Domain Bundle Boundaries in Single Crystal BaTiO3 Lamellae: Searching for Naturally Forming Dipole Flux-Closure/Quadrupole Chains

Naturally occurring boundaries between bundles of 90° stripe domains, which form in BaTiO3 lamellae on cooling through the Curie Temperature, have been characterized using both piezoresponse force microscopy (PFM) and scanning transmission electron microscopy (STEM). Detailed interpretation of the dipole configurations present at these boundaries (using data taken from PFM) shows that in the vast majority of cases they are composed of simple zigzag 180° domain walls. Topological information from STEM shows that occasionally domain bundle boundaries can support chains of dipole flux closure and quadrupole nanostructures, but these kinds of boundaries are comparatively rare; when such chains do exist, it is notable that singularities at the cores of the dipole
structures are avoided. The symmetry of the boundary shows that diads and centers of inversion exist at positions where core singularities should have been expected.

Investigating Hydraulically Active Fractures in A Shallow Meta-Sedimentary Bedrock Aquifer Using Single Well Tracer Testing, Mount Stewart, Northern Ireland

Knowledge of groundwater flow/mass transport, in poorly productive aquifers which underlie over 65% of the island of Ireland, is necessary for effective management of catchment water quality and aquatic ecology. This research focuses on a fractured low-grade Ordovician/Silurian greywacke sequence which underlies approximately 25% of the northern half of Ireland. Knowledge of the unit’s hydrogeological properties remain largely restricted to localised single well open hole “transmissivity” values. Current hydrogeological conceptual models of the Greywacke view the bulk of groundwater flowing through fractures in an otherwise impermeable bedrock mass.
Core analysis permits fracture characterisation, although not all identified fractures may be involved in groundwater flow. Traditional in-situ hydraulic characterisation relies on cumbersome techniques such as packer testing or geophysical borehole logging (e.g. flowmeters). Queen’s University Belfast is currently carrying out hydraulic characterization of 16 boreholes at its Greywacke Hydrogeological Research Site at Mount Stewart, Northern Ireland.
Development of dye dilution methods, using a recently-developed downhole fluorometer, provided a portable, user-friendly, and inexpensive means of detecting hydraulically active intervals in open boreholes. Measurements in a 55m deep hole, three days following fluorescent dye injection, demonstrated the ability of the technique to detect two discrete hydraulically active intervals corresponding to zones identified by caliper and heat-pulse flowmeter logs. High resolution acoustic televiewer logs revealed the zones to correspond to two steeply dipping fractured intervals. Results suggest the rock can have effective porosities of the order of 0.1%.
Study findings demonstrate dye dilution’s utility in characterizing groundwater flow in fractured aquifers. Tests on remaining holes will be completed at different times following injection to identify less permeable fractures and develop an improved understanding of the structural controls on groundwater flow in the uppermost metres of competent bedrock.

First report of the use of a saxitoxin-protein conjugate to develop a DNA aptamer to a small molecule toxin

Saxitoxin (STX) is a low molecular weight neurotoxin mainly produced by certain marine dinoflagellates that, along with its family of similarly related paralytic shellfish toxins, may cause the potentially fatal intoxication known as paralytic shellfish poisoning. Illness and fatality rates are low due to the effective monitoring programs that determine when toxins exceed the established regulatory action level and effectuate shellfish harvesting closures accordingly. Such monitoring programs rely on the ability to rapidly screen large volumes of samples. Many of the screening assays currently available employ antibodies or live animals. This research focused on developing an analytical recognition element that would eliminate the challenges associated with the limited availability of antibodies and the use of animals. Here we report the discovery of a DNA aptamer that targets STX. Concentration-dependent and selective binding of the aptamer to STX was determined using a surface plasmon resonance sensor. Not only does this work represent the first reported aptamer to STX, but also the first aptamer to any marine biotoxin. A novel strategy of using a toxin-protein conjugate for DNA aptamer selection was successfully implemented to overcome the challenges associated with aptamer selection to small molecules. Taking advantage of such an approach could lead to increased diversity and accessibility of aptamers to low molecular weight toxins, which could then be incorporated as analytical recognition elements in diagnostic assays for foodborne toxin detection. The selected STX aptamer sequence is provided here, making it available to any investigator for use in assay development for the detection of STX.

Room-temperature single phase multiferroic magnetoelectrics: Pb(Fe,M)x(Zr,Ti)(1−x)O3 [M=Ta, Nb]

We describe extensive studies on a family of perovskite oxides that are ferroelectric and ferromagnetic at ambient temperatures. The data include x-ray diffraction, Raman spectroscopy, measurements of ferroelectric and magnetic hysteresis, dielectric constants, Curie temperatures, electron microscopy
(both scanning electron microscope and transmission electron microscopy (TEM)) studies, and both longitudinal and transverse magnetoelectric constants a33 and a31. The study extends earlier work to lower Fe, Ta, and Nb concentrations at the B-site (from 15%–20% down to 5%). The magnetoelectric
constants increase supralinearly with Fe concentrations, supporting the earlier conclusions of a key role for Fe spin clustering. The room-temperature orthorhombic C2v point group symmetry inferred from earlier x-ray diffraction studies is confirmed via TEM, and the primitive unit cell size is found to be the basic perovskite Z¼1 structure of BaTiO3, also the sequence of phase transitions with increasing temperature from rhombohedral to orthorhombic to tetragonal to cubic mimics barium titanate.

Fluorescence enhancement and energy transfer in apertureless scanning near-field optical microscopy

We investigate the mechanisms for fluorescence enhancement and energy transfer near a gold tip in apertureless scanning near-field optical microscopy. Using a simple quasi-static model, we show that the observed enhancement of fluorescence results from competition between enhancement and quenching, and is dependent on a range of experimental parameters. We find good qualitative agreement with the results of measurements of the effect of both sharp and blunt tips on quantum dot fluorescence, and provide a demonstration of tip-enhanced fluorescence imaging with 60 nm resolution.

Effect of the surface water layer on the optical signal in apertureless scanning near field optical microscopy

Optical signals measured in apertureless scanning near field optical microscopy (ASNOM) under ambient conditions are found to be affected significantly by the thin water layer absorbed on the surface under investigation, the presence of which is detected through measurements of the shear force experienced by the tip. This water layer also results in a large hysteresis between optical signals measured during approach and withdrawal of the tip to the sample surface. The role of this effect in ASNOM is anticipated to be significant, with the possibility of resultant topographically induced artefacts for ASNOM involving intermittent contact of tip and sample, but also providing a potential mechanism for nanoscale optical resolution.

Tip-enhanced Raman microscopy: practicalities and limitations

The feasibility of apertureless scanning near-field Raman microscopy, exploiting the local enhancement in Raman scattering in the vicinity of a silver or gold tip, was investigated. Using the finite difference time domain method we calculated the enhancement of electric field strength, and hence Raman scattering, achieved through the resonant excitation of local modes in the tip. By modelling the frequency-dependent dielectric response of the metal tip we were able to highlight the resonant nature of the tip-enhancement and determine the excitation wavelength required for the strongest electric field enhancement, and hence Raman scattering intensity, which occurs for the excitation of modes localized at the tip apex. It is demonstrated that a peak Raman enhancement of 10(7)-fold should be achievable with <5 nm spatial resolution. We show that surface-enhanced Raman scattering from carbon contamination on a silver or gold tip can be significant. However, we find for a tip of radius of curvature 20 nm that the Raman enhancement should decay totally within 20 nm from the tip. Hence withdrawal of the tip by this distance should lead to the disappearance of the tip-enhanced signal, leaving only that from carbon contamination on the tip itself and the intrinsic signal from the sample. Copyright (C) 2003 John Wiley Sons, Ltd.

Evaluation of corneal endothelium and keratic precipitates by specular microscopy in anterior uveitis

Background - The study of corneal endothelium, by specular microscopy, in patients with anterior uveitis has largely been restricted to observations on the endothelial cells. In this prospective study 'keratic precipitates' (KP) in different types of uveitis were examined in different stages of the disease process and the endothelial changes occurring in the vicinity of the KP were evaluated in comparison with the endothelium of the uninvolved eye. Methods - 13 patients with active unilateral uveitis were recruited. The mean age was 42.9 years (range 20-76 years). A Tomey-1100 contact wide field specular (x10) microscope was used to capture endothelial images and KP until the resolution of uveitis. Data regarding type of uveitis, number, size, and nature of KP were recorded. Automated morphometric analysis was done for cell size, cell density and coefficient of variation, and statistical comparisons of cell size and cell density were made (Student's t test) between the endothelium in the vicinity of fresh and resolving KP, fresh KP and normal endothelium, and resolving KP and normal endothelium. Results - On specular microscopy, fresh KP were seen as dense, white glistening deposits occupying 5-10 endothelial cells in diameter and fine KP were widely distributed and were one or two endothelial cells in diameter. The KP in Posner-Schlossman syndrome had a distinct and different morphology. With clinical remission of uveitis, the KP were observed to undergo characteristic morphological changes and old KP demonstrated a large, dark halo surrounding a central white deposit and occasionally a dark shadow or a 'lacuna' replaced the site of the original KP. Endothelial blebs were noted as dark shadows or defects in the endothelial mosaic in patients with recurrent uveitis. There was significant statistical difference in the mean cell size and cell density of endothelial cells in the vicinity of fresh KP compared with normal endothelium of the opposite eye. Conclusion - This study elucidated the different specular microscopic features of KP in anterior uveitis. Distinct morphological features of large and fine KP were noted. These features underwent dramatic changes on resolution of uveitis. The endothelium was abnormal in the vicinity of KP, which returned to near normal values on resolution of uveitis.

Strain dependent microstructural modifications of BiCrO3 epitaxial thin films

Strain-dependent microstructural modifications were observed in epitaxial BiCrO3 (BCO) thin films fabricated on single crystalline substrates, utilizing pulsed laser deposition. The following conditions were employed to modify the epitaxial-strain: (i) in-plane tensile strain, BCOSTO [BCO grown on buffered SrTiO3 (001)] and in-plane compressive strain, BCONGO [BCO grown on buffered NdGaO3 (110)] and (ii) varying BCO film thickness. A combination of techniques like X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (TEM) was used to analyse the epitaxial growth quality and the microstructure of BCO. Our studies revealed that in the case of BCOSTO, a coherent interface with homogeneous orthorhombic phase is obtained only for BCO film with thicknesses, d < 50 nm. All the BCOSTO films with d = 50 nm were found to be strain-relaxed with an orthorhombic phase showing 1/2 <100> and 1/4 <101> satellite reflections, the latter oriented at 45° from orthorhombic diffraction spots. High angle annular dark field scanning TEM of these films strongly suggested that the satellite reflections, 1/2 <100> and 1/4 <101>, originate from the atomic stacking sequence changes (or “modulated structure”) as reported for polytypes, without altering the chemical composition. The unaltered stoichiometry was confirmed by estimating both valency of Bi and Cr cations by surface and in-depth XPS analysis as well as the stoichiometric ratio (1 Bi:1 Cr) using scanning TEM–energy dispersive X-ray analysis. In contrast, compressively strained BCONGO films exhibited monoclinic symmetry without any structural modulations or interfacial defects, up to d ~ 200 nm. Our results indicate that both the substrate-induced in-plane epitaxial strain and the BCO film thickness are the crucial parameters to stabilise a homogeneous BCO phase in an epitaxially grown film.

Toward Quantitative Electrochemical Measurements on the Nanoscale by Scanning Probe Microscopy: Environmental and Current Spreading Effects

The application of electric bias across tip–surface junctions in scanning probe microscopy can readily induce surface and bulk electrochemical processes that can be further detected though changes in surface topography, Faradaic or conductive currents, or electromechanical strain responses. However, the basic factors controlling tip-induced electrochemical processes, including the relationship between applied tip bias and the thermodynamics of local processes, remains largely unexplored. Using the model Li-ion reduction reaction on the surface in Li-ion conducting glass ceramic, we explore the factors controlling Li-metal formation and find surprisingly strong effects of atmosphere and back electrode composition on the process. We find that reaction processes are highly dependent on the nature of the counter electrode and environmental conditions. Using a nondepleting Li counter electrode, Li particles could grow significantly larger and faster than a depleting counter electrode. Significant Li ion depletion leads to the inability for further Li reduction. Time studies suggest that Li diffusion replenishes the vacant sites after 12 h. These studies suggest the feasibility of SPM-based quantitative electrochemical studies under proper environmental controls, extending the concepts of ultramicroelectrodes to the single-digit nanometer scale.

High energy resolution fluorescence detection XANES - an in situ method to study the interaction of adsorbed molecules with metal catalysts in the liquid phase

The change in the Pt electronic structure following the adsorption of an a,ß-unsaturated aldehyde and ketone was followed by in situ HERFD-XANES in the liquid phase. The resulting shift in the Pt Fermi energy is in good agreement with the molecule adsorption energy trends calculated by DFT and provides insight into the reaction selectivity.

Switching ferroelectric domain configurations using both electric and magnetic fields in Pb(Zr,Ti)O3–Pb(Fe,Ta)O3 single-crystal lamellae

Thin single-crystal lamellae cut from Pb(Zr,Ti)O3–Pb(Fe,Ta)O3 ceramic samples have been integrated into simple coplanar capacitor devices. The influence of applied electric and magnetic fields on ferroelectric domain configurations has been mapped, using piezoresponse force microscopy. The extent to which magnetic fields alter the ferroelectric domains was found to be strongly history dependent: after switching had been induced by applying electric fields, the susceptibility of the domains to change under a magnetic field (the effective magnetoelectric coupling parameter) was large. Such large, magnetic field-induced changes resulted in a remanent domain state very similar to the remanent state induced by an electric field. Subsequent magnetic field reversal induced more modest ferroelectric switching.

Influence of a Single Grain Boundary on Domain Wall Motion in Ferroelectrics

Epitaxial tetragonal 425 and 611 nm thick Pb(ZrTi)O (PZT) films are deposited by pulsed laser deposition on SrRuO-coated (100) SrTiO 24° tilt angle bicrystal substrates to create a single PZT grain boundary with a well-defined orientation. On either side of the bicrystal boundary, the films show square hysteresis loops and have dielectric permittivities of 456 and 576, with loss tangents of 0.010 and 0.015, respectively. Using piezoresponse force microscopy (PFM), a decrease in the nonlinear piezoelectric response is observed in the vicinity (720-820 nm) of the grain boundary. This region represents the width over which the extrinsic contributions to the piezoelectric response (e.g., those associated with the domain density/configuration and/or the domain wall mobility) are influenced by the presence of the grain boundary. Transmission electron microscope (TEM) images collected near and far from the grain boundary indicate a strong preference for (101)/(1-01) type domain walls at the grain boundary, whereas (011)/(01-1) and (101)/(1-01) are observed away from this region. It is proposed that the elastic strain field at the grain boundary interacts with the ferro-electric/elastic domain structure, stabilizing (101)/(1-01) rather than (011)/(01-1) type domain walls, which inhibits domain wall motion under applied field and decreases non-linearity. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pyroelectric and piezoelectric scanning microscopy applied to reveal the bipolar state of 4-iodo-4 '-nitrobiphenyl (INBP)

Two recent scanning probe techniques were applied to investigate the bipolar twin state of 4-iodo-4'-nitrobiphenyl (INBP) crystals. Solution grown crystals of INBP show typically a morphology which does not express that of a mono-domain polar structure (Fdd2, mm2). From previous X-ray diffraction a twinning volume ratio of similar to 70 : 30 is now explained by two unipolar domains (Flack parameter: 0.075(29)) of opposite orientation of the molecular dipoles, joined by a transition zone showing a width of similar to 140 mm. Scanning pyroelectric microscopy (SPEM) demonstrates a continuous transition of the polarization P from +P into -P across the zone. Application of piezoelectric force microscopy (PFM) confirms unipolar alignment of INBP molecules down to a resolution of similar to 20 nm. A previously proposed real structure for INBP crystals built from lamellae with antiparallel alignment is thus rejected. Anomalous X-ray scattering was used to determine the absolute molecular orientation in the two domains. End faces of the polar axis 2 are thus made up by NO2 groups. Using a previously determined negative pyroelectric coefficient pc leads to a confirmation also by a SPEM analysis. Calculated values for functional group interactions (D...A), (A...A), (D...D) and the stochastic theory of polarity formation allow us to predict that NO2 groups should terminate corresponding faces. Following the present analysis, INBP may represent a first example undergoing dipole reversal upon growth to end up in a bipolar state.

Polarization retention loss in PbTiO3 ferroelectric films due to leakage currents

The relationship between retention loss in single crystal PbTiO3 ferroelectric thin films and leakage currents is demonstrated by piezoresponse and conductive atomic force microscopy measurements. It was found that the polarization reversal in the absence of an electric field followed a stretched exponential behavior 1-exp[-(t/k)(d)] with exponent d>1, which is distinct from a dispersive random walk process with d <. The latter has been observed in polycrystalline films for which retention loss was associated with grain boundaries. The leakage current indicates power law scaling at short length scales, which strongly depends on the applied electric field. Additional information of the microstructure, which contributes to an explanation of the presence of leakage currents, is presented with high resolution transmission electron microscopy analysis.