The monoclinic phase of PZT ceramics: Raman and phenomenological theory studies

This work reports on the first Raman detection of the tetragonal to monoclinic phase transition in PZT ceramics near morphotropic phase boundary at low temperatures. The transition is characterized by changes in the frequency of lattice modes with the temperature. The results presented here confirm the previous one recently reported by Noheda et al. using high-resolution synchrotron X-ray powder diffraction technique and dielectric measurements. The stability of the new phase is discussed within the framework of phenomenological Landau-Devonshire Theory.Comment: 6 pages including 4 figures, Latex, submitted to Applied Physics Letter

Electrical Characterization of PbZr0.4Ti0.6O3 Capacitors

We have conducted a careful study of current-voltage (I-V) characteristics in fully integrated commercial PbZr0.4Ti0.6O3 thin film capacitors with Pt bottom and Ir/IrO2 top electrodes. Highly reproducible steady state I-V were obtained at various temperatures over two decades in voltage from current-time data and analyzed in terms of several common transport models including space charge limited conduction, Schottky thermionic emission under full and partial depletion and Poole-Frenkel conduction, showing that the later is the most plausible leakage mechanism in these high quality films. In addition, ferroelectric hysteresis loops and capacitance-voltage data were obtained over a large range of temperatures and discussed in terms of a modified Landau-Ginzburg-Devonshire theory accounting for space charge effects.Comment: 17 pages, 7 figure

A Raman Study of Morphotropic Phase Boundary in PbZr1-xTixO3 at low temperatures

Raman spectra of PbZr1-xTixO3 ceramics with titanium concentration varying between 0.40 and 0.60 were measured at 7 K. By observing the concentration-frequency dependence of vibrational modes, we identified the boundaries among rhombohedral, monoclinic, and tetragonal ferroelectric phases. The analysis of the spectra was made in the view of theory group analysis making possible the assignment of some modes for the monoclinic phase.Comment: 5 pages, 4 figure

Low-temperature phase transformations of PZT in the morphotropic phase-boundary region

We present anelastic and dielectric spectroscopy measurements of PbZr(1-x)Ti(x)O(3) with 0.455 < x < 0.53, which provide new information on the low temperature phase transitions. The tetragonal-to-monoclinic transformation is first-order for x < 0.48 and causes a softening of the polycrystal Young's modulus whose amplitude may exceed the one at the cubic-to-tetragonal transformation; this is explainable in terms of linear coupling between shear strain components and tilting angle of polarization in the monoclinic phase. The transition involving rotations of the octahedra below 200 K is visible both in the dielectric and anelastic losses, and it extends within the tetragonal phase, as predicted by recent first-principle calculations.Comment: 4 pages, 4 figure

Lateral Size and Thickness Dependence in Ferroelectric Nanostructures Formed by Localized Domain Switching

Ferroelectric nanostructures can be formed by local switching of domains using techniques such as piezo-force microscopy (PFM). Understanding lateral size effects is important to determine the minimum feature size for writing ferroelectric nanostructures. To understand these lateral size effects, we use the time-dependent-Ginzburg-Landau equations to simulate localized switching of domains for a PFM type and parallel-plate capacitor configurations. Our investigations indicate that fringing electric fields lead to switching via 90 deg domain wedge nucleation for thicker films while at smaller thicknesses, the polarization switches directly by 180 deg rotations. The voltage required to switch the domain increases by decreasing the lateral size and at very small lateral sizes the coercive voltage becomes so large that it becomes virtually impossible to switch the domain. In all cases, the width of the switched region extends beyond the electrodes, due to fringing.Comment: 21 pages, 11 figure

Superparaelectric phase in the ensemble of non-interacting ferroelectric nanoparticles

For the first time we predict the conditions of superparaelectric phase appearance in the ensemble of non-interacting spherical ferroelectric nanoparticles. The superparaelectricity in nanoparticle was defined by analogy with superparamagnetism, obtained earlier in small nanoparticles made of paramagnetic material. Calculations of correlation radius, energetic barriers of polarization reorientation and polarization response to external electric field, were performed within Landau-Ginzburg phenomenological approach for perovskites Pb(Zr,Ti)O3, BiFeO3 and uniaxial ferroelectrics rochelle salt and triglycine sulfate.Comment: 28 pages, 7 figures, 3 Appendices, to be submitted to Phys. Rev.

Phenomenological theory of phase transitions in highly piezoelectric perovskites

Recently discovered fine structure of the morphotropic phase boundaries in highly piezoelectric mixture compounds PZT, PMN-PT, and PZN-PT demonstrates the importance of highly non-linear interactions in these systems. We show that an adequate Landau-type description of the ferroelectric phase transitions in these compounds is achieved by the use of a twelfth-order expansion of the Landau potential in terms of the phenomenological order parameter. Group-theoretical and catastrophe-theory methods are used in constructing the appropriate Landau potential. A complete phase diagram is calculated in phenomenological parameter space. The theory describes both PZT and PZN-PT types of phase diagrams, including the newly found monoclinic and orthorhombic phases. Anomalously large piezoelectric coefficients are predicted in the vicinity of the phase transition lines.Comment: RevTex4, 8 pages, 2 figures. Dramatically changed after referees' Comments, to appear in Phys. Rev. B, 1 April 200

Thermodynamics of nanodomain formation and breakdown in Scanning Probe Microscopy: Landau-Ginzburg-Devonshire approach

Thermodynamics of tip-induced nanodomain formation in scanning probe microscopy of ferroelectric films and crystals is studied using the Landau-Ginzburg-Devonshire phenomenological approach. The local redistribution of polarization induced by the biased probe apex is analyzed including the effects of polarization gradients, field dependence of dielectric properties, intrinsic domain wall width, and film thickness. The polarization distribution inside subcritical nucleus of the domain preceding the nucleation event is very smooth and localized below the probe, and the electrostatic field distribution is dominated by the tip. In contrast, polarization distribution inside the stable domain is rectangular-like, and the associated electrostatic fields clearly illustrate the presence of tip-induced and depolarization field components. The calculated coercive biases of domain formation are in a good agreement with available experimental results for typical ferroelectric materials. The microscopic origin of the observed domain tip elongation in the region where the probe electric field is much smaller than the intrinsic coercive field is the positive depolarization field in front of the moving counter domain wall. For infinitely thin domain walls local domain breakdown through the sample depth appears. The results obtained here are complementary to the Landauer-Molotskii energetic approach.Comment: 35 pages, 8 figures, suplementary attached, to be submitted to Phys. Rev.