Abstract: 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 setups that allow bandgaps of high refractive index materials to be determined. Semi-convergence and collection angles in the mu rad 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. (C) 2017 Elsevier B.V. All rights reserved.

Abstract: A technique to measure the band gap of dielectric materials with high refractive index by means of energy electron loss spectroscopy (EELS) is presented. The technique relies on the use of a circular (Bessel) aperture and suppresses Cherenkov losses and surface-guided light modes by enforcing a momentum transfer selection. The technique also strongly suppresses the elastic zero loss peak, making the acquisition, interpretation and signal to noise ratio of low loss spectra considerably better, especially for excitations in the first few eV of the EELS spectrum. Simulations of the low loss inelastic electron scattering probabilities demonstrate the beneficial influence of the Bessel aperture in this setup even for high accelerating voltages. The importance of selecting the optimal experimental convergence and collection angles is highlighted. The effect of the created off-axis acquisition conditions on the selection of the transitions from valence to conduction bands is discussed in detail on a simplified isotropic two band model. This opens the opportunity for deliberately selecting certain transitions by carefully tuning the microscope parameters. The suggested approach is experimentally demonstrated and provides good signal to noise ratio and interpretable band gap signals on reference samples of diamond, GaN and AlN while offering spatial resolution in the nm range. (C) 2018 Elsevier B.V. All rights reserved.

Abstract: HAADF-STEM tomography is a widely used experimental technique for analyzing nanometer-scale crystalline structures of a large variety of materials in three dimensions. Unfortunately, the acquisition of conventional HAADF-STEM tilt series can easily take up one hour or more, depending on the complexity of the experiment. It is therefore far from straightforward to investigate samples that do not withstand long acquisition or to acquire large amounts of tilt series during a single TEM experiment. The latter would lead to the ability to obtain statistically meaningful 3D data, or to perform in situ 3D characterizations with a much shorter time resolution. Various HAADF-STEM acquisition strategies have been proposed to accelerate the tomographic acquisition and reduce the required electron dose. These methods include tilting the holder continuously while acquiring a projection “movie” and a hybrid, incremental, methodology which combines the benefits of the conventional and continuous technique. However, until now an experimental evaluation has been lacking. In this paper, the different acquisition strategies will be experimentally compared in terms of speed, resolution and electron dose. This evaluation will be performed based on experimental tilt series acquired for various metallic nanoparticles with different shapes and sizes. We discuss the data processing involved with the fast HAADF-STEM tilt series and provide a general guideline when which acquisition strategy should be preferentially used.

Abstract: A real-time image reconstruction method for scanning transmission electron microscopy (STEM) is proposed. With an algorithm requiring only the center of mass of the diffraction pattern at one probe position at a time, it is able to update the resulting image each time a new probe position is visited without storing any intermediate diffraction patterns. The results show clear features at high spatial frequency, such as atomic column positions. It is also demonstrated that some common post-processing methods, such as band-pass filtering, can be directly integrated in the real-time processing flow. Compared with other reconstruction methods, the proposed method produces high-quality reconstructions with good noise robustness at extremely low memory and computational requirements. An efficient, interactive open source implementation of the concept is further presented, which is compatible with frame-based, as well as event-based camera/file types. This method provides the attractive feature of immediate feedback that microscope operators have become used to, for example, conventional high-angle annular dark field STEM imaging, allowing for rapid decision-making and fine-tuning to obtain the best possible images for beam-sensitive samples at the lowest possible dose.

Abstract: We have studied the transport properties of LaTiO3/SrTiO3 (LTO/STO) heterostructures. In spite of 2D growth observed in reflection high energy electron diffraction, transmission electron microscopy images revealed that the samples tend to amorphize. Still, we observe that the structures are conducting, and some of them exhibit high conductance and/or superconductivity. We established that conductivity arises mainly on the STO side of the interface, and shows all the signs of the two-dimensional electron gas usually observed at interfaces between STO and LTO or LaAlO3, including the presence of two electron bands and tunability with a gate voltage. Analysis of magnetoresistance (MR) and superconductivity indicates the presence of spatial fluctuations of the electronic properties in our samples. That can explain the observed quasilinear out-of-plane MR, as well as various features of the in-plane MR and the observed superconductivity.

Abstract: Recently, topotactic fluorination has become an alternative way of doping epitaxial perovskite oxides through anion substitution to engineer their electronic properties instead of the more commonly used cation substitution. In this work, epitaxial oxyfluoride SrMnO2.5−δ F γ films were synthesized via topotactic fluorination of SrMnO2.5 films using polytetrafluoroethylene as the fluorine source. Oxidized SrMnO3 films were also prepared for comparison with the fluorinated samples. The F content, probed by x-ray photoemission spectroscopy, was systematically controlled by adjusting fluorination conditions. Electronic transport measurements reveal that increased F content (up to γ  =  0.14) systematically increases the electrical resistivity, despite the nominal electron-doping induced by F substitution for O in these films. In contrast, oxidized SrMnO3 exhibits a decreased resistivity and conduction activation energy. A blue-shift of optical absorption features occurs with increasing F content. Density functional theory calculations indicate that F acts as a scattering center for electronic transport, controls the observed weak ferromagnetic behavior of the films, and reduces the inter-band optical transitions in the manganite films. These results stand in contrast to bulk electron-doped La1−x Ce x MnO3, illustrating how aliovalent anionic substitutions can yield physical behavior distinct from A-site substituted perovskites with the same nominal B-site oxidation states.

Abstract: In this work, Yttria-stabilized zirconia (YSZ) thin films were deposited using dual reactive magnetron sputtering. By varying the deposition conditions, the film morphology and texture of the thin films are tuned and biaxial alignment is obtained. Studying the crystallographic and microstructural properties of the YSZ thin films, a tilted columnar growth was identified. This tilt is shown to be dependent on the compositional gradient of the sample. The variation of composition within a single YSZ column measured via STEM-EDX is demonstrated to be equal to the macroscopic variation on a full YSZ sample when deposited under the same deposition parameters. A simple stress model was developed to predict the tilt of the growing columns. The results indicate that this model not only determines the column bending of the growing film but also confirms that a macroscopic approach is sufficient to determine the compositional gradient in a single column of the YSZ thin films. (C) 2013 Elsevier B.V. All rights reserved.

Abstract: As electron energy-loss spectroscopy (EELS) and x-ray absorption spectroscopy (XAS) probe the same transitions from coreshell states to unoccupied states above the Fermi energy, it should always be possible to apply the two techniques to the same physical phenomena, such as magnetic dichroism, and obtain the same information. Indeed, the similarity in the expression of the electron and x-ray cross-sections had been already exploited to prove the equivalence of x-ray magnetic linear dichroism and anisotropy in EELS, by noting that the polarization vector of a photon plays the same role as the momentum transfer in electron scattering. Recently, the same was proven true for x-ray magnetic circular dichroism (XMCD) by establishing a new TEM technique called EMCD (electron energy-loss magnetic chiral dichroism) (Schattschneider P et al 2006 Nature 441 4868), which makes use of special electron scattering conditions to force the absorption of a circularly polarized virtual photon. The intrinsic advantage of EMCD over XMCD is the high spatial resolution of electron microscopes, which are readily available. Among the particular obstacles in EMCD that do not exist for synchrotron radiation, is the notoriously low signal and the very particular scattering conditions necessary to observe a chiral dichroic signal. In spite of that, impressive progress has been made in recent years. The signal strength could be considerably increased, and some innovations such as using a convergent beam have been introduced. EMCD has evolved into several techniques, which make full use of the versatility of the TEM and energy filtering, spectroscopy or STEM conditions (Rubino S 2007 Magnetic circular dichroism in the transmission electron microscope PhD Thesis Vienna University of Technology, Vienna, Austria).

Abstract: The early growth stages of chemical vapor deposition (CVD) diamond on a solgel TiO2 film with buried ultra dispersed diamond seeds (UDD) have been studied. In order to investigate the diamond growth mechanism and understand the role of the TiO2 layer in the growth process, high resolution transmission electron microscopy (HRTEM), energy-filtered TEM and electron energy loss spectroscopy (EELS) techniques were applied to cross sectional diamond film samples. We find evidence for the formation of TiC crystallites inside the TiO2 layer at different diamond growth stages. However, there is no evidence that diamond nucleation starts from these crystallites. Carbon diffusion into the TiO2 layer and the chemical bonding state of carbon (sp2/sp3) were both extensively investigated. We provide evidence that carbon diffuses through the TiO2 layer and that the diamond seeds partially convert to amorphous carbon during growth. This carbon diffusion and diamond to amorphous carbon conversion make the seed areas below the TiO2 layer grow and bend the TiO2 layer upwards to form the nucleation center of the diamond film. In some of the protuberances a core of diamond seed remains, covered by amorphous carbon. It is however unlikely that the remaining seeds are still active during the growth process.

Abstract: This work presents a morphological and structural analysis of CVD diamond growth on silicon from nanodiamond seeds covered by a 50 nm thick chromium layer. The role of carbon diffusion as well as chromium and carbon silicide formation is analyzed. The local diamond environment is investigated by scanning transmission electron microscopy in combination with electron energy-loss spectroscopy. The evolution of the diamond phase composition (sp3/sp2) is evaluated by micro-Raman spectroscopy. Raman and X-ray diffraction analysis are used to identify the interfacial phases formed during CVD growth. Based upon the observed morphological and structural evolution, a diamond growth model from nanodiamond seeds buried beneath a thin Cr layer is proposed.

Abstract: Moiré fringes are used throughout a wide variety of applications in physics and
engineering to bring out small variations in an underlying lattice by comparing with another reference lattice. This method was recently demonstrated in Scanning Transmission Electron Microscopy imaging to provide local strain measurement in crystals by comparing the crystal lattice with the scanning raster that then serves as the reference. The images obtained in this way contain a beating fringe pattern with a local period that represents the deviation of the lattice from the reference. In order to obtain the actual strain value, a region containing a full period of the fringe is required, which results in a compromise between strain sensitivity and spatial resolution. In this paper we propose an advanced setup making use of an optimised scanning pattern and a novel phase stepping demodulation scheme. We demonstrate the novel method on a series of 16 nm Si-Ge semiconductor FinFET devices in which strain plays a crucial role in modulating the charge carrier mobility. The obtained results are compared with both Nano-beam diffraction and the recently proposed Bessel beam diffraction technique. The setup provides a much improved spatial resolution over conventional moiré imaging in STEM while at the same time being fast and requiring no specialised diffraction camera as opposed to the diffraction techniques we compare to.

Abstract: In this paper convexity constraints are derived for a background model of electron energy loss spectra (EELS) that is linear in the fitting parameters. The model outperforms a power-law both on experimental and simulated backgrounds, especially for wide energy ranges, and thus improves elemental quantification results. Owing to the model’s linearity, the constraints can be imposed through fitting by quadratic programming. This has important advantages over conventional nonlinear power-law fitting such as high speed and a guaranteed unique solution without need for initial parameters. As such, the need for user input is significantly reduced, which is essential for unsupervised treatment of large datasets. This is demonstrated on a demanding spectrum image of a semiconductor device sample with a high number of elements over a wide energy range.

Abstract: In electron microscopy, the maximum a posteriori (MAP) probability rule has been introduced as a tool to determine the most probable atomic structure from high-resolution annular dark-field (ADF) scanning transmission electron microscopy (STEM) images exhibiting low contrast-to-noise ratio (CNR). Besides ADF imaging, STEM can also be applied in the annular bright-field (ABF) regime. The ABF STEM mode allows to directly visualize light-element atomic columns in the presence of heavy columns. Typically, light-element nanomaterials are sensitive to the electron beam, limiting the incoming electron dose in order to avoid beam damage and leading to images exhibiting low CNR. Therefore, it is of interest to apply the MAP probability rule not only to ADF STEM images, but to ABF STEM images as well. In this work, the methodology of the MAP rule, which combines statistical parameter estimation theory and model-order selection, is extended to be applied to simultaneously acquired ABF and ADF STEM images. For this, an extension of the commonly used parametric models in STEM is proposed. Hereby, the effect of specimen tilt has been taken into account, since small tilts from the crystal zone axis affect, especially, ABF STEM intensities. Using simulations as well as experimental data, it is shown that the proposed methodology can be successfully used to detect light elements in the presence of heavy elements.

Abstract: A new perovskite based compound Pb2Mn2O5 has been synthesized using a high pressure high temperature technique. The structure model of Pb2Mn2O5 is proposed based on electron diffraction, high angle annular dark field scanning transmission electron microscopy and high resolution transmission electron microscopy. The compound crystallizes in an orthorhombic unit cell with parameters a=5.736(1)Å≈√2a p p p (a p the parameter of the perovskite subcell) and space group Pnma. The Pb2Mn2O5 structure consists of quasi two-dimensional perovskite blocks separated by 1/2[110] p (1̄01) p crystallographic shear planes. The blocks are connected to each other by chains of edge-sharing MnO5 distorted tetragonal pyramids. The chains of MnO5 pyramids and the MnO6 octahedra of the perovskite blocks delimit six-sided tunnels accommodating double chains of Pb atoms. The tunnels and pyramidal chains adopt two mirror-related configurations (left L and right R) and layers consisting of chains and tunnels of the same configuration alternate in the structure according to an -LRLR-sequence. The sequence is sometimes locally violated by the appearance of -LL- or -RR-fragments. A scheme is proposed with a JahnTeller distortion of the MnO6 octahedra with two long and two short bonds lying in the ac plane, along two perpendicular orientations within this plane, forming a d-type pattern.

Abstract: A new layered perovskite Sr2Al0.78Mn1.22O5.2 has been synthesized by solid state reaction in a sealed evacuated silica tube. The crystal structure has been determined using electron diffraction, high-resolution electron microscopy, and high-angle annular dark field imaging and refined from X-ray powder diffraction data (space group P4/mmm, a=3.89023(5) Å, c=7.8034(1) Å, RI=0.023, RP=0.015). The structure is characterized by an alternation of MnO2 and (Al0.78Mn0.22)O1.2 layers. Oxygen atoms and vacancies, as well as the Al and Mn atoms in the (Al0.78Mn0.22)O1.2 layers are disordered. The local atomic arrangement in these layers is suggested to consist of short fragments of brownmillerite-type tetrahedral chains of corner-sharing AlO4 tetrahedra interrupted by MnO6 octahedra, at which the chain fragments rotate over 90°. This results in an averaged tetragonal symmetry. This is confirmed by the valence state of Mn measured by EELS. The relationship between the Sr2Al0.78Mn1.22O5.2 tetragonal perovskite and the parent Sr2Al1.07Mn0.93O5 brownmillerite is discussed. Magnetic susceptibility measurements indicate spin glass behavior of Sr2Al0.78Mn1.22O5.2. The lack of long-range magnetic ordering contrasts with Mn-containing brownmillerites and is likely caused by the frustration of interlayer interactions due to presence of the Mn atoms in the (Al0.78Mn0.22)O1.2 layers.