Origin of Polarization in Bismuth Sodium Titanate-Based Ceramics.

The classical view of the structural changes that occur at the ferroelectric transition in perovskite-structured systems, such as BaTiO3, is that polarization occurs due to the off-center displacement of the B-site cations. Here, we show that in the bismuth sodium titanate (BNT)-based composition 0.2(Ba0.4Sr0.6TiO3)-0.8(Bi0.5Na0.5TiO3), this model does not accurately describe the structural situation. Such BNT-based systems are of interest as lead-free alternatives to currently used materials in a variety of piezo-/ferroelectric applications. A combination of high-resolution powder neutron diffraction, impedance spectroscopy, and ab initio calculations reveals that Ti4+ contributes less than a third in magnitude to the overall polarization and that the displacements of the O2- ions and the A-site cations, particularly Bi3+, are very significant. The detailed examination of the ferroelectric transition in this system offers insights applicable to the understanding of such transitions in other ferroelectric perovskites, particularly those containing lone pair elements.

Charge-State-Enhanced Ion Sputtering of Metallic Gold Nanoislands.

Experimental results on the charge-state-dependent sputtering of metallic gold nanoislands are presented. Irradiations with slow highly charged ions of metallic targets were previously considered to show no charge state dependent effects on ion-induced material modification, since these materials possess enough free electrons to dissipate the deposited potential energy before electron-phonon coupling can set in. By reducing the size of the target material down to the nanometer regime and thus enabling a geometric energy confinement, a possibility is demonstrated to erode metallic surfaces by charge state related effects in contrast to regular kinetic sputtering.

Structure and Conductivity in LISICON Analogues within the Li4GeO4-Li2MoO4 System.

New solid electrolytes are crucial for the development of all-solid-state lithium batteries with advantages in safety and energy densities over current liquid electrolyte systems. While some of the best solid-state Li+-ion conductors are based on sulfides, their air sensitivity makes them less commercially attractive, and attention is refocusing on air-stable oxide-based systems. Among these, the LISICON-structured systems, such as Li2+2xZn1-xGeO4 and Li3+xV1-xGexO4, have been relatively well studied. However, other systems such as the Li4GeO4-Li2MoO4 system, which also show LISICON-type structures, have been relatively little explored. In this work, the Li4-2xGe1-xMoxO4 solid solution is investigated systematically, including the solid solution limit, structural stability, local structure, and the corresponding electrical behavior. It is found that a γ-LISICON structured solution is formed in the range of 0.1 ≤ x < 0.4, differing in structure from the two end members, Li4GeO4 and Li2MoO4. With increasing Mo content, the ß-phase becomes increasingly more stable than the γ-phase, and at x = 0.5, a pure ß-phase (ß-Li3Ge0.5Mo0.5O4) is readily isolated. The structure of this previously unknown compound is presented, along with details of the defect structure of Li3.6Ge0.8Mo0.2O4 (x = 0.2) based on neutron diffraction data. Two basic types of defects are identified in Li3.6Ge0.8Mo0.2O4 involving interstitial Li+-ions in octahedral sites, with evidence for these coming together to form larger defect clusters. The x = 0.2 composition shows the highest conductivity of the series, with values of 1.11 × 10-7 S cm-1 at room temperature rising to 5.02 × 10-3 S cm-1 at 250 °C.

Defect-Assisted Hard-X-Ray Microscopy with Capillary Optics.

Polycapillary x-ray focusing devices are built from hundreds of thousands of bent microcapillaries that are stacked into hexagonal arrays. We show that intrinsic point defects of the optics (e.g., missing or larger capillaries) lead to the formation of multiple x-ray images of an object positioned in the focal plane. These images can be recorded in parallel, and can provide spatial resolution that is limited by the defect size and not by the focal spot size. In a proof-of-principle experiment, we demonstrate submicron resolution, which has not yet been achieved with polycapillary focusing optics. Tailored optics with a controlled distribution of "defects" could be used for multimodal nanoscale x-ray imaging with laboratory setups.

Protocol of single cells preparation for time of flight secondary ion mass spectrometry.

There are several techniques like time of flight secondary ion mass spectrometry (ToF SIMS) that require a special protocol for preparation of biological samples, in particular, those containing single cells due to high vacuum conditions that must be kept during the experiment. Frequently, preparation methodology involves liquid nitrogen freezing what is not always convenient. In our studies, we propose and validate a protocol for preparation of single cells. It consists of four steps: (i) paraformaldehyde fixation, (ii) salt removal, (iii) dehydrating, and (iv) sample drying under ambient conditions. The protocol was applied to samples with single melanoma cells i.e. WM115 and WM266-4 characterized by similar morphology. The surface and internal structures of cells were monitored using atomic force, scanning electron and fluorescent microscopes, used to follow any potential protocol-induced alterations. To validate the proposed methodology for sample preparation, ToF SIMS experiments were carried out using C60(+) cluster ion beam. The applied principal component analysis (PCA) revealed that chemical changes on cell surface of melanoma cells were large enough to differentiate between primary and secondary tumor sites. Subject category: Mass spectrometry.

Island shape anisotropy in organic thin film growth induced by ion-beam irradiated rippled surfaces.

Controlling thin film growth of conjugated molecules is a key factor in organic electronics. Here, we report on the growth of the organic semiconductor para-hexaphenyl (6P) on ion bombarded, rippled TiO2(110) surfaces. These surfaces represent a one-dimensionally patterned substrate with alternating descending and ascending step trains with typical step distances below 1 nm. A clear island shape anisotropy and a discretization of the island width according to the ripple wavelength have been observed which are addressed to anisotropic detachment of molecules differently bound to the island rim at ascending and descending steps. By changing the average ripple length from ∼11 nm to ∼60 nm, the islands' length-to-width ratio could be tuned between ∼1.5 : 1 and ∼4.5 : 1. Further, strong diffusion anisotropy along and perpendicular to the ripples was found to be responsible for an increasing island density with decreasing ripple length.

Density functional theory study of Au-fcc/Ge and Au-hcp/Ge interfaces.

In recent years, nanostructures with hexagonal polytypes of gold have been synthesised, opening new possibilities in nanoscience and nanotechnology. As bulk gold crystallizes in the fcc phase, surface effects can play an important role in stabilizing hexagonal gold nanostructures. Here, we investigate several heterostructures with Ge substrates, including the fcc and hcp phases of gold that have been observed experimentally. We determine and discuss their interfacial energies and optimized atomic arrangements, comparing the theory results with available experimental data. Our DFT calculations for the Au-fcc(011)/Ge(001) junction show how the presence of defects in the interface layer can help to stabilize the atomic pattern, consistent with microscopic images. Although the Au-hcp/Ge interface is characterized by a similar interface energy, it reveals large atomic displacements due to significant mismatch. Finally, analyzing the electronic properties, we demonstrate that Au/Ge systems have metallic character, but covalent-like bonding states between interfacial Ge and Au atoms are also present.

Dendrite Formation on the Poly(methyl methacrylate) Surface Reactively Sputtered with a Cesium Ion Beam.

The development of topography plays an important role when low-energy projectiles are used to modify the surface or analyze the properties of various materials. It can be a feature that allows one to create complex structures on the sputtered surface. It can also be a factor that limits depth resolution in ion-based depth profiling methods. In this work, we have studied the evolution of microdendrites on poly(methyl methacrylate) sputtered with a Cs 1 keV ion beam. Detailed analysis of the topography of the sputtered surface shows a sea of pillars with islands of densely packed pillars, which eventually evolve to fully formed dendrites. The development of the dendrites depends on the Cs fluence and temperature. Analysis of the sputtered surface by physicochemical methods shows that the mechanism responsible for the formation of the observed microstructures is reactive ion sputtering. It originates from the chemical reaction between the target material and primary projectile and is combined with mass transport induced by ion sputtering. The importance of chemical reaction for the formation of the described structures is shown directly by comparing the change in the surface morphology under the same dose of a nonreactive 1 keV xenon ion beam.

Local Structure in α-BIMEVOXes (ME = Ge, Sn).

The BIMEVOXes are among the best oxide ion conductors at low and intermediate temperatures. Their high conductivity is associated with local defect structure. In this work, the local structures of two BIMEVOX compositions, Bi2V0.9Ge0.1O5.45 and Bi2V0.95Sn0.05O5.475, are examined using total neutron and X-ray scattering methods, with both compositions exhibiting the ordered α-phase at 25 °C and the disordered γ-phase at 700 °C. While the diffraction data for the α-phase do not allow for the polar (C2) and nonpolar (C2/m) structures to be readily distinguished, measurements of dielectric permittivity suggest the α-phase is weakly ferroelectric in character, consistent with calculations of spontaneous polarization based on a combination of density functional calculations and machine learning methodology. Reverse Monte Carlo (RMC) analysis of total scattering data reveals Ge preferentially adopts tetrahedral geometry at both temperatures, while Sn is found to predominantly adopt octahedral coordination in the α-phase and tetrahedral coordination in the γ-phase. In all cases, V polyhedra are found to consist of tetrahedral, pentacoordinate, and octahedral geometries, as also predicted by the crystallographic analysis and confirmed by 51V solid state NMR spectroscopy. Although similar long-range structures are observed at room temperature, the oxide ion vacancy distributions were found to be quite different between the two studied compositions, with a nonrandom deficiency in vacancy pairs in the second-nearest shell along the ⟨100⟩ tetragonal direction for BIGEVOX10, compared with a long-distance (>8.0 Å) ordering of equatorial vacancies for BISNVOX05. This is attributed to the differences in the preferred coordination geometries of the substituent cations in the two systems. Impedance spectroscopy measurements reveal both compositions show high conductivity in the order of 10-1 S cm-1 at 600 °C.

Atomic-scale friction on stepped surfaces of ionic crystals.

We report on high-resolution friction force microscopy on a stepped NaCl(001) surface in ultrahigh vacuum. The measurements were performed on single cleavage step edges. When blunt tips are used, friction is found to increase while scanning both up and down a step edge. With atomically sharp tips, friction still increases upwards, but it decreases and even changes sign downwards. Our observations extend previous results obtained without resolving atomic features and are associated with the competition between the Schwöbel barrier and the asymmetric potential well accompanying the step edges.

Automatic microscopic image analysis by moving window local Fourier Transform and Machine Learning.

Analysis of microscope images is a tedious work which requires patience and time, usually done manually by the microscopist after data collection. The results obtained in such a way might be biased by the human who performed the analysis. Here we introduce an approach of automatic image analysis, which is based on locally applied Fourier Transform and Machine Learning methods. In this approach, a whole image is scanned by a local moving window with defined size and the 2D Fourier Transform is calculated for each window. Then, all the Local Fourier Transforms are fed into Machine Learning processing. Firstly, a number of components in the data is estimated from Principal Component Analysis (PCA) Scree Plot performed on the data. Secondly, the data are decomposed blindly by Non-Negative Matrix Factorization (NMF) into interpretable spatial maps (loadings) and corresponding Fourier Transforms (factors). As a result, the microscopic image is analyzed and the features on the image are automatically discovered, based on the local changes in Fourier Transform, without human bias. The user selects only a size and movement of the scanning local window which defines the final analysis resolution. This automatic approach was successfully applied to analysis of various microscopic images with and without local periodicity i.e. atomically resolved High Angle Annular Dark Field (HAADF) Scanning Transmission Electron Microscopy (STEM) image of Au nanoisland of fcc and Au hcp phases, Scanning Tunneling Microscopy (STM) image of Au-induced reconstruction on Ge(001) surface, Scanning Electron Microscopy (SEM) image of metallic nanoclusters grown on GaSb surface, and Fluorescence microscopy image of HeLa cell line of cervical cancer. The proposed approach could be used to automatically analyze the local structure of microscopic images within a time of about a minute for a single image on a modern desktop/notebook computer and it is freely available as a Python analysis notebook and Python program for batch processing.

Mapping the conducting channels formed along extended defects in SrTiO3 by means of scanning near-field optical microscopy.

Mixed ionic-electronic-conducting perovskites such as SrTiO3 are promising materials to be employed in efficient energy conversion or information processing. These materials exhibit a self-doping effect related to the formation of oxygen vacancies and electronic charge carriers upon reduction. It has been found that dislocations play a prominent role in this self-doping process, serving as easy reduction sites, which result in the formation of conducting filaments along the dislocations. While this effect has been investigated in detail with theoretical calculations and direct observations using local-conductivity atomic force microscopy, the present work highlights the optical properties of dislocations in SrTiO3 single crystals. Using the change in optical absorption upon reduction as an indicator, two well-defined arrangements of dislocations, namely a bicrystal boundary and a slip band induced by mechanical deformation, are investigated by means of scanning near-field optical microscopy. In both cases, the regions with enhanced dislocation density can be clearly identified as regions with higher optical absorption. Assisted by ab initio calculations, confirming that the agglomeration of oxygen vacancies significantly change the local dielectric constants of the material, the results provide direct evidence that reduced dislocations can be classified as alien matter embedded in the SrTiO3 matrix.

Kelvin probe force microscopy work function characterization of transition metal oxide crystals under ongoing reduction and oxidation.

Controlling the work function of transition metal oxides is of key importance with regard to future energy production and storage. As the majority of applications involve the use of heterostructures, the most suitable characterization technique is Kelvin probe force microscopy (KPFM), which provides excellent energetic and lateral resolution. In this paper, we demonstrate precise characterization of the work function using the example of artificially formed crystalline titanium monoxide (TiO) nanowires on strontium titanate (SrTiO3) surfaces, providing a sharp atomic interface. The measured value of 3.31(21) eV is the first experimental work function evidence for a cubic TiO phase, where significant variations among the different crystallographic facets were also observed. Despite the remarkable height of the TiO nanowires, KPFM was implemented to achieve a high lateral resolution of 15 nm, which is close to the topographical limit. In this study, we also show the unique possibility of obtaining work function and conductivity maps on the same area by combining noncontact and contact modes of atomic force microscopy (AFM). As most of the real applications require ambient operating conditions, we have additionally checked the impact of air venting on the work function of the TiO/SrTiO3(100) heterostructure, proving that surface reoxidation occurs and results in a work function increase of 0.9 eV and 0.6 eV for SrTiO3 and TiO, respectively. Additionally, the influence of adsorbed surface species was estimated to contribute 0.4 eV and 0.2 eV to the work function of both structures. The presented method employing KPFM and local conductivity AFM for the characterization of the work function of transition metal oxides may help in understanding the impact of reduction and oxidation on electronic properties, which is of high importance in the development of effective sensing and catalytic devices.

Current channeling along extended defects during electroreduction of SrTiO3.

Electroreduction experiments on metal oxides are well established for investigating the nature of the material change in memresistive devices, whose basic working principle is an electrically-induced reduction. While numerous research studies on this topic have been conducted, the influence of extended defects such as dislocations has not been addressed in detail hitherto. Here, we show by employing thermal microscopy to detect local Joule heating effects in the first stage of electroreduction of SrTiO3 that the current is channelled along extended defects such as dislocations which were introduced mechanically by scratching or sawing. After prolonged degradation, the matrix of the crystal is also electroreduced and the influence of the initially present dislocations diminished. At this stage, a hotspot at the anode develops due to stoichiometry polarisation leading not only to the gliding of existing dislocations, but also to the evolution of new dislocations. Such a formation is caused by electrical and thermal stress showing dislocations may play a significant role in resistive switching effects.

Defect structure in δ-Bi5PbY2O11.5.

A detailed study of the defect structure in a di-substituted δ-Bi2O3 type phase, δ-Bi5PbY2O11.5, is presented. Using a combination of conventional Rietveld analysis of neutron diffraction data, reverse Monte Carlo (RMC) analysis of total neutron scattering data and ab initio molecular dynamics (MD) simulations, both average and local structures have been characterized. δ-Bi5PbY2O11.5 represents a model system for the highly conducting δ-Bi2O3 type phases, in which there is a higher nominal vacancy concentration than in the unsubstituted parent compound. Uniquely, the methodology developed in this study has afforded the opportunity to study both oxide-ion vacancy ordering as well as specific cation-cation interactions. Oxide-ion vacancies in this system have been found to show a preference for association with Pb2+ cations, with some evidence for clustering of these cations. The system shows a non-random distribution of vacancy pair alignments, with a preference for 〈100〉 ordering, the extent of which shows thermal variation. MD simulations indicate a predominance of oxide-ion jumps in the 〈100〉 direction.

"Command" surfaces with thermo-switchable antibacterial activity.

In the presented work "smart" antibacterial surfaces based on silver nanoparticles (AgNPs) embedded in temperature-responsive poly(di(ethylene glycol)methyl ether methacrylate) - (POEGMA188) as well as poly(4-vinylpyridine) - (P4VP) coatings attached to a glass surface were successfully prepared. The composition, thickness, morphology and wettability of the resulting coatings were analyzed using ToF-SIMS, XPS, EDX, ellipsometry, AFM, SEM and CA measurements, respectively. Temperature-switched killing of the bacteria was tested against Escherichia coli ATCC 25922 (representative of Gram-negative bacteria) and Staphylococcus aureus ATCC 25923 (representative of Gram-positive bacteria) at 4 and 37 °C. In general at 4 °C no significant difference was observed between the amounts of bacteria accounted on the grafted brush coatings and within the control sample. In contrast, at 37 °C almost no bacteria were visible for temperature-responsive coating with AgNPs, whereas the growth of bacteria remains not disturbed for "pure" coating, indicating strong temperature-dependent antibacterial properties of AgNPs integrated into brushes.

A bottom-up process of self-formation of highly conductive titanium oxide (TiO) nanowires on reduced SrTiO3.

Reduced titanium oxide structures are regarded as promising materials for various catalytic and optoelectronic applications. There is thus an urgent need for developing methods of controllable formation of crystalline nanostructures with tunable oxygen nonstoichiometry. We introduce the Extremely Low Oxygen Partial Pressure (ELOP) method, employing an oxygen getter in close vicinity to an oxide during thermal reduction under vacuum, as an effective bottom-up method for the production of nanowires arranged in a nanoscale metallic network on a SrTiO3 perovskite surface. We demonstrate that the TiO nanowires crystallize in a highly ordered cubic phase, where single nanowires are aligned along the main crystallographic directions of the SrTiO3 substrate. The dimensions of the nanostructures are easily tunable from single nanometers up to the mesoscopic range by varying the temperature of reduction. The interface between TiO and SrTiO3 (metal and insulator) was found to be atomically sharp providing the unique possibility of the investigation of electronic states, especially since the high conductivity of the TiO nanostructures is maintained after room temperature oxidation. According to the growth model we propose, TiO nanowire formation is possible due to the incongruent sublimation of strontium and crystallographic shearing, triggered by the extremely low oxygen partial pressure (ELOP). The controlled formation of conductive nanowires on a perovskite surface holds technological potential for implementation in memristive devices, organic electronics, or for catalytic applications, and provides insight into the mechanism of nanoscale phase transformations in metal oxides. We believe that the ELOP mechanism of suboxide formation is suitable for the formation of reduced suboxides on other perovskite oxides and for the broader class of transition metal oxides.

Urinary Extracellular Vesicles: Potential Biomarkers of Renal Function in Diabetic Patients.

The aim of this study was to check the relationship between the density of urinary EVs, their size distribution, and the progress of early renal damage in type 2 diabetic patients (DMt2). Patients were enrolled to this study, and glycated hemoglobin (HbA1c) below 7% was a threshold for properly controlled diabetic patients (CD) and poorly controlled diabetic patients (UD). Patients were further divided into two groups: diabetic patients without renal failure (NRF) and with renal failure (RF) according to the Glomerular Filtration Rate. Density and diameter of EVs were determined by Tunable Resistive Pulse Sensing. Additionally, EVs were visualized by means of Transmission and Environmental Scanning Electron Microscopy. Nano-liquid chromatography coupled offline with mass spectrometry (MALDI-TOF-MS/MS) was applied for proteomic analysis. RF had reduced density of EVs compared to NRF. The size distribution study showed that CD had larger EVs (mode) than UD (115 versus 109 nm; p < 0.05); nevertheless the mean EVs diameter was smaller in controls than in the CD group (123 versus 134 nm; p < 0.05). It was demonstrated that EVs are abundant in urine. Albumin, uromodulin, and number of unique proteins related to cell stress and secretion were detected in the EVs fraction. Density and size of urinary EVs reflect deteriorated renal function and can be considered as potential renal damage biomarkers.

Synthesis of new metastable nanoalloys of immiscible metals with a pulse laser technique.

The generation of nanoalloys of immiscible metals is still a challenge using conventional methods. However, because these materials are currently attracting much attention, alternative methods are needed. In this article, we demonstrate a simple but powerful strategy for the generation of a new metastable alloy of immiscible metals. Au(1-x)Ni(x) 3D structures with 56 at% of nickel in gold were successfully manufactured by the pulsed laser irradiation of colloidal nanoparticles. This technology can be used for preparing different metastable alloys of immiscible metals. We hypothesise that this technique leads to the formation of alloy particles through the agglomerations of nanoparticles, very fast heating, and fast cooling/solidification. Thus, we expect that our approach will be applicable to a wide range of inorganic solids, yielding even new metastable solids that fail to be stable in the bulk systems, and therefore do not exist in Nature.

Probing the electronic transport on the reconstructed Au/Ge(001) surface.

By using scanning tunnelling potentiometry we characterized the lateral variation of the electrochemical potential µec on the gold-induced Ge(001)-c(8 × 2)-Au surface reconstruction while a lateral current flows through the sample. On the reconstruction and across domain boundaries we find that µec shows a constant gradient as a function of the position between the contacts. In addition, nanoscale Au clusters on the surface do not show an electronic coupling to the gold-induced surface reconstruction. In combination with high resolution scanning electron microscopy and transmission electron microscopy, we conclude that an additional transport channel buried about 2 nm underneath the surface represents a major transport channel for electrons.