Nonlinear dielectric behavior in three-component ferroelectric superlattices

Three-component ferroelectric superlattices consisting of alternating layers of SrTiO3, BaTiO3, and CaTiO3 (SBC) with variable interlayer thickness were fabricated on Pt(111)/TiO2/SiO2/Si (100) substrates by pulsed laser deposition. The presence of satellite reflections in x-ray-diffraction analysis and a periodic concentration of Sr, Ba, and Ca throughout the film in depth profile of secondary ion mass spectrometry analysis confirm the fabrication of superlattice structures. The Pr (remnant polarization) and Ps (saturation polarization) of SBC superlattice with 16.4-nm individual layer thickness (SBC16.4) were found to be around 4.96 and 34 μC/cm2, respectively. The dependence of polarization on individual layer thickness and lattice strain were studied in order to investigate the size dependence of the dielectric properties. The dielectric constant of these superlattices was found to be much higher than the individual component layers present in the superlattice configuration. The relatively higher tunability ( ∼ 55%) obtained around 300 K indicates that the superlattice is a potential electrically tunable material for microwave applications at room temperature. The enhanced dielectric properties were thus discussed in terms of the interfacial strain driven polar region due to high lattice mismatch and electrostatic coupling due to polarization mismatch between individual layers.

Growth and ferroelectric properties of Bi2VO5.5 thin films with metallic LaNiO3 electrodes

Novel ferroelectric bismuth vanadate, Bi2VO5.5 (BVO), thin films have been grown between lattice matched metallic LaNiO3 (LNO) layers deposited on SrTiO3 (STO) by the pulsed laser deposition technique. LNO/BVO/LNO/STO and Au/BVO/LNO/STO trilayer structures exhibited c‐oriented (001) growth of BVO. LNO has been found to be a good metallic electrode with sheet resistance ∼20 Ω in addition to aiding c‐axis oriented BVO growth. The dielectric constant, ϵr of LNO/BVO/LNO/STO, at 300 K was about 12. However, when an Au electrode was used on top of BVO/LNO/STO film, it showed a significant improvement in the dielectric constant (ϵr=123). The ferroelectric properties of BVO thin films have been confirmed by hysteresis behavior with a remnant polarization, Pr=4.6×10−8 C/cm2 and coercive field, Ec=23 kV/cm at 300 K.

Improved ferroelectric and leakage properties in symmetric BiFeO3/SrTiO3 superlattice

Symmetric BiFeO3/SrTiO3 superlattices were fabricated by pulsed laser deposition on SrTiO3 (100) substrates. Frequency independent and near saturated P-E hysteresis was observed in the case of a superlattice (periodicity of ∼ 11 nm) as compared to leaky hysteresis observed in epitaxial BiFeO3. Room temperature leakage current density of the superlattice was almost two orders of magnitude lower than that of BiFeO3. Observed leakage current behavior in case of both BiFeO3 and superlattice indicates the dominance of space charge limited conduction. Improvement in ferroelectric property was discussed in connection to enhanced epitaxial strain, reduced leakage current, and electrostatic interaction between BiFeO3 and SrTiO3.

Ferroelectric interaction and polarization studies in BaTiO3/SrTiO3 superlattice

Ferroelectric superlattice structures consisting of alternating layers of BaTiO3 and SrTiO3 with variable interlayer thickness were grown on Pt (111)/TiO2/SiO2/Si (100) substrates by pulsed laser deposition. The presence of superlattice reflections in the x-ray diffraction pattern clearly showed the superlattice behavior of the fabricated structures over a range of 6.4–20 nm individual layer thicknesses. Depth profile conducted by secondary ion mass spectrometry analysis showed a periodic concentration of Ba and Sr throughout the film. Polarization hysteresis and the capacitance-voltage characteristics of these films show clear size dependent ferroelectric characteristics. The spontaneous (Ps) and remnant (Pr) polarizations increase gradually with decreasing periodicity, reach a maximum at a finite thickness and then decrease. The competition between the size effect and long-range ferroelectric interaction is suggested as a possible reason for this phenomenon. The temperature dependence of Ps and Pr shows a single ferroelectric phase transition, and the Curie temperature is estimated to be about 316 K. The curve shows that the ferroelectric superlattice tends to form an artificial material, responding as a single structure with an averaged behavior of both the parent systems.

Bi4Ti3O12–5BiFeO3 Aurivillius intergrowth: Structural and ferroelectric properties

Aurivillus intergrowth Bi4Ti3O12–5BiFeO3 was demonstrated to be ferroelectric that evoked the possibility of achieving high temperature magnetoelectric property in this family of compounds. X-ray diffraction studies confirmed its structure to be orthorhombic [Fmm2; a = 5.5061(11) Å, b = 5.4857(7) Å, c = 65.742(12) Å]. However, transmission electron microscopy established the random incidence of intergrowth at nanoscale corresponding to n = 6 and n = 7 members of the Aurivillius family. Diffuse ferroelectric orthorhombic to paraelectric tetragonal phase transition around 857 K was confirmed by dielectric and high temperature x-ray diffraction studies. Polarization versus electric field hysteresis loops associated with 2Pr of 5.2 μC/cm2 and coercive field of 42 kV/cm were obtained at 300 K.

Synthesis, structural characterization and ferroelectric properties of Pb(0.76)Ca(0.24)TiO(3) nanotubes

A capillary-enforced template-based method has been applied to fabricate Pb(0.76)Ca(0.24)TiO(3) (PCT24) nanotubes via filling PCT24 precursor solution, prepared by modified sol-gel method, into nanochannels of anodic aluminum oxide templates. The morphology and structure of as-prepared PCT24 were examined by scanning electron microscopy, transmission electron microscopy (TEM) and X-ray diffraction techniques. The obtained PCT24 nanotubes with diameter of similar to 200 nm and wall thickness of similar to 20 nm exhibited a tetragonal perovskite structure. High resolution TEM (HRTEM) analysis confirmed that as-obtained PCT24 nanotubes made up of nanoparticles (5-8 nm) which were randomly aligned in the nanotubes. Formation of some solid crystalline PCT24 nanorods, Y-junctions and multi-branches were observed. Interconnections in the pores of template are responsible for the growth of Y-junctions and multi-branches. The possible formation mechanism of PCT24 nanotubes/nanorods was discussed. Ferroelectric hysteresis loops of PCT24 nanotube arrays were measured, showing a room temperature ferroelectric characteristic of as-prepared PCT24 nanotubes. (C) 2011 Elsevier B.V. All rights reserved.

Relaxor Ferroelectric Behavior and Structural Aspects of SrNaBi2Nb3O12 Ceramics

The SrNaBi2Nb3O12 (SNBN) powder was prepared via the conventional solid-state reaction method. X-ray structural studies confirmed the phase to be a three-layered member of the Aurivillius family of oxides. The SNBN ceramics exhibited the typical characteristics of relaxor ferroelectrics, associated with broad and dispersive dielectric maxima. The variation of temperature of dielectric maxima (T-m) with frequency obeyed the Vogel-Fulcher relationship. Relaxor behavior was believed to be arising from the cationic disorder at A-site. Pinched ferroelectric hysteresis loops were observed well above T-m.

Incremental Cycle Detection, Topological Ordering, and Strong Component Maintenance

We present two online algorithms for maintaining a topological order of a directed n-vertex acyclic graph as arcs are added, and detecting a cycle when one is created. Our first algorithm handles m arc additions in O(m(3/2)) time. For sparse graphs (m/n = O(1)), this bound improves the best previous bound by a logarithmic factor, and is tight to within a constant factor among algorithms satisfying a natural locality property. Our second algorithm handles an arbitrary sequence of arc additions in O(n(5/2)) time. For sufficiently dense graphs, this bound improves the best previous bound by a polynomial factor. Our bound may be far from tight: we show that the algorithm can take Omega(n(2)2 root(2lgn)) time by relating its performance to a generalization of the k-levels problem of combinatorial geometry. A completely different algorithm running in Theta (n(2) log n) time was given recently by Bender, Fineman, and Gilbert. We extend both of our algorithms to the maintenance of strong components, without affecting the asymptotic time bounds.

Coupled phonons, magnetic excitations, and ferroelectricity in AlFeO3: Raman and first-principles studies

We determine the nature of coupled phonons and magnetic excitations in AlFeO3 using inelastic light scattering from 5 to 315 K covering a spectral range from 100 to 2200 cm(-1) and complementary first-principles density functional theory-based calculations. A strong spin-phonon coupling and magnetic ordering-induced phonon renormalization are evident in (1) anomalous temperature dependence of many modes with frequencies below 850 cm(-1), particularly near the magnetic transition temperature T-c approximate to 250 K, and (2) distinct changes in band positions of high-frequency Raman bands between 1100 and 1800 cm(-1); in particular, a broad mode near 1250 cm(-1) appears only below T-c, attributed to the two-magnon Raman scattering. We also observe weak anomalies in the mode frequencies similar to 100 K due to a magnetically driven ferroelectric phase transition. Understanding of these experimental observations has been possible on the basis of first-principles calculations of the phonons' spectrum and their coupling with spins.

Nucleation-Growth Mode of Cubic-Tetragonal Transition with Coexistence of Phases over a Wide Temperature Interval in the High Temperature Ferroelectric Systems PbTiO3-BiMeO3:Me = Sc , and Zn1/2Ti1/2

Temperature dependent X-ray powder diffraction and dielectric studies have been carried out on tetragonal compositions of (1-x) PbTiO 3(x) BiMeO 3; Me similar to Sc and Zn 1/2 Ti 1/2. The cubic and the tetragonal phases coexist over more than 100 degrees C for 0.70 PbTiO 30.3 Bi ( Zn 1/2 Ti 1/2) O 3 and 0.66 PbTiO 30.34 BiScO 3. The wide temperature range of phase coexistence is shown to be an intrinsic feature of the system, and is attributed to the increase in the degree of the covalent character of the ( Pb +Bi ) O bond with increasing concentration of Bi at the Pb -site. The d-values of the {111} planes of the coexisting phases are nearly identical, suggesting this plane to be the invariant plane for the martensitic type cubic-tetragonal transformation occurring in these systems.

Large nonlinear refraction and two photon absorption in ferroelectric Bi2VO5.5 thin films

Ferroelectric c-oriented Bi2VO5.5 (BVO) thin films (thickness approximate to 300 nm) were fabricated by pulsed laser deposition on corning glass substrates. Nonlinear refractive index (n(2)) and two photon absorption coefficient (beta) were measured by Z-scan technique at 532 nm wavelength delivering pulses with 10 ns duration. Relatively large values of n(2) = 2.05 +/- 0.2 x 10(-10) cm(2)/W and beta = 9.36 +/- 0.3 cm/MW were obtained for BVO thin films. Origin of the large optical nonlinearities in BVO thin films was discussed based on bond-orbital theory of transition metal oxides. (c) 2012 Elsevier B.V. All rights reserved.

Ferroelectric-ferroelectric phase coexistence in Na1/2Bi1/2TiO3

Morphotropic phase boundary (MPB) systems are characterized by the coexistence of two ferroelectric phases and are associated with anomalous piezoelectric properties. In general, such coexistence is brought about by composition induced ferroelectric-ferroelectric instability. Here we demonstrate that a pure ferroelectric compound Na1/2Bi1/2TiO3 (NBT) exhibits the coexistence of two ferroelectric phases, rhombohedral (R3c) and monoclinic (Cc), in its equilibrium state at room temperature. This was unravelled by adopting a unique strategy of comparative structural analysis of electrically poled and thermally annealed specimens using high resolution synchrotron x-ray powder diffraction data. The relative fraction of the coexisting phases was found to be highly sensitive to thermal, mechanical, and electrical stimuli. The coexistence of ferroelectric phases in the ground state of the pure compound will have significant bearing on the way MPB is induced in NBT-based lead-free piezoceramics. DOI: 10.1103/PhysRevB.87.060102

Competing structural phase transition scenarios in the giant tetragonality ferroelectric BiFeO3-PbTiO3: Isostructural vs multiphase transition

A systematic x-ray and neutron powder diffraction study of the giant tetragonality multiferroic (1-x) BiFeO3-(x) PbTiO3 have revealed that the compositions close to the morphotropic phase boundary present two different structural phase transition scenarios on cooling from the cubic phase: (i) cubic -> tetragonal (T-2) + tetragonal (T-1) -> tetragonal (T-1) and (ii) cubic -> tetragonal (T-2) + tetragonal (T-1) + rhombohedral (R3c) -> tetragonal (T-1) + rhombohedral (R3c). The comparatively larger tetragonality (c/a - 1) of the T-1 phase as compared to the coexisting isostructural T-2 phase is shown to be a result of significantly greater degree of overlap of the Pb/Bi-6s and Ti/Fe-3d with the O-2p orbitals as compared to that in the T-2 phase. The formation/suppression of the minor metastable rhombohedral phase seems to be governed by subtle play of local kinetic factors. In the scenario when the minor rhombohedral (R) phase is formed along with the tetragonal phases it is able to accommodate the large transformation stress in the system due to formation of the tetragonal phases, and prevent the solid from disintegration into powder after sintering. When the metastable rhombohedral phase is not formed, the large transformation strain ruptures the grain boundaries leading to fragmentation of the dense solid to powder. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4792215]

Effect of crystallite size and clustering in influencing the stability of phases of a very large tetragonality ferroelectric system 0.6BiFeO(3)-0.4PbTiO(3)

The role of crystallite size and clustering in influencing the stability of the structures of a large tetragonality ferroelectric system 0.6BiFeO(3)-0.4PbTiO(3) was investigated. The system exhibits cubic phase for a crystallite size similar to 25 nm, three times larger than the critical size reported for one of its end member PbTiO3. With increased degree of clustering for the same average crystallite size, partial stabilization of the ferroelectric tetragonal phase takes place. The results suggest that clustering helps in reducing the depolarization energy without the need for increasing the crystallite size of free particles.