Tungsten Bronze Barium Neodymium Titanate (Ba(6-3n)Nd(8+2n)Ti(18)O(54)): An Intrinsic Nanostructured Material and Its Defect Distribution.

We investigated the structure of the tungsten bronze barium neodymium titanates Ba(6-3n)Nd(8+2n)Ti(18)O(54), which are exploited as microwave dielectric ceramics. They form a complex nanostructure, which resembles a nanofilm with stacking layers of ∼12 Šthickness. The synthesized samples of Ba(6-3n)Nd(8+2n)Ti(18)O(54) (n = 0, 0.3, 0.4, 0.5) are characterized by pentagonal and tetragonal columns, where the A cations are distributed in three symmetrically inequivalent sites. Synchrotron X-ray diffraction and electron energy loss spectroscopy allowed for quantitative analysis of the site occupancy, which determines the defect distribution. This is corroborated by density functional theory calculations. Pentagonal columns are dominated by Ba, and tetragonal columns are dominated by Nd, although specific Nd sites exhibit significant concentrations of Ba. The data indicated significant elongation of the Ba columns in the pentagonal positions and of the Nd columns in tetragonal positions involving a zigzag arrangement of atoms along the b lattice direction. We found that the preferred Ba substitution occurs at Nd[3]/[4] followed by Nd[2] and Nd[1]/[5] sites, which is significantly different to that proposed in earlier studies. Our results on the Ba(6-3n)Nd(8+2n)Ti(18)O(54) "perovskite" superstructure and its defect distribution are particularly valuable in those applications where the optimization of material properties of oxides is imperative; these include not only microwave ceramics but also thermoelectric materials, where the nanostructure and the distribution of the dopants will reduce the thermal conductivity.

Atomic-scale surface roughness of rutile and implications for organic molecule adsorption.

Crystal surfaces provide physical interfaces between the geosphere and biosphere. It follows that the arrangement of atoms at the surfaces of crystals profoundly influences biological components at many levels, from cells through biopolymers to single organic molecules. Many studies have focused on the crystal-molecule interface in water using large, flat single crystals. However, little is known about atomic-scale surface structures of the nanometer- to micrometer-sized crystals of simple metal oxides typically used in batch adsorption experiments under conditions relevant to biogeochemistry and the origins of life. Here, we present atomic-resolution microscopy data with unprecedented detail of the circumferences of nanosized rutile (α-TiO2) crystals previously used in studies of the adsorption of protons, cations, and amino acids. The data suggest that one-third of the {110} faces, the largest faces on individual crystals, consist of steps at the atomic scale. The steps have the orientation to provide undercoordinated Ti atoms of the type and abundance for adsorption of amino acids as inferred from previous surface complexation modeling of batch adsorption data. A remarkably uniform pattern of step proportions emerges: the step proportions are independent of surface roughness and reflect their relative surface energies. Consequently, the external morphology of rutile nanometer- to micrometer-sized crystals imaged at the coarse scale of scanning electron microscope images is not an accurate indicator of the atomic smoothness or of the proportions of the steps present. Overall, our data strongly suggest that amino acids attach at these steps on the {110} surfaces of rutile.

Direct insight into grain boundary reconstruction in polycrystalline Cu(In,Ga)SE2 with atomic resolution.

This work presents results from high-resolution scanning transmission electron microscopy and electron energy-loss spectroscopy on twin boundaries (TBs) and nontwin grain boundaries (GBs) in Cu(In,Ga)Se(2) thin films. It is shown that the atomic reconstruction is different for different symmetries of the grain boundaries. We are able to confirm the model proposed by Persson and Zunger [Phys. Rev. Lett. 91, 266401 (2003)] for Se-Se-terminated Σ3 {112} TBs, showing Cu depletion and In enrichment in the two atomic planes closest to the TB. On the contrary, Cu depletion without In enrichment is detected for a cation-Se-terminated TB. At nontwin GBs, always a strong anticorrelation of Cu and In signals is detected suggesting that the formation of In(Cu) or Cu(In) antisites within a very confined region of smaller than 1 nm is an essential element in the reconstruction of these GBs.

Application of high-resolution EFTEM SI in an AEM.

In this work we show how energy-filtered imaging can be used to obtain spectrum images of electron energy-loss spectrometric data. Focus is placed on improved energy resolution within these data sets. Using two multilayer samples (GaN/AlN and InP/InAs), we demonstrate the advantages of spectrum-imaging and its extended mapping capabilities. Plasmon-ratio maps are used to quickly create high-contrast material maps with high signal-to-noise ratio, ratio-contrast plots are used to gain optimum settings for the ratio maps, and plasmon-position maps are used to map small shifts of the energy position of bulk plasmon peaks.

Automated three-dimensional X-ray analysis using a dual-beam FIB.

We present a fully automated method for three-dimensional (3D) elemental analysis demonstrated using a ceramic sample of chemistry (Ca)MgTiO(x). The specimen is serially sectioned by a focused ion beam (FIB) microscope, and energy-dispersive X-ray spectrometry (EDXS) is used for elemental analysis of each cross-section created. A 3D elemental model is reconstructed from the stack of two-dimensional (2D) data. This work concentrates on issues arising from process automation, the large sample volume of approximately 17 x 17 x 10 microm(3), and the insulating nature of the specimen. A new routine for post-acquisition data correction of different drift effects is demonstrated. Furthermore, it is shown that EDXS data may be erroneous for specimens containing voids, and that back-scattered electron images have to be used to correct for these errors.

EFTEM spectrum imaging at high-energy resolution.

This paper deals with the application of high-energy resolution EFTEM image series and the corrections needed for reliable data interpretation. The detail of spectral information gained from an image series is largely determined by the intrinsic energy resolution. In this work we show that energy resolution values of as low as 0.8 eV in spectra extracted from EFTEM image series can be obtained with a small energy-selecting slit. At this resolution level aberrations of the energy filter, in particular the non-isochromaticity, can no longer be neglected. We show that the four most prominent factors for EFTEM image series data correction--spatial drift, non-isochromaticity, energy drift and image distortion--must not be treated independently but have to be corrected in unison. We present an efficient algorithm for this correction, and demonstrate the applied correction for the case of a GaN/AlN multilayer sample.

Automated spatial drift correction for EFTEM image series.

Energy filtering transmission electron microscopy (EFTEM) is a widely used technique in many areas of scientific research. Image contrast in energy-filtered images arises from specific scattering events such as the ionization of atoms. By combining a set of two or more images, relative sample thickness maps or elemental distribution maps can be easily created. It is also possible to acquire a whole series of energy-filtered images to do more complex data analysis. However, whenever several images are combined to extract certain information, problems are introduced due to sample drift between the exposures. In order to obtain artifact-free information, this spatial drift has to be taken care of. Manual alignment by overlaying and shifting the images to find the best overlap is usually very accurate but extremely time consuming for larger data sets. When large amounts of images are recorded in an EFTEM series, manual correction is no longer a reasonable option. Hence, automatic routines have been developed that are mostly based on the cross-correlation algorithm. Existing routines, however, sometimes fail and again make time consuming manual adjustments necessary. In this paper we describe a new approach to the drift correction problem by incorporating a statistical treatment of the data and we present our statistically determined spatial drift (SDSD) correction program. We show its improved performance by applying it to a typical EFTEM series data block.

Energy-filtering TEM at high magnification: spatial resolution and detection limits.

Energy-filtering TEM (EFTEM) has turned out to be a very efficient and rapid tool for the chemical characterization of a specimen on a nanometer and even subnanometer length scale. Especially, the detection and measurement of very thin layers has become a great application of this technique in many materials science fields, e.g. semiconductors and hard disk technology. There, the reliability of compositional profiles is an important issue. However, the experimentally obtainable spatial resolution strongly influences the appearance of a thin layer in an EFTEM image, when dimensions reach subnanometer levels, which mainly leads to a broadening of the layer in the image. This fact has to be taken into account, when measuring the thickness of such a thin layer. Additionally, the convolution decreases contrast which makes the layer less visible in the image and finally determines the detection limit. In this work we present a systematic study on specifically designed Mn/PdMn multilayer test specimens to explore the practical aspects of spatial resolution and detection limits in EFTEM. Although specific to the ionization edges used, we will present general conclusions about the practical limitations in terms of EFTEM spatial resolution. Additionally, work will be shown about low energy-loss imaging of thin oxide layers, where delocalization is the main factor responsible for broadening.

Cross-section analysis of organic light-emitting diodes.

The 'lift-out' technique using a focused ion beam microscope was applied to prepare cross-sectional specimens of organic light-emitting diodes for use in transmission electron microscopy. The focused ion beam equally thins the organic/inorganic hybrid devices despite the difference in material hardness of the compounds. This allowed to overcome preparation difficulties of conventional techniques such as ion thinning or ultra-microtomy. Two different samples were prepared and studied by both conventional transmission electron microscopy and analytical electron microscopy to display some of the investigation possibilities which become available with this sample preparation method.

Width determination of SiO2-films in Si-based devices using low-loss EFTEM: image contrast as a function of sample thickness.

Energy filtering transmission electron microscopy (EFTEM) has become one of the most efficient tools for specimen characterization at nanometer length scales. EFTEM imaging is most often carried out in the core-loss region but image intensity becomes more and more a limiting factor with decreasing feature size. Alternatively, it is possible to record EFTEM images in the low-loss region, where intensities are essentially higher and where in many cases the images contain material specific contrasts. In this paper we investigate the influence of the important parameters on the material contrast between silicon and silicon dioxide, e.g. specimen thickness, specimen orientation, energy-loss and energy selecting slit width. We show that sample thickness plays an important role and present two methods to calculate material contrast as a function of energy-loss and sample thicknesses. The first method uses spectra taken from both materials at different sample thickness by electron energy-loss spectroscopy, the second calculates contrast directly from a series of energy filtered images. From the results we determine the ideal acquisition parameters for the Si/SiO(2) system and demonstrate imaging at sufficient resolution below 2nm with a test sample of thin SiO(2) layers on Si.

Sample preparation for atomic-resolution STEM at low voltages by FIB.

While FIB sample preparation for transmission electron microscopy is a well established technique, few examples exist of samples of sufficient quality for atomic resolution imaging by aberration corrected (scanning) transmission electron microscopy (STEM). In this work we demonstrate the successful preparation of such samples from five different materials and present the refined lift-out preparation technique, which was applied here. Samples with parallel surfaces and a general thickness between 20 and 40 nm over a range of several µm were repeatedly prepared and analyzed by Cs-corrected STEM at 60 and 100 kV. Here, a novel 'wedge pre-milling' step helps to keep the protective surface layers intact during the whole milling process, allowing features close to or at the sample surface to be analyzed without preparation damage. Another example shows the cross-sectional preparation of a working thin film solar cell device to a final thickness of 10 to 20 nm over µm sized areas in the region of interest, enabling atomic resolution imaging and elemental mapping across general grain boundaries without projection artefacts. All sample preparation has been carried out in modern Dual-Beam FIB microscopes capable of low-kV Ga(+) ion milling, but without additional preparation steps after the FIB lift-out procedure.