Laser assisted field evaporation of oxides in atom probe analysis

We have investigated the laser assisted field evaporation phenomena of ZnO, and MgO to explore the feasibility of quantitative three dimensional atom probe analyses of insulating oxides. To assist the field evaporation of these oxides, the usage of short wavelength 343 nm ultraviolet (UV) laser was found to be more effective than 515 nm green laser. We observed field ion microscopy (FIM) image expansion and mass peak shifting when 343 nm laser was irradiated on MgO. This phenomenon can be attributed to the laser induced electron excitation which causes the reduction of the resistivity of the specimen.     

Laser assisted atom probe analysis of thin film on insulating substrate

We demonstrate that the atom probe analyses of metallic thin films on insulating substrates are possible using laser assisted field evaporation. The tips with metallic thin film and insulating substrate (0.6-3 μm in thickness) were prepared by the lift-out and annular ion beam milling techniques on tungsten supports. In spite of the existence of thick insulating layer between the metallic film and the tungsten support, atom probe tomography with practical mass resolution, signal-to-noise ratio and spatial resolution was found to be possible using laser assisted field evaporation.     

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.     

Investigation of wüstite (Fe1-xO) by femtosecond laser assisted atom probe tomography

In this paper, we report results obtained from laser assisted three-dimensional (3-D) atom probe tomography (APT) on wüstite (Fe_1−xO). Oxides are generally insulating and hence hard to analyse in conventional electrical assisted APT. To overcome this problem, femtosecond laser pulses are used instead of voltage pulses. Here we discuss some aspects of pulsed laser field evaporation and optimization of parameters to achieve better chemical accuracy.     

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.     

Mechanism of laser assisted field evaporation from insulating oxides

To explain the recent successful three-dimensional atom probe (3DAP) analyses of insulating oxides by laser assisted field evaporation, we investigated the mechanism of the laser-induced field evaporation of oxides by ab initio calculations. The calculated potential energy surfaces (PESs) for the ground and excited states indicated that the activation barrier height for field evaporation is substantially reduced by the accumulation of holes near the tip apex. This would make the direct electronic excitation possible to promote field evaporation along with thermal excitation. These theoretical calculations are supported by experimental observations.     

Improvements in planar feature reconstructions in atom probe tomography

Standard atom probe tomography spatial reconstruction techniques have been reasonably successful in reproducing single crystal datasets. However, artefacts persist in the reconstructions that can be attributed to the incorrect assumption of a spherical evaporation surface. Using simulated and experimental field evaporation, we examine the expected shape of the evaporating surface and propose the use of a variable point projection position to mitigate to some degree these reconstruction artefacts. We show initial results from an implementation of a variable projection position, illustrating the effect on simulated and experimental data, while still maintaining a spherical projection surface. Specimen shapes during evaporation of model structures with interfaces between regions of low- and high-evaporation-field material are presented. Use of two-and three-dimensional projection-point maps in the reconstruction of more complicated datasets is discussed.     

Field evaporation behavior in [0 0 1] FePt thin films

Though the atom probe has provided unprecedented atomic identification and spatial imaging capability, the basic reconstruction assumption of a smooth hemispherical tip shape creates significant challenges in yielding high fidelity chemical information for atomic species with extreme differences in fields required for field evaporation. In the present study, the evaporation behavior and accompanying artifacts are examined for the super-cell lattice structure of L1₀ FePt, where alternating Fe and Pt planes exist in the [0 0 1] orientation. Elemental Fe and Pt have significant differences in field strengths providing a candidate system to quantify these issues. Though alloys can result in changes in the elemental field strength, the intrinsic nature of elemental planes in [0 0 1] L1₀ provides a system to determine to what extent basic assumptions of elemental field strengths can break down in understanding reconstruction artifacts in this intermetallic alloy. The reconstruction of field evaporation experiments has shown depletion of Fe at the (0 0 2) pole and zone axes. Compositional profiles revealed an increase in Fe and atom count moving outward from the pole. The depletion at the low indexed pole and zone axes was determined to be the result of local magnification and electrostatic effects. The experimental results are compared to an electrostatic simulation model.     

Quantitative laser atom probe analyses of hydrogenation-disproportionated Nd-Fe-B powders

We report a successful atom probe tomography of hydrides in hydrogenation-disproportionated Nd-Fe-B powder using a green femtosecond laser. The atom probe specimens were prepared from one particle of powder using the focused ion beam lift-out method. The atom probe tomography taken from an α-Fe/NdH₂ structure suggested that B and Ga (trace added element) were partitioned in the NdH₂ phase. The hydrogen concentration of 64 at% determined from the atom probe analysis was in excellent agreement with the stoichiometry of the NdH₂ phase.     

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.     

Evaporation mechanisms of MgO in laser assisted atom probe tomography

In this paper the field evaporation properties of bulk MgO and sandwiched MgO layers in Fe are compared using laser assisted Atom Probe Tomography. The comparison of flight time spectra gives an estimate of the evaporation times as a function of the wavelength and the laser energy. It is shown that the evaporation takes place in two steps on two different time scales in MgO. It is also shown that as long as the MgO layer is buried in Fe, the evaporation is dominated by the photon absorption in Fe layer at the tip apex. Eventually the evaporation process of MgO is discussed based on the difference between the bulk materials and the multilayer samples.     

Detecting density variations and nanovoids

A combination of simulated and experimental data has been used to investigate the size range of nanovoids that can be detected in atom probe tomography data. Simulated atom probe tomography data have revealed that nanovoids as small as 1 nm in diameter can be detected in atom probe tomography data with the use of iso-density surfaces. Iso-density surfaces may be used to quantify the size, morphology and number density of nanovoids and other variations in density in atom probe tomography data. Experimental data from an aluminum-yttrium-iron metallic glass ribbon have revealed the effectiveness of this approach. Combining iso-density surfaces with atom maps also permits the segregation of solute to the nanovoids to be investigated. Field ion microscopy and thin section atom maps have also been used to detect pores and larger voids.     

Quantitative atom probe analysis of carbides

Compared to atom probe analysis of metallic materials, the analysis of carbide phases results in an enhanced formation of molecular ions and multiple events. In addition, many multiple events appear to consist of two or more ions originating from adjacent sites in the material. Due to limitations of the ion detectors measurements generally underestimate the carbon concentration. Analyses using laser-pulsed atom probe tomography have been performed on SiC, WC, Ti(C,N) and Ti₂AlC grains in different materials as well as on large M₂₃C₆ precipitates in steel. Using standard evaluation methods, the obtained carbon concentration was 6-24% lower than expected from the known stoichiometry. The results improved remarkably by using only the ¹³C isotope, and calculating the concentration of ¹²C from the natural isotope abundance. This confirms that the main reason for obtaining a too low carbon concentration is the dead time of the detector, mainly affecting carbon since it is more frequently evaporated as multiple ions. In the case of Ti(C,N) and Ti₂AlC an additional difficulty arises from the overlap between C₂⁺, C₄²⁺ and Ti²⁺ at the mass-to-charge 24 Da.     

Application of Fourier transform and autocorrelation to cluster identification in the three-dimensional atom probe

Because of the increasing number of collected atoms (up to millions) in the three‐dimensional atom probe, derivation of chemical or structural information from the direct observation of three‐dimensional images is becoming more and more difficult. New data analysis tools are thus required. Application of a discrete Fourier transform algorithm to three‐dimensional atom probe datasets provides information that is not easily accessible in real space. Derivation of mean particle size from Fourier intensities or from three‐dimensional autocorrelation is an example. These powerful methods can be used to detect and image nano‐segregations. Using three‐dimensional ‘bright‐field’ imaging, single nano‐segregations were isolated from the surrounding matrix of an iron–copper alloy. Measurement of the inner concentration within clusters is, therefore, straightforward. Theoretical aspects related to filtering in reciprocal space are developed.     

Methods of quantitative matrix analysis of Zircaloy-2

The zirconium-based alloy Zircaloy-2 contains small amounts of iron, chromium and nickel dissolved in the matrix. Several attempts to measure these amounts have been made in the past, but the results are conflicting and inconclusive. The advent of wide angle, laser pulsed atom probe tomography motivates a new attempt to analyze the matrix. Large datasets are now easily obtained using laser pulsing but quantification is not straightforward due to rather complex mass spectra. Zircaloy-2 contains about 1 wt% tin, 0.1 wt% oxygen and trace amounts of Si, C and Al. Severe overlaps make quantification of any Fe⁺, Cr⁺ and Ni⁺ ions impossible. Quantification of Fe, Cr and Ni therefore requires that they appear as doubly charged ions only, and consequently the field must be kept high enough. In addition, adsorbed CO⁺ may appear at the main peak of Fe²⁺. In the paper a method is reported, which gives what we believe an accurate quantitative analysis of at least iron and chromium in the matrix.     

Macroscopic electrical field distribution and field-induced surface stresses of needle-shaped field emitters

One major concern since the development of the field ion microscope is the mechanical strength of the specimens. The macroscopic shape of the imaging tip greatly influences field-induced stresses and there is merit in further study of this phenomenon from a classical perspective. Understanding the geometrical, as opposed to localized electronic, factors that affect the stress might improve the quality and success rate of atom probe experiments. This study uses macroscopic electrostatic principles and finite element modelling to investigate field-induced stresses in relation to the shape of the tip. Three two-dimensional idealized models are considered, namely hyperbolic, parabolic and sphere-on-orthogonal-cone; the shapes of which are compared to experimental tips prepared by electro-polishing. Three dimensional morphologies of both a nano-porous and single-crystal aluminium tip are measured using electron tomography to quantitatively test the assumption of cylindrical symmetry for electro-polished tips. The porous tip was prepared and studied to demonstrate a fragile specimen for which such finite element studies could determine potential mechanical failure, prior to any exhaustive atom probe investigation.     

Fabrication and characterization of APT specimens from high dose heavy ion irradiated materials

The next generations of advanced energy systems will require materials that can withstand high doses of irradiation at elevated temperatures. Therefore, a methodology has been developed for the fabrication of high-dose ion-irradiated atom probe tomography specimens at a specific dose with the use of a focused ion beam milling system. The method also enables the precise ion dose of the atom probe tomography specimen to be estimated from the local concentration of the implanted ions. The method has been successfully applied to the characterization of the distribution of nanoclusters in a radiation-tolerant 14YWT nanostructured ferritic steel under ion irradiation to doses up to 400 displacements per atom.     

Some aspects of the silicon behaviour under femtosecond pulsed laser field evaporation

Three dimension atom probe analysis of semiconductor materials requires the ability to bring high electric field at the specimen apex to remove atoms. It is shown that, if voltage pulses are used to evaporate doped silicon, the resistivity of the material has to be lower than about 10(2) Omega cm. To overcome this problem, voltage pulses have been replaced by femtosecond laser pulses. The laser pulses give rise to field evaporation by two processes. Both thermal and optical field evaporation have been observed. Thermal evaporation takes place at high laser intensities and with short wavelengths while the evaporation is assisted by the rectification of the optical field for lower intensities and in the infrared domain. Using the optical field evaporation, reproducible and good analyses in term of spatial and mass resolutions could be conducted.     

Atom-probe for FinFET dopant characterization

With the continuous shrinking of transistors and advent of new transistor architectures to keep in pace with Moore's law and ITRS goals, there is a rising interest in multigate 3D-devices like FinFETs where the channel is surrounded by gates on multiple surfaces. The performance of these devices depends on the dimensions and the spatial distribution of dopants in source/drain regions of the device. As a result there is a need for new metrology approach/technique to characterize quantitatively the dopant distribution in these devices with nanometer precision in 3D.In recent years, atom probe tomography (APT) has shown its ability to analyze semiconductor and thin insulator materials effectively with sub-nm resolution in 3D. In this paper we will discuss the methodology used to study FinFET-based structures using APT. Whereas challenges and solutions for sample preparation linked to the limited fin dimensions already have been reported before, we report here an approach to prepare fin structures for APT, which based on their processing history (trenches filled with Si) are in principle invisible in FIB and SEM. Hence alternative solutions in locating and positioning them on the APT-tip are presented. We also report on the use of the atom probe results on FinFETs to understand the role of different dopant implantation angles (10° and 45°) when attempting conformal doping of FinFETs and provide a quantitative comparison with alternative approaches such as 1D secondary ion mass spectrometry (SIMS) and theoretical model values.     

Shaping the lens of the atom probe: fabrication of site specific, oriented specimens and application to grain boundary analysis

The random sampling provided by classical atom probe sample preparation methods is one of the major factors limiting the types of problems that can be addressed using this powerful technique. A focused ion beam enables not only site-specific preparation, but can also be used to give the specimen, which acts as the lens in an atom probe experiment, a specific shape. In this paper we present a technique that uses low accelerating voltages (10 and 5 kV) in the focused ion beam (FIB) to reproducibly produce specimens with selected grain boundaries <100 nm from the tip at any desired orientation. These tips have a high rate of successfully running in the atom probe and no Ga contamination within the region of interest.This technique is applied to the analysis of grain boundaries in a high purity iron wire and a strip-cast steel. Lattice resolution is achieved around the boundary in certain areas. Reconstruction of these datasets reveals the distribution of light and heavy elements around the boundary. Issues surrounding the uneven distribution of certain solute elements as a result of field-induced diffusion are discussed.