National Institute Of Materials Physics - Romania

Magnetic and electrical properties of the nanostructured ZnO films are affected by the nonrandom distribution of impurities in the film due to segregation at grain boundaries (GBs) or extended defects. However, mapping the nature and distribution of the impurities in the film is not trivial. Here we demonstrate a simple, statistically relevant, and nondestructive procedure of quantitative determination of the paramagnetic impurities segregated at the GBs in nanostructured semiconducting and insulating films. From correlated electron paramagnetic resonance and transmission electron microscopy investigations, we determined the localization of trace amounts of Mn2+ ions, present as native impurities in a ZnO film deposited by magnetron sputtering at room temperature. In the as-deposited ZnO film, the Mn2+ ions were all localized in nanosized pockets of highly disordered ZnO dispersed between nanocrystalline columns. After the samples had been annealed in air at >400 degrees C, the size of the intercrystalline region decreased and the diffusion in GBs was activated, resulting in the localization of a portion of the Mn2+ ions in the peripheral atomic layers of the ZnO columns neighboring the GBs. The proportion of Mn2+ ions still localized at the GBs after annealing at 600 degrees C was 37%. The proposed method for the assessment of the presence and nature of impurities and the quantitative evaluation of their distribution in semiconducting and insulating nanostructures is expected to find direct applications in nanotechnology, in the synthesis and quality assurance of thin films for spintronics and opto- and nanoelectronics.

Relaxor ferroelectrics have neither long range ferroelectric order nor structural transformation down to the lowest temperatures, and display isotropic optical properties like quadratic electro-optic effect. However, if an anisotropy is forced through an external agent, like electric field or uniaxial strain, a ferroelectric and structural long range order can be induced in these materials. Here, we show that epitaxial strain in relaxor ferroelectric thin films can be employed to induce a linear electro-optic effect, opening the path to new strain-controlled electro-optic materials. Epitaxial thin films with Pb1-3x/2LaxZr0.2Ti0.8O3 (x = 0.22) composition grown by pulsed laser deposition on (001) SrRuO3/SrTiO3 single crystal heterostructures become tetragonal below the susceptibility peak, which occurs at a temperature 140K higher as compared to bulk. These films show piezoelectric properties and almost linear electro-optic behaviour. (C) 2014 AIP Publishing LLC.

The GeTiO2 amorphous films were deposited by magnetron sputtering and subsequently annealed at 400, 550, 600 and 700 degrees C for nanostructuring. The structure of annealed films was investigated by X-ray diffraction and transmission electron microscopy. The transmittance spectra of all annealed GeTiO2 films were measured and simulated by using Bruggeman effective medium approximation considering components of TiO2 anatase, crystalline Ge, GeO2 and voids determined from the structure investigations. The electrical behavior of 400, 600 and 700 degrees C annealed films was studied by measuring current-voltage characteristics. We found that by increasing the annealing temperature the films thickness decreases from 330 nm (as-deposited films) to 290 nm (700 degrees C annealed films). The 400 degrees C annealed films are amorphous, while all the others annealed at higher temperatures are crystallized (X-ray diffraction and transmission electron microscopy). In the 550 and 600 degrees C annealed films we found the (TiGe)O-2 rutile structure which is formed by starting from the GeO2 tetragonal structure with high Ti content. Additionally, these films contain TiO2 anatase structure and cubic Ge nanocrystals. At 700 degrees C annealing temperature, a surface layer of GeO2 tetragonal nanocrystals is formed by Ge diffusion and a part of Ge is lost. The experimental transmittance spectra indicate a broadening of the transparency range by increasing the annealing temperature, and the simulated ones also indicate this behavior with the decrease of Ge content, the experimental and simulated spectra being in good agreement. Also, the increase of annealing temperature produces an increase of electrical conductivity. (C) 2014 Elsevier B.V. All rights reserved.

Voltage and frequency dependent capacitance measurements were performed on epitaxial BaTiO3 and Pb(Zr0.2Ti0.8)O-3 thin films deposited on single crystal SrTiO3 substrates with (001) and (111) orientations. The measured capacitors have common bottom SrRuO3 contact and different metals as top electrodes: SrRuO3, Pt, Cu, Al, and Au. The capacitance-voltage characteristics were used to extract information regarding the density of the free carriers and the linear contribution to the static dielectric constant. The frequency dependent impedance was used to develop a suitable equivalent circuit for the epitaxial ferroelectric capacitors. It was found that the frequency dependence of the imaginary part of the impedance can be well simulated, in all cases, using a circuit composed of Schottky-type capacitance related to electrode interfaces, contact resistance, and the R-C parallel connection related to the ferroelectric volume of the film. Values for the components of the equivalent circuit were obtained by fitting the experimental data with the simulated curves. These were then used to extract quantities such as dielectric constant in the ferroelectric volume, the width of the depletion layers, and the apparent built-in potential. It was found that, although the investigated capacitors are of different ferroelectric materials, grown on substrates with different orientations, and having different metals as top electrodes, the values for the capacitance associated with the Schottky contacts and the apparent built-in potential are not very different. The results suggest a strong influence of ferroelectric polarization on the electrode interface properties in the case of epitaxial ferroelectric films. (C) 2014 AIP Publishing LLC.

In this paper, we analyze the structural distortions observed by transmission electron microscopy in thin epitaxial SrRuO3 layers used as bottom electrodes in multiferroic coatings onto SrTiO3 substrates for future multiferroic devices. Regardless of the nature and architecture of the multilayer oxides deposited on the top of the SrRuO3 thin films, selected area electron diffraction patterns systematically revealed the presence of faint diffraction spots appearing in forbidden positions for the SrRuO3 orthorhombic structure. High-resolution transmission electron microscopy (HRTEM) combined with Geometric Phase Analysis (GPA) evidenced the origin of these forbidden diffraction spots in the presence of structurally disordered nanometric domains in the SrRuO3 bottom layers, resulting from a strain-driven phase transformation. The local high compressive strain (-4% divided by -5%) measured by GPA in the HRTEM images induces a local orthorhombic to monoclinic phase transition by a cooperative rotation of the RuO6 octahedra. A further confirmation of the origin of the forbidden diffraction spots comes from the simulated diffraction patterns obtained from a monoclinic disordered SrRuO3 structure. (C) 2014 AIP Publishing LLC.

Ge, GeO2 and Ge2C6H10O7 additions to MgB2 obtained by ex situ spark plasma sintering significantly enhance the critical current density J(c) in high magnetic fields. A J(c)(T = 20 K) of 102 A cm(-2) is obtained at 3.9 T in the pristine sample and at 5.8 T in the MgB2(Ge2C6H10O7)(0.0014) sample. The decrease in the critical temperature for added samples is less than 1 K and T-c(20 K, H = 0) shows a small decrease from 5.5 x 10(5) A cm(-2) in the pristine sample to 3.9 x 10(5) A cm(-2) in MgB2(Ge2C6H10O7)(0.0014) sample. Ge does not substitute into the MgB2 lattice. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

GeSi nanostructured films were obtained by cosputtering from two Ge and Si targets and subsequent annealing in furnace in N-2 for 5 h at 700, 800 and 900 degrees C, with the aim to show the correlation between electrical properties and crystalline structure of the films. The as-deposited films are amorphous, have a Ge: Si composition of 55: 45 and 185 nm thickness. The film structure was investigated by XRD and TEM, and the electrical behaviour was studied by measuring current-voltage (I-V) and current-temperature (I-T) characteristics and by discussing them in correlation with the structure. Different electrical behaviours of GeSi films corresponding to different structures have been evidenced. The 700 degrees C annealed GeSi films are formed of nanocrystals (7-15 nm) separated by amorphous regions (1-2 nm). These films present a superlinear I-V characteristic typical of high field-assisted tunnelling through potential barriers (amorphous regions) between nanocrystals. The I-T characteristic at low temperature follows a T-1/2 law showing a thermally activated tunnelling of carriers between neighboring GeSi nanocrystals. The films annealed at 800 and 900 degrees C have a like behavior, they are completely crystallized and present linear I-V and Arrhenius I-T dependences reflecting the polycrystalline behaviour. [GRAPHICS] . (C) 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The band bending at Cu/PZT(001) interfaces is investigated by X-ray photoelectron spectroscopy (XPS) for a PZT(001) layer which exhibits initial outwards ferroelectric polarization. Two competitive processes are identified: (a) formation of the Schottky barrier between the ferroelectric and unconnected Cu islands, and (b) coalescence of the Cu islands, realisation of an electrical contact to the ground of the system, inducing the apparent loss of the component of the ferroelectric polarization perpendicular to the sample surface, at least as it manifests in band bending. Three mechanisms are proposed to explain this loss of band bending when a full metal layer connected to ground is formed on the surface: (i) over-compensation of depolarization field in the sub-surface region, (ii) formation of domains with in-plane orientation of the polarization vector and (iii) loss of polarization in the near-surface layers of the ferroelectric due to electrons provided by the metal. These result in a non-monotonous variation of binding energies with the amount of Cu deposited. High resolution transmission electron microscopy and piezoresponse force microscopy confirmed these hypotheses. The XPS data allowed also to derive the surface PZT composition, its evolution with the deposition of copper and the formation of surface compounds.

Effects of Ni, Nb and Mn co-doping on microstructural, dielectric and electromechanical properties of lead titanate (PT) dense ceramics, obtained as a result of decreasing lattice anisotropy with increasing amount of co-dopants, were investigated. Different values of the average valence (AV) of Ni-Nb co-dopants were obtained by mutual valence compensation between these acceptor donor ions of various relative concentrations. Significantly higher amounts of Mn2+ (resulted by reduction of Mn4+ in presence of donor co-dopants) were found in materials with Ni-Nb AV >4+. These materials show higher coupling factors, correlated with higher mechanical quality factors, compared to the rest of materials. Hard-like piezoelectric behavior was manifested in materials with Ni-Nb AV <4+, whereas ceramics with Ni-Nb AV >4+, and without manganese, turned out to have a soft-like behavior. Electromechanical properties of PT ceramics are discussed in terms of average valence of Ni-Nb co-dopants and multivalence state of manganese. (C) 2013 Elsevier Ltd. All rights reserved.

Epitaxial TiC films were deposited on MgO (001) by DC magnetron sputtering in a reactive atmosphere of Ar and CH4 at 800 degrees C. The films elemental composition and chemical bonding was investigated by Auger electron spectroscopy (AE5), X-ray photoelectron spectroscopy (XPS) and micro-Raman spectroscopy. The crystallographic structure, investigated by X-ray diffraction, exhibited an increased degree of (001) orientation with the film thickness, with a cube-on-cube epitaxial relationship with the substrate. The films morphology and electrical properties were determined by atomic force microscopy (AFM) and Hall measurements in Van der Pauw geometry. The influences of the film thickness (57-545 nm) on the morphological and electrical properties were investigated. The thinnest film presented the lowest resistivity, 160 [152, cm, showing an atomically flat surface, while higher values were obtained for the thicker films, explained by their different morphology dominated by low aspect ratio nanoislands/ nanocolumns. (C) 2013 Elsevier B.V. All rights reserved