No Arabic abstract
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 optimised 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 analysing water ice layers which are several microns 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.
We present a morphological analysis of atom probe data of nanoscale microstructural features, using methods developed by the astrophysics community to describe the shape of superclusters of galaxies. We describe second-phase regions using Minkowski functionals, representing the regions volume, surface area, mean curvature and Euler characteristic. The alloy data in this work show microstructures that can be described as sponge-like, filament-like, plate-like, and sphere-like at different concentration levels, and we find quantitative measurements of these features. To reduce user decision-making in constructing isosurfaces and to enhance the accuracy of the analysis a maximum likelihood based denoising filter was developed. We show that this filter performs significantly better than a simple Gaussian smoothing filter. We also interpolate the data using natural cubic splines, to refine voxel sizes and to refine the surface. We demonstrate that it is possible to find a mathematically well-defined, quantitative description of microstructure from atomistic datasets, to sub-voxel resolution, without user-tuneable parameters.
Atom probe tomography is often introduced as providing atomic-scale mapping of the composition of materials and as such is often exploited to analyse atomic neighbourhoods within a material. Yet quantifying the actual spatial performance of the technique in a general case remains challenging, as they depend on the material system being investigated as well as on the specimens geometry. Here, by using comparisons with field-ion microscopy experiments and field-ion imaging and field evaporation simulations, we provide the basis for a critical reflection on the spatial performance of atom probe tomography 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 neighbourhoods, and directional neighbourhood 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.
We report a correlative microscopy study of a sample containing three stacks of InGaN/GaN quantum dots (QDs) grown at different substrate temperature, each stack consisting of 3 layers of QDs. Decreasing the substrate temperature along the growth axis leads to the proliferation of structural defects. However, the luminescence intensity increases towards the surface, in spite of the higher density of threading dislocations, revealing that the QD layers closer to the substrate behave as traps for non-radiative point defects. During atom probe tomography experiments combined with in-situ micro-photoluminescence, it was possible to isolate the optical emission of a single QD located in the topmost QD stack, closer to the sample surface. The single QD emission line displayed a spectral shift during the experiment confirming the relaxation of elastic strain due to material evaporation during atom probe tomography.
Understanding the structure and chemical composition at the liquid-nanoparticle (NP) interface is crucial for a wide range of physical, chemical and biological processes. In this study, direct imaging of the liquid-NP interface by atom probe tomography (APT) is reported for the first time, which reveals the distributions and the interactions of key atoms and molecules in this critical domain. The APT specimen is prepared by controlled graphene encapsulation of the solution containing nanoparticles on a metal tip, with an end radius in the range of 50 nm to allow field ionization and evaporation. Using Au nanoparticles (AuNPs) in suspension as an example, analysis of the mass spectrum and three-dimensional (3D) chemical maps from APT provides a detailed image of the water-gold interface with near-atomic resolution. At the water-gold interface, the formation of an electrical double layer (EDL) rich in water (H2O) molecules has been observed, which results from the charge from the binding between the trisodium-citrate layer and the AuNP. In the bulk water region, the density of reconstructed H2O has been shown to be consistent, reflecting a highly packed density of H2O molecules after graphene encapsulation. This study is the first demonstration of direct imaging of liquid-NP interface using APT with results providing an atom-by-atom 3D dissection of the liquid-NP interface.
Laser-assisted atom probe tomography (APT) was used to measure the indium mole fraction x of c-plane, MOCVD-grown, GaN/In(x)Ga(1-x)N/GaN test structures and the results were compared with Rutherford backscattering analysis (RBS). Four sample types were examined with (RBS determined) x = 0.030, 0.034, 0.056, and 0.112. The respective In(x)Ga(1-x)N layer thicknesses were 330 nm, 327 nm, 360 nm, and 55 nm. APT data were collected at (fixed) laser pulse energy (PE) selected within the range of (2-1000) fJ. Sample temperatures were = 54 K. PE within (2-50) fJ yielded x values that agreed with RBS (within uncertainty) and were comparatively insensitive to region-of-interest (ROI) geometry and orientation. By contrast, approximate stoichiometry was only found in the GaN portions of the samples provided PE was within (5-20) fJ and the analyses were confined to cylindrical ROIs (of diameters =20 nm) that were coaxial with the specimen tips. m-plane oriented tips were derived from c-axis grown, core-shell, GaN/In(x)Ga(1-x)N nanorod heterostructures. Compositional analysis along [0 0 0 1] (transverse to the long axis of the tip), of these m-plane samples revealed a spatial asymmetry in charge-state ratio (CSR) and a corresponding asymmetry in the resultant tip shape along this direction; no asymmetry in CSR or tip shape was observed for analysis along [-1 2-1 0]. Simulations revealed that the electric field strength at the tip apex was dominated by the presence of a p-type inversion layer, which developed under typical tip-electrode bias conditions for the n-type doping levels considered. Finally, both c-plane and m-plane sample types showed depth-dependent variations in absolute ion counts that depended upon ROI placement.