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Title: Pressure-induced ferroelectric to antiferroelectric phase transition in Pb{sub 0.99}(Zr{sub 0.95}Ti{sub 0.05}){sub 0.08}Nb{sub 0.2}O{sub 3}

Abstract

Zr-rich, Nb-doped lead zirconate titanate ceramic and powder samples with composition near Pb{sub 0.99}(Zr{sub 0.95}Ti{sub 0.05}){sub 0.98}Nb{sub 0.02}O{sub 3} [PZT95/5(2Nb)] have been studied in the range of hydrostatic pressure 0-6.2 kbar and temperature 12-295 K by time-of-flight neutron powder diffraction and dielectric measurements. The combination of the two techniques has led to further insights into the properties and pressure-induced ferroelectric rhombohedral R3c (F{sub R(LT)}) to antiferroelectric orthorhombic Pbam (A{sub O}) phase transition in this material, and the diffraction results have provided a detailed view of the ionic displacements induced by changes in pressure and temperature as well as the displacements accompanying the transition. At 295 K the diffraction results revealed a sharp transition at 2.1 kbar; at 200 K this transition occurs at 1.1 kbar. The transformation is incomplete: after the initial sharp drop in the F{sub R(LT)} content at the transition, 20 wt % of the sample remains in the low-pressure F{sub R(LT)} phase. Above the transition, the fraction of F{sub R(LT)}, which exists as a minority phase in the high-pressure A{sub O} phase, continues to decrease, but even at our highest pressure of 6.2 kbar, {approx}8 wt % of the sample remains in the F{sub R(LT)} phase. Themore » volume contraction at the F{sub R(LT)}-to-A{sub O} transition unexpectedly results in the retained minority F{sub R(LT)} being anisotropically ''clamped,'' with its a axis slightly expanded and c axis contracted at the transition. On pressure release to 1 bar at 295 K, only 26% of the F{sub R(LT)} phase is recovered, and this remains in the clamped state because of the surrounding majority A{sub O} phase. Heating the sample above 350 K at 1 bar followed by cooling to room temperature results in full recovery of the F{sub R(LT)} phase. The spontaneous polarization (P{sub S}) of the F{sub R(LT)} phase and its pressure and temperature dependences were determined from the ionic displacements. At 295 K, P{sub S}=38 {mu}C/cm{sup 2}--a value greater than the 31-32 {mu}C/cm{sup 2} commonly observed on ceramic PZT95/5(2Nb) samples. The difference is undoubtedly related to residual porosity in ceramic samples as well as the inability of the poling electric field to align all the polar domains. P{sub S} increases monotonically with decreasing temperature, reaching a value of {approx}44 {mu}C/cm{sup 2} at 12 K.« less

Authors:
; ; ; ; ; ;  [1];  [2]
  1. Argonne National Laboratory, Argonne, Illinois 60636 (United States)
  2. (United States)
Publication Date:
OSTI Identifier:
20787893
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Review. B, Condensed Matter and Materials Physics; Journal Volume: 73; Journal Issue: 6; Other Information: DOI: 10.1103/PhysRevB.73.064105; (c) 2006 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ANTIFERROELECTRIC MATERIALS; CERAMICS; DOPED MATERIALS; ELECTRIC FIELDS; FERROELECTRIC MATERIALS; HEAT TREATMENTS; NEUTRON DIFFRACTION; NIOBIUM; ORTHORHOMBIC LATTICES; PHASE TRANSFORMATIONS; POLARIZATION; POROSITY; POWDERS; PRESSURE DEPENDENCE; PRESSURE RELEASE; PZT; TEMPERATURE DEPENDENCE; TIME-OF-FLIGHT METHOD; TRIGONAL LATTICES

Citation Formats

Avdeev, Maxim, Jorgensen, James D., Short, Simine, Samara, George A., Venturini, Eugene L., Yang, Pin, Morosin, Bruno, and Sandia National Laboratories, Albuquerque, New Mexico 87185. Pressure-induced ferroelectric to antiferroelectric phase transition in Pb{sub 0.99}(Zr{sub 0.95}Ti{sub 0.05}){sub 0.08}Nb{sub 0.2}O{sub 3}. United States: N. p., 2006. Web. doi:10.1103/PHYSREVB.73.0.
Avdeev, Maxim, Jorgensen, James D., Short, Simine, Samara, George A., Venturini, Eugene L., Yang, Pin, Morosin, Bruno, & Sandia National Laboratories, Albuquerque, New Mexico 87185. Pressure-induced ferroelectric to antiferroelectric phase transition in Pb{sub 0.99}(Zr{sub 0.95}Ti{sub 0.05}){sub 0.08}Nb{sub 0.2}O{sub 3}. United States. doi:10.1103/PHYSREVB.73.0.
Avdeev, Maxim, Jorgensen, James D., Short, Simine, Samara, George A., Venturini, Eugene L., Yang, Pin, Morosin, Bruno, and Sandia National Laboratories, Albuquerque, New Mexico 87185. Wed . "Pressure-induced ferroelectric to antiferroelectric phase transition in Pb{sub 0.99}(Zr{sub 0.95}Ti{sub 0.05}){sub 0.08}Nb{sub 0.2}O{sub 3}". United States. doi:10.1103/PHYSREVB.73.0.
@article{osti_20787893,
title = {Pressure-induced ferroelectric to antiferroelectric phase transition in Pb{sub 0.99}(Zr{sub 0.95}Ti{sub 0.05}){sub 0.08}Nb{sub 0.2}O{sub 3}},
author = {Avdeev, Maxim and Jorgensen, James D. and Short, Simine and Samara, George A. and Venturini, Eugene L. and Yang, Pin and Morosin, Bruno and Sandia National Laboratories, Albuquerque, New Mexico 87185},
abstractNote = {Zr-rich, Nb-doped lead zirconate titanate ceramic and powder samples with composition near Pb{sub 0.99}(Zr{sub 0.95}Ti{sub 0.05}){sub 0.98}Nb{sub 0.02}O{sub 3} [PZT95/5(2Nb)] have been studied in the range of hydrostatic pressure 0-6.2 kbar and temperature 12-295 K by time-of-flight neutron powder diffraction and dielectric measurements. The combination of the two techniques has led to further insights into the properties and pressure-induced ferroelectric rhombohedral R3c (F{sub R(LT)}) to antiferroelectric orthorhombic Pbam (A{sub O}) phase transition in this material, and the diffraction results have provided a detailed view of the ionic displacements induced by changes in pressure and temperature as well as the displacements accompanying the transition. At 295 K the diffraction results revealed a sharp transition at 2.1 kbar; at 200 K this transition occurs at 1.1 kbar. The transformation is incomplete: after the initial sharp drop in the F{sub R(LT)} content at the transition, 20 wt % of the sample remains in the low-pressure F{sub R(LT)} phase. Above the transition, the fraction of F{sub R(LT)}, which exists as a minority phase in the high-pressure A{sub O} phase, continues to decrease, but even at our highest pressure of 6.2 kbar, {approx}8 wt % of the sample remains in the F{sub R(LT)} phase. The volume contraction at the F{sub R(LT)}-to-A{sub O} transition unexpectedly results in the retained minority F{sub R(LT)} being anisotropically ''clamped,'' with its a axis slightly expanded and c axis contracted at the transition. On pressure release to 1 bar at 295 K, only 26% of the F{sub R(LT)} phase is recovered, and this remains in the clamped state because of the surrounding majority A{sub O} phase. Heating the sample above 350 K at 1 bar followed by cooling to room temperature results in full recovery of the F{sub R(LT)} phase. The spontaneous polarization (P{sub S}) of the F{sub R(LT)} phase and its pressure and temperature dependences were determined from the ionic displacements. At 295 K, P{sub S}=38 {mu}C/cm{sup 2}--a value greater than the 31-32 {mu}C/cm{sup 2} commonly observed on ceramic PZT95/5(2Nb) samples. The difference is undoubtedly related to residual porosity in ceramic samples as well as the inability of the poling electric field to align all the polar domains. P{sub S} increases monotonically with decreasing temperature, reaching a value of {approx}44 {mu}C/cm{sup 2} at 12 K.},
doi = {10.1103/PHYSREVB.73.0},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 6,
volume = 73,
place = {United States},
year = {Wed Feb 01 00:00:00 EST 2006},
month = {Wed Feb 01 00:00:00 EST 2006}
}
  • No abstract prepared.
  • We have grown crack-free antiferroelectric (AFE) Pb{sub 0.92}La{sub 0.08}Zr{sub 0.95}Ti{sub 0.05}O{sub 3} (PLZT) films on nickel foils by chemical solution deposition. To eliminate the parasitic effect caused by the formation of a low-permittivity interfacial oxide, we applied a conductive buffer layer of lanthanum nickel oxide (LNO) on the nickel foil by chemical solution deposition prior to the PLZT deposition. Use of the LNO buffer allowed high-quality film-on-foil capacitors to be prepared at high temperatures in air. With the AFE PLZT deposited on LNO-buffered Ni foils, we observed field-induced phase transformations of AFE to ferroelectric (FE). The AFE-to-FE phase transition field,more » E{sub AF} = 260 kV cm{sup -1}, and the reverse phase transition field, E{sub FA} = 220 kV cm{sup -1}, were measured at room temperature on a {approx}1.15 {micro}m thick PLZT film grown on LNO-buffered Ni foils. The relative permittivities of the AFE and FE states were {approx}530 and {approx}740, respectively, with dielectric loss <0.05 at room temperature. P-E hysteresis loop measured at room temperature confirmed the field-induced phase transition. The time-relaxation current density was investigated under various applied electric fields. The leakage current density of a 1.15 {micro}m thick AFE PLZT film-on-foil capacitor was 5 x 10{sup -9} A cm{sup -2} at room temperature under 87 kV cm{sup -1} applied field. The breakdown behavior of the AFE PLZT film-on-foil capacitors was studied by Weibull analysis. The mean breakdown time decreased exponentially with increasing applied field. The mean breakdown time was over 610 s when a field of 1.26 MV cm{sup -1} was applied to a 1.15 {micro}m thick AFE PLZT film-on-foil capacitor.« less
  • Lattice dynamics and phase transition of MgO modified Pb{sub 0.99}(Zr{sub 0.95}Ti{sub 0.05}){sub 0.98}Nb{sub 0.02}O{sub 3} (PZTN-x wt. % MgO, x = 0, 0.1, 0.2, 0.5) ceramics have been investigated by far-infrared (FIR) reflectance in the temperature range of 5.5–300 K and Raman spectra between 77 and 300 K, respectively. With the aid of above complementary methods, the structure of all ceramics was defined as low-temperature ferroelectric rhombohedral phase [F{sub R(LT)}] at room temperature. The FIR dielectric functions were extracted from the multi-Lorentz oscillator dispersion model. The lowest frequency phonon mode, which is related to Pb-BO{sub 3} (B = Zr, Ti, Nb) vibration, mainly dominates the FIRmore » dielectric response. With increasing MgO composition, the dielectric constants ε(0) at room temperature are estimated to 85.4, 73.4, 73.9, and 41.9, respectively. The decreasing trend can be due to the doubly ionized oxygen vacancies induced by Mg substitution for B-site. The order-disorder phase transition located around 120 K can be clearly clarified from temperature evolution of phonon frequency, damping, and intensity. It decreases slightly with increasing MgO composition, which influence the distortion due to the broken correlation chains and local permanent dipoles creation. Moreover, the transformation from antiferroelectric orthorhombic A{sub O} to [ F{sub R(LT)} ] phase has been observed around 250 K, which is associated with the antiferroelectric displacement of Pb atoms along 〈 110 〉 and coupled rotations of the corner-connected oxygen octahedral. Furthermore, the transition from [ F{sub R(LT)} ] to [ F{sub R(HT)} ] (high-temperature ferroelectric rhombohedral phase) was identified around 290 K for MgO-doped PZTN ceramics. It arises from the shift of cation (Pb and Zr/Ti/Nb/Mg ions) along the 〈 111 〉 direction and the transition temperature slightly decreases compared to the pure ceramic.« less
  • Most antiferroelectric ceramics are modified from the prototype PbZrO{sub 3} by adding Sn and Ti in conjunction with small amount of Nb or La to optimize their properties. These modifiers introduce unique nanoscale structural feature to the ceramics in the form of incommensurate modulations. It was shown previously that the modulation is strongly responsive to a change in chemical composition or temperature. However, its response to an electric field, the driving force in real applications, has not been explored before. In the present work the dynamic evolution of the incommensurate modulation during the electric field-induced antiferroelectric-to-ferroelectric transformation was observed withmore » an in situ transmission electron microscopy (TEM) technique. The results indicate that the incommensurate modulation exists as a transverse Pb-cation displacement wave. The wavelength was found to be quite stable against external electrical stimuli, in sharp contrast to the dramatic change under thermal stimuli reported previously. It is suggested that the appeared incommensurate modulation is an average effect of a mixture of two commensurate modulations. The electric field-induced antiferroelectric-to-ferroelectric transformation proceeds with aligning the Pb-cation displacements, which resembles the process of 90 deg. reorientation and 180 deg. reversal in normal ferroelectrics.« less
  • Lanthanum substituted lead zirconate-titanate (PLZT) ceramics of composition 11.1/55/45 have been studied by measuring high electric field properties. Dc bias, dielectric and P-E hysteresis loop measurements have been employed to construct an E (electric field) versus T (temperature) phase diagram. At lower temperatures and small electric fields an antiferroelectric phase with tetragonal symmetry has been found. Applying high electric fields gives rise to a field-induced phase transition from the antiferroelectric to the ferroelectric state, however, without x-ray detectable change in crystal symmetry.