Characterization of structure and mixing in nanoparticle hetero-aggregates using convolutional neural networks: 3D-reconstruction versus 2D-projection.

Structural and chemical characterization of nanomaterials provides important information for understanding their functional properties. Nanomaterials with characteristic structure sizes in the nanometer range can be characterized by scanning transmission electron microscopy (STEM). In conventional STEM, two-dimensional (2D) projection images of the samples are acquired, information about the third dimension is lost. This drawback can be overcome by STEM tomography, where the three-dimensional (3D) structure is reconstructed from a series of projection images acquired using various projection directions. However, 3D measurements are expensive with respect to acquisition and evaluation time. Furthermore, the method is hardly applicable to beam-sensitive materials, i.e. samples that degrade under the electron beam. For this reason, it is desirable to know whether sufficient information on structural and chemical information can be extracted from 2D-projection measurements. In the present work, a comparison between 3D-reconstruction and 2D-projection characterization of structure and mixing in nanoparticle hetero-aggregates is provided. To this end, convolutional neural networks are trained in 2D and 3D to extract particle positions and material types from the simulated or experimental measurement. Results are used to evaluate structure, particle size distributions, hetero-aggregate compositions and mixing of particles quantitatively and to find an answer to the question, whether an expensive 3D characterization is required for this material system for future characterizations.

Synergizing ICP-MS, STEM-EDXS, and SMPS single particle analytics exemplified by superlattice L10 Pt/Fe aerosol nanoparticles produced by spark ablation.

Spark ablation was used to continuously synthesize bimetallic L10 Pt/Fe nanoparticles in an aerosol process involving a furnace and hydrogen as a reducing process gas. For the formation of Pt/Fe in the favorable L10 crystal configuration, which is a promising electrocatalyst, the Pt-Fe ratio plays a crucial role. State-of-the-art analytics for such multi-element nanoparticles include, among others, electron microscopy (EM) with an element mapping function, such as scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy (STEM-EDXS). Morphological characteristics, local compositions, and element distributions within single particles can be easily derived from EM for a small number of particles. However, a statistical evaluation aiming at the composition of hundreds of single Pt/Fe particles can barely be addressed with such analytics. Driven by the lack of analytical setups aiming at the recording of composition and size distribution of nanoparticles by online diagnostics, this work focuses on a single-particle inductively coupled plasma mass spectrometry (spICP-MS) setup able to resolve this issue. The combination of nanoparticle dilution and classification with spICP-MS allows for the analysis of thousands of multi-element aerosol nanoparticles within minutes. Hence, this article elaborates on the synergy of conducting STEM-EDXS and spICP-MS measurements in parallel, giving the opportunity to multi-dimensionally characterize nanoparticles consisting of more than one element. Beyond metallic particles, the presented setup even allows for the analysis of hetero-aggregated oxidic particles, such as Pt/Fe2O3. Including further offline analytics like X-ray diffraction (XRD), the formation of L10 Pt/Fe was found to be process gas-dependent and to set in at 400 °C, yielding particles with 56% L10 content at 1000 °C under a reducing atmosphere.

Tuning the morphology and chemical distribution of Ag atoms in Au rich nanoparticles using electrochemical dealloying.

Dealloying of Ag-Au alloy nanoparticles (NPs) strongly differs from the corresponding bulk alloy materials. Here, we have investigated the effects of potentiodynamic and potentiostatic dealloying on structure and distribution of residual Ag atoms for Au rich NPs. Two different sizes of Ag rich alloy NPs, 77 ± 26 nm Ag77Au23 and 12 ± 5 nm Ag86Au14, were prepared. 77 nm Ag77Au23 NPs form a homogeneous alloy, while 12 nm Ag86Au14 NPs show an Ag rich shell-Au rich core arrangement. The two groups of as-prepared NPs were dealloyed either under potentiodynamic (0.2-1.3 VRHE) or potentiostatic (0.9, 1.2, and 1.6 VRHE) conditions in 0.1 M HClO4. For the initial 77 nm Ag77Au23 NPs, both dealloying protocols lead to pore evolution. Interestingly, instead of homogenous Ag distribution, numerous Ag rich regions form and locate near the pores and particle edges. The critical dealloying potential also differs by ∼500 mV depending on the dealloying method. The initial 12 nm Ag86Au14 NPs remain dense and solid, but Ag distribution and thickness of the Au passivation layer vary between both dealloying protocols. When the Au passivation layer is very thin, the residual Ag atoms tend to segregate to the particle surface after dealloying. Due to the size effect, small NPs are less electrochemically stable and show a lower critical dealloying potential. In this systematic study, we demonstrate that the mobility of Au surface atoms and dealloying conditions control the structure and residual Ag distribution within dealloyed NPs.

GaN atomic electric fields from a segmented STEM detector: Experiment and simulation.

Atomic electric fields in a thin GaN sample are measured with the centre-of-mass approach in 4D-scanning transmission electron microscopy (4D-STEM) using a 12-segmented STEM detector in a Spectra 300 microscope. The electric fields, charge density and potential are compared to simulations and an experimental measurement using a pixelated 4D-STEM detector. The segmented detector benefits from a high recording speed, which enables measurements at low radiation doses. However, there is measurement uncertainty due to the limited number of segments analysed in this study.

Atom counting based on Voronoi averaged STEM intensities using a crosstalk correction scheme.

If quantitative scanning transmission electron microscopy is used for very precise thickness measurements with atomic resolution, it is commonly referred to as ¼atom counting«. Due to scattering and the finite probe extent the signal recorded in one atomic column is dependent not only on its own height but also on the height of its neighbours. Especially for thicker specimens this crosstalk effect can have significant impact on the measured intensity. If it is not appropriately accounted for in the evaluation, it can result in a deterioration of accuracy that impedes the possibility of actual atom counting. However, as the number of possible neighbour configurations can be excessively large, a comprehensive consideration of all in the evaluation reference is neigh impossible. This work proposes a method that allows for the a-posteriori reduction of crosstalk during the evaluation by algebraic means. Based on a parametric model, which is described in detail in the article, the crosstalk is expressed by an invertible matrix. Applying the inverted matrix to the measurement yields crosstalk corrected intensity values with very little computational effort. These can subsequently be evaluated by direct comparison to simple reference data. The working principle of the method is presented on the example of crystalline gold. The crosstalk parametrisation is found by fitting a model to sets of specifically created multislice simulations. The parameters are given for both aberration corrected and uncorrected STEM. Subsequently the abilities and potential of the technique are assessed in simulative studies on multiple model systems including gold nanoparticles. Overall a significant and robust improvement of the attainable precision can be demonstrated making the proposed method a promising tool for reference-based atom counting.

New Perspectives for Evaluating the Mass Transport in Porous Catalysts and Unfolding Macro- and Microkinetics.

In this article we shed light on newly emerging perspectives to characterize and understand the interplay of diffusive mass transport and surface catalytic processes in pores of gas phase metal catalysts. As a case study, nanoporous gold, as an interesting example exhibiting a well-defined pore structure and a high activity for total and partial oxidation reactions is considered. PFG NMR (pulsed field gradient nuclear magnetic resonance) measurements allowed here for a quantitative evaluation of gas diffusivities within the material. STEM (scanning transmission electron microscopy) tomography furthermore provided additional insight into the structural details of the pore system, helping to judge which of its features are most decisive for slowing down mass transport. Based on the quantitative knowledge about the diffusion coefficients inside a porous catalyst, it becomes possible to disentangle mass transport contributions form the measured reaction kinetics and to determine the kinetic rate constant of the underlying catalytic surface reaction. In addition, predictions can be made for an improved effectiveness of the catalyst, i.e., optimized conversion rates. This approach will be discussed at the example of low-temperature CO oxidation, efficiently catalysed by npAu at 30 °C. The case study shall reveal that novel porous materials exhibiting well-defined micro- and mesoscopic features and sufficient catalytic activity, in combination with modern techniques to evaluate diffusive transport, offer interesting new opportunities for an integral understanding of catalytic processes.

Systematic Errors of Electric Field Measurements in Ferroelectrics by Unit Cell Averaged Momentum Transfers in STEM.

When using the unit cell average of first moment data from four-dimensional scanning transmission electron microscopy (4D-STEM) to characterize ferroelectric materials, a variety of sources of systematic errors needs to be taken into account. In particular, these are the magnitude of the acceleration voltage, STEM probe semi-convergence angle, sample thickness, and sample tilt out of zone axis. Simulations show that a systematic error of calculated electric fields using the unit cell averaged momentum transfer originates from violation of point symmetry within the unit cells. Thus, values can easily exceed those of potential polarization-induced electric fields in ferroelectrics. Importantly, this systematic error produces deflection gradients between different domains seemingly representing measured fields. However, it could be shown that for PbZr0.2Ti0.8O3, many adjacent domains exhibit a relative crystallographic mistilt and in-plane rotation. The experimental results show that the method gives qualitative domain contrast. Comparison of the calculated electric field with the systematic error showed that the domain contrast of the unit cell averaged electric fields is mainly caused by dynamical scattering effects and the electric field plays only a minor role, if present at all.

Nanoporous Gold: From Structure Evolution to Functional Properties in Catalysis and Electrochemistry.

Nanoporous gold (NPG) is characterized by a bicontinuous network of nanometer-sized metallic struts and interconnected pores formed spontaneously by oxidative dissolution of the less noble element from gold alloys. The resulting material exhibits decent catalytic activity for low-temperature, aerobic total as well as partial oxidation reactions, the oxidative coupling of methanol to methyl formate being the prototypical example. This review not only provides a critical discussion of ways to tune the morphology and composition of this material and its implication for catalysis and electrocatalysis, but will also exemplarily review the current mechanistic understanding of the partial oxidation of methanol using information from quantum chemical studies, model studies on single-crystal surfaces, gas phase catalysis, aerobic liquid phase oxidation, and electrocatalysis. In this respect, a particular focus will be on mechanistic aspects not well understood, yet. Apart from the mechanistic aspects of catalysis, best practice examples with respect to material preparation and characterization will be discussed. These can improve the reproducibility of the materials property such as the catalytic activity and selectivity as well as the scope of reactions being identified as the main challenges for a broader application of NPG in target-oriented organic synthesis.

Flame Aerosol Synthesis of Metal Sulfides at High Temperature in Oxygen-Lean Atmosphere.

The development of a novel reactive spray technology based on the well-known gas-phase metal oxide synthesis route provides innumerable opportunities for the production of non-oxide nanoparticles. Among these materials, metal sulfides are expected to have a high impact, especially in the development of electrochemical and photochemical high-surface-area materials. As a proof-of-principle, MnS, CoS, Cu2 S, ZnS, Ag2 S, In2 S3 , SnS, and Bi2 S3 are synthesized in an O2 -lean and sulfur-rich environment. In addition, the formation of Cu2 S in a single-droplet combustion experiment is reported. The multiscale approach combining flame sprays with single-droplet combustion is expected to pave the way toward a fundamental understanding of the gas-phase formation of metal sulfides in the future. The knowledge acquired can open the possibility for the development of a next-generation gas-phase technology facilitating the scalable synthesis of functional binary/ternary metal sulfides.

Correlative analysis on InGaN/GaN nanowires: structural and optical properties of self-assembled short-period superlattices.

The influence of self-assembled short-period superlattices (SPSLs) on the structural and optical properties of InGaN/GaN nanowires (NWs) grown by PAMBE on Si (111) was investigated by STEM, EDXS, µ-PL analysis and k·p simulations. STEM analysis on single NWs indicates that in most of the studied nanostructures, SPSLs self-assemble during growth. The SPSLs display short-range ordering of In-rich and In-poor InxGa1-xN regions with a period of 2-3 nm that are covered by a GaN shell and that transition to a more homogenous InxGa1-xN core. Polarization- and temperature-resolved PL analysis performed on the same NWs shows that they exhibit a strong parallel polarized red-yellow emission and a predominantly perpendicular polarized blue emission, which are ascribed to different In-rich regions in the nanostructures. The correlation between STEM, µ-PL and k·p simulations provides better understanding of the rich optical emission of complex III-N nanostructures and how they are impacted by structural properties, yielding the significant impact of strain on self-assembly and spectral emission.

Origin of the spectral red-shift and polarization patterns of self-assembled InGaN nanostructures on GaN nanowires.

The luminescence of InxGa1-xN nanowires (NWs) is frequently reported with large red-shifts as compared to the theoretical value expected from the average In content. Both compositional fluctuations and radial built-in fields were considered accountable for this effect, depending on the size, structure, composition, and surrounding medium of the NWs. In the present work, the emission properties of InGaN/GaN NWs grown by plasma-assisted molecular beam epitaxy are investigated in a comprehensive study combining ultraviolet-Raman and photoluminescence spectroscopy (PL) on vertical arrays, polarization-dependent PL on bundles of a few NWs, scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, and calculations of the band profiles. The roles of inhomogeneous In distribution and radial fields in the context of optical emission properties are addressed. The radial built-in fields are found to be modest, with a maximum surface band bending below 350 meV. On the other hand, variations in the local In content have been observed that give rise to potential fluctuations whose impact on the emission properties is shown to prevail over band-bending effects. Two luminescence bands with large positive and moderate negative polarization ratios of ≈+80% and ≤-60%, respectively, were observed. The red-shift in the luminescence is associated with In-rich inclusions in the NWs due to thermodynamic decomposition during growth. The negative polarization anisotropy is suggested to result from spontaneously formed superlattices in the In-rich regions of the NWs. The NWs show a preferred orthogonal absorption due to the dielectric boundary conditions and highlight the extreme sensitivity of these structures towards light polarization.

Dose efficient annular bright field contrast with the ISTEM method: A proof of principle demonstration.

The ISTEM mode for TEM has been demonstrated to have several advantages in regard to resolution and precision. While previous works primarily focussed on the advantages due to the reduced spatial coherence, the actual image contrast, i.e. how bright or dark certain atom columns are imaged, has mostly been of secondary concern. The present work sets out to achieve the contrast of annular bright field STEM in ISTEM, producing the high contrast of light elements, for which this method is popular. It is shown from theoretical considerations that using an annular condenser aperture this aim can be realised. The optimal size of this aperture is found by simulative studies. It is then manufactured from platinum foil and installed in an image-aberration corrected microscope. ABF-like ISTEM images of strontium titanate in [100] projection are acquired. The pure oxygen columns are clearly resolved with significant contrast. The image pattern is indeed identical to what is achieved by ABF STEM. A close look at the image formation also shows that the dose needed for a given signal-to-noise ratio is at least a quarter smaller for ABF-like ISTEM compared to ABF STEM, assuming detectors of similar detective quantum efficiency.

Angle-dependence of ADF-STEM intensities for chemical analysis of InGaN/GaN.

In this paper we perform angular resolved annular-dark field (ADF) scanning-transmission electron microscopy (STEM) to study the scattered intensity in an InGaN layer buried in GaN as a function of the scattering angle. We achieved angular resolution with a motorized iris aperture in front of the ADF detector. Using this setup, we investigated how the intensities measured in various angular ranges agree with multislice simulations in the frozen-lattice approximation. We observed a strong influence of relaxation induced surface-strain fields on the ADF intensity, measured its angular characteristics and compared the result with simulations. To assess the agreement of the measured intensity with simulations, we evaluated the specimen thickness in GaN and the indium concentration in InGaN for each angular interval by comparing the measured intensities with simulations. The thickness was strongly overestimated for scattering angles below 40mrad and also the evaluated indium concentration varies with the considered angular range. Using simulations, we investigated which angular ranges show a high sensitivity to variations of the thickness and which intervals strongly depend on the indium concentration. By combining two angular intervals, the indium concentration and the specimen thickness were determined simultaneously, which has potential advantages over the usual quantification method. It is shown that inelastic scattering, surface contamination and mistilt can have an influence on the measured intensity, especially at lower scattering angles below 30-50mrad, which might explain the observed difference between the frozen lattice simulation and the experiment.

Towards the interpretation of a shift of the central beam in nano-beam electron diffraction as a change in mean inner potential.

The measurement of electric fields in scanning transmission electron microscopy (STEM) is a highly investigated field of research. The constant improvement of spatial resolution in STEM and the development of new hardware for the fast acquisition of diffraction patterns even paved the way for the measurement of atomic electric fields. Although the basic principle that an electric field leads to a tilt of the focussed electron probe that can be detected as a shift of the diffraction pattern in the back focal plane of the objective lens seems quite simple, many challenges arose in the measurement of fields in a quantitative way. In the present study we investigate whether a shift of the diffraction pattern that occurs at an interface between two materials can be related to the electric field which is caused by the difference of the mean inner potentials of the two materials. To this end, experiments and simulations are compared. It is demonstrated that the difference in mean inner potential has an influence on the observed effect, but a quantitative interpretation is difficult. The influence of image recording effects such as shot noise and the modulation transfer function are investigated as well as further effects such as e.g. sample tilt. In addition, the influence of the observed effect on a strain measurement is shown.

Synthesis and Characterization of Ligand-Linked Pt Nanoparticles: Tunable, Three-Dimensional, Porous Networks for Catalytic Hydrogen Sensing.

Porous networks of Pt nanoparticles interlinked by bifunctional organic ligands have shown high potential as catalysts in micro-machined hydrogen gas sensors. By varying the ligand among p-phenylenediamine, benzidine, 4,4''-diamino-p-terphenyl, 1,5-diaminonaphthalene, and trans-1,4-diaminocyclohexane, new variants of such networks were synthesized. Inter-particle distances within the networks, determined via transmission electron microscopy tomography, varied from 0.8 to 1.4 nm in accordance with the nominal length of the respective ligand. While stable structures with intact and coordinatively bonded diamines were formed with all ligands, aromatic diamines showed superior thermal stability. The networks exhibited mesoporous structures depending on ligand and synthesis strategy and performed well as catalysts in hydrogen gas microsensors. They demonstrate the possibility of deliberately tuning micro- and mesoporosity and thereby transport properties and steric demands by choice of the right ligand also for other applications in heterogeneous catalysis.

Double Flame-Fabricated High-Performance AlPO4/LiMn2O4 Cathode Material for Li-Ion Batteries.

The spinel LiMn2O4 (LMO) is a promising cathode material for rechargeable Li-ion batteries due to its excellent properties, including cost effectiveness, eco-friendliness, high energy density, and rate capability. The commercial application of LiMn2O4 is limited by its fast capacity fading during cycling, which lowers the electrochemical performance. In the present work, phase-pure and crystalline LiMn2O4 spinel in the nanoscale were synthesized using single flame spray pyrolysis via screening 16 different precursor-solvent combinations. To overcome the drawback of capacity fading, LiMn2O4 was homogeneously mixed with different percentages of AlPO4 using versatile multiple flame sprays. The mixing was realized by producing AlPO4 and LiMn2O4 aerosol streams in two independent flames placed at 20° to the vertical axis. The structural and morphological analyses by X-ray diffraction indicated the formation of a pure LMO phase and/or AlPO4-mixed LiMn2O4. Electrochemical analysis indicated that LMO nanoparticles of 17.8 nm (d BET) had the best electrochemical performance among the pure LMOs with an initial capacity and a capacity retention of 111.4 mA h g-1 and 88% after 100 cycles, respectively. A further increase in the capacity retention to 93% and an outstanding initial capacity of 116.1 mA h g-1 were acquired for 1% AlPO4.

Control of Porous Layer Thickness in Thermophoretic Deposition of Nanoparticles.

The film thickness plays an important role in the performance of materials applicable to different technologies including chemical sensors, catalysis and/or energy materials. The relationship between the surface and volume of the functional layers is key to high performance evaluations. Here we demonstrate the thermophoretic deposition of different thicknesses of the functional layers designed using flame combustion of tin 2-ethylhexanoate dissolved in xylene, and measurement of thickness by scanning electron microscopy and focused ion beam. The parameters such as spray fluid concentration (differing Sn2+ content), substrate-nozzle distance and time of the spray were considered to investigate the layer growth. The results showed ≈ 23, 124 and 161 µm thickness of the SnO2 layer after flame spray of 0.1, 0.5 M and 1.0 M tin 2-EHA-Xylene solutions for 1200 s. While Sn2+ concentration was 0.5 M for all the flame sprays, the substrates placed at 250, 220 and 200 mm from the flame nozzle had layer thicknesses of 113, 116 and 132 µm, respectively. Spray time dependent thickness growth showed a linear increase from 8.5 to 152.1 µm when the substrates were flame sprayed for 30 s to 1200 s using 0.5 M tin 2-EHA-Xylene solutions. Changing the dispersion oxygen flow (3-7 L/min) had almost no effect on layer thickness. Layers fabricated were compared to a model found in literature, which seems to describe the thickness well in the domain of varied parameters. It turned out that primary particle size deposited on the substrate can be tuned without altering the layer thickness and with little effect on porosity. Applications depending on porosity, such as catalysis or gas sensing, can benefit from tuning the layer thickness and primary particle size.

Quantitative 3D Characterization of Nanoporous Gold Nanoparticles by Transmission Electron Microscopy.

Quantitative structural characterization of nanomaterials is important to tailor their functional properties. Corrosion of AgAu-alloy nanoparticles (NPs) results in porous structures, making them interesting for applications especially in the fields of catalysis and surface-enhanced Raman spectroscopy. For the present report, structures of dealloyed NPs were reconstructed three-dimensionally using scanning transmission electron microscopy tomography. These reconstructions were evaluated quantitatively, revealing structural information such as pore size, porosity, specific surface area, and tortuosity. Results show significant differences compared to the structure of dealloyed bulk samples and can be used as input for simulations of diffusion or mass transport processes, for example, in catalytic applications.

4D-STEM at interfaces to GaN: Centre-of-mass approach & NBED-disc detection.

4D-scanning transmission electron microscopy (4D-STEM) can be used to measure electric fields such as atomic fields or polarization-induced electric fields in crystal heterostructures. The paper focuses on effects occurring in 4D-STEM at interfaces, where two model systems are used: an AlN/GaN nanowire superlattice as well as a GaN/vacuum interface. Two different methods are applied: First, we employ the centre-of mass (COM) technique which uses the average momentum transfer evaluated from the intensity distribution in the diffraction pattern. Second, we measure the shift of the undiffracted disc (disc-detection method) in nano-beam electron diffraction (NBED). Both methods are applied to experimental and simulated 4D-STEM data sets. We find for both techniques distinct variations in the momentum transfer at interfaces between materials: In both model systems, peaks occur at the interfaces and we investigate possible sources and routes of interpretation. In case of the AlN/GaN superlattice, the COM and disc-detection methods are used to measure internal polarization-induced electric fields and we observed a reduction of the measured fields with increasing specimen thickness.

Accuracy and precision of position determination in ISTEM imaging of BaTiO3.

In this paper we study the effect of lens aberrations (spherical aberration and astigmatism), beam tilt, contamination and shot noise on the accuracy and precision of position determination in imaging scanning transmission electron microscopy (ISTEM) on the example of BaTiO3. ISTEM images are simulated as a function of sample thickness and defocus starting from a nearly perfect microscope setting. A defocus range was identified, in which atom column positions were reliably visible and could be decently measured. By averaging over this defocus and thickness range a figure of merit was defined and used to study the influence of above mentioned disturbing effects as a function of their strength. It turned out that column positions might become inaccurate, but distances are measured accurately. These were used to obtain recommendations for the experimental setup to measure the atomic arrangement that induces ferroelectric switching of BaTiO3.