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. 

On the optical properties of bismuth oxide thin films prepared by pulsed laser deposition

The optical properties of bismuth oxide films prepared by pulsed laser deposition (PLD), absorption in the photon energy range 2.50-4.30 eV and optical functions (n, k, epsilon(1), and epsilon(2)) in the domain 3.20-6.50 eV, have been investigated. As-prepared films (d = 0.05-1.50 mum) are characterized by a mixture of polycrystalline and amorphous phases. The fundamental absorption edge is described by direct optical band-to-band transitions with energies 2.90 and 3.83 eV The dispersion of the optical functions provided values of 4.40-6.25 eV for electron energies of respective direct transitions. In the spectral range 400-1000 nm, bismuth oxide films show a normal dispersion, which can be interpreted in the frame of a single oscillator model. (C) 2004 Elsevier B.V. All rights reserved.

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.

A review of high magnetic moment thin films for microscale and nanotechnology applications

The creation of large magnetic fields is a necessary component in many technologies, ranging from magnetic resonance imaging, electric motors and generators, and magnetic hard disk drives in information storage. This is typically done by inserting a ferromagnetic pole piece with a large magnetisation density MS in a solenoid. In addition to large MS, it is usually required or desired that the ferromagnet is magnetically soft and has a Curie temperature well above the operating temperature of the device. A variety of ferromagnetic materials are currently in use, ranging from FeCo alloys in, for example, hard disk drives, to rare earth metals operating at cryogenic temperatures in superconducting solenoids. These latter can exceed the limit on MS for transition metal alloys given by the Slater-Pauling curve. This article reviews different materials and concepts in use or proposed for technological applications that require a large MS, with an emphasis on nanoscale material systems, such as thin and ultra-thin films. Attention is also paid to other requirements or properties, such as the Curie temperature and magnetic softness. In a final summary, we evaluate the actual applicability of the discussed materials for use as pole tips in electromagnets, in particular, in nanoscale magnetic hard disk drive read-write heads; the technological advancement of the latter has been a very strong driving force in the development of the field of nanomagnetism.

Chalcogenide thin films for solar cells: growth and properties

Thin film solar cells have in recent years gained market quota against traditional silicon photovoltaic panels. These developments were in a large part due to CdTe solar panels on whose development started earlier than their competitors. Panels based on Cu(In,Ga)Se2 (CIGS), despite being more efficient in a laboratory and industrial scale than the CdTe ones, still need a growth technology cheaper and easier to apply in industry. Although usually presented as a good candidate to make cheap panels, CIGS uses rare and expensive materials as In and Ga. The price evolution of these materials might jeopardize CIGS future. This thesis presents three different studies. The first is the study of different processes for the incorporation of Ga in a hybrid CIGS growth system. This system is based on sputtering and thermal evaporation. This technology is, in principle, easier to be applied in the industry and solar cells with efficiencies around to 7% were fully made in Aveiro. In the second part of this thesis, a new material to replace CIGS in thin film solar cells is studied. The growth conditions and fundamental properties of Cu2ZnSnSe4 (CZTSe) were studied in depth. Suitable conditions of temperature and pressure for the growth of this material are reported. Its band gap energy was estimated at 1.05 eV and the Raman scattering peaks were identified. Solar cells made with this material showed efficiencies lower than 0.1%. Finally, preliminary work regarding the incorporation of selenium in Cu2ZnSnS4 (CZTS) thin films was carried out. The structural and morphological properties of thin films of Cu2ZnSn(S,Se)4 have been studied and the results show that the incorporation of selenium is higher in films with precursors rather with already formed Cu2SnS3 or Cu2ZnSnS4 thin films. A solar cell with 0.9 % of efficiency was prepared.

Chemical vapour deposition of vanadium oxide thermochromic thin films

Thermochromic materials change optical properties, such as transmittance or reflectance, with a variation in temperature. An ideal intelligent (smart) material will allow solar radiation in through a window in cold conditions, but reflect that radiation in warmer conditions. The variation in the properties is often associated with a phase change, which takes place at a definite temperature, and is normally reversible. Such materials are usually applied to window glass as thin films. This thesis presents the work on the development of thermochromic vanadium (IV) oxide (VO2) thin films – both undoped and doped with tungsten, niobium and gold nanoparticles – which could be employed as solar control coatings. The films were deposited using Chemical Vapour Deposition (CVD), using improved Atmospheric Pressure (APCVD), novel Aerosol Assisted (AACVD) and novel hybrid AP/AACVD techniques. The effects of dopants on the metalto- semiconductor transition temperature and transmittance/reflectance characteristics were also investigated. This work significantly increased the understanding of the mechanisms behind thermochromic behaviour, and resulted in thermochromic materials based on VO2 with greatly improved properties.

Effects of sulphurization time on Cu2ZnSnS4 absorbers and thin films solar cells obtained from metallic precursors

We report the results of a study of the sulphurization time effects on Cu2ZnSnS4 absorbers and thin film solar cells prepared from dc-sputtered tackedmetallic precursors. Three different time intervals, 10 min, 30min and 60 min, at maximum sulphurization temperature were considered. The effects of this parameter' change were studied both on the absorber layer properties and on the final solar cell performance. The composition, structure, morphology and thicknesses of the CZTS layers were analyzed. The electrical characterization of the absorber layer was carried out by measuring the transversal electrical resistance of the samples as a function of temperature. This study shows an increase of the conductivity activation energy from 10 meV to 54meV for increasing sulphurization time from 10min to 60min. The solar cells were built with the following structure: SLG/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Ni:Al grid. Several ac response equivalent circuit models were tested to fit impedance measurements. The best results were used to extract the device series and shunt resistances and capacitances. Absorber layer's electronic properties were also determined using the Mott–Schottky method. The results show a decrease of the average acceptor doping density and built-in voltage, from 2.0 1017 cm−3 to 6.5 1015 cm−3 and from 0.71 V to 0.51 V, respectively, with increasing sulphurization time. These results also show an increase of the depletion region width from approximately 90 nm–250 nm.