Search

A tripod molecule incorporating a C60 photocatalyst into a rigid scaffold with disulfide legs was designed and synthesized for the stable and robust attachment of C60 onto an Au-coated atomic force microscope (AFM) tip. The "tripod-C60"was immobilized onto the tip by forming S-Au bonds in the desired orientation and a dispersed manner, rendering it suitable for the oxidation and scission of single molecules on a countersurface, thereby functioning as "molecular shears". A DNA origami with a well-defined structure was chosen as the substrate for the tip-induced oxidation. The gold-coated, C60-functionalized AFM tip was used for both AFM imaging and oxidation of DNA origami upon visible-light irradiation. The localized and temporally controlled oxidative damage of DNA origami was successfully performed at the single-molecule level via singlet-oxygen (1O2) generation from the immobilized C60 on the AFM tip. This oxidative damage to DNA origami can be carried out under ambient conditions in a fluid cell at room temperature, rendering it well-suited for the manipulation of a variety of species on surfaces via a spatially and temporally controlled oxidation reaction triggered by 1O2 locally generated from the immobilized C60 on the AFM tip. ISSN:1936-0851 ISSN:1936-086X

The efficient and bioorthogonal chemical ligation reaction between potassium acyltrifluoroborates (KATs) and hydroxylamines (HAs) was used for the surface functionalization of a self-assembled monolayer (SAM) with biomolecules. An alkane thioether molecule with one terminal KAT group (S-KAT) was synthesized and adsorbed onto a gold surface, placing a KAT group on the top of the monolayer (KAT-SAM). As an initial test case, an aqueous solution of a hydroxylamine (HA) derivative of poly(ethylene glycol) (PEG) (HA-PEG) was added to this KAT-SAM at room temperature to perform the surface KAT ligation. Quartz crystal microbalance with dissipation (QCM-D) monitoring confirmed the rapid attachment of the PEG moiety onto the SAM. By surface characterization methods such as contact angle and ellipsometry, the attachment of PEG layer was confirmed, and covalent amide-bond formation was established by X-ray photoelectron spectroscopy (XPS). In a proof-of-concept study, the applicability of this surface KAT ligation for the attachment of biomolecules to surfaces was tested using a model protein, green fluorescent protein (GFP). A GFP was chemically modified with an HA linker to synthesize HA-GFP and added to the KAT-SAM under aqueous dilute conditions. A rapid attachment of the GFP on the surface was observed in real time by QCM-D. Despite the fact that such biomolecules have a variety of unprotected functional groups within their structures, the surface KAT ligation proceeded rapidly in a chemoselective manner. Our results demonstrate the versatility of the KAT ligation for the covalent attachment of a variety of water-soluble molecules onto SAM surfaces under dilute and biocompatible conditions to form stable, natural amide bonds.

ISO 18516:2019 Surface chemical analysis-Determination of lateral resolution and sharpness in beam-based methods with a range from nanometres to micrometres revises ISO 18516:2006 Surface chemical analysis-Auger electron spectroscopy and X-ray photoelectron spectroscopy-Determination of lateral resolution. It implements three different methods delivering parameters useful to express the lateral resolution: (1) the straight edge method, (2) the narrow line method and (3) the grating method. The theoretical background of these methods is introduced in ISO/TR 19319:2013 Surface chemical analysis-Fundamental approaches to determination of lateral resolution and sharpness in beam-based methods. The revised International Standard ISO 18516 delivers standardized procedures for the determination of the (1) effective lateral resolution by imaging of square-wave gratings, the (2) lateral resolution expressed as the parameter D12-88 characterizing the steepness of the sigmoidal edge spread function (ESF) determined by imaging a straight edge and (3) the lateral resolution expressed as the full width of half maximum of the line spread function (LSF), w(LSF), determined by imaging a narrow line. The last method also delivers information on the shape of the LSF, which characterizes an individual imaging instrument. Finally, the implementation of all three standardized methods in the field of imaging laboratory X-ray photoelectron spectroscopy (XPS) is shortly presented. This part of the letter is based on the use of a new test sample developed at ETH Zurich, Switzerland. This test sample displays a micrometre scaled pattern motivated by the resolving power of recent imaging XPS instruments., Surface and Interface Analysis, 54 (4), ISSN:0142-2421, ISSN:1096-9918

The functional properties of metal oxide semiconductors depend on intrinsic and extrinsic defects. The population of intrinsic defects is strongly affected by the synthesis method and subsequent treatments of the material, while extrinsic defects can originate from suitable doping. Stoichiometric ZrO2 is a nonreducible oxide with a large band gap. Therefore, controlling and modulating its defect profile to induce energy states in the band gap is the sole possibility to make it a photocatalyst responsive to visible light. We report a method, based on low temperature sol−gel synthesis coupled with treatments performed in mild conditions, to obtain undoped visible light-responsive ZrO2−x. The electronic structure of these materials is interpreted in relation to their oxygen vacancy defect population. On the basis of a wide set of experimental measurements (X-ray photoelectron, steady-state and time-resolved photoluminescence, electron paramagnetic resonance, and UV−visible diffuse reflectance spectroscopy) and supported by density functional theory calculations, we demonstrate, for the first time, the predominance of positively charged F-center oxygen vacancies that do not give rise to Zr3+ species.

The efficient and bioorthogonal chemical ligation reaction between potassium acyltrifluoroborates (KATs) and hydroxylamines (HAs) was used for the surface functionalizationof a self-assembled monolayer (SAM) with biomolecules. An alkane thioether molecule with one terminal KAT group (S-KAT) was synthesized and adsorbed onto a gold surface, placing a KATgroup on the top of the monolayer (KAT-SAM). As an initial test case, an aqueous solution of a hydroxylamine (HA) derivative of PEG (HA-PEG) was added to this KAT-SAM at room temperature to perform the surface KAT ligation. Quartz crystal microbalance with dissipation (QCM-D) monitoring confirmed the rapid attachment of the PEG moiety onto the SAM.The covalent conjugation of PEG by amide-bond formation was established by complementary surface characterization methods including contact angle, ellipsometry, and X-ray photoelectron spectroscopy (XPS). To test the applicability of this surface KAT ligation for the attachment of biomolecules to the surfaces, this KAT-SAM was subjected to the reaction with HA derivative of protein. A HA-derivatized green fluorescent protein (HA-GFP) was added in dilute concentrations to the KAT-SAM under aqueous conditions and rapid protein attachment was observed in real-time by QCM. Despite the fact that such biomolecules have a variety of unprotected functional groups within their structures, the surface KAT reaction proceeded efficiently in a selective manner. Our results clearly demonstrate the versatile applicability of the KAT ligation for the covalent attachment of a variety of biomolecules onto surfaces under dilute and biocompatible conditions to form stable, natural amide bonds.

Low-cost and largely available industrial by-products such as calcite (CaCO

Spatially controlled single-molecule oxidation of DNA was performed by photocatalytic generation of singlet oxygen on chemically functionalized AFM tips. A waffle-type DNA origami deposited on a mica surface is site-specifically destroyed by generation of reactive oxygen species at the AFM tip, which was modified with C60-tripod photocatalyst. Upon AFM scanning under photoirradiation, DNA morphology changes, corresponding to oxidative damage were clearly observed at the single-molecule level. The DNA cleavage occurred with strict dependence on photoirradiation and the presence of C60 on the AFM tip.

Nanostructured spinel cobalt ferrite samples having crystallite size ranging between 5.6 and 14.1 nm were characterized by X-ray photoelectron spectroscopy and X-ray induced Auger electron spectroscopy in order to determine the chemical state of the elements, the iron/cobalt ratio and the cation distribution within tetrahedral and octahedral sites. The presence of size-dependent trends in the binding energy of the main photoelectron peaks and in the kinetic energy of the X-ray induced O KLL signal was also investigated. The results showed that iron is present as FeIII and cobalt is present as CoII. The iron/cobalt ratio determined by XPS ranges between 1.8 and 1.9 and it is in very good agreement, within experimental uncertainty, with the expected 2 : 1 ratio. The percentage of Fe in octahedral sites ranges between 62% and 64% for all samples. The kinetic energy of the O KLL signals increases with crystallite size. These results are explained in terms of changes in the ionicity of the metal–oxygen bonds. The results of this investigation highlight how the XPS technique represents a powerful tool to investigate the composition, the chemical state and inversion degree of cobalt spinel ferrites, contributing to the comprehension of their properties.

Small-area/spot photoelectron spectroscopy (SAXPS) is a powerful tool for the investigation of small surface features like microstructures of electronic devices, sensors or other functional surfaces, and so forth. For evaluating the quality of such microstructures, it is often crucial to know whether a small signal in a spectrum is an unwanted contamination of the field of view (FoV), defined by the instrument settings, or it originated from outside. To address this issue, the d80/20 parameter of a line scan across a chemical edge is often used. However, the typical d80/20 parameter does not give information on contributions from the long tails of the X-ray beam intensity distribution or the electron-optical system as defined by apertures. In the VAMAS TWA2 A22 project “Applying planar, patterned, multi-metallic samples to assess the impact of analysis area in surface-chemical analysis,” new test specimen was developed and tested. The here presented testing material consists of a silicon wafer substrate with an Au-film and embedded Cr circular and square spots with decreasing dimensions from 200 μm down to 5 μm. The spot sizes are traceable to the length unit due to size measurements with a metrological SEM. For the evaluation of the FoV, we determined the Au4f intensities measured with the center of the FoV aligned with the center of the spot and normalized to the Au4f intensity determined on the Au-film. With this test specimen, it was possible to characterize, as an example, the FoV of a Kratos AXIS Ultra DLD XPS instrument., Surface and Interface Analysis, 52 (12), ISSN:0142-2421, ISSN:1096-9918

Imaging and small-spot (small area) XPS have become increasingly important components of surface chemical analysis during the last three decades, and its use is growing. Some ambiguity in the use of terminology, understanding of concepts, and lack of appropriate reference materials leads to confusing and not always reproducible data. In this paper, it is shown that by using existing knowledge, appropriate test specimens, and standardized approaches, problems of comparability and such reproducibility issues recently observed for XPS data reported in the scientific literature can be overcome. The standardized methods of ISO 18516:2019, (i) the straight-edge, (ii) the narrow-line, and (iii) the grating method, can be used to characterize and compare the lateral resolution achieved by imaging XPS instruments and are described by reporting examples. The respective measurements are made using new test specimens. When running an XPS instrument in the small-spot (small area) mode for a quantitative analysis of a feature of interest, the question arises as to what contribution to the intensity originates from outside the analysis area. A valid measurement approach to control the intensity from outside the nominal analysis area is also described. As always, the relevant resolution depends on the specific question that needs to be addressed. The strengths and limitations of methods defining resolution are indicated.

This work examines gold thin films of various thicknesses varying from 5 to over 100 nm along a 7 cm distance to investigate the effect on the surface sensitivity of the XPS Au4f signal. Increasing the relative intensity of the surface XPS signal can be useful for studying properties of the surface atoms in case of functionalized gold, and for shedding light on reactions occurring at the interface with the metal surface as well as adsorption geometry. The surface-to-bulk signal ratio increased with decreasing thickness for thicknesses greater than 15 nm. Below this value, the intensity of the surface signal decreased. The binding-energy shift of the surface component with respect to the bulk component was found to be in agreement with that calculated by density functional theory (DFT). The calculated shift was found to be essentially unaffected, whether or not final-state effects were included. KPFM was also performed to investigate correlations between the measured work function and the surface/bulk BE shift, revealing that the contact potential difference changes with thickness because of the influence of the substrate. Gradients were prepared by a novel evaporation method, by template stripping, and by photolithography, yielding stripes of increasing thickness in the same sample.

Micropatterns and nanopatterns of gold embedded in silver and titanium embedded in gold have been prepared by combining either photolithography or electron-beam lithography with a glue-free template-stripping procedure. The obtained patterned surfaces have been topographically characterized using atomic force microscopy and scanning electron microscopy, showing a very low root-mean-square roughness (0.5 nm), high coplanarity between the two metals (maximum height difference ≈ 2 nm), and topographical continuity at the bimetallic interface. Spectroscopic characterization using X-ray photoelectron spectroscopy (XPS), time-of-flight secondary-ion mass spectrometry (ToF-SIMS), and Auger electron spectroscopy (AES) has shown a sharp chemical contrast between the two metals at the interface for titanium patterns embedded in gold, whereas diffusion of silver into gold was observed for gold patterns embedded in silver. Surface flatness combined with a high chemical contrast makes the obtained surfaces suitable for applications involving functionalization with molecules by orthogonal adsorption chemistries or for instrumental calibration. The latter possibility has been tested by determining the image sharpness and the analyzed area on circular patterns of different sizes for each of the spectroscopic techniques applied for characterization.This is the first study in which the analyzed area has been determined using XPS and AES on a flat surface, and the first example of a method for determining the analyzed area using ToF-SIMS.