Observation of ferroelectricity induced by defect dipoles in the strain-free epitaxial CaTiO3 thin film

CaTiO₃ is a well-known incipient ferroelectric material that does not undergo a ferroelectric phase transition in spite of the intriguing dielectric constant behavior. Especially, unlike a prototypical incipient ferroelectric SrTiO₃, the paraelectric state of CaTiO₃ cannot be easily destroyed by small perturbations, including cation doping and epitaxial strain. We present that a nearly strain-free epitaxial CaTiO₃ film grown at a low oxygen partial pressure exhibits polarization–voltage hysteresis loops and the distinct difference of piezoresponse force microscopy phase signals, implying that a ferroelectric phase is induced. Such results are shown even at room temperature. We suggest that the observed ferroelectric behavior in CaTiO₃ film comes from the defect dipoles composed of vacancies inside the film. Using electron-probe microanalysis and optical absorption spectra measurements, we found that CaTiO₃ film has considerable Ca and O vacancies, forming the localized defect state in electronic structure. This work highlights the importance of vacancies and their clusters, such as defect dipoles, in understanding the electronic properties of perovskite oxide thin films, including ferroelectricity.     

Asymmetric reversible diode-like resistive switching behaviors in ferroelectric BaTiO3 thin films

In this work, the resistive switching behaviors of ferroelectrictric BaTiO3/La0.67Sr0.33MnO3 .heterostructures de- posited by pulsed laser deposition are investigated. The BaTiO3 films show both well-established P-E hysteresis loops, and asymmetric reversible diode-like resistive switching behaviors, involving no forming process. It is found that both the ON/OFF ratio and the stability of resistive switching are substantially dependent on operation voltage （Vmax）. At a Vmax of 15 V, a large ON/OFF resistance ratio above 1000 is obtained at a Vmax of 15 V, which is able to maintain stability up to 70-switching cycles. The above resistive switching behaviors can be understood by modulating interface Schottky barriers as demonstrated by I-V curve fitting.     

Effect of optical pump on the dielectric properties of SrTiO_3 in terahertz range

Tuning the dielectric permittivity spectra of strontium titanate （SrTiO3） single crystals in an extemal optical field is investigated at room temperature by means of terahertz time-domain spectroscopy. The application of the optical field leads to an appreciable tuning of the permittivity, reaching up to 2.8%, with the dielectric loss changing about 3%. The observed behavior is interpreted in terms of soft-mode hardening due to the anharmonic character of its potential. We also find that the change of the refractive index responds linearly to the applied light power. These findings are attributed to a linear electro-optical effect of the internal space charge field of the crystal.     

The Order Parameters of Some Nematic Liquid Crystals Measured by the Resonance Raman Effect and Its Relevance to the Nematic-Isotropic Phase Transition

The second and fourth order parameters of nematic MBBA and 5CB have been determined near the nematic-isotropic transition temperatures by means of resonance Raman measurements on β-carotene dissolved as an orientational probe. The limiting behaviour of the second order parameter of MBBA near the transition point has been investigated on the basis of its fluctuation, which is deduced from the 2nd and 4th order parameter values.     

Second harmonic generation and dielectric study of the fine and coarse grain PMN-35PT ceramics

We investigated the grain size effect on the high temperature behaviour of PMN-35PT ceramics around the tetragonal–cubic phase transition using second harmonic generation (SHG) and dielectric spectroscopy. Our data revealed coexistence of the first-order ferroelectric phase transition and relaxor behaviour in the coarse grain (grain size ～4 µm) µ_PMN-35PT. The phase transition is hindered and relaxor features prevail in the fine grain (grain size ～150 nm) n_PMN-35PT ceramics. Effect of the grain-size reduction on the SHG and dielectric response could be attributed to stabilisation of intermediate domain configurations between the frozen polar nanoclusters and large ferroelectric domains and to the enhanced stability of polar nanoclusters in the fine grain ceramics.     

Electrical second harmonic generation by TGSe and TGS-Se in the autostabilized state

Second harmonic generation and TANDEL effect studies on ferroelectric triglycine selenate and triglycine sulphate-Selenate crystals near the Curie temperature indicate that the generated second harmonic is linear for low biasing fields with a zero off-set, while it decreases sharply at higher biasing fields. In the autostabilized state, the TANDEL elements adjust their impedance against the variation of a.c. field. The experiments on annealed crystals establish that the zero offset is due to the internal bias that owes its origin to the defect structure.     

Sound attenuation in doped displacive ferroelectrics

An expression is obtained for the sound attenuation constant in a doped displacive ferroelectrics in the presence of an external electric field, using double-time temperature-dependent Green’s function technique. The mass and force constant changes due to impurity atoms, are taken into account along with higher order anharmonic and electric dipole moment terms, in the Silverman-Joseph Hamiltonian. The attenuation constant increases with an external electric field. The soft mode is responsible for the anomalously increasing behaviour of the attenuation constant in the vicinity of the Curie temperature. The results agree with those attained by Tani and Tsuda and Heuter and Neuhaus.     

Dielectric relaxation behaviour of liquid crystals with opposite orientation of -COO ester group in molecular core

Dielectric measurements were performed for two smectogens, being structurally analogous with the opposite space orientation of the-COO ester group in the molecular core, using a HP4192A impedance analyser. Gold coated electrode cells of different thicknesses were used. Temperature dependences of the relaxation frequency fR and the inverse of the dielectric strength Δε′_┴ ⁻¹ obtained by fitting experimental values of perpendicular components, i.e., the real ε′_┴ and the imaginary ε″_┴ parts of the complex dielectric permittivity to the Cole-Cole equation as well as the investigation of modification of relaxation processes under bias were determined for the SmC_*, SmA_*, and N_* phases of studied compounds. One can conclude, on the basis of the above results, that dielectric relaxation processes observed by us in the studied compounds are similar to those of the soft and Goldstone mode typically observed by others in the SmC_*, SmA_*, and N_* phases. It is concluded from acomparison of their properties with other related compounds that the link between the biphenyl moiety and-COO ester group is closely related to the stability of smectic phases.     

Multielement XRF Semimicroanalysis of Pb(Zr,Ti)O3 Type Ferroelectric Ceramic Materials Doped with Pb(Nb,Mn)O3 and Bi2O3 by the Thin Layer Method

A method of wavelength-dispersive XRF analysis of Pb(Zr,Ti)O₃ type ferroelectric ceramics doped with Pb(Nb,Mn)O₃ and Bi₂O₃ is presented. The major elements Pb, Zr, Ti and minor elements Nb, Mn, Bi were determined. Matrix effects were minimized by using the thin layer method. Standards of the same chemical composition but varied masses were prepared to simplify calibration. To minimize errors resulting from inhomogeneity of a mass per unit area, the internal standard was used. Preparation of the sample consisted in digesting 25mg of the materials (with nickel as the internal standard) in sulfuric acid, evaporating to dryness and digesting in nitric acid and hydrogen peroxide, filling up to 25mL, and dropping 0.5mL of the solution onto a substrate. Standard samples were prepared by dropping different amounts of the multielement solution onto the substrate. The residual standard deviation for the reference sample of mass from 0.25mg to 0.7mg was within the range of 0.001–0.009mg (correlation coefficient 0.998–0.999) for major elements and within the range of 0.00003–0.0009mg (correlation coefficient 0.989–0.993) for minor elements. The detection limits for 0.5mg samples were within the range of 0.015%–0.35% for manganese and zirconium, respectively.     

Preparation and Characterization of the Nanocomposites SiO2/H-Bond Hydrogensulphate (Hydrogenselenate)

The nanocomposites representing interesting H-bond compounds (Na₃H(SO₄)₂, RbHSO₄, RbHSeO₄, and Rb₃H(SeO₄)₂) in the silica matrix were prepared by the sol-gel method. Resulting samples were characterised by X-ray diffraction, IR spectroscopy and electron microscopy. Transition temperatures of the nanocomposites were determined using DSC and compared with the T _C of the pure bulk active compounds. The shifts of the T _C towards lower temperatures or the disappearing of the certain effects in the case nanocomposites were observed. A possible explanation of these phenomena was proposed using the analogy with the superparamagnetic compounds.