Theoretical and experimental study of the relation between photoluminescence and structural disorder in barium and strontium titanate thin films

Thin films of barium and strontium titanate (BST), synthesized by the polymeric precursor solution and spin coated on [Pt (140nm)/Ti (10 nM)/SiO2(1000 nm)/Si] substrates were found to be photoluminescent at room temperature when heat treated below 973 K, i.e. before their crystallization. First principles quantum mechanical techniques, based on density functional theory (DFT) were employed to study the electronic structure of two periodic models: one is standing for the crystalline BST thin film and the other one for the structurally disordered thin film. The aim is to compare the photoluminescence (PL) spectra of the crystalline and disordered thin films with their UV-vis spectra and with their computed electronic structures. The calculations show that new localized states are created inside the band gap of the crystalline model, as predicted by the UV-vis spectra. The study of the charge repartition in the structure before and after deformation of the periodic model shows that a charge gradient appears among the titanate clusters. This charge gradient, together with the new localized levels, gives favorable conditions for the trapping of holes and electrons in the structure, and thus to a radiative recombination process. Our models are not only consistent with the experimental data, they also allow to explain the relations between structural disorder and photoluminescence at room temperature. (c) 2005 Elsevier Ltd. All rights reserved.

Barium titanate screen-printed thick films

Barium titanate (BT) thick films were prepared from mechanically activated powders based on BaCO(3) and TiO(2). After homogenization and milling in a high-energy vibro mill, the powders were calcined at 700 degreesC for 2 h by slow heating and cooling rates. A thick film paste was prepared by mixing BT fine powders with small amount of low temperature sintering aid and organic binder. The thick films were screen-printed on alumina substrates electroded with Ag-Pd. The BT films were sintered at 850 degreesC for 1 h. The thickness was 25-75 mum depending of number of layers. The microstructure of thick films and the compatibility between BT layers and substrate were investigated by SEM Results of dielectric property measurements are also reported. (C) 2002 Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.

Influence of barium and strontium addition on the ratio c/a of PZT obtained by the polymeric precursor method

Lead zirconate titanate powder, with Zr/Ti ratio of 50/50 was prepared by Pechini method after adding up to 10,0 mol% of Ba +2 and Sr +2 ions. Tetragonal phase is favored by the increase of barium and strontium concentration in the LiNbO 3 crystal lattice. The ratio c/a for tetragonal phase increases with the content of Ba +2 and Sr +2.

Structure study of donor doped barium titanate prepared from citrate solutions

Barium titanates doped with Nb5+, and Y3+, were prepared. The starting powders were synthesized from citrate solutions by the Pechini process and partial Pechini process in two steps. Sintering was performed in the range from 1310° up to 1380°C for 2 hours in air atmosphere. The structural study concerning the incorporation of Nb and Y ions in the barium titanate crystal lattice was performed by XRD, XANES and EXAFS techniques. The dielectric properties were analyzed and the relationship between properties and structure of doped barium titanate was established.

Effects of the addition of ions barium on the structural and electrical properties of PZT ceramic

Lead zirconate titanate, with Zr/Ti ratio of 53/47 was prepared by the polymeric precursor method. It was investigated the barium (II) modification at 0.0, 0.2, 0.4 and 0.6 mol% in substitution to the lead (II) cation in A site of perovskite structure. The powder samples were characterized by XRD and the diffraction patterns were used to Rietveld refinement. The percentages of tetragonal and rhombohedral phases and a systematic study of the effect of barium (II) on the morphology and the dielectric properties of PZT were carried out. The results showed that the tetragonal phase is favored and the ceramic density is improved with the barium (II) insertion. The Curie temperature (Tc) is increased besides the slight reduction of dielectric constant (Kc).

Yttrium barium copper oxide thin films on yttria-stabilized zirconia: growth and properties

Y Ba Cu oxide thin films were grown epitaxially on single cryst. yttria-stabilized zirconia substrates by laser deposition. [on SciFinder(R)]

Very thin yttrium barium copper oxide films made by coevaporation

Superconducting YBa2Cu3O7 thin films with various thicknesses from 100 Å to 5000 Å were deposited on (100) SrTiO3 substrates with std. BaF2 coevaporation process. The films had crit. temps. of up to 93 K. The best crit. currents were 1 × 106 A/cm2 at 77 K and 3 × 107 A/cm2 at 4.2 K. The crit. current was generally higher for thinner films. Two different etching methods were used to pattern the films for jc measurements: Ar ion etching and EDTA wet etching. The wet etching was found to work well for thicker films (>1000 Å). For the thinner films, the ion etching process was preferred because of the reduced film surface degrdn. [on SciFinder(R)]

Growth and study of antiferroelectric lead zirconate thin films by pulsed laser ablation

Antiferroelectric lead zirconate (PZ) thin films were deposited by pulsed laser ablation on platinum-coated silicon substrates. Films showed a polycrystalline pervoskite structure upon annealing at 650 degrees C for 5-10 min. Dielectric properties were investigated as a function of temperature and frequency. The dielectric constant of PZ films was 220 at 100 kHz with a dissipation factor of 0.03. The electric field induced transformation from the antiferroelectric phase to the ferroelectric phase was observed through the polarization change, using a Sawyer-Tower circuit. The maximum polarization value obtained was 40 mu C/cm(2). The average fields to excite the ferroelectric state, and to reverse to the antiferroelectric state were 71 and 140 kV/cm, respectively. The field induced switching was also observed through double maxima in capacitance-voltage characteristics. Leakage current was studied in terms of current versus time and current versus voltage measurements. A leakage current density of 5x10(-7) A/cm(2) at 3 V, for a film of 0.7 mu m thickness, was noted at room temperature. The trap mechanism was investigated in detail in lead zirconate thin films based upon a space charge limited conduction mechanism. The films showed a backward switching time of less than 90 ns at room temperature.

Influence of lanthanum doping on the dielectric, ferroelectric and relaxor behaviour of barium bismuth titanate ceramics

Barium lanthanum bismuth titanate (Ba1−(3/2)xLaxBi4Ti4O15, x = 0–0.4) ceramics were fabricated using the powders synthesized via the solid-state reaction route. X-ray powder diffraction analysis confirmed the above compositions to be monophasic and belonged to the m = 4 member of the Aurivillius family of oxides. The effect of the partial presence of La3+ on Ba2+ sites on the microstructure, dielectric and relaxor behaviour of BaBi4Ti4O15 (BBT) ceramics was investigated. For the compositions pertaining to x ≤ 0.1, the dielectric constant at both room temperature and in the vicinity of the temperature of the dielectric maximum (Tm) of the parent phase (BBT) increased significantly with an increase in x while Tm remained almost constant. Tm shifted towards lower temperatures accompanied by a decrease in the magnitude of the dielectric maximum (εm) with an increase in the lanthanum content (0.1 < x ≤ 0.4). The dielectric relaxation was modelled using the Vogel–Fulcher relation and a decrease in the activation energy for frequency dispersion with increasing x was observed. The frequency dispersion of Tm was found to decrease with an increase in lanthanum doping, and for compositions corresponding to x ≥ 0.3, Tm was frequency independent. Well-developed P(polarization)–E(electric field) hysteresis loops were observed at 150 °C for all the samples and the remanent polarization (2Pr) was improved from 6.3 µC cm−2 for pure BBT to 13.4 µC cm−2 for Ba0.7La0.2Bi4Ti4O15 ceramics. Dc conductivities and associated activation energies were evaluated using impedance spectroscopy.

Direct precipitation of lead zirconate titanate by the hydrothermal method

Direct precipitation of fine powders of lead zirconate titanate (PZT) in the complete range of solid solution, is investigated under hydrothermal conditions, starting from lead oxide and titania/zirconia mixed gels. The perovskite phase is formed in the temperature range of 165 – 340°C. Sequence of the hydrothermal reactions is studied by identifying the intermediate phases. The initial formation of PbO: TiO2 solid solution is followed by the reaction of the same with the remaining mixed gels giving rise to X-ray amorphous PZT phase. Further, through crystallite growth, the X-ray crystalline PZT is formed. This method can be extended for the preparation of PLZT powder as well. The resulting powders are sinterable to high density ceramics.

X-ray and ultraviolet photoelectron spectroscopy studies of the interaction of carbon monoxide with oxygen adsorbed on silver covered with potassium, caesium or barium

X-ray and He(II) ultraviolet photoelectron spectroscopy studies of the interaction of CO with oxygen on potassium-, caesium- and barium-covered Ag surfaces have shown the formation of carbonate at 300 K. While on a caesium-covered surface only carbonate formation takes place, on the potassium- and barium-covered surfaces molecularly chemisorbed CO is also formed. The variation of the surface concentrations of carbon and oxygen with temperature has been examined and a reaction sequence for the interaction of CO with adsorbed oxygen on potassium-, caesium- and barium-covered Ag surfaces is suggested.

ESR Studies of Phase Transitions in Double Propionates: Dicalcium Barium Propionate Ca2Ba(C2H5COO)6

Single crystal [(111) and (100) planes], and powder ESR of Mn2+ (substituting for Ca2+) in Ca2Ba(C2H5COO)6 in the temperature range 220°C to -160°C shows (i) a doubling of both the physically and chemically inequivalent sites, and a change in the magnitude (150 G at -6°C to 170 G at -8°C) as well as the orientation of the D tensor across the -6°C transition and (ii) an inflection point in the D vs T plot across the -75°C transition. The oxygen octahedra around the Ca2+ sites are inferred to undergo alternate rotations, showing the participation of the carboxyl oxygens in the -6°C transition. A relation of the type D=D0(1+αT+βT2) seems to fit the D variation satisfactorily.

O2- and O1- types of oxygen species on Ni and barium-dosed Ni and Cu surfaces

He II UPS and XPS study of oxygen adsorption on Ni and barium-dosed Ni and Cu surfaces at 300 K show two types of oxygen species which are assigned to O2- and O1- (ad).