Abstract: A widely used performance criterion in high-resolution transmission electron microscopy (HRTEM) is the information limit. It corresponds to the inverse of the maximum spatial object frequency that is linearly transmitted with sufficient intensity from the exit plane of the object to the image plane and is limited due to partial temporal coherence. In practice, the information limit is often measured from a diffractogram or from Young's fringes assuming a weak phase object scattering beyond the inverse of the information limit. However, for an aberration corrected electron microscope, with an information limit in the sub-angstrom range, weak phase objects are no longer applicable since they do not scatter sufficiently in this range. Therefore, one relies on more strongly scattering objects such as crystals of heavy atoms observed along a low index zone axis. In that case, dynamical scattering becomes important such that the non-linear and linear interaction may be equally important. The non-linear interaction may then set the experimental cut-off frequency observed in a diffractogram. The goal of this paper is to quantify both the linear and the non-linear information transfer in terms of closed form analytical expressions. Whereas the cut-off frequency set by the linear transfer can be directly related with the attainable resolution, information from the non-linear transfer can only be extracted using quantitative, model-based methods. In contrast to the historic definition of the information limit depending on microscope parameters only, the expressions derived in this paper explicitly incorporate their dependence on the structure parameters as well. In order to emphasize this dependence and to distinguish from the usual information limit, the expressions derived for the inverse cut-off frequencies will be referred to as the linear and non-linear structural information limit. The present findings confirm the well-known result that partial temporal coherence has different effects on the transfer of the linear and non-linear terms, such that the non-linear imaging contributions are damped less than the linear imaging contributions at high spatial frequencies. This will be important when coherent aberrations such as spherical aberration and defocus are reduced.

Abstract: An extension to model-based electron energy loss spectroscopy (EELS) quantification is reported to improve the possibility of modelling fine structure changes in electron energy loss spectra. An equalisation function is used in the energy loss near edge structure (ELNES) region to model the differences between a single atom differential cross section and the cross section for an atom in a crystal. The equalisation function can be shown to approximate the relative density of unoccupied states for the given excitation edge. On a set of 200 experimental h-BN spectra, this technique leads to statistically acceptable models resulting into unbiased estimates of relative concentrations and making the estimated precisions come very close to the Cramer-Rao lower bound (CRLB). The method greatly expands the useability of model-based EELS quantification to spectra with pronounced fine structure. Another benefit of this model is that one also gets an estimate of the unoccupied density of states for a given excitation edge, without having to do background removal and deconvolution, making the outcome intrinsically more reliable and less noisy. (c) 2006 Elsevier B.V. All rights reserved.

Abstract: Tomography with high angular annular dark field scanning transmission electron microscopy at atomic resolution can be greatly improved if one is able to take advantage of prior knowledge. In this paper we present a reconstruction technique that explicitly takes into account the microscope parameters and the atomic nature of the projected object. This results in a more accurate estimate of the atomic positions and in a good resistance to noise. The reconstruction is a maximum likelihood estimator of the object. Moreover, the limits to the precision have been explored, allowing for a prediction of the amount of expected noise in the reconstruction for a certain experimental setup. We believe that the proposed reconstruction technique can be generalized to other tomographic experiments.

Abstract: In oxide heterostructures, different materials are integrated into a single artificial crystal, resulting in a breaking of inversion symmetry across the heterointerfaces. A notable example is the interface between polar and nonpolar materials, where valence discontinuities lead to otherwise inaccessible charge and spin states. This approach paved the way for the discovery of numerous unconventional properties absent in the bulk constituents. However, control of the geometric structure of the electronic wave functions in correlated oxides remains an open challenge. Here, we create heterostructures consisting of ultrathin SrRuO3, an itinerant ferromagnet hosting momentum-space sources of Berry curvature, and
LaAlO3, a polar wide-band-gap insulator. Transmission electron microscopy reveals an atomically sharp LaO/RuO2/SrO interface configuration, leading to excess charge being pinned near the LaAlO3/SrRuO3 interface. We demonstrate through magneto-optical characterization, theoretical calculations and transport measurements that the real-space charge reconstruction drives a reorganization of the topological charges in the band structure, thereby modifying the momentum-space Berry curvature in SrRuO3. Our results illustrate how the topological and magnetic features of oxides can be manipulated by engineering charge discontinuities at oxide interfaces.

Abstract: Colloidal CsPbX3 (X = Br, Cl, and I) perovskite nanocrystals (NCs) have emerged as promising phosphors and solar cell materials due to their remarkable optoelectronic properties. These properties can be tailored by not only controlling the size and shape of the NCs but also postsynthetic composition tuning through topotactic
anion exchange. In contrast, property control by cation exchange is still underdeveloped for colloidal CsPbX3 NCs. Here, we present a method that allows partial cation exchange in colloidal CsPbBr3 NCs, whereby Pb2+ is exchanged for several isovalent cations, resulting in doped CsPb1−xMxBr3 NCs (M= Sn2+, Cd2+, and Zn2+; 0 < x ≤ 0.1), with preservation of the original NC shape. The size of the parent NCs is also preserved in the product NCs, apart from a small (few
%) contraction of the unit cells upon incorporation of the guest cations. The partial Pb2+ for M2+ exchange leads to a blue-shift of the optical spectra, while maintaining the high photoluminescence quantum yields (>50%), sharp absorption features, and narrow emission of the parent CsPbBr3 NCs. The blue-shift in the optical spectra is attributed to the lattice contraction that accompanies the Pb2+ for M2+ cation exchange and is observed to scale linearly with the lattice contraction. This work opens up new possibilities to engineer the properties of halide perovskite NCs, which to date are demonstrated to be the only known
system where cation and anion exchange reactions can be sequentially combined while preserving the original NC shape, resulting in compositionally diverse perovskite NCs.

Abstract: The three-dimensional (3D) atomic structure of nanomaterials, including strain, is crucial to understand their properties. Here, we investigate lattice strain in Au nanodecahedra using electron tomography. Although different electron tomography techniques enabled 3D characterizations of nanostructures at the atomic level, a reliable determination of lattice strain is not straightforward. We therefore propose a novel model-based approach from which atomic coordinates are measured. Our findings demonstrate the importance of investigating lattice strain in 3D.

Abstract: Oriented attachment of PbSe nanocubes can result in the formation of two-dimensional (2D) superstructures with long-range nanoscale and atomic order. This questions the applicability of classic models in which the superlattice grows by first forming a nucleus, followed by sequential irreversible attachment of nanocrystals, as one misaligned attachment would disrupt the 2D order beyond repair. Here, we demonstrate the formation mechanism of 2D PbSe superstructures with square geometry by using in situ grazing-incidence X-ray scattering (small angle and wide angle), ex situ electron microscopy, and Monte Carlo simulations. We observed nanocrystal adsorption at the liquid/gas interface, followed by the formation of a hexagonal nanocrystal monolayer. The hexagonal geometry transforms gradually through a pseudo-hexagonal phase into a phase with square order, driven by attractive interactions between the {100} planes perpendicular to the liquid substrate, which maximize facet-to-facet overlap. The nanocrystals then attach atomically via a necking process, resulting in 2D square superlattices.

Abstract: In the present paper, the principles of detection theory are used to quantify the probability of error for atom-counting from high resolution scanning transmission electron microscopy (HR STEM) images. Binary and multiple hypothesis testing have been investigated in order to determine the limits to the precision with which the number of atoms in a projected atomic column can be estimated. The probability of error has been calculated when using STEM images, scattering cross-sections or peak intensities as a criterion to count atoms. Based on this analysis, we conclude that scattering cross-sections perform almost equally well as images and perform better than peak intensities. Furthermore, the optimal STEM detector design can be derived for atom-counting using the expression for the probability of error. We show that for very thin objects LAADF is optimal and that for thicker objects the optimal inner detector angle increases.

Abstract: A new version of the open source program MULTEM is presented here. It includes a graphical user interface, tapering truncation of the atomic potential, CPU multithreading functionality, single/double precision calculations, scanning transmission electron microscopy (STEM) simulations using experimental detector sensitivities, imaging STEM (ISTEM) simulations, energy filtered transmission electron microscopy (EFTEM) simulations, STEM electron energy loss spectroscopy (EELS) simulations along with other improvements in the algorithms. We also present a mixed channeling approach for the calculation of inelastic excitations, which allows one to considerably speed up time consuming EFTEM/STEM-EELS calculations.

Abstract: In the present paper, the optimal detector design is investigated for both detecting and locating light atoms from high resolution scanning transmission electron microscopy (HR STEM) images. The principles of detection theory are used to quantify the probability of error for the detection of light atoms from HR STEM images. To determine the optimal experiment design for locating light atoms, use is made of the so-called Cramer-Rao Lower Bound (CRLB). It is investigated if a single optimal design can be found for both the detection and location problem of light atoms. Furthermore, the incoming electron dose is optimised for both research goals and it is shown that picometre range precision is feasible for the estimation of the atom positions when using an appropriate incoming electron dose under the optimal detector settings to detect light atoms.

Abstract: Recently, imaging scanning transmission electron microscopy (ISTEM) has been proposed as a promising new technique combining the advantages of conventional TEM (CTEM) and STEM [1]. The ability to visualize light and heavy elements together makes it a particularly interesting new, spatially incoherent imaging mode. Here, we evaluate this technique in term of precision with which atomic column locations can be measured. By using statistical parameter estimation theory, we will show that these locations can be accurately measured with a precision in the picometer range. Furthermore, a quantitative comparison is made with HAADF STEM imaging to investigate the advantages of ISTEM.

Abstract: Aberration correction in scanning transmission electron microscopy (STEM) has greatly improved the lateral and depth resolution. When using depth sectioning, a technique during which a series of images is recorded at different defocus values, single impurity atoms can be visualised in three dimensions. In this paper, we investigate new possibilities emerging when combining depth sectioning and precise atom-counting in order to reconstruct nanosized particles in three dimensions. Although the depth resolution does not allow one to precisely locate each atom within an atomic column, it will be shown that the depth location of an atomic column as a whole can be measured precisely. In this manner, the morphology of a nanoparticle can be reconstructed in three dimensions. This will be demonstrated using simulations and experimental data of a gold nanorod.

Abstract: Semiconductor heterostructures are used for the fabrication of optoelectronic devices. Performance of such devices is governed by their chemical morphology. The composition distribution of quantum wells and dots is influenced by kinetic growth processes which are not understood completely at present. To obtain more information about these effects, methods for composition determination with a spatial resolution at a near atomic scale are necessary. In this paper we focus on the present state of the composition evaluation by the lattice fringe analysis (CELFA) technique and explain the basic ideas, optimum imaging conditions, precision and accuracy.

Abstract: Nowadays, aberration corrected transmission electron microscopy (TEM) is a popular method to characterise nanomaterials at the atomic scale. Here, atomically resolved images of nanomaterials are acquired, where the contrast depends on the illumination, imaging and detector conditions of the microscope. Visualization of light elements is possible when using low angle annular dark field (LAADF) STEM, annular bright field (ABF) STEM, integrated differential phase contrast (iDPC) STEM, negative spherical aberration imaging (NCSI) and imaging STEM (ISTEM). In this work, images of a NdGaO3-La0.67Sr0.33MnO3 (NGO-LSMO) interface are quantitatively evaluated by using statistical parameter estimation theory. For imaging light elements, all techniques are providing reliable results, while the techniques based on interference contrast, NCSI and ISTEM, are less robust in terms of accuracy for extracting heavy column locations. In term of precision, sample drift and scan distortions mainly limits the STEM based techniques as compared to NCSI. Post processing techniques can, however, partially compensate for this. In order to provide an outlook to the future, simulated images of NGO, in which the unavoidable presence of Poisson noise is taken into account, are used to determine the ultimate precision. In this future counting noise limited scenario, NCSI and ISTEM imaging will provide more precise values as compared to the other techniques, which can be related to the mechanisms behind the image recording.