Inorganic species of arsenic in soil solution determined by microcartridges and ferrihydrite-based diffusive gradient in thin films

The bioavailability of soil arsenic (As) is determined by its speciation in soil solution, i.e., arsenite [As(III)] or arsenate [As(V)]. Soil bioavailability studies require suitable methods to cope with small volumes of soil solution that can be speciated directly after sampling, and thereby minimise any As speciation change during sample collection. In this study, we tested a self-made microcartridge to separate both As species and compared it to a commercially available cartridge. In addition, the diffusive gradient in thin films technique (DGT), in combination with the microcartridges, was applied to synthetic solutions and to a soil spiked with As. This combination was used to improve the assessment of available inorganic As species with ferrihydrite(FH)-DGT, in order to validate the technique for environmental analysis, mainly in soils. The self-made microcartridge was effective in separating As(III) from As(V) in solution with detection by inductively coupled plasma optical emission spectrometry (ICP-OES) in volumes of only 3 ml. The DGT study also showed that the FH-based binding gels are effective for As(III) and As(V) assessment, in solutions with As and P concentrations and ionic strength commonly found in soils. The FH-DGT was tested on flooded and unflooded As spiked soils and recoveries of As(III) and As(V) were 85–104% of the total dissolved As. This study shows that the DGT with FH-based binding gel is robust for assessing inorganic species of As in soils.

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.

Nanoscale mapping of oxygen vacancy kinetics in nanocrystalline Samarium doped ceria thin films

The position-dependent oxygen vacancy dynamics induced by a biased scanning probe microscopy tip in Samarium doped ceria thin films grown on MgO (100) substrates is investigated. The granularity of the samples gives rise to spatially dependent local electrochemical activity, as explored by electrochemical strain microscopy. The kinetics of the oxygen vacancy relaxation process is investigated separately for grain boundaries and grains. Higher oxygen vacancy concentration variation and slower diffusion are observed in the grain boundary regions as compared to the grains.

Epitaxial ferroelectric Pb(Mg1/3Nb2/3)O3-PbTiO3 thin films on La0.7Sr0.3MnO3 bottom electrode

Epitaxial (001)-oriented 0.7Pb(Mg_0.33Nb_0.67)O₃-0.3PbTiO₃ (PMN-PT) thin films were deposited by pulsed laser deposition on vicinal SrTiO₃ (001) substrates using La_0.7Sr_0.3MnO₃ as bottom electrode. Detailed microstructural investigations of these films were carried out using X-ray diffraction (XRD), atomic force microscopy (AFM) and transmission electron microscopy (TEM). Polarization-field hysteresis curves were measured at room temperature. Spontaneous polarization P s , remnant polarization P r and coercive voltage V c were found to be 25 μC/cm², 15 μC/cm² and 0.81 V, respectively. Field dependent dielectric constant measurements exhibited butterfly shaped curves, indicating the true ferroelectric nature of these films at room temperature. The dielectric constant and the dielectric loss at 100 kHz were found to be 238 and 0.14, respectively. The local piezoelectric properties of PMN-PT films were investigated by piezoelectric force microscopy and were found to exhibit a local piezoelectric coefficient of 7.8 pm/V.

Ferroelectric nanostructures fabricated by focused-ion-beam milling in epitaxial BiFeO3 thin films

We studied a suitable route to fabricate ferroelectric islands by focused-ion-beam milling in bismuth ferrite epitaxial thin films. Piezoresponse force microscopy shows that the damage induced by the milling process is extended to 1 mu m away from the edge of the focused-ion-beam patterned islands. After a combined vacuum and oxygen atmosphere annealing procedure, ferroelectricity is fully recovered in structures with sizes down to 500 nm, while for 250 nm islands the defects at the interfaces induce polarization direction pinning.

Piezoelectric properties of PbTiO(3) thin films characterized with piezoresponse force and high resolution transmission electron microscopy

In this paper we investigate the piezoelectric properties of PbTiO(3) thin films grown by pulsed laser deposition with piezoresponse force microscopy and transmission electron microscopy. The as-grown films exhibit an upward polarization, inhomogeneous distribution of piezoelectric characteristics concerning local coercive fields, and piezoelectric coefficient. In fact, the data obtained reveal imprints during piezoresponse force microscopy measurements, nonlinearity in the piezoelectric deformation, and limited polarization reversal. Moreover, transmission electron microscopy shows the presence of defects near the film/substrate interface, which can be associated with the variations of piezoelectric properties.

Monodomain strained ferroelectric PbTiO(3) thin films: Phase transition and critical thickness study

This work demonstrates that instead of paraelectric PbTiO(3), completely c-oriented ferroelectric PbTiO(3) thin films were directly grown on (001)-SrTiO(3) substrates by pulsed-laser deposition with thickness up to 340 nm at a temperature well above the Curie temperature of bulk PbTiO(3). The influence of laser-pulse frequency, substrate-surface termination on growth, and functional properties were studied using x-ray diffraction, transmission electron microscopy, and piezoresponse force microscopy. At low growth rates (frequency 8 Hz) a domains were formed for film thickness above 20-100 nm. Due to coherency strains the Curie temperature (T(c)) of the monodomain films was increased approximately by 350 degrees C with respect to the T(c) of bulk PbTiO(3) even for 280-nm-thick films. Nonetheless, up to now this type of growth mode has been considered unlikely to occur since the Matthews-Blakeslee (MB) model already predicts strain relaxation for films having a thickness of only similar to 10 nm. However, the present work disputes the applicability of the MB model. It clarifies the physical reasons for the large increase in T(c) for thick films, and it is shown that the experimental results are in good agreement with the predictions based on the monodomain model of Pertsev et al. [Phys. Rev. Lett. 80, 1988 (1998)].

Piezoresponse force microscopy of ferroelectric thin films: Frequency dependence of phase imaging

The objective of this work is an evaluation of quantitative measurements of piezoresponse force microscopy for nanoscale characterization of ferroelectric films. To this end, we investigate how the piezoresponse phase difference Delta Phi between c domains depends on the frequency omega of the applied ac field much lower than the cantilever first resonance frequency. The main specimen under study was a 102 nm thick film of Pb(Zr(0.2)Ti(0.8))O(3). For the sake of comparison, a 100 nm thick PbTiO(3) film was also used. From our measurements, we conclude a frequency dependent behavior Delta Phi similar to omega(-1), which can only be partially explained by the presence of adsorbates on the surface. (C) 2008 American Institute of Physics.

Improved diffusive gradients in thin films (DGT) measurement of total dissolved inorganic arsenic in waters and soils using a hydrous zirconium oxide binding layer

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A high-capacity diffusive gradients in thin films (DGT) technique has been developed for measurement of total dissolved inorganic arsenic (As) using a long shelf life binding gel layer containing hydrous zirconium oxide (Zr-oxide). Both As(III) and As(V) were rapidly accumulated in the Zr-oxide gel and could be quantitatively recovered by elution using 1.0 M NaOH for freshwater or a mixture of 1.0 M NaOH and 1.0 M H2O2 for seawater. DGT uptake of As(III) and As(V) increased linearly with deployment time and was independent of pH (2.0–9.1), ionic strength (0.01–750 mM), the coexistence of phosphate (0.25–10 mg P L–1), and the aging of the Zr-oxide gel up to 24 months after production. The capacities of the Zr-oxide DGT were 159 μg As(III) and 434 μg As(V) per device for freshwater and 94 μg As(III) and 152 μg As(V) per device for seawater. These values were 5–29 times and 3–19 times more than those reported for the commonly used ferrihydrite and Metsorb DGTs, respectively. Deployments of the Zr-oxide DGT in As-spiked synthetic seawater provided accurate measurements of total dissolved inorganic As over the 96 h deployment, whereas ferrihydrite and Metsorb DGTs only measured the concentrations accurately up to 24 and 48 h, respectively. Deployments in soils showed that the Zr-oxide DGT was a reliable and robust tool, even for soil samples heavily polluted with As. In contrast, As in these soils was underestimated by ferrihydrite and Metsorb DGTs due to insufficient effective capacities, which were likely suppressed by the competing effects of phosphate.

Ferromagnetism in DyRh and DyRhX (X = Fe, Ni, Co, Gd) thin films

In an effort to achieve large high-field magnetization and increased Curie temperature, polycrystalline DyRh, (DyRh)95X5 and (DyRh)85X15 (X = Fe, Co, Ni, Gd) thin films have been prepared via ultra-high vacuum DC co-sputtering on SiO2 and Si wafers, using Ta as seed and cap material. A body-centred cubic CsCl-like crystal formation (B2 phase) was achieved for DyRh around the equiatomic equilibrium, known from single crystals. The maximum in-plane spontaneous magnetization at T = 4K in fields of μ0H = 5T of was found to be μ0MS,4K = (1.50 ± 0.09)T with a ferromagnetic transition at TC = (5 ± 1)K and a coercivity of μ0HC,4K[D] = (0.010 ± 0.001)T (at T = 4K) for layers deposited on substrates heated to 350°C. Samples prepared at room temperature exhibited poorer texture, smaller grains and less B2-phase content; this did impact on the Curie temperature which was higher compared to those layers with best crystallisation; however the maximal magnetization stayed unaffected. Ferromagnetic coupling was observed in ternary alloys of DyRhGd and DyRhNi with an increased Curie temperature, larger initial permeability, and
high-field magnetization which was best for (DyRh)85Gd15 with μ0MS,4K[Gd15] = (2.10 ± 0.13)T. DyRhFe and DyRhCo showed antiparallel coupling of the spontaneous magnetic moments.

Photobactericidal effects of TiO 2 thin films at low temperatures - A preliminary study

The efficacy of TiO ₂ photocatalysis for the destruction of pathogenic bacteria has been demonstrated by a number of groups over the past two decades. Pathogenic bacteria represent a significant hazard for the food and drink industry. Current practices in this industry dictate that rigorous sanitizing regimes must be regularly implemented resulting in lost production time. The incorporation of a TiO ₂ antibacterial surface coating in this setting would be highly desirable. In this paper we report a preliminary study of the efficacy of a TiO ₂ coating, doped with the lanthanide, neodymium, at low temperature conditions such as those utilised in the food and drink sector. The rapid destruction of Staphylococcus aureus, a common foodborne pathogen, was observed using TiO ₂ films coated to glass and steel substrates. 

Structural and electrical anisotropy of (001)-, (116)-, and (103)-oriented epitaxial SrBi2Ta2O9 thin films on SrTiO3 substrates grown by pulsed laser deposition

Epitaxial SrBi2Ta2O9 (SBT) thin films with well-defined (001), (116), and (103) orientations have been grown by pulsed laser deposition on (001)-, (011)-, and (111)-oriented Nb-doped SrTiO3 substrates. X-ray diffraction pole figure and phi -scan measurements revealed that the three-dimensional epitaxial orientation relation SBT(001)parallel to SrTiO3(001), and SBT[1(1) over bar 0]parallel to SrTiO3[100] is valid for all cases of SET thin films on SrTiO3 substrates, irrespective of their orientations. Atomic force microscopy images of the c-axis-oriented SET revealed polyhedron-shaped grains showing spiral growth around screw dislocations. The terrace steps of the c-axis-oriented SET films were integral multiples of a quarter of the lattice parameter c of SBT (similar to 0.6 nm). The grains of (103)-oriented SET films were arranged in a triple-domain configuration consistent with the symmetry of the SrTiO3(111) substrate. The measured remanent polarization (2P(r)) and coercive field (2E(c)) of (116)-oriented SBT films were 9.6 muC/cm(2) and 168 kV/cm, respectively, for a maximum applied electric field of 320 kV/cm. Higher remanent polarization (2P(r)=10.4 muC/cm(2)) and lower coercive field (2E(c)=104 kV/cm) than those of SBT(116) films were observed in (103)-oriented SET thin films, and (001)-oriented SET revealed no ferroelectricity along the [001] axis. The dielectric constants of (001)-, (116)-, and (103)-oriented SBT were 133, 155, and 189, respectively. (C) 2000 American Institute of Physics.

Epitaxial growth of non-c-oriented ferroelectric SrBi2Ta2O9 thin films on Si(100) substrates

Epitaxial SrBi2Ta2O9 (SBT) thin films with well-defined (116) orientation have been grown by pulsed laser deposition on Si(100) substrates covered with an yttria-stabilized ZrO2 (YSZ) buffer layer and an epitaxial layer of electrically conductive SrRuO3. Studies on the in-plane crystallographic relations between SrRuO3 and YSZ revealed a rectangle-on-cube epitaxy with respect to the substrate. X-ray diffraction pole figure measurements revealed well defined orientation relations, viz. SBT(116)\\ SrRuO3(110)\\ YSZ(100)\\ Si(100), SBT[110]\\ SrRuO3[001], and SrRuO3[111]\\ YSZ[110]\\ Si[110].

Ferroelectricity in epitaxial pulsed laser deposited bismuth-layered perovskite thin films of different crystallographic orientations

Epitaxial thin films Of various bismuth-layered perovskites SrBi(2)Ta(2)O(9), Bi(4)Ti(3)O(12), BaBi(4)Ti(4)O(15), and Ba(2)Bi(4)Ti(5)O(18) were deposited by pulsed laser deposition onto epitaxial conducting LaNiO(3) or SrRuO(3) electrodes on single crystalline SrTiO(3) substrates with different crystallographic orientations or on top of epitaxial buffer layers on (100) silicon. The conductive perovskite electrodes and the epitaxial ferroelectric films are strongly influenced by the nature of the substrate, and bismuth-layered perovskite ferroelectric films with mixed (100), (110)- and (001)-orientations as well as with uniform (001)-, (116)- and (103)- orientations have been obtained. Structure and morphology investigations performed by X-ray diffraction analysis, scanning probe microscopy, and transmission electron microscopy reveal the different epitaxial relationships between films and substrates. A clear correlation of the crystallographic orientation of the epitaxial films with their ferroelectric properties is illustrated by macroscopic and microscopic measurements of epitaxial bismuth-layered perovskite thin films of different crystallographic orientations.