Interplay of Octahedral Tilts and Polar Order in BiFeO3 Films

Heterointerface stabilization of a distinct nonpolar BiFeO3 phase occurs simultaneously with changes in octahedral tilts. The resulting phase arises via suppression of polarization by a structural order parameter and can thus be identified as anti-ferroelectric (Fe displacements - bottom panel). The phase is metastable and can be switched into a polar ferroelectric state (top panel) under an applied electric bias.

Nanoscale Origins of Nonlinear Behavior in Ferroic Thin Films

The nonlinear response of a ferroic to an applied field has been studied through the phenomenological Rayleigh Law for over a hundred years. Yet, despite this, the fundamental physical mechanisms at the nanoscale that lead to macroscopic Rayleigh behavior have remained largely elusive, and experimental evidence at small length scales is limited. Here, it is shown using a combination of scanning probe techniques and phase field modeling, that nanoscale piezoelectric response in prototypical Pb(Zr,Ti)O3 films appears to follow a distinctly non-Rayleigh regime. Through statistical analysis, it is found that an averaging of local responses can lead directly to Rayleigh-like behavior of the strain on a macroscale. Phase-field modeling confirms the twist of the ferroelastic interface is key in enhancing piezoelectric response. The studies shed light on the nanoscale origins of nonlinear behavior in disordered ferroics.

Stripe domain structure in epitaxial (001) BiFeO3 thin films on orthorhombic TbScO3 substrate

We have analyzed the ferroelastic and ferroelectric domain structure of high crystalline quality (001) BiFeO3 films on orthorhombic (110) TbScO3 substrates. Two domains were present in stripes separated by (010) vertical boundaries, with spontaneous polarizations in adjacent domains rotated by 109 degrees. The striped morphology was caused by nucleation of only two ferroelastic domains on the low symmetry GdFeO3-type substrate. Domain engineering through substrate symmetry is an important finding for rhombohedral ferroelectric epitaxial thin films. The stripe pattern with vertical walls may be useful for extracting domain wall contributions to magnetism and electrical transport properties of BiFeO3 materials.

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.

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.

Stability of 71 degrees stripe domains in epitaxial BiFeO3 films upon repeated electrical switching

The 71 degrees stripe domain patterns of epitaxial BiFeO3 thin films are frequently being explored to achieve new functional properties, dissimilar from the BiFeO3 bulk properties. We show that in-plane switching and out-of-plane switching of these domains behave very differently. In the in-plane configuration the domains are very stable, whereas in the out-of-plane configuration the domains change their size and patterns, depending on the applied switching voltage frequency.

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.

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.

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.

Application of surface plasmon polaritons in the laser ablation and characterisation of thin aluminium films

Surface modification of thin aluminium films is both produced and characterised by exciting surface plasmon polaritons in an attenuated total reflection geometry: silica prism/aluminium/aluminium oxide system. The modification is performed, under ambient conditions, by exposure to a low fluence (

Contrasting damage characteristics in direct incidence and surface plasmon mediated single-shot laser ablation of aluminium films

Thin, oxidised Al films grown an one face of fused silica prisms are exposed. tinder ambient conditions, to single shots from an excimer laser operating at wavelength 248 nm. Preliminary characterisation of the films using attenuated total reflection yields optical and thickness data for the Al and Al oxide layers; this step facilitates the subsequent, accurate tuning of the excimer laser pulse to the: surface plasmon resonance at the Al/(oxide)/air interface and the calculation of the fluence actually absorbed by the thin film system. Ablation damage is characterised using scanning electron, and atomic force microscopy. When the laser pulse is incident, through the prism on the sample at less than critical angle, the damage features are molten in nature with small islands of sub-micrometer dimension much in evidence, a mechanism of film melt-through and subsegment blow-off due to the build up of vapour pressure at the substrate/film interface is appropriate. By contrast, when the optical input is surface plasmon mediated, predominately mechanical damage results with the film fragmenting into large flakes of dimensions on the order of 10 mu m. It is suggested that the ability of surface plasmons to transport energy leads to enhanced, preferential absorption of energy at defect sites causing stress throughout the film which exceeds the ultimate tensile stress for the film: this in turn leads to film break-up before melting can onset. (C) 1998 Elsevier Science B.V.