TY - JOUR A1 - Traulsen, C.H.-H. A1 - Kunz, V. A1 - Heinrich, Thomas A1 - Richter, S. A1 - Holzweber, Markus A1 - Schulz, A. A1 - von Krbek, L.K.S. A1 - Scheuschner, U.T.J. A1 - Poppenberg, J. A1 - Unger, Wolfgang A1 - Schalley, C.A. T1 - Synthesis and coordinative layer-by-layer deposition of pyridine-functionalized gold nanoparticles and tetralactam macrocycles on silicon substrates N2 - Coordination chemistry was applied to deposit pyridine-functionalized gold nanoparticles on silicon substrates. The particles were synthesized through the Brust/Schiffrin route with a subsequent ligand exchange reaction yielding well-defined particles of two different sizes. Multilayer deposition was carried out on a pyridine-terminated SAM, anchored on a hydroxyl-terminated silicon surface. Analogously, Hunter/Vögtle-type tetralactam macrocycle multilayers were deposited as well as mixed layers containing both either in an alternating sequence or as a macrocycle multilayer with a terminating nanoparticle layer. These composite layers were examined with respect to their ability to bind squaraine axles in the macrocycle cavities. The amount of guest bound is higher for the composite layer with alternating macrocycles and nanoparticles. KW - Layer-by-layer deposition KW - Functionalized Au nanoparticles KW - SEM KW - TEM KW - DLS KW - XPS KW - NEXAFS KW - ToF-SIMS KW - IR KW - UV-vis PY - 2013 U6 - https://doi.org/10.1021/la403222x SN - 0743-7463 SN - 1520-5827 VL - 29 IS - 46 SP - 14284 EP - 14292 PB - American Chemical Society CY - Washington, DC AN - OPUS4-29699 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ehlert, Christopher A1 - Holzweber, Markus A1 - Lippitz, Andreas A1 - Unger, Wolfgang A1 - Saalfrank, Peter T1 - A detailed assignment of NEXAFS resonances of imidazolium based ionic liquids N2 - In Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy X-Ray photons are used to excite tightly bound core electrons to low-lying unoccupied orbitals of the system. This technique offers insight into the electronic structure of the system as well as useful structural information. In this work, we apply NEXAFS to two kinds of imidazolium based ionic liquids ([CnC₁im]⁺[NTf₂]⁻ and [C₄C₁im]⁺[I]⁻). A combination of measurements and quantum chemical calculations of C K and N K NEXAFS resonances is presented. The simulations, based on the transition potential density functional theory method (TP-DFT), reproduce all characteristic features observed by the experiment. Furthermore, a detailed assignment of resonance features to excitation centers (carbon or nitrogen atoms) leads to a consistent interpretation of the spectra. KW - Ionic liquids KW - NEXAFS KW - DFT spectrum simulations PY - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-367223 SN - 1463-9076 SN - 1463-9084 VL - 18 IS - 12 SP - 8654 EP - 8661 PB - Royal Society of Chemistry CY - Cambridge, UK AN - OPUS4-36722 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ortel, Erik A1 - Häusler, Ines A1 - Österle, Werner A1 - Narbey, S. A1 - Oswald, F. A1 - Andersen, I. H. A1 - Holzweber, Markus A1 - Unger, Wolfgang A1 - Hodoroaba, Vasile-Dan T1 - In-depth structural and chemical characterization of engineered TiO2 films N2 - Analytical routines for a comprehensive in-depth morphological, structural, and chemical characterization of functionalized TiO2 films by using different state-of-the-art analytical techniques are presented and discussed with the main objective to identify potential reference TiO2 coating parameters able to be certified at a later stage. TiO2 films fabricated by two different synthetic procedures as representative for two main large-scale applications were selected: (i) pulsed d.c. magnetron sputtering for photocatalytic applications and (ii) screen printing from preformed anatase nanoparticles. The screen-printed films were further loaded with a sensitizing dye for application as a dye-sensitized solar cell. Film properties such as microstructure and crystallographic texture of pulsed d.c. magnetron sputtering synthesized films were systematically studied by means of scanning nanobeam electron diffraction in a transmission electron microscope and the surface and inner morphology by scanning electron microscopy. The dye distribution over the depth of screen-printed TiO2 layers was analyzed before and after dye-loading by means of energy dispersive X-ray spectroscopy at scanning electronmicroscope, Auger electron spectroscopy and time-of-flight secondary ion mass spectrometry. The long-term goal of the present study is the improvement of quality of the TiO2 film parameters as measured by using different types of reference TiO2 coatings having specific parameters certified. T2 - 16th European Conference on Applications of Surface and Interface Analysis ECASIA'15 CY - Granada, Spain DA - 28.09.2015 KW - Mapping KW - Line scan KW - Depth profiling KW - TiO2 films KW - Crystallinity KW - Ru dye sensitizer PY - 2016 U6 - https://doi.org/10.1002/sia.5966 SN - 0142-2421 SN - 1096-9918 VL - 48 SP - 664 EP - 669 PB - John Wiley & Sons, Ltd. AN - OPUS4-36791 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sobol, Oded A1 - Holzlechner, Gerald A1 - Holzweber, Markus A1 - Lohninger, H. A1 - Böllinghaus, Thomas A1 - Unger, Wolfgang T1 - First use of data fusion and multivariate analysis of ToF-SIMS and SEM image data for studying deuterium-assisted degradation processes in duplex steels N2 - Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and high-resolution scanning electron microscopy are well-acknowledged tools in materials characterization. The ability to map chemical species on the surface of an investigated sample with often low mass detection limits makes ToF-SIMS an essential tool in fields where many question marks concerning Degradation processes and damage mechanisms exist. The aim of this paper is to describe the power of data fusion of ToF-SIMS and high-resolution scanning electron microscopy results employing computational methods for multivariate data Analysis such as principal component analysis. As a case study the investigation of hydrogen distribution in an artificially charged Duplex stainless steel microstructure is presented aiming on a better understanding of hydrogen embrittlement. T2 - 16th European Conference on Applications of Surface and Interface Analysis CY - Granada, Spain DA - 28.09.2015 KW - ToF-SIMS KW - HR-SEM KW - Data fusion KW - Duplex stainless steel KW - Hydrogen embrittlement PY - 2016 UR - http://onlinelibrary.wiley.com/doi/10.1002/sia.6015/full U6 - https://doi.org/10.1002/sia.6015 VL - 48 IS - 7 SP - 474 EP - 478 PB - John Wiley & Sons, Ltd CY - Surface and Interface Analysis AN - OPUS4-36832 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Holzweber, Markus A1 - Unger, Wolfgang A1 - Hodoroaba, Vasile-Dan T1 - Ionic liquids as a reference material candidate for the quick performance check of energy dispersive X-ray spectrometers for the low energy range below 1 keV N2 - Ionic liquids (ILs) are proposed as simple and efficient test materials to evaluate the performance of energy dispersive X-ray spectrometers (EDS) in the low energy range below 1 keV. By only one measurement, C Kα, N Kα, O Kα, and F Kα X-ray lines can be excited. Additionally, the S Kα line at 2.3 keV and, particularly, the S L series at 149 eV complete the picture with X-ray lines offered by the selected ILs. The well-known (certifiable) elemental composition of the ILs selected in the present study can be used to check the accuracy of results produced with the available EDS quantification routines in the low energy range, simultaneously, for several low atomic number elements. A comparison with other reference materials in use for testing the performance of EDS in the low energy range is included. KW - Ionic liquids KW - EDX KW - CRM KW - Reference material KW - Low energy KW - X-rays PY - 2016 UR - http://pubs.acs.org/doi/abs/10.1021/acs.analchem.6b01444 U6 - https://doi.org/10.1021/acs.analchem.6b01444 SN - 0003-2700 SN - 1520-6882 VL - 88 IS - 14 SP - 6967 EP - 6970 PB - ACS Publications CY - 1155 Sixteenth Street N.W., Washington, DC 20036 AN - OPUS4-36912 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dietrich, Paul A1 - Hennig, Andreas A1 - Holzweber, Markus A1 - Thiele, T. A1 - Borcherding, H. A1 - Lippitz, Andreas A1 - Schedler, U. A1 - Resch-Genger, Ute A1 - Unger, Wolfgang T1 - Surface analytical study of poly(acrylic acid)-grafted microparticles (beads): characterization, chemical derivatization, and quantification of surface carboxyl groups N2 - We report a surface analytical study of poly(methyl methacrylate) (PMMA) microparticles (beads) with a grafted shell of poly(acrylic acid) (PAA) with thicknesses up to 4 nm using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and near-edge X-ray adsorption fine structure (NEXAFS) spectroscopy. These polymer microparticles were analyzed before and after reaction of the surface carboxyl (CO2H) groups with 2,2,2-trifluoroethylamine (TFEA) to gain a better understanding of methods with use of covalently bound probe molecules for surface group analysis. The results obtained with chemical derivatization XPS using TFEA are discussed in terms of surface quantification of reactive CO2H groups on these PAA-coated microparticles. A labeling yield of about 50% was found for TFEA-derivatized particles with amounts of surface-grafted CO2H groups of 99 µmol/g or more, which is consistent with predicted reaction yields for homogeneously dispersed PAA hydrogels. KW - Polymer microparticles KW - Poly(acrylic acid)-grafted microparticles KW - Beads KW - XPS KW - SEM KW - NEXAFS KW - Surface analysis KW - Fluorine labeling PY - 2014 U6 - https://doi.org/10.1021/jp505519g SN - 1932-7447 SN - 1089-5639 VL - 118 IS - 35 SP - 20393 EP - 20404 PB - Soc. CY - Washington, DC AN - OPUS4-31326 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Holzweber, Markus A1 - Heinrich, T. A1 - Kunz, V. A1 - Richter, S. A1 - Traulsen, C.H.-H. A1 - Schalley, C.A. A1 - Unger, Wolfgang T1 - Principal component analysis (PCA)-assisted time-of-flight secondary-ion mass spectrometry (ToF-SIMS): a versatile method for the investigation of self-assembled monolayers and multilayers as precursors for the bottom-up approach of nanoscaled devices N2 - The production of high-quality self-assembled monolayers (SAMs) followed by layer-by-layer (LbL) self-assembly of macrocycles is essential for nanotechnology applications based on functional surface films. To help interpret the large amount of data generated by a standard ToF-SIMS measurement, principal component analysis (PCA) was used. For two examples, the advantages of a combination of ToF-SIMS and PCA for quality control and for the optimization of layer-by-layer self-assembly are shown. The first example investigates how different cleaning methods influence the quality of SAM template formation. The second example focuses on the LbL self-assembly of macrocycles and the corresponding stepwise surface modification. KW - ToF-SIMS KW - Principal component analysis KW - Self assembled monolayer KW - Layer by layer PY - 2014 U6 - https://doi.org/10.1021/ac500059a SN - 0003-2700 SN - 1520-6882 VL - 86 IS - 12 SP - 5740 EP - 5748 PB - American Chemical Society CY - Washington, DC AN - OPUS4-30963 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Holzweber, Markus A1 - Hodoroaba, Vasile-Dan A1 - Unger, Wolfgang T1 - What about ionic liquids as a 'hot' certified reference material candidate to check your EDS below 1 keV? N2 - Energy-dispersive X-ray spectrometry (EDX) is one of the most applied methods used for the analysis of the chemical composition of solids and thin films. Recent progress in EDS (Energy Dispersive X-ray Spectrometer) technology has increased the general performance also in the energy range < 1 keV addressing low Z elements. Suitable test materials to be employed especially to check the low-energy EDS performance – also in line with ISO 15632 - are rather limited and mainly based on C K and F K lines. In order to obtain valid results in laboratories accredited in compliance with ISO/IEC 17025 it is necessary to periodically check the instrument performance. T2 - M&M 2015 - Microscopy & Microanalysis CY - Portland, Oregon, USA DA - 02.08.2015 KW - Reference material KW - EDX KW - Ionic liquids PY - 2015 U6 - https://doi.org/10.1017/S1431927615009356 VL - 21 SP - Suppl. 3, Paper 0856 AN - OPUS4-34211 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Heinrich, Thomas A1 - Traulsen, Christoph Hans-Henning A1 - Holzweber, Markus A1 - Richter, S. A1 - Kunz, V. A1 - Kastner, S.K. A1 - Krabbenborg, S.O. A1 - Huskens, J. A1 - Unger, Wolfgang A1 - Schalley, C.A. T1 - Coupled molecular switching processes in ordered mono- and multilayers of stimulus-responsive rotaxanes on gold surfaces N2 - Interfaces provide the structural basis for function as, for example, encountered in nature in the membrane-embedded photosystem or in technology in solar cells. Synthetic functional multilayers of molecules cooperating in a coupled manner can be fabricated on surfaces through layer-by-layer self-assembly. Ordered arrays of stimulus-responsive rotaxanes undergoing well-controlled axle shuttling are excellent candidates for coupled mechanical motion. Such stimulus-responsive surfaces may help integrate synthetic molecular machines in larger systems exhibiting even macroscopic effects or generating mechanical work from chemical energy through cooperative action. The present work demonstrates the successful deposition of ordered mono- and multilayers of chemically switchable rotaxanes on gold surfaces. Rotaxane mono- and multilayers are shown to reversibly switch in a coupled manner between two ordered states as revealed by linear dichroism effects in angle-resolved NEXAFS spectra. Such a concerted switching process is observed only when the surfaces are well packed, while less densely packed surfaces lacking lateral order do not exhibit such effects. KW - Molecular machine KW - Rotaxane KW - LBL growth KW - XPS KW - NEXAFS KW - SIMS PY - 2015 U6 - https://doi.org/10.1021/ja512654d SN - 0002-7863 SN - 1520-5126 VL - 137 IS - 13 SP - 4382 EP - 4390 PB - American Chemical Society CY - Washington, DC, USA AN - OPUS4-33077 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Holzweber, Markus A1 - Lippitz, Andreas A1 - Krüger, K. A1 - Jankowski, J. A1 - Unger, Wolfgang T1 - Surface characterization of dialyzer polymer membranes by imaging ToF-SIMS and quantitative XPS line scans N2 - The surfaces of polymeric dialyzer membranes consisting of polysulfone and polyvinylpyrrolidone were investigated regarding the lateral distribution and quantitative surface composition using time-of-flight secondary-ion-mass-spectrometry and x-ray photoelectron spectroscopy. Knowledge of the distribution and composition on the outer surface region is of utmost importance for understanding the biocompatibility of such dialyzer membranes. Both flat membranes and hollow fiber membranes were studied. KW - Tof SIMS KW - XPS KW - Dialyzer membrane KW - Surface analysis KW - Polymer PY - 2015 U6 - https://doi.org/10.1116/1.4907937 SN - 1934-8630 SN - 1559-4106 VL - 10 IS - 1 SP - 019011-1 EP - 019011-7 PB - AVS CY - New York, NY, USA AN - OPUS4-32740 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -