Investigation of phase transition in ferroelectric Pb0.70Sr0.30TiO3 thin films

We have carried out dielectric and Raman spectroscopy studies at the 298-623 K temperature range in polycrystalline Pb0.70Sr0.30TiO3 thin films grown by a soft chemical method. The diffuse phase-transition behavior of the thin films was observed by means of the dielectric constant versus temperature curves, which show a broad peak. Such behavior was confirmed later by Raman spectroscopy measurements up to 823 K, indicating that a diffuselike phase transition takes place at around 548-573 K. The damping factor of the E(1TO) soft mode was calculated using the damped simple harmonic oscillator model. on the other hand, Raman modes persist above the tetragonal to cubic phase transition temperature although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of a breakdown of the microscopic local cubic symmetry by chemical disorder. The lack of a well-defined transition temperature and the presence of broad bands at some temperature interval above the ferroelectric-paraelectric phase-transition temperature suggested a diffuse nature of the phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in this thin film. (C) 2004 American Institute of Physics.

Absence of relaxor-like ferroelectric phase transition in (Pb,Sr)TiO3 thin films

We have performed dielectric and micro-Raman spectroscopy measurements in the 298 - 673 K temperature range in polycrystalline Pb0.50Sr0.50TiO3 thin films prepared by a soft chemical method. The phase transition have been investigated by dielectric measurements at various frequencies during the heating cycle. It was found that the temperature corresponding to the peak value of the dielectric constant is frequency-independent, indicating a non-relaxor ferroelectric behavior. However, the dielectric constant versus temperature curves associated with the ferroelectric to paraelectric phase transition showed a broad maximum peak at around 433 K. The observed behavior is explained in terms of a diffuse phase transition. The obtained Raman spectra indicate the presence of a local symmetry disorder, due to a higher strontium concentration in the host lattice. The monitoring of some modes, conducted in the Pb0.50Sr0.50TiO3 thin films, showed that the ferroelectric tetragonal phase undergoes a transition to the paraelectric cubic phase at around 423 K. However, the Raman activity did not disappear, as would be expected from a transition to the cubic paraelectric phase. The strong Raman spectrum observed for this cubic phase is indicative that a diffuse-type phase transition is taking place. This behavior is attributed to distortions of the perovskite structure, allowing the persistence of low-symmetry phase features in cubic phase high above the transition temperature. This result is in contrast to the forbidden first-order Raman spectrum, which would be expected from a cubic paraelectric phase, such as the one observed at high temperature in pure PbTiO3 perovskite.

Study of potassium additive on the phase formation and ferroelectric properties of 0.9PMN-0.1PT ceramics

A recent and innovative method to include Ti into the columbite precursor has permitted to synthesize 0.9PMN-0.1PT powders with high homogeneity. The present work describes this methodology, named modified columbite method, showing that the reaction between MN(T)and PbO at 800 degrees C for 2 h results in perovskite single-phase. The crystal structure alterations in the columbite and perovskite phases obtained by this methodology and the effects of potassium doping were investigated by the Rietveld method. Changes in the powder morphology, density and weight loss during the sintering process were also studied. Conclusively, potassium does not affect significantly the perovskite amount, but reduces the particle and grain sizes. This dopant also changes the relaxor behavior of 0.9PMN-0.1 PT ceramic, reducing the dielectric loss and enhancing the diffuseness of the phase transition. (C) 2005 Published by Elsevier Ltd and Techna Gronp S.r.l.

Preparation and properties of ferroelectric Pb1-xCaxTiO3 thin films produced by the polymeric precursor method

Pb1- xCaxTiO3 thin films with x = 0.24 composition were prepared by the polymeric precursor method on Pt/Ti/SiO2/Si substrates. The surface morphology and crystal structure, and the ferroelectric and dielectric properties of the films were investigated. X-ray diffraction patterns of the films revealed their polycrystalline nature. 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. The multilayer Pb1-xCaxTO3 thin films were granular in structure with a grain size of approximately 60-70 nm. The dielectric constant and dissipation factor were, respectively, 174 and 0.04 at a 1 kHz frequency. The 600-nm thick film showed a current density leakage in the order of 10(-7) A/cm(2) in an electric field of about 51 kV/cm. The C-V characteristics of perovskite thin films showed normal ferroelectric behavior. The remanent polarization and coercive field for the deposited films were 15 muC/cm(2) and 150 kV/cm, respectively. (C) 2001 Kluwer Academic Publishers.

Ferroelectric and optical properties of Ba0.8Sr0.2TiO3 thin film

Barium strontium titanate (Ba0.8Sr0.2TiO3) thin films have been prepared on Pt/Ti/SiO2/Si substrates using a soft solution processing. X-ray diffraction and also micro-Raman spectroscopy showed that the Ba0.8Sr0.2TiO3 thin films exhibited a tetragonal structure at room temperature. The presence of Raman active modes was clearly shown at the 299 and 725 cm(-1) peaks. The tetragonal-to-cubic phase transition in the Ba0.8Sr0.2TiO3 thin films is broadened, and suppressed at about 35 degreesC, with a maximum dielectric constant of 948 (100 kHz). Electrical measurements for the prepared Ba0.8Sr0.2TiO3 thin films showed a remnant polarization (P-r) of 6.5 muC/cm(2), a coercive field (E-c) of 41 kV/cm, and good insulating properties. The dispersion of the refractive index is interpreted in terms of a single electronic oscillator at 6.97 eV. The direct band gap energy (E-g) and the refractive index (n) are estimated to be 3.3 eV and n = 2.27-2.10, respectively. (C) 2002 American Institute of Physics.

Ferroelectric and piezoelectric properties of bismuth titanate thin films grown on different bottom electrodes by soft chemical solution and microwave annealing

Bismuth titanate (Bi4Ti3O12, BIT) films were evaluated for use as lead-free piezoelectric thin films in micro-electromechanical systems. The films were grown by the polymeric precursor method on LaNiO3/SiO2/Si (1 0 0) (LNO), RuO2/SiO2/Si (1 0 0) (RuO2) and Pt/Ti/SiO2/Si (1 0 0) (Pt) bottom electrodes in a microwave furnace at 700 degrees C for 10 min. The domain structure was investigated by piezoresponse force microscopy (PFM). Although the converse piezoelectric coefficient, d(33), regardless of bottom electrode is around (similar to 40 pm/V), those over RuO2 and LNO exhibit better ferroelectric properties, higher remanent polarization (15 and 10 mu C/cm(2)), lower drive voltages (2.6 and 1.3 V) and are fatigue-free. The experimental results demonstrated that the combination of the polymeric precursor method assisted with a microwave furnace is a promising technique to obtain films with good qualities for applications in ferroelectric and piezoelectric devices. (c) 2006 Elsevier Ltd. All rights reserved.

Ferroelectric ceramic/polymer composite for measuring X-ray intensity in the ortovoltage range

Pyroelectric sensors work as a thermal transducer converting the non-quantified thermal flux into the output measurable quantity of electrical charge, voltage or current. Ferroelectric ceramics and ferroelectric polymers have been extensively used as thermal detectors. More recently the research in the field of pyroelectricity has been concentrated on discovering materials with higher figures of merit (FOM), which means better sensing materials. Composite materials obtained with ferroelectric ceramics embedded in polymer host have received great attention because of their formability, mechanical resistance and the possibility to change their dielectric property varying the volume fraction of ceramic particles. In this work composite films made of modified lead titanate (PZ34) and poly(ether-ether-ketone) (PEEK) were characterized and used as sensing element to measure X-ray intensity in the ortovoltage range (120 - 300 kVp). The sensor response varies from 2.70 V to 0.80 V in the energy fluency range of 6.30 to 37.20 W/m(2). Furthermore the absorbed energy was analyzed as a function of the ionizing energy. The results indicate that the PZ34/PEEK composite with 60/40 vol.% can be useful to monitor X-ray radiation therapy.

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.

SrBi2Ta2O9 ferroelectric thick films prepared by electrophoretic deposition using aqueous suspension

SrBi2Ta2O9 ferroelectric thick films were prepared by electrophoretic deposition (EPD). For that, ceramic powders were prepared by chemical method in order to obtain compounds with chemical homogeneity. The polymeric precursor method was used for the synthesis of the SrBi2Ta2O9 powder. The crystallographic structure of the powder was examined by X-ray diffraction, and the surface area was determined by single point BET adsorption. The 0.03 vol.% suspension was formed by dispersing the powder in water using two different polymers as dispersants: an ester polyphosphate (C213) and an ammonium polyacrilate (Darvan 821-A). It was investigated the influence of the different dispersants in the surface properties of the powder by zeta potential measurements. The films were deposited on platinum-coated alumina and Pt/Ti/SiO2/Si substrates by a 4 mA constant current, for 10 min, using two parallel electrodes placed at a separation distance of 3 min in the suspension. Several cycles of deposition-drying of the deposit were carried out until reaching the desired thickness. After thermal treatment at temperatures ranging from 700 to 1000 degreesC, the films were characterized by X-ray diffraction and scanning electron microscopy for the microstructure observation. (C) 2003 Elsevier Ltd. All rights reserved.

High Curie point CaBi2Nb2O9 thin films: A potential candidate for lead-free thin-film piezoelectrics

CaBi2Nb2O9 (CBNO) thin films deposited on platinum coated silicon substrates by the polymeric precursor method exhibited good structural, dielectric, and piezoelectric characteristics. Capacitance-voltage measurements indicated good ferroelectric polarization switching characteristics. Remanent polarization and drive voltage values were 4.2 mu C/cm(2) and 1.7 V for a maximum applied voltage of 10 V. The film has a piezoelectric coefficient d(33) equal to 60 pm/V, current density of 0.7 mu A/cm(2), and Curie temperature of 940 degrees C. The polar-axis-oriented CBNO is a promising candidate for use in lead-free high Curie point in ferroelectric and piezoelectric devices. (c) 2006 American Institute of Physics.

Mechanical and electrical driving field induced high-frequency dielectric anomalies in ferroelectric systems

Polycrystalline or single-crystal ferroelectric materials present dielectric dispersion in the frequency range 100 MHz-1 GHz that has been attributed to a dispersive ( relaxation-like) mechanism as well as a resonant mechanism. Particularly in 'normal' ferroelectric materials, a dielectric response that is indistinguishable from dispersion or a resonance has been reported. Nevertheless, the reported results are not conclusive enough to distinguish each mechanism clearly. A detailed study of the dielectric dispersion phenomenon has been carried out in PbTiO3-based ferroelectric ceramics, with the composition Pb1-xLaxTiO3 (x = 0.15), over a wide range of temperatures and frequencies, including microwave frequencies. The dielectric response of La-modified lead titanate ferroelectric ceramics, in 'virgin' and poled states, has been investigated in the temperature and frequency ranges 300-450 K and 1 kHz-2 GHz, respectively. The results revealed that the frequency dependence of the dielectric anomalies, depending on the measuring direction with respect to the orientation of the macroscopic polarization, may be described as a general mechanism related to an 'over-damped' resonant process. Applying either a uniaxial stress along the measurement field direction or a poling electric field parallel and/or perpendicular to the measuring direction, a resonant response of the real and imaginary components of the dielectric constant is observed, in contrast to the dispersion behavior obtained in the absence of the stress, for the 'virgin' samples. Both results, resonance and/or dispersion, can be explained by considering a common mechanism involving a resonant response (damped and/or over-damped) which is strongly affected by a ferroelastic-ferroelectric coupling, contributing to the low-field dielectric constant.

Experimental and theoretical study of the ferroelectric and piezoelectric behavior of strontium-doped PZT

Theoretical data using ab initio perturbed ion calculation were compared with ferroelectric and piezoelectric experimental data of strontium doped PZT. Various concentrations of SrO in PZT at constant temperature and sintering time were carried out. Experimental results, such as the remanent polarization, P-R of 6.9-8.9 muC/Cm-2, the coercive field, E-C of 6.6-7.8 kVcm, and the planar coupling factor, Kp of 0.45-0.53, were compared with the energy of Zr4+ and Ti4+ ion dislocation and the lattice interaction energy which show that strontium increment in PZT alter the energies and increase the values of piezoelectric and ferroelectric variables. Calculations of lattice energy of the rhombohedral phase show that a phase non-stability is coincident with increasing experimental values of the P-R, E-C and Kp. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Electrical conduction mechanism and phase transition studies using dielectric properties and Raman spectroscopy in ferroelectric Pb0.76Ca0.24TiO3 thin films

We have studied the phase transition behavior of Pb0.76Ca0.24TiO3 thin films using Raman scattering and dielectric measurement techniques. We also have studied the leakage current conduction mechanism as a function of temperature for these thin films on platinized silicon substrates. A Pb0.76Ca0.24TiO3 thin film was prepared using a soft chemical process, called the polymeric precursor method. The results showed that the dependence of the dielectric constant upon the frequency does not reveal any relaxor behavior. However, a diffuse character-type phase transition was observed upon transformation from a cubic paraelectric phase to a tetragonal ferroelectric phase. The temperature dependency of Raman scattering spectra was investigated through the ferroelectric phase transition. The soft mode showed a marked dependence on temperature and its disappearance at about 598 K. on the other hand, Raman modes persist above the tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive above the phase transition temperature. The origin of these modes must be interpreted in terms of a local breakdown of cubic symmetry by some kind of disorder. The lack of a well-defined transition temperature suggested a diffuse-type phase transition. This result corroborate the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in the thin film. The leakage current density of the PCT24 thin film was studied at elevated temperatures, and the data were well fitted by the Schottky emission model. The Schottky barrier height of the PCT24 thin film was estimated to be 1.49 eV. (C) 2003 American Institute of Physics.

Improvement of the ferroelectric properties of ABO(3) (A= Pb, Ca, Ba; B=Ti, Zr) films

High-quality ABO(3)/LaNiO3 (A = Ph, Ca, Ba; B = Ti, Zr) hetero structures have been grown on LaAlO3 (1 0 0) substrate by the chemical solution deposition method and crystallized by a microwave oven technique. The structural, morphological and electric properties were characterized by means of X-ray diffraction (XRD), atomic force microscope (AFM), and dielectric and ferroelectric measurements. XRD patterns revealed single-phase polycrystalline and oriented thin films whose feature depends on the composition of the films. The AFM surface morphologies showed a smooth and crack-free surface with the average grain size ranging from 116 to 300 nm for both LaNiO3 electrode and the ferroelectric films. Dielectric measurements on these samples revealed dielectric constants as high as 1800 at frequency of 100 KHz. Such results showed that the combination of the chemical solution method with the microwave process provides a promising technique to grow high-quality thin films with good dielectric and ferroelectric properties. (c) 2005 Elsevier Ltd. All rights reserved.