Structure of the noncubic phase in the ferroelectric state of Pr-substituted SrTiO3

Sr1−xPrxTiO3 has recently been shown to exhibit ferroelectricity at room temperature. In this paper powder x-ray and neutron-diffraction patterns of this system at room temperature have been analyzed to show that the system exhibits cubic (Pm-3m) structure for x<=0.05 and tetragonal (I4/mcm) for x>0.05. The redundancy of the noncentrosymmetric structural model (I4cm) in the ferroelectric state suggests the absence of long-range ordered ferroelectric domains and supports the relaxor ferroelectric model for this system.

Electron paramagnetic-resonance and electron-nuclear double-resonance observations of domains in the irradiated ferroelectrics KH2AsO4 and KD2AsO4

A direct observation of ferroelectric domains in x-irradiated KH2AsO4 and KD2AsO4 using electron paramagnetic resonance (EPR), and in the case of KH2AsO4 also using electron-nuclear double-resonance (ENDOR), is reported. The nature of the observed domain splittings and consequently the effects of an externally applied electric field on the EPR and ENDOR spectra are explained. Moreover, the higher resolution possible with the ENDOR technique, has, for the first time, made it possible to use protons as microscopic probes and to identify in general lines from individual domains in all directions.

Transmission electron microscopy study of domain structures in ferroelectric SrBi2Nb2O9 ceramics

A transmission electron microscopy study has been carried out on the domain structures of SrBi2Nb2O9 (SBN) ferroelectric ceramics which belong to the Aurivillius family of bismuth layered perovskite oxides. SBN is a potential candidate for Ferroelectric Random access memory (FeRAM) applications. The 90° ferroelectric domains and antiphase boundaries (APBs) were identified with dark field imaging techniques using different superlattice reflections which arise as a consequence of octahedral rotations and cationic shifts. The 90° domain walls are irregular in shape without any faceting. The antiphase boundaries are less dense compared to that of SrBi2Ta2O9(SBT). The electron microscopy observations are correlated with the polarization fatigue nature of the ceramic where the domain structures possibly play a key role in the fatigue- free behavior of the Aurivillius family of ferroelectric oxides.

High energy Li ion irradiation effects in ferroelectric PZT and SBT thin films

The ferroelectric Pb(Zr0.53Ti0.47)O-3 (PZT) and SrBi2Ta2O9 (SBT) thin films were prepared by laser ablation technique. The dielectric analysis, capacitance-voltage, ferroelectric hysteresis and DC leakage current measurements were performed before and after 50 MeV Li3+ ion irradiation. In both thin films, the irradiation produced some amount of amorphisation, considerable degradation in the ferroelectric properties and change in DC conductivity. On irradiation of these thin films, the phase transition temperature [T-c] of PZT decreased considerably from 628 to 508 K, while SBT exhibited a broad and diffuse transition with its T-c decreased from 573 to 548 K. The capacitance-voltage curve at 100 kHz showed a double butterfly loop with a large decrease in the capacitance and switching voltage. There was decrease in the ferroelectric hysteresis loop, remanant polarisation and coercive field. After annealing at a temperature of 673 K for 10 min while PZT partially regained the ferroelectric properties, while SBT did not. The DC conductivity measurements showed a shift in the onset of non-linear conduction region in irradiated SBT. The degradation of ferroelectric properties of the irradiated thin films is attributed to the irradiation-induced partial amorphization and the pinning of the ferroelectric domains by trapped charges. The regaining of properties after annealing is attributed to the thermal annealing of the defects generated during the irradiation. (C) 2003 Elsevier Science B.V. All rights reserved.

High energy oxygen ion induced modifications in lead based perovskite thin films

The lead based ferroelectric PbZr0.53Ti0.47O3 (PZT), (Pb0.90La0.10)TiO3 (PLT10) and (Pb0.80La0.20)TiO3 (PLT20) thin films, prepared by pulsed laser ablation technique, were studied for their response to the 70 MeV oxygen ion irradiation. The dielectric analysis, capacitance-voltage (C- V) and DC leakage current measurements were performed before and after the irradiation to high-energy oxygen ions. The irradiation produced considerable changes in the dielectric, C-V, leakage characteristics and induced some amount of amorphization. The PZT films showed partial recrystallization after a thermal annealing at 400 degrees C for 10 min. The phase transition temperature [T-c] of PLT20 increased from 115 degrees C to 120 degrees C. The DC conductivity measurements showed a shift in the onset of non-linear conduction region. The current density decreased by two orders of magnitude after irradiation. After annealing the irradiated films at a temperature of 400 degrees C for 10 min, the films partially regained the dielectric and electrical properties. The results are discussed in terms of the irradiation-induced amorphization, the pinning of the ferroelectric domains by trapped charges and the thermal annealing of the defects generated during the irradiation. (C) 2007 Elsevier B.V. All rights reserved.

Influence of growth below and above T-c on the morphology and domain structure in flux-grown KTP crystals

KTP crystals have been grown below and above the ferroelectric transition temperature by flux method employing both spontaneous and top-seeded solution growth techniques. A slight morphological difference has been observed in these crystals when grown below and above the T-c. Ferroelectric domains are studied in these crystals by selective domain etching. It is seen that the ferroelectric domains in crystals grown spontaneously below T, show a complicated structure. A systematic investigation of the factors influencing domain structure has been carried out. Stress to some extent has been shown to affect the domain structure. Finally, a convenient way of converting the multidomain crystals into monodomain ones is described.

Microstructural and dielectric properties of KCl-added bismuth vanadate ceramics

The effect of KCI addition on the microstructural, structural and dielectric properties of bismuth vanadate, Bi2VO5.5 (BiV) has been examined. The average grain size of BN ceramics increases with increase in KCl content (from an average grain size of TO to 80 mu m) as a result of the increased liquid-phase formation of KCI, at the grain boundaries. Differential scanning calorimetry (DSC) carried out on the KCl-added samples indicates an upward shift in the transition temperature (T-c), from 723 K (for BN) to 734 K (for 5 mol% KCl-added BiV). On further increase in the KCI content, T-c shifts down to about 722 K for 10 mol%. This trend is consistent with that of the lattice strain data. The relative permittivity as well as the dielectric loss decrease by more than half of the original values upon the addition of KCI. The relative permittivities of the KCl-added ceramics are comparable with the values predicted by the logarithmic mixture rule. Impedance analyses suggest that the grain boundary resistance of the KCl-added BiV ceramics is higher by two orders of magnitude than that of BN ceramics. The KCl-added BN ceramics exhibit ferroelectric domains and the domain density decreases as the grain boundary region is approached.

Switching Process in Ferroelectric Triglycine Selenate

Triglycine selenate (TGSe) is isomorphous with Triglycine sulphate and is ferroelectric below 22°C. It is interesting to study the switching process in TGSe in the ferro-state with a view to comparing the results with TSG. The switching process was studied by applying electrical square pulses to produce fields up to 5 kV/cm on the sample, and measuring the parameters characterizing the transient current flowing in the sample, according to the Merz method. The temperature range in which the process was studied was 15°C to -20°C. The results were analysed by applying the Pulvari-Kuebler theory and the parameters α the activation field and µ the mobility of the domains were evaluated. It is found that µ varies with temperature in TGSe in a manner similar to TGS. µ is lesser for TGSe than for TGS for the same shift of temperature from Tc. The switching behaviour of γ-irradiated TGSe is qualitatively similar to that of unirradiated crystal eventhougth the process gets slowed down as a result of irradiation.

Unconventional mechanism of stabilization of a tetragonal phase in the perovskite ferroelectric (PbTiO3)(1-x)(BiFeO3)(x)

Temperature-dependent x-ray powder-diffraction study of the tetragonal compositions of PbTiO3-BiFeO3 series has revealed that, unlike for all the known ferroelectric perovskites, the compositions exhibiting giant tetragonality is stabilized from the cubic phase via a complex transition pathway which involve (i) formation of minor monoclinic phase with a large pseudotetragonality along with an intermediate tetragonal phase (major) with a small tetragonality, (ii) gradual vanishing of the intermediate tetragonal phase and concomitant increase in the monoclinic regions, and finally (iii) gradual transformation of the monoclinic phase to the tetragonal phase with giant tetragonality.The system seems to adopt such a complex transition pathway to create amicrostructure with very large number of domains and interfaces for stress relief, which would not have been possible in case of a direct cubic-tetragonal transition.

Switching studies and the effect of irradiation on ferroelectric properties of TAAP and DTAAP

Polarization switching processes in TAAP and DTAAP have been studied by the Merz method. The switching process in DTAAP is slower than in TAAP. The temperature dependence of switching time indicates that the crystal might contain groups of domain nuclei with different activation energies. X-ray irradiation causes an increase in the threshold field below which switching could not occur and decrease in the mobility of domain walls. Irradiation decreases the peak value of dielectric constant, Tc and increases the value of coercive field. Domain structure studies on TAAP crystals have shown that the crystals grow as both predominantly single domain and multi domains, depending on which the internal bias increases or remains unaffected upon irradiation.

Polarization switching studies in ferroelectric glycine phosphite single crystals

Glycine Phosphite [NH3CH2COOH3PO3], abbreviated as GPI, undergoes a para-ferroelectric phase transition from the monoclinic symmetry P2(1)/a to P2(1) at 224.7 K. We report here a systematic study of the polarization switching process in this crystal. Growth of these crystals from aqueous solution has been undertaken employing both solvent evaporation and slow cooling methods. Hysteresis loop measurements along the polar b-axis yielded a spontaneous polarization value of 0.5 muC/cm(2) and a coercive field of 2.5 kV/cm. Conventional Merz technique was employed for polarization switching studies, wherein bipolar square pulses were applied to the sample to induce domain reversal. The transient switching pulse that flows through the sample on application of the field was recorded. The maximum switching time required for domain switching was measured both as a function of electric field and temperature. The experimentally observed switching curves were fitted with the model based on the Pulvari-Kuebler theory of nucleation and growth of domains. From the experimental data, the values of mobility and activation field were obtained. It was observed that switching process in this crystal is predominantly governed by the forward growth of domain walls in the high field region. However, switching process in GPI crystal was found to be slower than that found in other glycine based ferroelectric crystals.

Influence of lanthanum doping on the dielectric, ferroelectric and relaxor behaviour of barium bismuth titanate ceramics

Barium lanthanum bismuth titanate (Ba1−(3/2)xLaxBi4Ti4O15, x = 0–0.4) ceramics were fabricated using the powders synthesized via the solid-state reaction route. X-ray powder diffraction analysis confirmed the above compositions to be monophasic and belonged to the m = 4 member of the Aurivillius family of oxides. The effect of the partial presence of La3+ on Ba2+ sites on the microstructure, dielectric and relaxor behaviour of BaBi4Ti4O15 (BBT) ceramics was investigated. For the compositions pertaining to x ≤ 0.1, the dielectric constant at both room temperature and in the vicinity of the temperature of the dielectric maximum (Tm) of the parent phase (BBT) increased significantly with an increase in x while Tm remained almost constant. Tm shifted towards lower temperatures accompanied by a decrease in the magnitude of the dielectric maximum (εm) with an increase in the lanthanum content (0.1 < x ≤ 0.4). The dielectric relaxation was modelled using the Vogel–Fulcher relation and a decrease in the activation energy for frequency dispersion with increasing x was observed. The frequency dispersion of Tm was found to decrease with an increase in lanthanum doping, and for compositions corresponding to x ≥ 0.3, Tm was frequency independent. Well-developed P(polarization)–E(electric field) hysteresis loops were observed at 150 °C for all the samples and the remanent polarization (2Pr) was improved from 6.3 µC cm−2 for pure BBT to 13.4 µC cm−2 for Ba0.7La0.2Bi4Ti4O15 ceramics. Dc conductivities and associated activation energies were evaluated using impedance spectroscopy.

Dynamics of the ammonium ion in the ferroelectric transition in sodium ammonium selenate, NaNH4SeO4·2H2O-an E.S.R. study

E.S.R. investigations of γ-irradiated ferroelectric Sodium ammonium selenate, NaNH4SeO4•2H2O and its deuteriated analogue in powder and single crystal forms have led to a deeper understanding of the nature of the ferroelectric transition of 180 K. A number of paramagnetic species formed due to γ-irradiation have been identified on the basis of their g-factors and hyperfine features from 77Se. The radical SeO4 has been used as a microprobe in studying the phase transition.

Competing A-site and B-site driven ferroelectric instabilities in the (1-x)PbTiO3-(x)BiAlO3 system

The system (1-x)PbTiO3-(x)BiAlO3 has been investigated with regard to its solid solubility, crystal structure, microstructure, and ferroelectric transition. The unit cell volume and the tetragonality exhibit anomalous behavior near x=0.10. The Curie point (T-C) of PbTiO3 was however found to be nearly unchanged. The study seems to suggest that the decrease in the stability of the ferroelectric state due to dilution of the Ti-sublattice by smaller sized Al+3 ions is compensated by the increase in the ferroelectric stability by the Bi+3 ions.

Esr study of (SO4)2- dynamics in relation to the ferroelectric phase transition in ammonium sulfate

Ferroelectric phase transition in ammonium sulfate has been studied by ESR of CrO43- radical substituting for SO42- ion in (NH4)2SO4. In addition to discontinuous changes at Tc, certain continuous changes are observed in ESR parameters of this probe below Tc, which reflect the role of the sulfate ion in the phase transition. A microscopic mechanism of the phase transition is proposed and discussed in terms of the change of orientation of the sulfate tetrahedron through a finite angle. The degree of the change of orientation below Tc is thought to be the possible order parameter of the phase transition.