiometric analysis were readily achieved, a more limited range of analysis conditions that yielded an accurate Al site fraction for AlGaN was observed because the Al was typically overestimated. Moreover, the low index planes of the material resulted in pole and zone lines given their lower evaporation fields and are clearly observed on the detector due to related ion trajectory aberrations representative of local field variations present. As a result of the strong compositional bias of GaN analysis with field, the Ga and N concentrations were found to vary by ∼20 at.% over the tip apex. For the AlGaN this variation was smaller (<4 at.%), even for a similar magnitude of tip field variation.

An Automated Computational Approach for Complete In-Plane Compositional Interface Analysis by Atom Probe Tomography.

We introduce an efficient, automated computational approach for analyzing interfaces within atom probe tomography datasets, enabling quantitative mapping of their thickness, composition, as well as the Gibbsian interfacial excess of each solute. Detailed evaluation of an experimental dataset indicates that compared with the composition map, the interfacial excess map is more robust and exhibits a relatively higher resolution to reveal compositional variations. By field evaporation simulations with a predefined emitter mimicking the experimental dataset, the impact of trajectory aberrations on the measurement of the thickness, composition, and interfacial excess of the decorated interface are systematically analyzed and discussed.

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.

Using complimentary microscopy methods to examine Ni-Mn-Si-precipitates in highly-irradiated reactor pressure vessel steels

Nano-scale Ni-Mn-Si-rich precipitates formed in a reactor pressure vessel steel under high neutron fluence have been characterized using highly complimentary atom probe tomography (APT) and scanning transmission electron microscopy with energy dispersive spectroscopy (STEM-EDS) combined with STEM-EDS modeling. Using these techniques in a synergistic manner to overcome the well-known trajectory aberrations in APT data, the average upper limit Fe concentration within the precipitates was found to be ∼6 at.%. Using this knowledge, accurate compositions of the precipitates was determined and it was found that the spread of precipitate compositions was large, but mostly centered around the Γ2-and G-phases. The use of STEM-EDS also allowed for larger areas to be examined, and segregation of minor solutes was observed to occur on grain boundaries, along with Ni-Mn-Si-rich precipitates that were smaller in size than those in the matrix. Solute segregation at the grain boundaries is proposed to occur through a radiation induced segregation or radiation enhanced diffusion mechanism due to the presence of a denuded zone about the grain boundary. It is also proposed that the reduced precipitate size at the grain boundaries is due to the structure of the grain boundary. The lack of Ni-Mn-Si precipitates observed in larger Mo-rich precipitates is also discussed, and the absence of the minor solutes required to form the Ni-Mn-Si precipitates results in the lack of nucleation. This is in contrast to cementite phases in which Ni-Mn-Si precipitates have been observed to have formed. It was also determined through this work that the exclusion of all the Fe ions during atom probe analysis is a reasonable approximation.

Atom probe tomography analysis of SiGe fins embedded in SiO2: Facts and artefacts

We present atom probe analysis of 40nm wide SiGe fins embedded in SiO2 and discuss the root cause of artefacts observed in the reconstructed data. Additionally, we propose a simple data treatment routine, relying on complementary transmission electron microscopy analysis, to improve compositional analysis of the embedded SiGe fins. Using field evaporation simulations, we show that for high oxide to fin width ratios the difference in evaporation field thresholds between SiGe and SiO2 results in a non-hemispherical emitter shape with a negative curvature in the direction across, but not along the fin. This peculiar emitter shape leads to severe local variations in radius and hence in magnification across the emitter apex causing ion trajectory aberrations and crossings. As shown by our experiments and simulations, this translates into unrealistic variations in the detected atom densities and faulty dimensions in the reconstructed volume, with the width of the fin being up to six-fold compressed. Rectification of the faulty dimensions and density variations in the SiGe fin was demonstrated with our dedicated data treatment routine.

(Keynote) Metrology for Nanoscale Complex Semiconductor Systems

Pushing the limits in IC-technology towards the nanometer scale, led to the development of complex systems and 3D-devices (like Finfets, TFET, nanowires) whereby novel materials and in particular interfacial interactions play a crucial role. These increasing technological challenges have boosted the importance of metrology and created a demand for concepts suited to probe very small volumes and enable atomic scale observations. One obvious solution is then to abandon 1D-metrology completely and to focus on metrology such as Atom probe tomography (APT) which is an extremely powerful method providing composition analysis within very small volumes (a few nm3) with high sensitivity and accuracy. Due to its excellent spatial and depth resolution (in many cases with the ability to resolve lattice planes and individual atoms) alloy composition analysis in small trenches, unexpected in diffusion in such volumes, dopant distribution and dopants decorating defects can in principle be identified. Nevertheless the presence of many materials with different evaporation fields does induce severe artefacts and trajectory aberrations which cannot always be corrected, causing severe measurement inaccuracies. Complementary to the resolving power of APT, is the application of scanning probes (spm, ssrm, c-afm) which enables to grasp the electrical activity of dopants or identify conduction paths within such volumes. As SPM is inherently a 2D-method, concepts for expanding into the depth dimension are explored (cfr Scalpel SPM, ion beam sputtering icw SPM,..). Applications in logic device engineering, failure analysis and memory cell development (RRAM, CBRAM, NAND) demonstrate the power of this approach. Moreover “standard” solutions like STM to image crystal structure and defects at the surface may need to be modified in view of the very close proximity of insulating regions.Despite their unique 3D-resolving power, APT and SPM suffer from a poor productivity and a lack of statistical averaging over large areas as required in more production oriented metrology. A solution can be found through ensemble measurements whereby spatial resolution is provided by the device under investigation and not by the probing beam. We will illustrate this concept through applications of “self focusing SIMS” which allows to determine the composition from trenches (SiGe, InGaAs,..) as small as 20 nm without having an ion beam with nm-resolution. Similarly crystallinity of III-V growth in narrow trenches (< 50 nm) can be obtained through channeling RBS whereby again we use a large beam but nevertheless probe the information from an array of very fine features. In all these cases, the averaging over a large array provides excellent statistics and in some cases dramatically improved productivity through the enhanced signal versus the case of a very focused probe beam. The latter is ultimately exemplified in Raman experiments on narrow SiGe-trenches where we demonstrate that the signal from very narrow features (20 nm) is significantly enhanced (50-100x) as compared to it blanket counterpart enabling to probe composition and structural properties from a small volume.

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.

Impact of dynamic specimen shape evolution on the atom probe tomography results of doped epitaxial oxide multilayers: Comparison of experiment and simulation

The experimental atom probe tomography (APT) results from two different specimen orientations (top-down and sideways) of a high oxygen ion conducting Samaria-doped-ceria/Scandia-stabilized-zirconia multilayer thin film solid oxide fuel cell electrolyte was compared with level-set method based field evaporation simulations for the same specimen orientations. This experiment-simulation comparison explains the dynamic specimen shape evolution and ion trajectory aberrations that can induce density artifacts in final reconstruction, leading to inaccurate estimation of interfacial intermixing. This study highlights the importance of comparing experimental results with field evaporation simulations when using APT to study oxide heterostructure interfaces.

Imaging of radiation damage using complementary field ion microscopy and atom probe tomography

Radiation damage in tungsten and a tungsten–tantalum alloy, both of relevance to nuclear fusion research, has been characterized using a combination of field ion microscopy (FIM) imaging and atom probe tomography (APT). While APT provides 3D analytical imaging with sub-nanometer resolution, FIM is capable of imaging the arrangements of single atoms on a crystal lattice and has the potential to provide insights into radiation induced crystal damage, all the way down to its smallest manifestation – a single vacancy. This paper demonstrates the strength of combining these characterization techniques. In ion implanted tungsten, it was found that atomic scale lattice damage is best imaged using FIM. In certain cases, APT reveals an identifiable imprint in the data via the segregation of solute and impurities and trajectory aberrations. In a W–5at%Ta alloy, a combined APT–FIM study was able to determine the atomic distribution of tantalum inside the tungsten matrix. An indirect method was implemented to identify tantalum atoms inside the tungsten matrix in FIM images. By tracing irregularities in the evaporation sequence of atoms imaged with FIM, this method enables the benefit of FIM's atomic resolution in chemical distinction between the two species.

Quantification of oxide particle composition in model oxide dispersion strengthened steel alloys

Oxide dispersion strengthened ferritic steels (ODS) are being considered for structural components of future designs of fission and fusion reactors because of their impressive high-temperature mechanical properties and resistance to radiation damage, both of which arise from the nanoscale oxide particles they contain. Because of the critical importance of these nanoscale phases, significant research activity has been dedicated to analysing their precise size, shape and composition (Odette et al., Annu. Rev. Mater. Res. 38 (2008) 471–503 [1]; Miller et al., Mater. Sci. Technol. 29(10) (2013) 1174–1178 [2]).As part of a project to develop new fuel cladding alloys in India, model ODS alloys have been produced with the compositions, Fe–0.3Y2O3, Fe–0.2Ti–0.3Y2O3 and Fe–14Cr–0.2Ti–0.3Y2O3. The oxide particles in these three model alloys have been studied by APT in their as-received state and following ion irradiation (as a proxy for neutron irradiation) at various temperatures. In order to adequately quantify the composition of the oxide clusters, several difficulties must be managed, including issues relating to the chemical identification (ranging and variable peak-overlaps); trajectory aberrations and chemical structure; and particle sizing. This paper presents how these issues can be addressed by the application of bespoke data analysis tools and correlative microscopy. A discussion follows concerning the achievable precision in these measurements, with reference to the fundamental limiting factors.

The maximum separation cluster analysis algorithm for atom-probe tomography: parameter determination and accuracy.

Atom-probe tomography is a materials characterization method ideally suited for the investigation of clustering and precipitation phenomena. To distinguish the clusters from the surrounding matrix, the maximum separation algorithm is widely employed. However, the results of the cluster analysis strongly depend on the parameters used in the algorithm and hence, a wrong choice of parameters leads to erroneous results, e.g., for the cluster number density, concentration, and size. Here, a new method to determine the optimum value of the parameter dmax is proposed, which relies only on information contained in the measured atom-probe data set. Atom-probe simulations are employed to verify the method and to determine the sensitivity of the maximum separation algorithm to other input parameters. In addition, simulations are used to assess the accuracy of cluster analysis in the presence of trajectory aberrations caused by the local magnification effect. In the case of Cu-rich precipitates (Cu concentration 40-60 at% and radius 0.25-1.0 nm) in a bcc Fe-Si-Cu matrix, it is shown that the error in concentration is below 10 at% and the error in radius is <0.15 nm for all simulated conditions, provided that the correct value for dmax, as determined with the newly proposed method, is employed.

Atom probe tomography in nanoelectronics

The role of laser assisted atom probe tomography (APT) in microelectronics is discussed on the basis of various illustrations related to SiGe epitaxial layers, bipolar transistors or MOS nano-devices including gate all around (GAA) devices that were carried out at the Groupe de Physique des Materiaux of Rouen (France). 3D maps as provided by APT reveal the atomic-scale distribution of dopants and nanostructural features that are vital for nanoelectronics. Because of trajectory aberrations, APT images are subjected to distortions and local composition at the nm scale may either be biased. Procedures accounting for these effects were applied so that to correct images.

Defining clusters in APT reconstructions of ODS steels

Oxide nanoclusters in a consolidated Fe-14Cr-2W-0.3Ti-0.3Y₂O₃ ODS steel and in the alloy powder after mechanical alloying (but before consolidation) are investigated by atom probe tomography (APT). The maximum separation method is a standard method to define and characterise clusters from within APT data, but this work shows that the extent of clustering between the two materials is sufficiently different that the nanoclusters in the mechanically alloyed powder and in the consolidated material cannot be compared directly using the same cluster selection parameters. As the cluster selection parameters influence the size and composition of the clusters significantly, a procedure to optimise the input parameters for the maximum separation method is proposed by sweeping the d(max) and N(min) parameter space. By applying this method of cluster parameter selection combined with a 'matrix correction' to account for trajectory aberrations, differences in the oxide nanoclusters can then be reliably quantified.

Quantifying the composition of yttrium and oxygen rich nanoparticles in oxide dispersion strengthened steels

Atom probe tomography (APT) is used to investigate the composition of oxygen rich nanoparticles within a ferritic matrix in Fe-14Cr-2W-0.1Ti oxide-dispersion-strengthened (ODS) steel. This study investigates whether artifacts associated with APT analysis are the cause of a sub-stoichiometric oxide composition measurement. Bulk Y₂O₃ is analyzed by APT, thus demonstrating the ability of the technique to measure near-stoichiometric composition measurements in insulating oxides. Through analysis of the sequence of ion hits on the detector during APT data acquisition, it is shown that a proportion of yttrium hits are spatially correlated but oxygen hits are not. Y-O based nanoparticles in a ferritic matrix are analyzed by APT using voltage pulsing and a laser pulsing with a range of laser energies from 0.3-0.8 nJ. When the material is analyzed using a high effective evaporation field, this influences the effect of trajectory aberrations, and the apparent size of the nanoparticles is reduced. Some reduction in Y:O ratio is observed, caused by high instances of multiple-ion evaporation events. From a detailed comparison between the results of APT analysis of the bulk Y₂O₃ the nanoparticles in the ODS material are concluded to have an approximate Y:O ratio of 1:1.

Atomic-scale imaging and analysis of single layer GP zones in a model steel

The first experimental evidence of single-layered NbN GP zones in steel was shown through the combined use of advanced atomic-scale resolution techniques. A model low-alloyed steel was developed that contained very low, controlled amounts of solute species. Field ion micrographs were obtained using neon as imaging gas at a pressure of 10 -3 Pa and a base temperature of 40 K. The bright contrast of the GP zone indicates that this latter has a higher cohesive energy than the ferrite matrix. The bright spots corresponding to the solute atoms in the GP zones form platelets, clearly evidenced in the reconstructed volume. GP zone is preferentially retained at the specimen surface, causing ion trajectory aberrations, and thus biasing the 3D reconstructions. The amount of nitrogen atoms being equal to the one of niobium, the local chemistry in the GP zone is assumed to be stoichiometric niobium nitride (NbN).

Carbide characterization in low-temperature tempered steels

The nature of the initial carbides formed during the early stages of the tempering of steels is still a matter of debate. Conventionally, the main transition carbide is described as epsilon carbide, with a composition of approximately Fe 2.4C. However, earlier one-dimensional atom probe (1DAP) results indicated the existence of carbon-rich regions having much lower carbon contents, with maxima of around 10 at%. There was some uncertainty about the interpretation of the 1DAP results, because of possible problems with alignment of the aperture and with trajectory aberration effects. We have therefore re-visited this topic, using the three-dimensional (3D) atom probe, and studying both a model Fe–Ni–C alloy and a well-known engineering steel (AISI4340). We demonstrate that, for both materials, low-temperature (20–150 °C) aging produces carbon-rich regions with average peak carbon contents of up to 10%. We show for the first time the three-dimensional structure of these carbon-rich regions, and demonstrate that fine-scale faulting exists within them.

Spatial Distribution Maps for Atom Probe Tomography

A real-space technique for finding structural information in atom probe tomographs, spatial distribution maps (SDM), is described. The mechanics of the technique are explained, and it is then applied to some test cases. Many applications of SDM in atom probe tomography are illustrated with examples including finding crystal lattices, correcting lattice strains in reconstructed images, quantifying trajectory aberrations, quantifying spatial resolution, quantifying chemical ordering, dark-field imaging, determining orientation relationships, extracting radial distribution functions, and measuring ion detection efficiency.