Dynamical,scattering and dielectric properties of ferroelectric crystals

A unified treatment is given of various properties of ferroelectric crystals in their non-polar phases, typified by BaTiO₃, KH₂PO₄ and NaNO₂. Certain relations are established between measurable dielectric and scattering properties. Critical scattering is discussed in terms of lattice dynamics.     

Studies of the electrical properties of nearly perfect K2ZnCl4 single crystals as measured during commensurate incommensurate-paraelectric phase transitions

Electrical conductivity and dielectric measurements were carried in the temperature range covering the commensurate ferroelectric-incommensurate-paraelectric normal phases (300-600 K) for the three main crystallographic axes of K₂ZnCl₄ single crystals. The values of activation energies in the three phases were calculated and discussed. A thermal hysteresis of about 12 K is observed which deduce the presence of first order transition for the lock-in ferroelectric transition at T_c=404 K. Conductivity anomalies were observed in both ferroelectric and paraelectric phases. The conduction mechanism was discussed. The suggested occurrence of discommensuration in K₂ZnCl₄ crystals upon the lock-in transition in contrast with conductivity and dielectric results explains the anomalous behavior for the b-axis measurements. The orientation of these discommensuration was discussed on a view of projection in the three standard crystallographic directions.     

Features of the behavior of longitudinal static and dynamic dielectric, piezoelectric, and elastic characteristics of KH2PO4 and NH4H2PO4 crystals

Along with their electromechanical coupling coefficients, the longitudinal dielectric, piezoelectric and elastic characteristics in ferroelectric KH₂PO₄ and antiferroelectric NH₄H₂PO₄ crystals are calculated using a modified proton ordering model that considers piezoelectric coupling and the four-particle cluster approximation. The possibility of detecting piezoactivity in solid solutions of K_{1 − x} (NH₄)xH₂PO₄ is substantiated.     

Pyroelectric properties of some compounds based on protein aminoacids

Protein aminoacid-based compounds were synthesized, and their single crystals were grown. The dielectric and pyroelectric properties of the crystals were studied in the temperature ranges 80–340 and 140–340 K, respectively. It was established that three of the compounds studied (L-His(H₃PO₄)₂, L-TyrHCl, L-Ala₂H₃PO₃ · H₂O) are linear pyroelectrics, with their room-temperature pyroelectric figures of merit being close to those of ferroelectric triglycine sulfate crystals.     

Crystal stability and the theory of ferroelectricity

The phenomenon of ferroelectricity in pseudo-cubic crystals is discussed in terms of the normal modes of vibration. It is shown that the parameters which determine the lattice vibrations of a diatomic ionic crystal may be chosen in such a way that the crystal will exhibit ferroelectric properties, and that ferroelectric or anti-ferroelectric transitions may be regarded as the result of an instability of the crystal for a certain normal mode of vibration. The theory is extended to apply to other cubic crystals, including barium titanate, and the concepts of ‘ionic polarizability’ and ‘a polarizability catastrophe’ are discussed in terms of lattice dynamics. Certain of the parameters which appear in Devonshire's phenomenological theory of ferroelectricity are found to be expressible in terms of atomic parameters. Values for the latter which are physically reasonable are found to account quite well for the dielectric properties of barium titanate and for the relative movements of the atoms which occur at the cubic-tetragonal transition. The lowest dielectric dispersion frequency is calculated to be about 3 × 10¹¹ c.p.s. for barium titanate, and to be a function of temperature in the cubic phase. Other predictions of the theory are discussed.     

Light scattering spectra of polarization fluctuations and models of the phase transition in KDP type ferroelectrics

Abstract

Recent light scattering studies in KH₂PO₄ type hydrogen-bonded crystals are reviewed. Dynamical properties of these crystals have been discussed in terms of the coupled tunneling proton-optical phonon model up to date. Light scattering spectra in several GHz and cm^?1 regions with various scattering geometries observed in KH₂PO₄, KD₂PO₄ and their mixed crystals, however, revealed that all these spectra are well analysed in terms of a coupled polarization relaxation mode-acoustic phonon system. Since most of the spontaneous polarization is due to shifts of K, P and O ions, relaxation motions of H₂PO₄ dipoles arc concluded to be the origin of these low-frequency spectra. Models of the phase transition mechanism are discussed on the basis of these results and other recent experimental studies including the explanation of large isotope effects in these crystals.     

Anisotropic compressible Ising model for quasi-one-dimensional hydrogen-bonded ferroelectrics

A compressible pseudo-spin Ising model hamiltonian is used to calculate the pressure-temperature phase diagram of quasi-one-dimensional hydrogen-bonded ferroelectric crystals such as CsD₂PO₄. We assume strong effective interactions, which are treated exactly, along chains, and weak volume dependent interactions, which are treated in the mean field approximation, between chains. In agreement with the experimental findings, the phase diagram exhibits a triple point and transition lines between ferroelectric, antiferroelectric, and paraelectric phases. However, the results suggest that the Ising model may be too simple to account for the detailed form of the phase diagram of CsD₂PO₄.     

Effects of oxygen partial pressure on the ferroelectric properties of pulsed laser deposited Ba0.8Sr0.2TiO3 thin films

The Ba_0.8Sr_0.2TiO₃ thin films were grown on the Pt–Si substrate at 700 °C by using a pulsed laser deposition technique at different oxygen partial pressure (PO₂) in the range of 1–20 Pa and their properties were investigated. It is observed that the PO₂ during the deposition plays an important role on the tetragonal distortion ratio, surface morphology, dielectric permittivity, ferroelectric polarization, switching response, and leakage currents of the films. With an increase in PO₂, the in-plane strain for the BST films changes from tensile to compressive. The films grown at 7.5 Pa show the optimum dielectric and ferroelectric properties and also exhibit the good polarization stability. It is assumed that a reasonable compressive strain, increasing the ionic displacement, and thus promotes the in-plane polarization in the field direction, could improve the dielectric permittivity. The butterfly features of the capacitance–voltage (C–V) characteristics and the bell shape curve in polarization current were attributed to the domain reversal process. The effect of pulse amplitude on the polarization reversal behavior of the BST films grown at PO₂ of 7.5 Pa was studied. The peak value of the polarization current shows exponential dependence on the electric field.     

An aspect on relaxor behaviours and phase boundaries in ferroelectric mixed crystals

In order to search for Pb-free relaxor substances and to define relaxor behaviour, a theoretical aspect is presented from not only microscopic but also phenomenological viewpoint. In order–disorder type mixed crystals, the microscopic approach is attempted under conditions similar to those for relaxor perovskite-type oxides. Basing on the theory for the precursor to glass state, two kinds of technique of X-ray diffuse scattering (static properties) and quadrupole perturbed nuclear magnetic resonance (NMR-NQR) (dynamic properties) are discussed in ferroelectric (FE) -- antiferroelectric (AFE) mixed crystals of Rb_1?x(NH₄)_xH₂PO₄. After investigating both boundary regions between FE and glass (G) phases, and between AFE and G phases, relaxor-like behaviours as a large dispersion in dielectric constants are found in the AFE-G phase boundary region where the gradual growth of wave number to make the energy minimum and a discontinuous broad NMR-NQR spectrum appear in quite different forms from those of the FE-G phase boundary region. On the other hand, in perovskite-oxides, the conditions for relaxor appearance are discussed within the phenomenological theory by comparing with the microscopic analysis in hydrogen-bonded systems.     

Ultrasonic stress wave interaction with domain walls in KD2PO4

The experimental results on ultrasonic stress wave interaction with domain walls in KD₂PO₄ crystals are presented. It is shown that the interaction takes place only if stress waves are piezoelectrically coupled to ferroelectric polarization. The temperature dependence of domain wall mobility is found.     

Ferrielectric dielectric behaviour and the nature of phase transition of ammonium sulphate

Phenomenological treatments of ferrielectrics are made in terms of two non-equivalent sublattice polarizations in the paraelectric phase. Unlike the Curie-Weiss behaviour of usual proper ferro- and antiferro-electrics, the dielectric susceptibility does not depend linearly on temperature. Particularly in the case of a first order phase transition, the Curie-Weiss constant seems to be unusually small. As an example, the dielectric properties of (NH₄)₂SO₄, which was known to be a peculiar ferroelectric, is discussed from the ferrielectric point of view. The true Curie-Weiss constant is of a comparable order of magnitude to that of the order-disorder ferroelectric.     

A dynamic study of the quasi-one-dimensional hydrogen-bonded ferroelectric crystal CsH2PO4

The dynamics of the strong-anisotropic Ising model in a transverse field is used with the purpose to explain the dielectric critical slowing down observed experimentally in the quasi-one-dimensional hydrogen-bonded ferroelectric crystal CsH₂PO₄. A good agreement with the experimental data of the temperature dependence of the dielectric constant and the relaxation time is obtained.     

Sodium dithorium trisphosphate — A new ferroelectric substance

Some analyses of polycrystalline samples with the formula MTh₂(PO₄)₃ (M = Li, Na, K, Rb and Cs) have shown that only NaTh₂(PO₄)₃ has piezoelectric properties as well as the ability to retain polarization after the action of an electric field.In the following experiments the hysteresis loops in single crystals of NaTh₂(PO₄)₃ were recorded and ferroelectric parameters at room temperature were determined.     

Rotations of eigenvibration direction in anisotropic crystals

The electric field of incident light induces dipoles in anisotropic media, vibrating in two perpendicular directions of the principal axes. Because of the tensor property of the dielectric constant, an induced dipole is subject to a torque, tending to rotate it about the axis parallel to the propagation direction. The directions of eigenvibration of the ordinary (o-ray) and extraordinary (e-ray) waves are no longer perpendicular in this sense. We propose here the relationships to describe the rotation of the induced dipole in the perpendicular electric fields. The rotation angles are found to increase with increasing dielectric constants and electric field strength of the incident light, exhibiting large values near the resonance frequencies in the infrared range at the azimuth angle /4 of the polarized incident light. Piezoelectric and ferroelectric crystals have a large value of the dielectric constant in the infrared frequency range. Rotations of the vibration direction of the o-ray and the e-ray waves are shown in the infrared transmission spectra recorded by incidence of the polarized light and transmission through piezoelectric and ferroelectric crystals (-quartz, LiNbO₃, and LiTaO₃). Interference of the o-ray and the e-ray waves transmitted through the crystals confirms the rotations of the vibration directions, a self-modulation effect of light in piezoelectric and ferroelectric crystals induced by the electric field of the propagating light.     

Spontaneous phase transition from relaxor to macrodomain ferroelectric state in single-crystal PbSc0.5Nb0.5O3-BaSc0.5Nb0.5O3 solid solutions

The cooling of Pb_1?x Ba_xSc_0.5Nb_0.5O₃ solid solutions with x≤0.04 leads to a spontaneous transition from a relaxor to a macrodomain ferroelectric state, accompanied by anomalous variation of the dielectric and optical properties of the material. As the barium content in the system increases, the relaxor state becomes more stable and eventually “freezes” at x≈0.05. The crystals with x=0.06 exhibited the appearance of a macrodomain ferroelectric phase induced both by an external electric field with a strength of 1.5 kV/cm and by an internal electric field formed in the course of dielectric aging.     

Displacive and order-disorder behavior of KDP-type ferroelectrics on the local scale

The modified strong dipole-proton coupling (MSDPC) model, which predicted several static and dynamic dielectric properties of KH₂PO₄ or KDP-type ferroelectrics, was used to investigate the properties of these crystals on the local scale. Results calculated by molecular dynamics (MD) simulation show that both order-disorder and displacive characteristics of one PO₄ dipole are present in KDP and KD₂PO₄ (DKDP). These results correlate with experimental data from NMR and neutron scattering studies of local properties.     

Growth and characterization of ferroelectric SrBi2Ta2O9 single crystals via high-temperature self-flux solution method

SrBi₂Ta₂O₉ (SBT) single crystals were produced by the high-temperature self-flux solution method using a Bi₂O₃ flux modified with B₂O₃. The processing conditions were optimized to obtain large and translucent SBT crystals with a layered habit and typical dimensions of approximately 7 × 5 × 0.2 mm. X-ray diffraction and x-ray topography measurements revealed that the major faces of the crystals with natural rectangular platelet morphology are perfectly (001)-oriented with edges directed along the [110] directions. The high quality of the crystals was confirmed by rocking curves (half-width of 0.04° for the (0018) reflection) and by ferroelectric measurements. The anisotropy in the dielectric and ferroelectric properties was investigated both along the [110] (ab plane) and the [001] (c axis) directions. The growth mechanism, morphology, and dielectric anisotropy of the SBT crystal platelets are discussed based on its crystallographic structure. This article was submitted by the authors in English     

Light scattering from soft modes in ferroelectric BaZnF4 and BaMgF4

Crystals of the BaM²⁺F₄ family are known to be ferroelectric with extra-polated Curie temperatures lying 100 K or less above their melting points. In the present Raman study the anomalous temperature dependences of frequency and intensity for one vibrational mode in BaZnF₄ and BaMgF₄ are correlated with dielectric properties.     

Far-infrared reflectivity spectrum of potassium dihydrogen phosphate,polarized along the c axis,reinvestigated in the ferroelectric phase

The infrared (IR) reflectivity spectrum of KH₂PO₄, polarized along the c axis, has been carefully reinvestigated in the vicinity of the phase transition temperature and in the ferroelectric phase, between 10 and 600 cm⁻¹. Two new results are displayed by the present study of the A₁, spectrum in the ferroelectric phase of KH₂PO₄: first, the activity of the expected A¹ librational lattice mode is evidenced, the lattice mode parameters of this mode were never previously determined by IR spectroscopy in KH₂PO₄; and second, the peculiar behaviour of the broad reflection band corresponding to the A₁ translational lattice mode is observed for the first time in KH₂PO₄, and discussed.