A. Rosenauer

Use of a Rapid Cytotoxicity Screening Approach to Engineer a Safer Zinc Oxide Nanoparticle through Iron Doping

The establishment of verifiably safe nanotechnology requires the development of assessment tools to identify hazardous nanomaterial properties that could be modified to improve nanomaterial safety. While there is a lot of debate of what constitutes appropriate safety screening methods, one approach is to use the assessment of cellular injury pathways to collect knowledge about hazardous material properties that could lead to harm to humans and the environment. We demonstrate the use of a multiparameter cytotoxicity assay that evaluates toxic oxidative stress to compare the effects of titanium dioxide (TiO(2)), cerium oxide (CeO(2)), and zinc oxide (ZnO) nanoparticles in bronchial epithelial and macrophage cell lines. The nanoparticles were chosen on the basis of their volume of production and likelihood of spread to the environment. Among the materials, dissolution of ZnO nanoparticles and Zn(2+) release were capable of ROS generation and activation of an integrated cytotoxic pathway that includes intracellular calcium flux, mitochondrial depolarization, and plasma membrane leakage. These responses were chosen on the basis of the compatibility of the fluorescent dyes that contemporaneously assess their response characteristics by a semiautomated epifluorescence procedure. Purposeful reduction of ZnO cytotoxicity was achieved by iron doping, which changed the material matrix to slow Zn(2+) release. In summary, we demonstrate the utility of a rapid throughput, integrated biological oxidative stress response pathway to perform hazard ranking of a small batch of metal oxide nanoparticles, in addition to showing how this assay can be used to improve nanosafety by decreasing ZnO dissolution through Fe doping.

Gain studies of (Cd, Zn)Se quantum islands in a ZnSe matrix

By inserting stacked sheets of nominally 0.7 monolayer CdSe into a ZnSe matrix we create a region with strong resonant excitonic absorption. This leads to an enhancement of the refractive index on the low-energy side of the absorption peak. Efficient waveguiding can thus be achieved without increasing the average refractive index of the active layer with respect to the cladding. Processed high-resolution transmission electron microscopy images show that the CdSe insertions form Cd-rich two-dimensional (Cd, Zn)Se islands with lateral sizes of about 5 nm. The islands act as quantum dots with a three-dimensional confinement for excitons. Zero-phonon gain is observed in the spectral range of excitonic and biexcitonic waveguiding. At high excitation densities excitonic gain is suppressed due to the population of the quantum dots with biexcitons.

Measurement of specimen thickness and composition in Al(x)Ga(1-x)N/GaN using high-angle annular dark field images.

In scanning transmission electron microscopy using a high-angle annular dark field detector, image intensity strongly depends on specimen thickness and composition. In this paper we show that measurement of image intensities relative to the intensity of the incoming electron beam allows direct comparison with simulated image intensities, and thus quantitative measurement of specimen thickness and composition. Simulations were carried out with the frozen lattice and absorptive potential multislice methods. The radial inhomogeneity of the detector was measured and taken into account. Using a focused ion beam (FIB) prepared specimen we first demonstrate that specimen thicknesses obtained in this way are in very good agreement with a direct measurement of the thickness of the lamella by scanning electron microscopy in the FIB. In the second step we apply this method to evaluate the composition of Al(x)Ga(1-x)N/GaN layers. We measured ratios of image intensities obtained in regions with unknown and with known Al-concentration x, respectively. We show that estimation of the specimen thickness combined with evaluation of intensity ratios allows quantitative measurement of the composition x. In high-resolution images we find that the image intensity is well described by simulation if the simulated image is convoluted with a Gaussian with a half-width at half-maximum of 0.07 nm.

Composition mapping in InGaN by scanning transmission electron microscopy

We suggest a method for chemical mapping that is based on scanning transmission electron microscopy (STEM) imaging with a high-angle annular dark field (HAADF) detector. The analysis method uses a comparison of intensity normalized with respect to the incident electron beam with intensity calculated employing the frozen lattice approximation. This procedure is validated with an In(0.07)Ga(0.93)N layer with homogeneous In concentration, where the STEM results were compared with energy filtered imaging, strain state analysis and energy dispersive X-ray analysis. Good agreement was obtained, if the frozen lattice simulations took into account static atomic displacements, caused by the different covalent radii of In and Ga atoms. Using a sample with higher In concentration and series of 32 images taken within 42 min scan time, we did not find any indication for formation of In rich regions due to electron beam irradiation, which is reported in literature to occur for the parallel illumination mode. Image simulation of an In(0.15)Ga(0.85)N layer that was elastically relaxed with empirical Stillinger-Weber potentials did not reveal significant impact of lattice plane bending on STEM images as well as on the evaluated In concentration profiles for specimen thicknesses of 5, 15 and 50 nm. Image simulation of an abrupt interface between GaN and In(0.15)Ga(0.85)N for specimen thicknesses up to 200 nm showed that artificial blurring of interfaces is significantly smaller than expected from a simple geometrical model that is based on the beam convergence only. As an application of the method, we give evidence for the existence of In rich regions in an InGaN layer which shows signatures of quantum dot emission in microphotoluminescence spectroscopy experiments.

Extracting quantitative information from high resolution electron microscopy

Despite the development of high-resolution electron microscopy (HREM) that allows imaging of most materials, the extraction of quantitative information at atomic scale still requires considerable additional efforts. This review presents the recent developments on techniques that can be used to determine the local strain, chemical composition or atomic structure retrieval in HREM. The source of noise in images and effective methods for improving the signal-to-noise ratio in direct or Fourier space are discussed. The artefacts of filtering are commented. In all the methods, the sample thickness has to be determined. A detailed analysis of the thin foil relaxation effect on the measured distortion fields is presented as well as the possibilities of using finite element calculations for its modelling. The local composition measurement based on the chemically sensitive reflections; pattern recognition and the measurement of lattice parameters are described. Examples from semiconductor heterostructures are discussed. The current state of the strategies used for the retrieval of the atomic configuration of defects from HRTEM images is briefly presented. The limits of detection and the accuracy of the methods are summarised; and it is pointed out that electron holography, focal series reconstruction and the coming Cs corrected microscopes will help to obtain this information with better accuracy.

Protein adsorption on colloidal alumina particles functionalized with amino, carboxyl, sulfonate and phosphate groups.

Colloidal oxide particles in biomedical or biotechnological applications immediately become coated with proteins of the biological medium, a process which is strongly influenced by the surface characteristics of the particles. Fundamental correlations between surface characteristics and the, so far mainly uncontrollable, protein adsorption are still not clear. In this study the surface of colloidal alumina particles (d(50)=179 ± 8 nm) was systematically adjusted with NH(2), COOH, SO(3)H and PO(3)H(2) functional groups to investigate the influence on the adsorption of the three model proteins, bovine serum albumin (BSA), lysozyme (LSZ) and trypsin (TRY). The surface functionalization is characterized and discussed in detail with regard to the morphology, isoelectric point, zeta potential, hydrophilic/hydrophobic properties, functional group density and stability. Protein-particle interaction was then assessed by evaluating the amount of protein adsorbed and the zeta potentials of protein-particle conjugates. Protein adsorption was found to be influenced by the type of functional group as well as the expected electrostatic forces under the given experimental conditions. The level of protein adsorption might, hence, be specifically controlled by the type of surface functionalization. Possible adsorption modes of BSA, LSZ and TRY on the particles are suggested by considering the spatial surface potential distribution of the proteins calculated from the protein database file. The particles presented provide an excellent prerequisite for further investigation of fundamental particle-protein interactions and the design of functionally graded materials for biomedical and biotechnological applications, e.g. as drug carriers or for protein purification.

Investigations on the Stranski-Krastanow growth of CdSe quantum dots

We have investigated the growth kinetics of the self-assembled formation of coherently strained CdSe islands. We have found that two distinctly different types of islands are formed in succession. Analyzing the density distribution function of the two dominating size classes of islands, we show that islands of an average diameter of about 16 nm (type B islands) are correlated with a phase transition via a Stranski–Krastanow growth process. The other islands with a diameter of less than 10 nm (type A islands) is formed during the growth of the first 2 ML. At a coverage of about 3.1 ML CdSe stacking faults appear, indicating the beginning of the plastic relaxation of the quantum dot structure.

Investigations of voids in the aragonite platelets of nacre

We studied the structure of the aragonite platelets of Haliotis laevigata nacre, using conventional transmission electron microscopy, Z-contrast, electron tomography, energy-dispersive X-ray analysis and electron energy-loss spectroscopy. We observed faceted voids several nanometers wide within the aragonite platelets. The electron tomography investigations showed that the voids are distributed more or less randomly in the studied specimen and allowed an estimation of the order of magnitude of the width and the volumetric content of the voids. Further investigations of these voids revealed that they contain an increased amount of carbon, which suggests the existence of organic material within the voids.

Composition Fluctuations in InGaN Analyzed by Transmission Electron Microscopy

A series of GaN/InxGa1—xN/GaN quantum well structures was investigated by transmission electron microscopy (TEM) and photoluminescence spectroscopy (PL). The structures were grown by metal organic chemical vapor deposition on Al2O3(0001) substrates varying only the substrate temperature between 800 and 860 °C for the InGaN growth under otherwise unaltered growth conditions. A strong shift of the PL emission wavelength from 390 to 480 nm is observed. Composition analyses were carried out by measuring local lattice parameters, which are directly related to the local In concentration, from high-resolution TEM lattice fringe images. An increase of the average In concentration from 9% to 18% is found as the growth temperature is lowered. A laterally inhomogeneous In concentration is observed in all samples with inclusions of high In content embedded in a quantum well with lower In concentration indicating that phase separation occurs even at a low average In concentration of 9%.

Atomic electric fields revealed by a quantum mechanical approach to electron picodiffraction.

By focusing electrons on probes with a diameter of 50 pm, aberration-corrected scanning transmission electron microscopy (STEM) is currently crossing the border to probing subatomic details. A major challenge is the measurement of atomic electric fields using differential phase contrast (DPC) microscopy, traditionally exploiting the concept of a field-induced shift of diffraction patterns. Here we present a simplified quantum theoretical interpretation of DPC. This enables us to calculate the momentum transferred to the STEM probe from diffracted intensities recorded on a pixel array instead of conventional segmented bright-field detectors. The methodical development yielding atomic electric field, charge and electron density is performed using simulations for binary GaN as an ideal model system. We then present a detailed experimental study of SrTiO3 yielding atomic electric fields, validated by comprehensive simulations. With this interpretation and upgraded instrumentation, STEM is capable of quantifying atomic electric fields and high-contrast imaging of light atoms.