National Institute Of Materials Physics - Romania

The competition between interface barrier in the Schottky-Mott limit and polarization driven mechanism is established during gradual formation of metal (Au) - ferroelectric (BaTiO3) interface. X-ray photoelectron spectroscopy provides core level energies and valence band positions in the contact region, to monitor the band alignment from the very first stages of metal deposition on BaTiO3. The band bending at metal/ferroelectric (FE) interface is extracted from the shift of core levels (Ba 3d, Ti 2p) as a function of the metal thickness. It is shown that the interface band alignment mechanism involves a well-defined polarization orientation washing out the bending expected from the work function difference. The sudden modification of the binding energies within ferroelectric at the first 2 angstrom Au indicates that the ferroelectric compensation mechanism triggered by the metal overlayer initiates already at ultrathin top layer, while subsequent growth contributes only at a gradual correction of the potential in the FE. The emerging picture is confirmed in first-principle calculation indicating the preferences of Au to grow preferentially to different terminated regions and to stabilize distinct ferroelectric polarization.

We report on the influence of dilute doping combined with the processing conditions on the morphological, structural, chemical states, photoluminescence and magnetic properties of Zn1-xNixO nanopowders. Ni doping changes the ZnO powder morphology from randomly-aggregated nanocrystals to densely-packed nanocrystals arranged in columnar particles, modifies the high-energy-component of O1 s spectrum and increases the modified Auger parameter in XPS, enhances the blue photoluminescence (PL) emission, suppresses the green PL emission and the intensity of the g = 1.997 EPR signal. Ni-ZnO nanostructures show room-temperature ferro-magnetism (implying they can serve as dilute magnetic semiconductors). The saturation magnetization, crystallite size and microstrain increase with the doping level; the c-axis constant and unit cell volume decrease, however, being unexpectedly higher with respect to a (reference) ZnO powder with a relaxed lattice. We demonstrate that the investigated properties were controlled by both (dilute) doping level and donor native defects produced by non-equilibrium (oxygen-deficiency and high rate of) ZnO formation.

In this work, the effect of deposition time on the structural and optical properties of ZnO films deposited by Ultrasonic Spray Mist-CVD was studied aiming the application in perovskite solar cells, as holes blocking layer. Crystallinity, surface morphology and optical properties of the ZnO films were investigated by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), conventional and Photoluminescence (PL) spectroscopies, respectively. The XRD measurement proves the existence of the hexagonal wurtzite phase and a high degree of crystallinity with [001] preferential orientation. The SEM study shows that the films possess a compact structure. Smooth and homogenous surface was confirmed also by AFM. The obtained results indicate that ZnO films deposited by a simple, safe and cost-effective method present a great potential for application in perovskite solar cells.

Multi-layered structures, composed of thin films from materials with different compositions or physical properties, represents a way to obtain enhanced properties or even new functionalities. In this work, lead zirconate titanate PbZrxTi1-xO3 (PZT; x = 0.20, 0.52, 0.80) multilayers were grown by pulsed laser deposition (PLD) on a single crystal strontium titanate (SrTiO3, STO) substrate, using a strontium ruthenate (SrRuO3, SRO) film as buffer layer for epitaxial growth, and also as back electrode. Up and down multi-layers were grown and their physical and structural properties were compared, up being the structure in which Zr concentration was varied from 20% near the STO substrate to 80% at the surface, while down is for the structure in which the Zr concentration starts with 80% near the substrate and ends with 20% at the surface. It was found that the electric and pyroelectric properties of the two graded structures are significantly different. The up structure presents electric properties that are comparable with those of single composition PZT films while the properties of the down structure are deteriorated, especially in terms of the leakage current magnitude. Pyroelectric signal could be measured only for the up structure. These differences were attributed to larger density of structural defects in the down structure compared to the up one. This is due to the different growth sequence: Lop structure starts with tetragonal PZT on cubic substrate (lower lattice mismatch, 1.1%) while down structure starts with rhombohedral PZT on cubic substrate (larger lattice mismatch, almost 5%).

The present work describes a new simple procedure for the direct immobilization of biomolecules on Ni electrodes using magnetic Ni nanoparticles (NiNPs) as biomolecule carriers. Ni electrodes were fabricated by electroplating, and NiNPs were chemically synthesized. The chemical composition, crystallinity, and granular size of Ni electrodes, NiNP, and NiNP-modified Ni electrodes (NiNP/Ni) were determined by X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS). The electrochemical characterization of Ni electrodes by cyclic voltammetry and electrochemical impedance spectroscopy confirmed the existence of nickel oxides, hydroxides, and oxohydroxide films at the surface of Ni. Magnetic characterization and micromagnetic simulations were performed in order to prove that the magnetic force is responsible for the immobilization process. Further, Ni electrodes were employed as amperometric sensors for the detection of hydrogen peroxide because it is an important performance indicator for a material to be applied in biosensing. The working principle for magnetic immobilization of the enzyme-functionalized NiNP, without the use of external magnetic sources, was demonstrated for glucose oxidase (GOx) as a model enzyme. XPS results enabled to identify the presence of GOx attached to the NiNP (GOx-NiNP) on Ni electrodes. Finally, glucose detection and quantification were evaluated with the newly developed GOx-NiNP/Ni biosensor by amperometry at different potentials, and control experiments at different electrode materials in the presence and absence of NiNP demonstrated their importance in the biosensor architecture.

This study presents the synthesis and characterization of lanthanum-modified alumina supported cerium-manganese mixed oxides, which were prepared by three different methods (coprecipitation, impregnation and citrate-based sol-gel method) followed by calcination at 500 degrees C. The physicochemical properties of the synthesized materials were investigated by various characterization techniques, namely: nitrogen adsorption-desorption isotherms, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and H-2-temperature programmed reduction (TPR). This experimental study demonstrated that the role of the catalytic surface is much more important than the bulk one. Indeed, the incipient impregnation of CeO2-MnOx catalyst, supported on an optimized amount of 4 wt.% La2O3-Al2O3, provided the best results of the catalytic combustion of methane on our catalytic micro-convertors. This is mainly due to: (i) the highest pore size dimensions according to the Brunauer-Emmett-Teller (BET) investigations, (ii) the highest amount of Mn4+ or/and Ce4+ on the surface as revealed by XPS, (iii) the presence of a mixed phase (Ce2MnO6) as shown by X-ray diffraction; and (iv) a higher reducibility of Mn4+ or/and Ce4+ species as displayed by H-2-TPR and therefore more reactive oxygen species.

Berry phase (BP) polarization calculations have been investigated for several ferroelectric materials from the point of view of practical calculations. It was shown that interpretation of the results is particular to each case due to the multivalued aspect of polarization in the modern theory. Almost all of the studied examples show ambiguous polarization results which can be difficult to solve especially for super-cells containing large number of atoms. For this reason, a procedure has been proposed to minimize the number of calculations required to produce an unambiguous polarization result from BP polarization investigations.

We investigate how far the hysteresis-free behavior of perovskite solar cells can be reproduced using particular pre-conditioning and measurement conditions. As there are currently more and more reports of perovskite solar cells without J-V hysteresis it is crucial to distinguish between genuine performance improvements and measurement artifacts. We focus on two of the parameters that influence the dynamic J-V scans, namely the bias scan rate and the bias poling voltage, and point out measurement conditions for achieving a hysteresis-free behavior. In this context we discuss the suitability of defining a hysteresis index (HI) for the characterization of dynamic J-V scans. Using HI, aging effects are also investigated, establishing a potential connection between the sample degradation and the variation of the maximal hysteresis on one hand, and the relaxation time scale of the slow process on the other hand. Pre-poling induced recombination effects are identified. In addition, our analysis based on sample pre-biasing reveals potential indications regarding two types of slow processes, with two different relaxation time scales, which provides further insight regarding ionic migration.

We report on the fabrication of dye-sensitized solar cells with a TiO2 buffer layer between the transparent conductive oxide substrate and the mesoporous TiO2 film, in order to improve the photovoltaic conversion efficiency of the device. The buffer layer was fabricated by pulsed laser deposition whereas the mesoporous film by the doctor blade method, using TiO2 paste obtained by the sol-gel technique. The buffer layer was deposited in either oxygen (10 Pa and 50 Pa) or argon (10 Pa and 50 Pa) onto transparent conducting oxide glass kept at room temperature. The cross-section scanning electron microscopy image showed differences in layer morphology and thickness, depending on the deposition conditions. Transmission electron microscopy studies of the TiO2 buffer layers indicated that films consisted of grains with typical diameters of 10 nm to 30 nm. We found that the photovoltaic conversion efficiencies, determined under standard air mass 1.5 global (AM 1.5G) conditions, of the solar cells with a buffer layer are more than two times larger than those of the standard cells. The best performance was reached for buffer layers deposited at 10 Pa O-2. We discuss the processes that take place in the device and emphasize the role of the brush-like buffer layer in the performance increase.

Laser melting deposition is a 3D printing method usually studied for the manufacturing of machine parts in the industry. However, for the medical sector, although feasible, applications and actual products taking advantage of this technique are only scarcely reported. Therefore, in this study, Ti6Al4V orthopedic implants in the form of plates were 3D printed by laser melting deposition. Tuning of the laser power, scanning speed and powder feed rate was conducted, in order to obtain a continuous deposition after a single laser pass and to diminish unwanted blown powder, stuck in the vicinity of the printed elements. The fabrication of bone plates is presented in detail, putting emphasis on the scanning direction, which had a decisive role in the 3D printing resolution. The printed material was investigated by optical microscopy and was found to be dense, with no visible pores or cracks. The metallographic investigations and X-ray diffraction data exposed an unusual biphasic alpha+beta structure. The energy dispersive X-ray spectroscopy revealed a composition very similar to the one of the starting powder material. The mapping of the surface showed a uniform distribution of elements, with no segregations or areas with deficient elemental distribution. The in vitro tests performed on the 3D printed Ti6Al4V samples in osteoblast-like cell cultures up to 7 days showed that the material deposited by laser melting is cytocompatible.