On the Use of a Cluster Identification Method and a Statistical Approach for Analyzing Atom Probe Tomography Data for GP Zones in Al-Zn-Mg(-Cu) Alloys.

Early-stage clustering in two Al-Mg-Zn(-Cu) alloys has been investigated using atom probe tomography and transmission electron microscopy. Cluster identification by the isoposition method and a statistical approach based on the pair correlation function have both been applied to estimate the cluster size, composition, and volume fraction from atom probe data sets. To assess the accuracy of the quantification of clusters of different mean sizes, synthesized virtual data sets were used, accounting for a simulated degraded spatial resolution. The quality of the predictions made by the two complementary methods is discussed, considering the experimental and simulated data sets.

Atomic Structure of Hardening Precipitates in Al-Mg-Si Alloys: Influence of Minor Additions of Cu and Zn.

Shifting toward sustainability and low carbon emission necessitates recycling. Aluminum alloys can be recycled from postconsumer scrap with approximately 5% of the energy needed to produce the same amount of primary alloys. However, the presence of certain alloying elements, such as copper and zinc, as impurities in recycled Al-Mg-Si alloys is difficult to avoid. This work has investigated the influence of tiny concentrations of Cu (0.05 wt %) and Zn (0.06 wt %), individually and in combination, on the precipitate crystal structures in Al-Mg-Si alloys in peak aged and overaged conditions. To assess whether such concentrations can affect the hardening precipitate structures, atomic resolution high-angle annular dark-field scanning transmission electron microscopy and atom probe tomography were adopted. The results indicate that low levels of Cu or Zn have a significant influence. Both elements showed a relatively high tendency to incorporate into precipitate structures, where Cu occupies specific atomic sites, creating its own local atomic configurations. However, Zn exhibited distinct behavior through the formation of extended local areas with 2-fold symmetry and mirror planes, not previously observed in precipitates in Al-Mg-Si alloys. Incorporation of Cu and/or Zn will influence the precipitates' electrochemical potential relative to matrix- and precipitate-free zones and thus the corrosion resistance. Furthermore, the presence of Cu/Zn structures (e.g., ß'Cu, Q'/C) enhances the thermal stability of these precipitates and, accordingly, the mechanical properties of the material. The results obtained from this work are highly relevant to the topic of recycling of aluminum alloys, where accumulation of certain alloying elements is almost unavoidable; thus, tight compositional control might be critical to avoid quality degradation.

AutomAl 6000: Semi-automatic structural labelling of HAADF-STEM images of precipitates in Al-Mg-Si(-Cu) alloys.

When the Al-Mg-Si(-Cu) alloy system is subjected to age hardening, different types of precipitates nucleate depending on the composition and thermomechanical treatment. The main hardening precipitates extend as needles, laths or rods along the <100> directions in the aluminium matrix. It has been found that the structures of all metastable precipitates may be generalized as stacks of <100> columns, where most of these columns are replaced by solute elements. In the precipitates, a column relates to neighbour columns by a set of simple structural principles, which allows identification of species and relative longitudinal displacement over the (100) cross-section. Aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) is an important tool for studying such precipitates. With the goal of analysing atomic resolution HAADF-STEM images of precipitate cross-sections in the Al-Mg-Si(-Cu) system, we have developed the stand-alone software AutomAl 6000, which features a column characterization algorithm based on the symbiosis of a statistical model and the structural principles formulated in a digraph-like framework. The software can semi-autonomously determine the 3D column positions in the image, as well as column species. In turn, AutomAl 6000 can then display, analyse and/or export the structure data. This paper describes the methodology of AutomAl 6000 and applies it on three different HAADF-STEM images, which demonstrate the methodology. The software, as well as other resources, are available at http://automal.org. The source code is also directly available from https://github.com/Haawk666/AutomAl-6000.

Effect of Multiply Twinned Ag(0) Nanoparticles on Photocatalytic Properties of TiO2 Nanosheets and TiO2 Nanostructured Thin Films.

Ag-decorated TiO2 nanostructured materials are promising photocatalysts. We used non-standard cryo-lyophilization and ArF laser ablation methods to produce TiO2 nanosheets and TiO2 nanostructured thin films decorated with Ag nanoparticles. Both methods have a common advantage in that they provide a single multiply twinned Ag(0) characterized by {111} twin boundaries. Advanced microscopy techniques and electron diffraction patterns revealed the formation of multiply twinned Ag(0) structures at elevated temperatures (500 °C and 800 °C). The photocatalytic activity was demonstrated by the efficient degradation of 4-chlorophenol and Total Organic Carbon removal using Ag-TiO2 nanosheets, because the multiply twinned Ag(0) served as an immobilized photocatalytically active center. Ag-TiO2 nanostructured thin films decorated with multiply twinned Ag(0) achieved improved photoelectrochemical water splitting due to the additional induction of a plasmonic effect. The photocatalytic properties of TiO2 nanosheets and TiO2 nanostructured thin films were correlated with the presence of defect-twinned structures formed from Ag(0) nanoparticles with a narrow size distribution, tuned to between 10 and 20 nm. This work opens up new possibilities for understanding the defects generated in Ag-TiO2 nanostructured materials and paves the way for connecting their morphology with their photocatalytic activity.

Detecting minute amounts of nitrogen in GaNAs thin films using STEM and CBED.

Nitrogen (N) is a common element added to GaAs for band gap engineering and strain compensation. However, detection of small amounts of N is difficult for electron microscopy as well as for other chemical analysis techniques. In this work, N in GaAs is examined by using different transmission electron microscopy (TEM) techniques. While both dark-field TEM imaging using the composition sensitive (002) reflections and selected area diffraction reveal a significant difference between the doped thin-film and the GaAs substrate, spectroscopy techniques such as electron energy loss and energy dispersive X-ray spectroscopy are not able to detect N. To quantify the N content, quantitative convergent beam electron diffraction (QCBED) is used, which gives a direct evidence of N substitution and As vacancies. The measurements are enabled by the electron energy-filtered scanning CBED technique. These results demonstrate a sensitive method for composition analysis based on quantitative electron diffraction.

Data on atomic structures of precipitates in an Al-Mg-Cu alloy studied by high resolution transmission electron microscopy and first-principles calculations.

The dataset refers to the research article "Precipitation processes and structural evolutions of various GPB zones and two types of S phases in a cold-rolled Al-Mg-Cu alloy" [1]. Transmission electron microscopy (TEM) and density functional theory (DFT) were used to investigate precipitates in an Al-Cu-Mg alloy aged at 443 K for various times. High-angle annular dark-field scanning TEM (HAADF-STEM) images in <100> Al orientations were analyzed. Characteristic contrast and symmetries of columns [2] yielded atoms and positions, used to build precipitate models which could be refined and compared with solid solution reference energies. A calculation cell is an Al supercell compatible with symmetry and morphology of a precipitate, which is fully or partly surrounded by Al, allowing periodicity continuation via neighbor cells. The given crystallographic data include two S-phase variants and Guinier-Preston-Bagaryatsky (GPB) zones, of which the "GPBX" is new.

In situ heating TEM observations of evolving nanoscale Al-Mg-Si-Cu precipitates.

This research concerns the precipitation and subsequent dissolution of precipitate phases in an Al-0.86Mg-0.62Si-0.1Cu (at.%) alloy subjected to varying thermal exposure during an in situ heating transmission electron microscope (TEM) experiment. The distribution and crystal structure of precipitates were determined by a scanning diffraction approach at multiple stages, pinpointing the precipitates that underwent phase transformations during heating. Obtained results were compared with TEM studies of the material heated ex situ. This revealed differences in the transformation kinetics of precipitates in an electron transparent lamella (thickness ⪆ 90 nm ) to that of macroscopic bulk specimens. LAY DESCRIPTION: The precipitate phases that are formed in age-hardenable Al alloys are conventionally studied using the TEM, with electron transparent specimens prepared from bulk materials heat treated for various times. We demonstrate here that the growth, phase transformation and subsequent dissolution of precipitate phases in the Al-Mg-Si-Cu system can be studied successfully by in situ heating TEM. Imaging and scanning diffraction combined with data postprocessing were used to study the distribution and structure of transforming precipitates. This enabled us to track the precipitates that underwent phase transformations during heating, hence offering a direct quantitative assessment of the precipitation occurring in these materials. The narrow thickness of the electron transparent specimen (≈90 nm) may potentially have affected the resulting precipitation. Therefore, thickness effects were assessed by comparing obtained results with TEM studies of ex situ heated bulk specimens.

Nano-scale characterisation of sheared ß" precipitates in a deformed Al-Mg-Si alloy.

This paper compares the nano-scale structure of ß" precipitates in a peak-aged Al-Mg-Si alloy before and after deformation. Three complementary advanced transmission electron microscopy techniques are used to reveal the structures and elucidate the interaction between dislocations and ß" precipitates. We show that the needle-like and semi-coherent ß" precipitates are sheared several times on different planes by dislocations during deformation, with no indications that they are bypassed or looped. Our results show that dislocations cut through precipitates and leave behind planar defects lying on planes inclined to 〈100〉 directions inside the precipitates. The results also indicate that precipitates are sheared in single steps, and the implication of this observation is discussed in terms of slip behaviour.

Controlling Phase Purity and Texture of K0.5Na0.5NbO3 Thin Films by Aqueous Chemical Solution Deposition.

Aqueous chemical solution deposition (CSD) of lead-free ferroelectric K0.5Na0.5NbO3 (KNN) thin films has a great potential for cost-effective and environmentally friendly components in microelectronics. Phase purity of KNN is, however, a persistent challenge due to the volatility of alkali metal oxides, usually countered by using excess alkali metals in the precursor solutions. Here, we report on the development of two different aqueous precursor solutions for CSD of KNN films, and we demonstrate that the decomposition process during thermal processing of the films is of detrimental importance for promoting nucleation of KNN and suppressing the formation of secondary phases. Based on thermal analysis, X-ray diffraction and IR spectroscopy of films as well as powders prepared from the solutions, it was revealed that the decomposition temperature can be controlled by chemistry resulting in phase pure KNN films. A columnar microstructure with out-of-plane texturing was observed in the phase pure KNN films, demonstrating that the microstructure is directly coupled to the thermal processing of the films.

Bandgap measurement of high refractive index materials by off-axis EELS.

In the present work Cs aberration corrected and monochromated scanning transmission electron microscopy electron energy loss spectroscopy (STEM-EELS) has been used to explore experimental set-ups that allow bandgaps of high refractive index materials to be determined. Semi-convergence and -collection angles in the µrad range were combined with off-axis or dark field EELS to avoid relativistic losses and guided light modes in the low loss range to contribute to the acquired EEL spectra. Off-axis EELS further supressed the zero loss peak and the tail of the zero loss peak. The bandgap of several GaAs-based materials were successfully determined by simple regression analyses of the background subtracted EEL spectra. The presented set-up does not require that the acceleration voltage is set to below the Cerenkov limit and can be applied over the entire acceleration voltage range of modern TEMs and for a wide range of specimen thicknesses.

Optimising multi-frame ADF-STEM for high-precision atomic-resolution strain mapping.

Annular dark-field scanning transmission electron microscopy is a powerful tool to study crystal defects at the atomic scale but historically single slow-scanned frames have been plagued by low-frequency scanning-distortions prohibiting accurate strain mapping at atomic resolution. Recently, multi-frame acquisition approaches combined with post-processing have demonstrated significant improvements in strain precision, but the optimum number of frames to record has not been explored. Here we use a non-rigid image registration procedure before applying established strain mapping methods. We determine how, for a fixed total electron-budget, the available dose should be fractionated for maximum strain mapping precision. We find that reductions in scanning-artefacts of more than 70% are achievable with image series of 20-30 frames in length. For our setup, series longer than 30 frames showed little further improvement. As an application, the strain field around an aluminium alloy precipitate was studied, from which our optimised approach yields data whos strain accuracy is verified using density functional theory.

Atomap: a new software tool for the automated analysis of atomic resolution images using two-dimensional Gaussian fitting.

Scanning transmission electron microscopy (STEM) data with atomic resolution can contain a large amount of information about the structure of a crystalline material. Often, this information is hard to extract, due to the large number of atomic columns and large differences in intensity from sublattices consisting of different elements. In this work, we present a free and open source software tool for analysing both the position and shapes of atomic columns in STEM-images, using 2-D elliptical Gaussian distributions. The software is tested on variants of the perovskite oxide structure. By first fitting the most intense atomic columns and then subtracting them, information on all the projected sublattices can be obtained. From this, we can extract changes in the lattice parameters and shape of A-cation columns from annular dark field images of perovskite oxide heterostructures. Using annular bright field images, shifts in oxygen column positions are also quantified in the same heterostructure. The precision of determining the position of atomic columns is compared between STEM data acquired using standard acquisition, and STEM-images obtained as an image stack averaged after using non-rigid registration.

Quantitative strain analysis of InAs/GaAs quantum dot materials.

Geometric phase analysis has been applied to high resolution aberration corrected (scanning) transmission electron microscopy images of InAs/GaAs quantum dot (QD) materials. We show quantitatively how the lattice mismatch induced strain varies on the atomic scale and tetragonally distorts the lattice in a wide region that extends several nm into the GaAs spacer layer below and above the QDs. Finally, we show how V-shaped dislocations originating at the QD/GaAs interface efficiently remove most of the lattice mismatch induced tetragonal distortions in and around the QD.

Atomic-resolution chemical mapping of ordered precipitates in Al alloys using energy-dispersive X-ray spectroscopy.

Scanning transmission electron microscopy (STEM) coupled with energy-dispersive X-ray spectroscopy (EDS) is a common technique for chemical mapping in thin samples. Obtaining high-resolution elemental maps in the STEM is jointly dependent on stepping the sharply focused electron probe in a precise raster, on collecting a significant number of characteristic X-rays over time, and on avoiding damage to the sample. In this work, 80kV aberration-corrected STEM-EDS mapping was performed on ordered precipitates in aluminium alloys. Probe and sample instability problems are handled by acquiring series of annular dark-field (ADF) images and simultaneous EDS volumes, which are aligned and non-rigidly registered after acquisition. The summed EDS volumes yield elemental maps of Al, Mg, Si, and Cu, with sufficient resolution and signal-to-noise ratio to determine the elemental species of each atomic column in a periodic structure, and in some cases the species of single atomic columns. Within the uncertainty of the technique, S and ß" phases were found to have pure elemental atomic columns with compositions Al2CuMg and Al2Mg5Si4, respectively. The Q' phase showed some variation in chemistry across a single precipitate, although the majority of unit cells had a composition Al6Mg6Si7.2Cu2.

Assessing electron beam sensitivity for SrTiO3 and La0.7Sr0.3MnO3 using electron energy loss spectroscopy.

Thresholds for beam damage have been assessed for La0.7Sr0.3MnO3 and SrTiO3 as a function of electron probe current and exposure time at 80 and 200kV acceleration voltage. The materials were exposed to an intense electron probe by aberration corrected scanning transmission electron microscopy (STEM) with simultaneous acquisition of electron energy loss spectroscopy (EELS) data. Electron beam damage was identified by changes of the core loss fine structure after quantification by a refined and improved model based approach. At 200kV acceleration voltage, damage in SrTiO3 was identified by changes both in the EEL fine structure and by contrast changes in the STEM images. However, the changes in the STEM image contrast as introduced by minor damage can be difficult to detect under several common experimental conditions. No damage was observed in SrTiO3 at 80kV acceleration voltage, independent of probe current and exposure time. In La0.7Sr0.3MnO3, beam damage was observed at both 80 and 200kV acceleration voltages. This damage was observed by large changes in the EEL fine structure, but not by any detectable changes in the STEM images. The typical method to validate if damage has been introduced during acquisitions is to compare STEM images prior to and after spectroscopy. Quantifications in this work show that this method possibly can result in misinterpretation of beam damage as changes of material properties.

Elemental electron energy loss mapping of a precipitate in a multi-component aluminium alloy.

The elemental distribution of a precipitate cross section, situated in a lean Al-Mg-Si-Cu-Ag-Ge alloy, has been investigated in detail by electron energy loss spectroscopy (EELS) and aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). A correlative analysis of the EELS data is connected to the results and discussed in detail. The energy loss maps for all relevant elements were recorded simultaneously. The good spatial resolution allows elemental distribution to be evaluated, such as by correlation functions, in addition to being compared with the HAADF image. The fcc-Al lattice and the hexagonal Si-network within the precipitates were resolved by EELS. The combination of EELS and HAADF-STEM demonstrated that some atomic columns consist of mixed elements, a result that would be very uncertain based on one of the techniques alone. EELS elemental mapping combined with a correlative analysis have great potential for identification and quantification of small amounts of elements at the atomic scale.

Mackay icosahedron explaining orientation relationship of dispersoids in aluminium alloys.

The orientation relations (ORs) of the cubic icosahedral quasicrystal approximant phase α-Al(Fe,Mn)Si have been studied after low temperature annealing of a 3xxx wrought aluminium alloy by transmission electron microscopy. From diffraction studies it was verified that the most commonly observed OR for the α-Al(Fe,Mn)Si dispersoids is [1\bar 11]α // [1\bar 11]Al, (5\bar 2\bar 7)α // (011)Al. This orientation could be explained by assuming that the internal Mackay icosahedron (MI) in the α-phase has a fixed orientation in relation to Al, similar to that of the icosahedral quasi-crystals existing in this alloy system. It is shown that mirroring of the normal-to-high-symmetry icosahedral directions of the MI explains the alternative orientations, which are therefore likely to be caused by twinning of the fixed MI. Only one exception was found, which was related to the Bergman icosahedron internal to the T-phase of the Al-Mg-Zn system.