Lead zirconate titanate/polyurethane (PZT/PU) composite for acoustic emission sensors

Piezoelectric composite, made from ferroelectric ceramic lead zirconate titanate (PZT) and vegetable based polyurethane (PU) polymer, was doped with a semiconductor filler, graphite. The resulting composite (PZT/C/PU) with 49/1/50- vol. % composition could be poled at lower field and shorter time due to the increased conductivity of the polymer phase following the introduction of graphite. The PZT/C/PU composite showed higher pyroelectric coefficient in comparison with the undoped PZT/PU composite with 50/50-vol. % composition. Also, the PZT/C/PU composite has shown the ability to detect both extensional and flexural modes of simulated acoustic emission (AE) at a distance up to 8.0 m from the source, thus indicating that it may be used for detection of structural damages.

Thickness dependence of structure and piezoelectric properties at nanoscale of polycrystalline lead zirconate titanate thin films

Lead zirconate titanate Pb(Zr0.50Ti0.50)O3 (PZT) thin films were deposited by a polymeric chemical method on Pt(111)/Ti/SiO2/Si substrates to understand the mechanisms of phase transformations and the effect of film thickness on the structure, dielectric, and piezoelectric properties in these films. PZT films pyrolyzed at temperatures higher than 350 °C present a coexistence of pyrochlore and perovskite phases, while only perovskite phase grows in films pyrolyzed at temperatures lower than 300 °C. For pyrochlore-free PZT thin films, a small (100)-orientation tendency near the film-substrate interface was observed. Finally, we demonstrate the existence of a self-polarization effect in the studied PZT thin films. The increase of self-polarization with the film thickness increasing from 200 nm to 710 nm suggests that Schottky barriers and/or mechanical coupling near the film-substrate interface are not primarily responsible for the observed self-polarization effect in our films. © 2013 AIP Publishing LLC.

Synthesis and characterization of lead zirconate titanate (PZT) obtained by two chemical methods

Lead zirconate titanate (PZT) was synthesized at the ratio of Zr/Ti=52/48 using two synthesis methods: the polymeric precursor method (PPM) and the microwave-assisted hydrothermal method (MAHM). The synthesized materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), particle size distribution by sedimentation, hysteresis measurements and photoluminescence (PL). The results showed that PZT powders are composed of tetragonal and rhombohedral phases. Different particle sizes and morphologies were obtained depending upon the synthesis method. From the hysteresis loop verified that PZT powders synthesized by the PPM have a typical loop of ferroelectric material and are more influenced by spatial charges while particles synthesized by the MAHM have a hysteresis loop similar to paraelectric material and are less influenced by spatial charges. Both samples showed PL behavior in the green region (525 nm) whereas the sample synthesized by the PPM showed higher intensity in spectra. © 2013 Elsevier Ltd and Techna Group S.r.l.

Thickness of the near-interface regions and central bulk ohmic resistivity in lead lanthanum zirconate titanate ferroelectric thin films

Thickness of the near-interface regions (NIR) and central bulk ohmic resistivity in lead lanthanum zirconate titanate ferroelectric thin films were investigated. A method to separate the low-resistive near-interface regions (NIRs) from the high-resistive central bulk region (CBR) in ferroelectric thin films was presented. Results showed that the thickness of the NIRs depended on the electrode materials in use and the CBR resistivity depended on the impurity doping levels.

Preparation and structural characterization of rare-earth doped lead lanthanum zirconate titanate ceramics

A new preparation route towards rare-earth (RE) doped polycrystalline lead lanthanum zirconate titanate (PLZT) ceramics (RE = Y(3+), Nd(3+), Yb(3+)), based on the use of doped lanthanum oxide or zirconia, is reported. Structural characterization by X-ray powder diffraction reveals that secondary phase formation can be substantially diminished in comparison to conventional preparation methods. The distribution of the rare-earth dopants was investigated as a function of concentration by static (207)Pb spin echo NMR spectra, using Fourier Transformation of Carr-Purcell-Meiboom-Gill spin echo trains. For the Nd- and Yb-doped materials, the interaction of the (207)Pb nuclei with the unpaired electron spin density results in significant broadening and shifting of the NMR signal, whereas these effects are absent in the diamagnetic Y(3+) doped materials. Based on different concentration dependences of the NMR lineshape parameters, we conclude that the structural role of the Nd(3+) dopants differs significantly from that of Yb(3+). While the Nd(3+) ions appear to be statistically distributed in the PLZT lattice, incorporation of Yb(3+) into PLZT appears to be limited by the appearance of doped cubic zirconia as a secondary phase. (C) 2009 Elsevier Masson SAS. All rights reserved.

Solid state NMR as a new approach for the structural characterization of rare-earth doped lead lanthanum zirconate titanate laser ceramics

To facilitate the design of laser host materials with optimized emission properties, detailed structural information at the atomic level is essential, regarding the local bonding environment of the active ions (distribution over distinct lattice sites) and their extent of local clustering as well as their population distribution over separate micro- or nanophases. The present study explores the potential of solid state NMR spectroscopy to provide such understanding for rare-earth doped lead lanthanum zirconate titanate (PLZT) ceramics. As the NMR signals of the paramagnetic dopant species cannot be observed directly, two complementary approaches are utilized: (1) direct observation of diamagnetic mimics using Sc-45 NMR and (2) study of the paramagnetic interaction of the constituent host lattice nuclei with the rare-earth dopant, using Pb-207 NMR lineshape analysis. Sc-45 MAS NMR spectra of scandium-doped PLZT samples unambiguously reveal scandium to be six-coordinated, suggesting that this rare-earth ion substitutes in the B site. Static Pb-207 spin echo NMR spectra of a series of Tm-doped PLZT samples reveal a clear influence of paramagnetic rare-earth dopant concentration on the NMR lineshape. In the latter case high-fidelity spectra can be obtained by spin echo mapping under systematic incrementation of the excitation frequency, benefiting from the signal-to-noise enhancement afforded by spin echo train Fourier transforms. Consistent with XRD data, the Pb-207 NMR lineshape analysis suggests that statistical incorporation into the PLZT lattice occurs at dopant levels of up to 1 wt.% Tm3+, while at higher levels the solubility limit is reached. (C) 2008 Elsevier Masson SAS. All rights reserved.

Processing and structural properties of random oriented lead lanthanum zirconate titanate thin films

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Schottky barrier heights of tantalum oxide, barium strontium titanate, lead titanate, and strontium bismuth tantalate

The Schottky barrier heights of various metals on the high permitivity oxides tantalum pentoxide, barium strontium titanate, lead zirconate titanate, and strontium bismuth tantalate have been calculated as a function of the metal work function. It is found that these oxides have a dimensionless Schottky barrier pinning factor S of 0.28-0.4 and not close to 1 because S is controlled by Ti-O-type bonds not Sr-O-type bonds, as assumed in earlier work. The band offsets on silicon are asymmetric with a much smaller offset at the conduction band, so that Ta2O5 and barium strontium titanate are relatively poor barriers to electrons on Si. © 1999 American Institute of Physics.

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.

Dielectric and dc electrical studies of antiferroelectric lead zirconate thin films

Antiferroelectric lead zirconate thin films were deposited using KrF (248 nm) excimer laser ablation technique. Utilization of antiferroelectric materials is proposed in high charge storage capacitors and microelectromechanical (MEMs) devices. The antiferroelectric nature of lead zirconate thin films was confirmed by the presence of double hysteresis behavior in polarization versus applied field response. By controlling the processing parameters, two types of microstructures evolved, namely columnar (or in-situ) and multi-grained (or ex-situ) in PZ thin films. The dielectric and electrical properties of the lead zirconate thin films were studied with respect to the processing parameters. Analysis on charge transport mechanism, using space charge limited conduction phenomenon, showed the presence of both shallow and deep trap sites in the PZ thin films. The estimated shallow trap energies were 0.448 and 0.491 eV for in-situ and ex-situ films, with respective concentrations of approximate to 7.9 x 10(18)/cc and approximate to 2.97 x 10(18)/cc. The deep trap energies with concentrations were 1.83 eV with 1.4 x 10(16)/cc for ex-situ and 1.76 eV with 3.8 x 10(16)/cc for in-situ PZ thin films, respectively. These activation energies were found to be consistent with the analysis from Arrhenius plots of de current densities. (C) 2000 Elsevier Science S.A. All rights reserved.

Reactive magnetron co?sputtered antiferroelectric lead zirconate thin films

Antiferroelectric lead zirconate thin films were formed on platinum coated silicon substrates by a reactive magnetron co-sputtering method. The films showed (240) preferred orientation. The crystallization temperatures and the preferred orientation were affected by the lead content in the films. The electric field forced transformation from the antiferroelectric phase to the ferroelectric phase was observed at room temperature with a maximum polarization value of 36 mu C/cm(2). The average field to excite the ferroelectric state and that for the reversion to the antiferroelectric state were 267 and 104 kV/cm respectively. (C) 1995 American Institute of Physics.

Antiferroelectric lead zirconate thin films by pulsed laser ablation

Lead Zirconate (PbZrO3) thin films were deposited by pulsed laser ablation method. Pseudocubic (110) oriented in-situ films were grown at low pressure. The field enforced anti-ferroelectric (AFE) to ferroelectric (FE) phase transformation behaviour was investigated by means of a modified Sawyer Tower circuit as well as capacitance versus applied voltage measurements. The maximum polarisation obtained was 36 mu C cm(-2) and the critical field to induce ferroelectric state and to reverse the antiferroelectric slates were 65 and 90 kV cm(-1) respectively. The dielectric properties were investigated as a function of frequency and temperature. The dielectric constant of the AFE lead zirconate thin him was 190 at 100 kHz which is more than the bulk ceramic value (120) with a dissipation factor of less than 0.07. The polarisation switching kinetics of the antiferroelectric PbZrO3 thin films showed that the switching time to be around 275 ns between antipolar state to polar states. (C) 1999 Elsevier Science S.A. All rights reserved.

ac transport studies of La-modified antiferroelectric lead zirconate thin films

In recent times antiferroelectric thin-film material compositions have been identified as one of the most significant thin films for development of devices such as high charge storage, charge couplers/decouplers, and high strain microelectromechanical systems. Thus, understanding the dielectric and electrical properties under an ac signal drive in these antiferroelectric thin-film compositions, such as lead zirconate thin films, and the effect of donor doping on them is very necessary. For this purpose, thin films of antiferroelectric lead zirconate and La-modified lead zirconate thin films with mole % concentrations of 0, 3, 5, and 9 have been deposited by pulsed excimer laser ablation. The dielectric and hysteresis properties have confirmed that with a gradual increase of the La content, the room-temperature antiferroelectric lead zirconate thin films can be modified into ferroelectric and paraelectric phases. ac electrical studies revealed that the polaronic related hopping conduction is responsible for the charge transport phenomenon in these films. With a La content of less than or equal to3 mole % in pure lead zirconate, the conductivity of the films has been reduced and followed by an increase of its conductivity for a greater than or equal to3% addition of La to lead zirconate thin films. The polaronic activation energies are also found to follow a similar trend as that of the conductivity.

Reversible and irreversible switching processes in pure and lanthanum modified lead zirconate thin films

The mechanism of field induced phase switching in antiferroelectric lead zirconate and La-modified lead zirconate thin films has been analysed in terms of reversible and irreversible switching process under weak fields as a function of donor concentration. Extension of Rayleigh law of ferromagnetic materials to the present antiferroelectric and modified antiferroelectric compositions have clearly showed that origin of small signal dielectric permittivity is due to reversible domain wall motion. Rayleigh's constant, a measure of irreversible switching process, exhibited a slight increase with lower La3+ concentrations and followed by a gradual fall for higher concentration. This clearly illustrates that donor addition to antiferroelectric thin films controls the domain switching even under weak fields. (C) 2002 Elsevier Science B.V. All rights reserved.

Gibbs energy of formation of lead zirconate

The Gibbs energy of formation of zirconia-saturated lead zirconate was determined by emf measurements on the solid state cells and at 800 to 1400 K. The results obtained differ significantly from those reported in the literature based on vapor-pressure measurements, using Knudsen effusion and transportation techniques and assuming that the vapor phase consisted entirely of monomeric PbO molecules. A reanalysis of the data obtained in the earlier vapor-pressure studies, using mass-spectrometric measurements on polymeric PbO species in the gas phase, gives Gibbs energies of formation of lead zirconate which are in better agreement with those obtained in this study. Recent electrochemical measurements using CaO-ZrO2 and PbF2 solid electrolytes are in good agreement with the present study. The results obtained in this study are also consistent with the phase diagram which shows decomposition of the zirconate to tetragonal zirconia and a liquid phase rich in PbO at 1843 K.