Imaging of liquids and cryogenic biological materials by electron microscopy has been recently enabled by innovative approaches for specimen preparation and the fast development of optimized instruments for cryo-enabled electron microscopy (cryo-EM). Yet, cryo-EM typically lacks advanced analytical capabilities, in particular for light elements. With the development of protocols for frozen wet specimen preparation, atom probe tomography (APT) could advantageously complement insights gained by cryo-EM. Here, we report on different approaches that have been recently proposed to enable the analysis of relatively large volumes of frozen liquids from either a flat substrate or the fractured surface of a wire. Both allowed for analyzing water ice layers which are several micrometers thick consisting of pure water, pure heavy water, and aqueous solutions. We discuss the merits of both approaches and prospects for further developments in this area. Preliminary results raise numerous questions, in part concerning the physics underpinning field evaporation. We discuss these aspects and lay out some of the challenges regarding the APT analysis of frozen liquids.

Atom probe tomography (APT) is often introduced as providing “atomic-scale” mapping of the composition of materials and as such is often exploited to analyze atomic neighborhoods within a material. Yet quantifying the actual spatial performance of the technique in a general case remains challenging, as it depends on the material system being investigated as well as on the specimen's geometry. Here, by using comparisons with field-ion microscopy experiments, field-ion imaging and field evaporation simulations, we provide the basis for a critical reflection on the spatial performance of APT in the analysis of pure metals, low alloyed systems and concentrated solid solutions (i.e., akin to high-entropy alloys). The spatial resolution imposes strong limitations on the possible interpretation of measured atomic neighborhoods, and directional neighborhood analyses restricted to the depth are expected to be more robust. We hope this work gets the community to reflect on its practices, in the same way, it got us to reflect on our work.

First-principles calculations were performed on the evaporation field of Fe, Cu, Mn, and Si in Fe (001) and on the evaporation field and roll-up effect of Fe, Cu, and Mn in the Fe (001) step structure. The larger the evaporation barrier energy tendency, at an electric field of 0 V/nm (absorption energy), the larger was the evaporation field. Electric field evaporation calculation results indicate that the order in which the electric field is easily evaporated is Mn > Cu > Fe > Si. The tendency that Mn and Cu evaporate more easily than does Fe and that the evaporation of Si is less probable is consistent with the experiment of a dilute element in steel. In the Fe (001) step structure, when the electric field is low, the roll-up effect where the evaporated atoms move on the step is large, and when the electric field is large, the roll-up effect is small. The roll-up effect of Cu was almost the same as that of Fe, and the roll-up effect of Mn was small because the chemical bond between Mn and Fe was weak.

Atom probe tomography (APT) analysis conditions play a major role in the composition measurement accuracy. Preferential evaporation (PE), which significantly biases the apparent composition, more than other well-known phenomena in APT, is strongly connected to those analysis conditions. One way to optimize them, in order to have the most accurate measurement, is therefore to be able to predict and then to estimate their influence on the apparent composition. An analytical model is proposed to quantify the PE. This model is applied to three different alloys such as NiCu, FeCrNi, and FeCu. The model explains not only the analysis temperature dependence, as in an already existing model, but also the dependence to the pulse fraction and the pulse frequency. Moreover, the model can also provide an energetic constant directly linked to the energy barrier required to field evaporate atom from the sample surface.

In this work, the correlation between composition and relative evaporation field was investigated by tracking the statistics of multi-hit detector events in atom probe tomography (APT). This approach is applied systematically to a GaN-based nitride heterostructure with five AlxGa1−xN layers of varying Al composition. The relative field evaporation and the percentage of multi-hit events were found to increase with higher Al concentration. Furthermore, the comparison of the relative evaporation fields of AlN with respect to the constituent ions is found to be less than GaN with respect to its constituent ions. Despite equivalent compositions between opposing interfaces of the same AlxGa1−xN interlayer, the rate of change in multiplicity exhibits a consistent asymmetric trend with a steeper slope across the AlxGa1−xN/GaN interface compared to the GaN/AlxGa1−xN interface. The AlxGa1−xN/GaN heterostructure serves as a test structure for exploring field evaporation and neighborhood chemistry, which can be applied to any material chemistry and particularly other nitride systems.

First-principles calculations were performed to determine the Fe on Fe (001) evaporation field and to characterize the surface diffusion of Fe and Cu on Fe (001) and on a step structure under an applied electric field. The evaporation field of Fe on Fe (001) was calculated by the nudged elastic band (NEB) method, using the combination of the effective screening medium and constant electrode potential methods to obtain a condition of constant electric field. The calculated evaporation field of Fe on Fe (001) was 32.4 V/nm, which agrees well with the experimental value. In the surface diffusion of Fe and Cu on Fe (001) and on a step structure, the activation barrier energies were determined by the NEB method with constant applied electric field. It was found that Cu diffuse more easily on the Fe (001) and step structure than Fe under an applied electric field. The activation barrier energy of surface diffusion in the saddle point configuration is small when the distance between Cu and Fe on the surface is larger, and the activation barrier energy becomes smaller when passing through a path far away from the surface due to the effect of the electric field.

Atom probe tomography (APT) of a nanocrystalline Cu–7 at.% V thin film annealed at 400°C for 1 h revealed chemical partitioning in the form of solute segregation. The vanadium precipitated along high angle grain boundaries and at triple junctions, determined by cross-correlative precession electron diffraction of the APT specimen. Upon field evaporation, the V2+/(V1+ + VH1+) ratio from the decomposed ions was ~3 within the matrix grains and ~16 within the vanadium precipitates. It was found that the VH1+ complex was prevalent in the matrix, with its presence explained in terms of hydrogen's ability to assist in field evaporation. The change in the V2+/(V1+ + VH1+) charge-state ratio (CSR) was studied as a function of base temperature (25–90 K), laser pulse energy (50–200 pJ), and grain orientation. The strongest influence on changing the CSR was with the varied pulse laser, which made the CSR between the precipitates and the matrix equivalent at the higher laser pulse energies. However, at these conditions, the precipitates began to coarsen. The collective results of the CSRs are discussed in terms of field strengths related to the chemical coordination.

Accuracy of atom probe tomography measurements is strongly degraded by the presence of phases that have different evaporation fields. In particular, when there are perpendicular interfaces to the tip axis in the specimen, layers thicknesses are systematically biased and the resolution is degraded near the interfaces. Based on an analytical model of field evaporated emitter end-form, a new algorithm dedicated to the 3D reconstruction of multilayered samples was developed. Simulations of field evaporation of bilayer were performed to evaluate the effectiveness of the new algorithm. Compared to the standard state-of-the-art reconstruction methods, the present approach provides much more accurate analyzed volume, and the resolution is clearly improved near the interface. The ability of the algorithm to handle experimental data was also demonstrated. It is shown that the standard algorithm applied to the same data can commit an error on the layers thicknesses up to a factor 2. This new method is not constrained by the classical hemispherical specimen shape assumption.

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.

Elemental distributions in a magnetic multilayer system with the structure Si substrate/Ta/NiFe/Ru/CoFeB/Ru/NiFe were studied using atom probe tomography (APT) along different analysis directions. The distributions of Ru and B atoms, which require a high evaporation field, were strongly influenced by the APT analysis direction. In particular, B in the CoFeB layer appeared near the interface with the lower Ru layer when the analysis was anti-parallel to the film growth direction, while B atoms were observed at the other side of the CoFeB layer when the analysis was parallel to the film growth direction. Moreover, when the analysis was perpendicular to the film growth direction, a homogenous distribution of B atoms was found within the CoFeB layer. Owing to this B behavior, the underlying Ru layer was affected in both of these analysis directions. In APT measurements of such a multilayer system composed of a stack of different evaporation field materials, evaluation of the elemental distribution around interfaces should be performed from more than one analysis direction.

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.

The ability to accurately reconstruct original spatial positions of field-evaporated ions emitted from a surface is fundamental to the success of atom probe tomography. As such, a clear understanding of the evolution of specimen shape and the resultant ions' trajectories during field evaporation plays an important role in improving reconstruction accuracy. To further this understanding, field-evaporation simulations of a bilayer specimen composed of two materials having an evaporation field difference of 20% were performed. The simulated field-evaporation patterns qualitatively compare favorably with experimental data, which provides confidence in the accuracy of specimen shapes predicted by the simulation. Correlations of known original atom positions with detector hit positions as a function of lateral detector position and evaporated depth were derived from the simulation. These correlations are contrasted with the current state-of-the-art reconstruction method thus outlining limitations of the current methodology. A pair of transformations are defined that take into account field-evaporated specimen shapes, and the resulting radial magnifications, to relate recorded ion positions in detector space to reconstructed atomic positions in specimen space. This novel process, when applied to simulated data, results in approximately a factor of 2 improvement in accuracy for reconstructions of interfaces with unequal fields (most general interfaces). This method is not constrained by the fundamental assumption of a hemispherical specimen shape.

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.