Dielectric response in ferroelectric BaTiO3

The far-infrared optical and dielectric properties of ferroelectric perovskite titanate powder BaTiO₃ are reported. The terahertz time-domain spectroscopy (THz-TDS) measurement reveals that the low frequency dielectric response of BaTiO₃ is closely related to the lowest pair of transverse optical (TO) and longitudinal optical (LO) modes near at 180 cm⁻¹, which is verified by Raman spectroscopy. This result provides a better understanding of the relation of low-frequency dielectric function with the optical phonon mode for ferroelectric materials. Combining terahertz TDS with Raman spectra, the overall low frequency optical phonon response of BaTiO₃ is presented in an extended spectral range from 6.7 to 1200 cm⁻¹.     

Strain and temperature-dependent dielectric permittivity of cubic SrTiO3: Self-consistent phonon theory calculations

We examine the strain effect on the dielectric permittivity of cubic SrTiO₃ (STO) with Self-Consistent Phonon (SCP) theory calculations. Despite the soft mode frequency overestimation with this theory scheme and workflow, our calculations predict the correct tendency of TO1 with respect to temperature and strain. We found that a uniform tensile strain leads to softer TO1 modes. In addition, the TO1 frequency drops suddenly to zero at a specific temperature in the presence of a ferroelectric transition. The square linear relation between TO1 and temperature is used to estimate the Curie Temperature (T_C), and the STO dielectric permittivity calculated with the Lyddane-Sachs-Teller relation follows the Curie-Weiss (CW) law; which can also be used to determine another T_C value. Results from both approaches are in good agreement with each other and show that T_C increases significantly even when the applied tensile strain is only a few percent.     

Soft modes and phonon interactions in studied by neutron scattering

The low frequency lattice dynamics and its relationship to the second order paraelectric-to-ferroelectric transition in Sn₂P₂S₆ is studied. The dispersion branches of the acoustic and lowest lying optical phonons in the a^*-c^* plane have been obtained in the ferroelectric phase, for x-polarized phonons. Close to the phase transition a considerable softening is found for the lowest optical mode (P_x), comparable to the behaviour observed in previous Raman investigations. As found previously in Sn₂P₂Se₆, a strong coupling between the TO(P_x) and TA(u_xz) phonons is observed, although, apparently, not strong enough to lead to an incommensurate phase. The soft TO(P_x) mode at the zone center is observed. The temperature dependence of its frequency and damping shows that the transition is not entirely displacive. At low temperatures an unusual apparent negative LO-TO splitting is observed which is shown to arise from the coupling of the x-polarized soft mode to the nearby z-polarized optical phonon. For comparison, the soft TO(P_x) dispersion in the a^*-b^* plane is measured in both the paraelectric and ferroelectric phases. Consistent frequency changes and LO-TO splitting are observed, revealing a significant interaction between the TA(u_yx) and LA(u_xx) acoustics branches and the TO and LO soft optic branches, respectively. In contrast, the nearby y-polarized optic branch shows almost no temperature dependence. Finally, the influence of piezoelectric effects on the limiting acoustic slopes in the ferroelectric phase is discussed. Received: 11 May 1998 / Revised and Accepted: 15 June 1998     

‘Soft’ optical phonons and the morphotropic phase transition of the Pb(Ti1−x, Zrx)O3 system

Room temperature Raman scattering results for the Pb(Ti_1?x, Zr_x)O₃ system in its tetragonal ferroelectric phase are analyzed. For x ≤ 0.25, the square of the frequency of the ‘soft’ E(TO) phonon is linear in the Zr concentration. In addition, we find that the morphotropic phase transition at x = 0.535 may be associated with an instability of this ‘soft’ phonon. It is shown that changes in the short-range harmonic forces play an important role in the x-dependence of the ‘soft’ E(TO) phonon frequency.     

Ba_(1-x)Sr_xTiO_3相结构的拉曼光谱研究

本文测定了不同Sr含量的钛酸锶钡(Ba1-xSrxTiO3)纳米晶的拉曼光谱,发现了随着Sr含量的增加,517cm-1[E(TO)与A1(TO)]光学声子模劈裂为双峰和相对低频声子模向低频漂移,而相对高频声子模向高频漂移现象。当x=0.4时,软模解冻,Ba1-xSrxTiO3铁电相不能维持而呈现顺电相结构。     

Thickness dependence of the soft ferroelectric mode in SrTiO3 thin films deposited on MgO

We have measured the complex dielectric constants of SrTiO₃ thin films deposited on MgO substrate, by using the broadband terahertz time-domain spectroscopy. The dielectric dispersion of SrTiO₃ thin films with thickness of 1046, 460 and 55 nm has been observed in the frequency range from 0.1 to 8 THz. The dispersion mainly consists of the TO1 ferroelectric soft mode with a slight absorption of the TO2 phonon mode. From the analysis of the obtained dispersion, we found that the soft mode frequency hardens as the thickness of the film becomes thinner, and is extremely large compared with the bulk crystals. The damping of the soft mode is also larger than that of bulk SrTiO₃, which suggests the extrinsic nature of the broadening of the soft mode dispersion. In the thinnest film of 55 nm, even the shape of the dielectric dispersion changes, which may be related to integrated defects near the interface.     

Broad-band dielectric response of 0.5Ba(Ti0.8Zr0.2)O3–0.5(Ba0.7Ca0.3)TiO3 piezoceramics: soft and central mode behaviour

ABSTRACT

Dielectric properties of 0.5Ba(Ti_0.8Zr_0.2)O₃–0.5(Ba_0.7Ca_0.3)TiO₃ ceramics were probed in the frequency range from 10 Hz to 100 THz in a broad temperature range (10–900 K). Polar soft phonon observed in infrared spectra softens with cooling; however, below 500 K, its frequency becomes temperature independent. Simultaneously, a central mode activates in terahertz and microwave spectra; and it actually drives the ferroelectric phase transitions. Consequently, the phase transitions strongly resemble a crossover between the displacive and order–disorder type. The central mode vanishes below 200 K. The dielectric relaxation in the radiofrequency and microwave range anomalously broadens on cooling below T_C1, resulting in the nearly frequency independent dielectric loss below 200 K. This broadening comes from a broad frequency distribution of ferroelectric domain wall vibrations. Raman spectra reveal new phonons below 400 K, i.e. already 15 K above T_C1. Several weak modes are detected in the paraelectric phase up to 500 K in Raman spectra. Activation of these modes is ascribed to the presence of polar nanoclusters in the material.     

Microwave dielectric dispersion in ferroelectric telluric acid ammonium phosphate

The paper presents the results of the investigation of dielectric dispersion in monoclinic telluric acid ammonium phosphate crystal over the frequency range 1 MHz to 77 GHz. It is shown that ferroelectric dispersion of the Debye type along the direction perpendicular to the plane (101) occurs in the frequency range 10⁸ to 10¹¹ Hz and is caused by a single relaxational soft mode. The relaxational soft mode is caused by the flipping motion of protons between two potential minima in a hydrogen bond. The frequency of the flipping proton mode in the paraelectric phase varies according to v_s = 0.94 (T – T_o ) GHz and decreases to 1.75 GHz at T_c = 317.3 K. The relaxational mode gives the main contribution to the high static dielectric permittivity of this crystal which fits the Curie-Weiss law. The results confirm the order-disorder nature of a proper ferroelectric phase transition of second order.     

LiNbO3:MgO晶体的喇曼光谱研究

首次获得了LiNbO₃:MgO晶体的喇曼光谱。与纯LiNbO₃晶体的喇曼光谱相比较,A₁(TO)模和E(TO)模的谱线数目、频率和相对强度均基本不变,线宽略有增加。这说明,LiNbO₃晶体较强的A₁(TO)和E(TO)振动模的喇曼光谱主要是由氧八面体(NbO₆)特征基团所贡献的。 关键词：     

Raman scattering in the magnetically frustrated double perovskite Sr2YRuO6

The spin correlations and excitations of the Sr₂YRuO₆ double perovskite are investigated by means of Raman scattering, complemented by synchrotron X‐ray diffraction measurements. Anomalous softening of a breathing mode of the oxygen octahedra is observed below ~200 K, much above the long‐range antiferromagnetic ordering temperature, T_N1 = 32 K, due to a spin‐phonon coupling mechanism in the presence of magnetic correlations. A diffusive Raman signal is also observed, possibly associated with spin excitations within magnetically correlated regions. Our results point to a characteristic energy and temperature scale of ~25 meV/200 K below which unusual behavior associated with magnetic correlations is observed in this material. Copyright © 2013 John Wiley & Sons, Ltd.     

Lattice dynamics and ferroelectric instability in ordered and disordered PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

The dynamic Born charges and the frequency spectra of lattice oscillations in the crystals of ordered and disordered PbSc_1/2Ta_1/2O₃ (PST) and PbSc_1/2Nb_1/2O₃ (PSN) solid solutions have been calculated within the framework of the generalized Gordon-Kim model with allowance for the dipole and quadrupole polarizabilities. The phonon spectra of both compounds contain ferroelectric soft modes. The influence of various interactions on the magnitude of dynamic charges and ferroelectric instability in PSN and PST solid solutions has been studied and it is shown that both these charges and the ferroelectric instability are determined by the competition between long-range dipole-dipole interactions and short-range dipole-charge interactions, the determining role played by the interaction of Nb (Ta) cations and oxygen anions in the Nb-O (Ta-O) bond direction.     

Melting of the cooperative Jahn-Teller distortion in LaMnO 3 single crystal studied by Raman spectroscopy

We have studied the behavior of the Raman phonons of a stoichiometric LaMnO₃ single crystal as a function of temperature in the range between 77 K and 900 K. We focus on the three main phonon peaks of the Pbnm structure, related to the tilt, antisymmetric stretching (Jahn-Teller mode) and stretching modes of Mn-O octahedra. The phonon frequencies show a strong softening that can be fit taking into account their renormalization because of three phonon anharmonic effects in the pseudoharmonic approximation. Thermal expansion effects, in particular the variation of Mn-O bond lengths with temperature, are not relevant above 300 K. On the contrary, phonon width behavior deviates from the three phonon scattering processes well bellow T _c . The correlation between the magnitude of the cooperative Jahn-Teller distortion, that disappears at 800 K, and the amplitude of the Raman phonons in the orthorhombic phase is shown. Nevertheless, Pbnm phonons are still observable above this temperature. Phonon width and intensity behavior around T _c can be explained by local melting of the orbital order that begins quite below T _c and by fluctuations of the regular Mn-O octahedra that correspond to dynamic Jahn-Teller distortions. Received 25 January 2001 and Received in final form 14 March 2001     

Microwave study of the soft ferroelectric mode in Sn2P2S6 crystals

This paper presents the results of the investigation of dielectric dispersion in semiconductive ferroelectric Sn₂P₂S₆ crystals over the frequency range 1 kHz to 78.5 GHz. The main dielectric dispersion in Sn₂P₂S₆ is caused by the soft ferroelectric B_u mode and in the vicinity of the Curie point it occurs in the millimeter region. The frequency of the soft mode in the paraelectric phase varies according to v_s = 35 (T-T_c )^½ GHz on approaching the Curie point. The soft mode is strongly overdamped. Close to T_c the relative damping is y/v_s = 14. The dielectric contribution of the soft mode is equal to the static dielectric permittivity and it explains its whole temperature-dependence.     

Geometrical effects in nanodimensional epitaxial films of barium strontium titanate

The effect of the thickness of 6- to 950-nm-thick Ba_0.8Sr_0.2TiO₃ films epitaxially grown on (001)MgO on their ferroelectric properties is investigated. Raman scattering and X-ray diffraction data indicate a structural phase transition taking place at a film thickness of ≈70 nm, which changes drastically the lattice parameters of the film. Raman spectra taken of the films confirm that they are in the ferroelectric state and that their symmetry changes in going over a critical thickness, as revealed by a sharp displacement of the peaks corresponding to the A ₁(TO) and E(TO) components of the soft mode. At film thicknesses of <100 nm, the permittivity versus thickness dependence exhibits two peaks at thicknesses of ～18 and ～36 nm. Near the first peak, the dielectric nonlinearity is considerably higher than near the second one.     

Phonon mode softening at the ferroelectric transition in Eu0.5Ba0.5TiO3

We have observed the effects of phonon mode softening at the ferroelectric transition in Eu_0.5Ba_0.5TiO₃ by ¹⁵¹Eu Mössbauer spectroscopy. Both Eu²⁺ and Eu³⁺ spectral components are observed in the relative area ratio of 90% : 10% and both show a decrease in subspectral area at the transition, centred at 175 K, due to phonon mode softening. Surprisingly, the temperature dependence of the f-factor shows a much stronger response in the Eu³⁺ component than in the Eu²⁺ one. Preliminary analysis of neutron powder diffraction data rules out the possibility that some of the europium might be located on titanium sites.     

Infrared reflectivity spectra of <Emphasis Type="Italic">η</Emphasis>-Na<Subscript>1.3</Subscript>V<Subscript>2</Subscript>O<Subscript>5</Subscript> in the charge disordered and ordered phase

We have measured the far-infrared reflectivity spectra of the sodium vanadium oxide η-Na_1.3V₂O₅ polycrystals in the wide temperature (80–300 K) and frequency (150–1500 cm⁻¹) range. Appearance of new phonon oscillators, phonon oscillator mode splitting and step-like shift of TO and LO frequencies at low temperatures are correlated with the charge-ordering phase transition, which takes place at about 120 K in this vanadium oxide.     

Ferroelectric phenomena in CdSnO<Subscript>3</Subscript>: A first-principles studies

The phonon spectrum of cubic cadmium metastannate and parameters of the crystal structure of its distorted phases were calculated from first principles within the density functional theory. It is shown that the phonon spectrum and the energy spectrum of the distorted phases in α-CdSnO₃ resemble surprisingly the corresponding characteristics of CdTiO₃. The ground state of α-CdSnO₃ is the ferroelectric Pbn2₁ phase, the energy gain from the phase transition to this phase from the nonpolar phase Pbnm is ∼30 meV, and the spontaneous polarization is 0.25 C/m². The analysis of the eigenvector of the ferroelectric mode in α-CdSnO₃ and the partial densities of states indicates that the ferroelectric instability in this crystal, which does not contain transition d-element atoms, is associated with the formation of a covalent bonding between Cd and O atoms.     

The lifetime of the “ferroelectric” phonon in some perovskite crystals at low temperatures

The lifetime of a low-lying transverse optic phonon with the wave vectork=0 (ferroelectric phonon) in perovskite crystals having the Curie point at low temperatures is investigated. Using a phenomenological Hamiltonian it is shown that mainly the process, in which the ferroelectric phonon and the transverse acoustic phonon are destroyed in order to create another optic phonon from the same branch, determines the lifetime of a ferroelectric phonon. The general result is specialized for SrTiO₃, and the temperature dependence of, exhibiting anomalies in comparison with normal ionic crystals, is discussed.The author thanks Dr. M. Marvan of the Physical Faculty of Charles University in Prague and Dr. P. Glogar and Dr. M. Trlifaj of the Institute of Physics, Czechoslovak Academy of Sciences, in Prague for valuable remarks.     

Influence of the soft phonon mode on charge carrier hopping transfer in bismuth-containing layered ferroelectric ceramic oxides

Formulas and calculations explaining the experimental data on maxima frequency displacement for imaginary dielectric components in a low frequency range with a rise in temperature within the limits of the ferroelectric phase were obtained for the ceramic structure SrBi₂(W _x/2Ti _x/2Nb_{1 − x} )₂O₉. At the heart of our consideration lies our assumption of the interaction of jumping charge carriers with a soft phonon mode.     

Proton conductivity and ferroelectric phase transition in hydrogen-bonded ferroelectric NH4IO3

We report on the ac dielectric permittivity (ε) and the electric conductivity (σ_ω), as function of the temperature 300?K?T4IO₃. The main feature of our measured parameters is that, the compound undergoes a ferroelectric phase transition of an improper character, at (368?±?1)K from a high temperature paraelectric phase I (Pm2₁ b) to a low temperature ferroelectric phase II (Pc21n). The electric conduction seems to be protonic. The frequency dependent conductivity has a linear response following the universal power law (σ_{( ω )}?=?A(T)ω ^{s (T)}). The temperature dependence of the frequency exponent s suggests the existence of two types of conduction mechanisms.