Evidence for diffusional coupling in electrochemical thin layers: implications for surface coverage calibration via electrochemical infrared spectroscopy

The time dependence of the concentration of CO2 in an electrochemical thin layer cavity is studied with Fourier transform infrared spectroscopy (FTIR) in order to evaluate the extent to which the thin layer cavity is diffusionally decoupled from the surrounding bulk electrolyte. For the model system of CO on Pt(111) in 0.1 M HClO4, it is found that the concentration of CO2, formed by electro-oxidation of CO, equilibrates rapidly with the surrounding bulk electrolyte. This rapid equilibration indicates that there is diffusion out of the thin layer, even on the short time scales of typical infrared experiments (1-3 min). However, since the measured CO2 absorbance intensity as a function of time is reproducible to within 10%, a new time-dependent method for surface coverage calibration using solution-phase species is proposed.

Preparation and characterization of ordered intermetallic platinum phases for electrocatalytic applications

Ordered intermetallic phases of Pt with several transition metals have been prepared and their electrocatalytic properties studied. In light of these tests it is proposed that these catalysts could be used as electrodes in fuel cells, as they combine an excellent capacity to adsorb organic fuels at the Pt sites with low susceptibility to being poisoned by intermediates and reaction products at the transition-metal sites. An experimental procedure used to obtain the four intermetallic phases Pt-M (M = Mn, Pb, Sb and Sn) is described. The phases thus produced were characterized by X-ray diffraction, scanning electron microscopy with surface analysis by energy-dispersive X-ray spectrometry, scanning tunneling microscopy and X-ray photoelectron spectroscopy. The data thus obtained support the conclusion that the method described here is highly effective for the preparation of Pt-M phases featuring a range of structural and electronic modifications that will allow a useful relation to be established between their physicochemical properties and predicted electrocatalytic activity. (C) 2007 Elsevier Ltd. All rights reserved.

A surface-enhanced infrared absorption spectroscopic (SEIRAS) study of the oscillatory electro-oxidation of methanol on platinum

The oscillatory electro-oxidation of methanol was studied by means of in situ infrared (IR) spectroscopy in the attenuated total reflection (ATR) configuration using a platinum film on a Si prism as working electrode. The surface-enhanced infrared absorption (SEIRA) effect considerably improves the spectroscopic resolution, allowing at following the coverage of some adsorbing species during the galvanostatic oscillations. Carbon monoxide was the main adsorbed specie observed in the induction period and within the oscillatory regime. The system was investigated at two distinct time-scales and its dynamics characterized accordingly. During the induction period the main transformation observed as the system move through the phase space towards the oscillatory region was the decrease of the coverage of adsorbed carbon, coupled to the increase of the electrode potential. Similar transition characterizes the evolution within the oscillatory region, but at a considerably slower rate. Experiments with higher time resolution revealed that the electrode potential oscillates in-phase with the frequency of the linearly adsorbed CO vibration and that the amount of adsorbed CO oscillates with small amplitude. Adsorbed formate was found to play, if any, a very small role. Results are discussed and compared with other systems. (C) 2010 Elsevier B.V. All rights reserved.

Voltammetric characterization of stepped platinum single crystal surfaces vicinal to the (110) pole

Platinum stepped surfaces vicinal to the (1 1 0) crystallographic pole have been investigated voltammetrically in 0.1 M HClO(4) and 0.1 M H(2)SO(4) solutions. Changes in the voltammetric profile with the step density suggest the existence of two types of surface sites, that has been ascribed to linear and bidimensional domains. This result indicates the existence of important restructuring processes that separate the real surface distribution from the nominal one. The electronic properties of the surfaces have been characterized with the CO charge displacement method and the potential of zero total charge has been calculated as a function of the step density. (c) 2009 Elsevier B.V. All rights reserved.

Improvement of fatigue resistance on La modified BiFeO(3) thin films

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Very Intense Distinct Blue and Red Photoluminescence Emission in MgTiO3 Thin Films Prepared by the Polymeric Precursor Method: An Experimental and Theoretical Approach

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Soft chemical deposition of BiFeO3 multiferroic thin films

BiFeO3 thin films free of secondary phases were obtained by the soft chemical solution on Pt(111)/Ti/SiO2/Si substrates after annealing at 500 degrees C for 2 h. The film grown in the (100) direction presented a remanent polarization P-r of 31 mu C/cm(2) at room temperature. Electrical measurements using both quasistatic hysteresis and pulsed polarization confirm the existence of ferroelectricity with a switched polarization of 60-70 mu C/cm(2), Delta P=(P-*-P). Low leakage conduction and an out-of-plane piezoelectric (d(3)) coefficient of 40 pm/V were obtained by the improvement of preparation technology.

Microstructure and dielectric properties of (Ba,Sr)TiO3 thin film produced by the polymeric precursor method

BaxSr1-xTiO3 (x = 0.6) (BST) thin films were successfully prepared on a Pt(111)/TiO2/SiO2/Si(100) substrate by spin coating, using the polymeric precursor method. BST films with a perovskite single phase were obtained after heat treatment at 700 degrees C. The multilayer BST thin films had a granular structure will a grain size of approximately 60 nm. A 480-nm-thick film was obtained by carrying out five cycles of the spin-coating/heating process. Scanning electron microscopy and atomic force microscopy analyses showed that the thin films had a smooth, dense, crack-free surface with low surface roughness (3.6 nm). At room temperature and at a frequency of 100 kHz, the dielectric constant and the dissipation factor were, respectively, 748 and 0.042. The high dielectric constant value was due to the high microstructural quality and chemical homogeneity of the thin films obtained by the polymeric precursor method.

Microstructural investigation of the PZT films prepared from the suspension of nanocrystalline powders

PZT thin films of composition Pb(Zr0.52Ti0.48)O-3 were prepared by a novel method from the suspension of nanocrystalline PZT powders. The powders were obtained by mechanochemical synthesis. Films were deposited on silicon (100) and platinum covered silicon substrates (Pt (111) /Ti/SiO2/Si) Using spin-on technique. Substrate type has influence on films crystallinity, orientation and can react with the films changing its phase composition. Films microstructure strongly depends on thermal treatment conditions due to phase and compositional changes of the films. (C) 2003 Elsevier Ltd. All rights reserved.

Microstructural and ferroelectric properties of PbZr1-xTi(x)O(3) thin films prepared by the polymeric precursor method

The polymeric precursor method was employed in the preparation of PZT thin films on Pt(111)Ti/SiO2/Si(100) substrates. X-ray diffraction patterns revealed the polycrystalline nature of the PZT (53:47) thin films, which had a granular structure and a grain size of approximately 70 nm. A 350-nm thick film was obtained by running three cycles of the dip-coating/heating process. Atomic force microscopy (AFM) analyses showed the surface of these thin films to be smooth, dense and crack-free with low surface roughness (= 2.0 nm). The PZT (53:47) thin films annealed at 700 degreesC showed a well-saturated hysteresis loop. The C-V curves of perovskite thin film displayed normal ferroelectric behavior, while the remanent polarization (2P(r)) and coercive field (E-e) of the film deposited and measured at room temperature were 40 muC/cm(2) and 110 kV/cm, respectively. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Textured PbZr0.3Ti0.7O3 thin films produced by polymeric precursor method using microwave oven

PbZr0.3Ti0.7O3 (PZT) films were produced by polymeric precursor route and deposited by spin-coater technique on Pt(111)/Ti/SiO2/Si(100) substrates. The films were heat-treated using different furnaces: (a) a conventional furnace, at 700 degrees C; and (b) a domestic microwave oven, at 600 degrees C. The X-ray patterns revealed that both films are single phase and reflections were identified as belongs to the PZT phase. The intensity of these reflections showed a (111), (001) and (100) preferred orientation. Morphological and electrical characterizations showed that all samples present a rather different microstructure and both with high spontaneous polarization.

Low temperature synthesis and electrical properties of PbTiO3 thin films prepared by the polymeric precursor method

Ferroelectric PbTiO3 thin films were successfully prepared on a Pt(111)Ti/SiO2/Si(100) substrate for the first time by spin coating, using the polymeric precursor method. X-ray diffraction patterns of the films indicate that they are polycrystalline in nature. This method allows low temperature (500 degrees C) synthesis and high electrical properties. The multilayer PbTiO3 thin films were granular in structure with a grain size of approximately 110-120 nm. A 380-nm-thick film was obtained by carrying out four cycles of the spin-coating/heating process. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses showed the surface of these thin films to be smooth, dense and crack-free with low surface roughness (=3.4 nm). At room temperature and at a frequency of 100 kHz, the dielectric constant and the dissipation factor were, respectively, 570 and 0.016. The C-V characteristics of perovskite thin film prepared at low temperature show normal ferrolectric behavior. The remanent polarization and coercive field for the films deposited were 13.62 mu C/cm(2) and 121.43 kV/cm, respectively. The high electrical property values are attributed to the excellent microstrutural quality and chemical homogeneity of thin films obtained by the polymeric precursor method. (C) 2000 Elsevier B.V. S.A. All rights reserved.

Ferroelectric characteristics of BiFeO3 thin films prepared via a simple chemical solution deposition

BiFeO3 (BFO) thin films were fabricated on Pt(111)/Ti/SiO2/Si substrates by using a polymeric precursor solution under appropriate crystallization conditions. The capacitance dependence on voltage is strongly nonlinear, confirming the ferroelectric properties of the films resulting from the domain switching. The leakage current density increases with annealing temperature. The polarization electric field curves could be obtained in BFO films annealed at 500 degrees C, free of secondary phases. X-ray photoelectron spectroscopy spectra of films annealed at 500 degrees C indicated that the oxidation state of Fe was purely 3+, demonstrating that our films possess stable chemical configurations. (c) 2007 American Institute of Physics.

Dielectric properties and microstructure of SrTiO3/BaTiO3 multilayer thin films prepared by a chemical route

Multilayer thin films with perovskite structures were produced by the polymeric precursor method. SrTiO3/BaTiO3 (STO/BTO) multilayers were deposited on Pt(111)/Ti/SiO2/Si(100) substrates by the spin-coating technique and heated in air at 700 degreesC. The microstructure and crystalline phase of the multilayered thin films were examined by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), resolution-high transmission electron microscopy (HRTEM), atomic force microscopy (AFM) and X-ray diffraction. The SrTiO3/BaTiO3 multilayer thin films consisted of grainy structures with an approximate grain size of 60 nm. The multilayered thin films showed a very clear interface between the components. The SrTiO3/BaTiO3 multilayer thin films revealed dielectric constants of approximately 527 and loss tangents of 0.03 at 100 kHz. The dielectric constant calculated for this multilayer film system is the value of the sum of each individual component of the film, i.e. The total value of the sum of each SrTiO3 (STO) and BaTiO3 (BTO) layer. The multilayer SrTiO3/BaTiO3 obtained by the polymeric precursor method, also showed a ferroelectric behavior with a remanent polarization of 2.5 muC/cm(2) and a coercive field of 30 kV/cm. The multilayer films displayed good fatigue characteristics under bipolar stressing after application of 10(10) switching cycles. (C) 2001 Published by Elsevier B.V. B.V. All rights reserved.

Microstructure and electrical properties of perovskite (Pb, La)TiO3 thin film deposited at low temperature by the polymeric precursor method

High-quality (Pb, La)TiO3 ferroelectric thin films were successfully prepared on a Pt(111)/Ti/SiO2/Si(100) substrate for the first time by spin coating, using the polymeric precursor method. The X-ray diffraction patterns show that the films are polycrystalline in nature. This method allows for low temperature (500 degrees C) synthesis, a high quality microstructure and superior dielectric properties. The effects on the microstructure and electrical properties were studied by changing the La content. The films annealed at 500 degreesC have a single perovskite phase with only a tetragonal or pseudocubic structure. As the La content is increased, the dielectric constant of PLT thin films increases from 570 up to 1138 at room temperature. The C-V and P-E characteristics of perovskite thin films prepared at a low temperature show normal ferroelectric behavior, representing the ferroelectric switching property. The remanent polarization and coercive field of the films deposited decreased due to the transformation from the ferroelectric to the paraelectric phase with an increased La content. (C) 2001 Kluwer Academic Publishers.