Dynamical behavior of the phase transition of strained from atomistic simulations

Using an atomistic shell model we study the temperature dependence of the ferroelectric properties of BaTiO₃ under biaxial compressive strain applicable to growth on perovskites substrate. Molecular dynamics simulations show a “r→c→p” sequence of phase transitions when temperature is increased, and the absence of an “ac phase”. The first-order paraelectric-to-ferroelectric phase transition presents in bulk changes to a second-order one as a consequence of the in-plane constraint imposed by the mechanical boundary conditions. From the tetragonal ferroelectric c phase, the transition takes place in a finite range of temperature where the lattice parameter normal to the plane keeps approximately constant until T_c is reached. Analysis of the local polarization behavior reveals an order–disorder dynamics as the dominant mechanism of the transition.     

Fluctuations and Landau-Devonshire expansion for barium titanate

The experimentally observed temperature dependence of the quartic coefficients in the Landau-Devonshire expansion for BaTiO₃ is naturally accounted for within a proper fluctuation model. It is explained, in particular, why one of the quartic coefficients varies with temperature above T _c , while the second is constant. It is argued that the tetragonal phase in BaTiO₃ exists essentially due to thermal fluctuations, while the true Landau-Devonshire expansion with temperature-independent coefficients favors the rhombohedral ferroelectric phase.     

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.     

Mode dependent scattering of phonons by domain walls in ferroelectric KDP

Thermal conductivity and ballistic phonon imaging measurements in KH₂PO₄ (KDP) at low temperature (T<3K) indicate that scattering from domain walls has a large effect on phonon transport. kDP has a ferroelectric phase transition from tetragonal to orthorhombic structure atT _c =122 K. BelowT _c domains of opposite electric polarization and crystal orientation form unless the sample is colled in an electric field. Thermal conductivity measured along the [100] (tetragonal) axis drops 30% when domain walls are present, which is independent of sample size and temperature. We attribute this decrease to phonon polarization-dependent scattering at the domain boundaries. This is verified by measurements of ballistic transport, using phonon imaging techniques, which reveal the phonon polarization and mode dependence of the scattering. The scattering is successfully modelled using continuum acoustics with simple acoustic mismatch at the domainwall. The interface scattering is found to be mode dependent: Caustic structures in the phonon images due to slow transverse phonons are most affected by the domain wall scattering, which channels these phonons along parallel planes by multiple reflections without mode conversion. Mode conversion scattering, though possible for a number of phonons, has little effect on the overall phonon transmission.     

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.     

Effect of ferroelectric polarization on the adsorption and reaction of ethanol on BaTiO3

The effect of ferroelectric polarization on the adsorption and reaction of ethanol on BaTiO₃ was studied using temperature-programmed desorption (TPD). Consistent with previous studies for methanol, the reactive sticking coefficient for ethanol on the surfaces of the ferroelectric, tetragonal phase of BaTiO₃ was found to be dependent on the orientation of the ferroelectric domains with a higher sticking coefficient on the c⁺ surface relative to the c⁻ surface. TPD peak shapes and the relative product yields were also found to be polarization dependent suggesting that ferroelectric polarization may affect the intrinsic reactivity of the surface.     

First-order phase transition from an antiferromagnetic ferroelectric to a cycloidal multiferroic with weak ferromagnetism during the joint action of applied magnetic and electric fields

The thermodynamics of the phase transition in a perovskite-like multiferroic, in which an antiferromagnetic ferroelectric transforms into a new magnetic state where a spiral spin structure and weak ferromagnetism can coexist in applied magnetic field H, is described. This state forms as a result of a first-order phase transition at a certain temperature (below Néel temperature T _N ), where a helicoidal magnetic structure appears due to the Dzyaloshinskii-Moriya effect. In this case, the axes of electric polarization and the helicoid of magnetic moments are mutually perpendicular and lie in the ab plane, which is normal to principal axis c. Additional electric polarization p, which decreases the total polarization of the ferroelectric P, appears in the ab plane. The effect of applied magnetic and electric fields on the properties of a multiferroic with a helicoidal magnetic structure is described. An alternating electric field is shown to cause a field-linear change in magnetic moment m, whose sign is opposite to the sign of the change of electric field E. The detected hysteretic phenomena that determine the temperature ranges of overheating and supercooling of each phase are explained. A comparison with the experimental data is performed.     

Electric-field influence on the neutron diffuse scattering near the ferroelectric transition of Sr0.61Ba0.39Nb2O6

ABSTRACT

Uniaxial relaxor ferroelectric Sr_0.61Ba_0.39Nb₂O₆ single crystal has been investigated in the vicinity of its phase transition using neutron scattering and dielectric spectroscopy. A global-type thermal hysteresis is evidenced by both techniques in the ferroelectric phase and up to about 15 K above T_c. In addition, a part of the transverse neutron diffuse scattering in the 001 Brillouin zone, presumably related to static nanodomain structure, can be suppressed by prior poling the crystal in electric field of 3 kV/cm. The remaining part of the transverse neutron diffuse scattering and the real part of permittivity show a similar temperature dependence. The temperature position of the maximal scattering intensity T_max depends significantly on the scattering wave vector. T_max shifts monotonically to higher temperature with the increasing wave vector in all investigated cooling and heating regimes. It is concluded that the critical fluctuations have space correlations which depend on frequency and wave vector.     

Dielectric and ferroelectric properties of NBT-BT systems

ABSTRACT

The (1-x)Na_0.5Bi_0.5TiO₃- xBaTiO₃ ceramics (x = 0.1, 0.135 and 0.17) were fabricated by a conventional solid phase sintering process. The bulk density of the obtained samples exceeded 95% of the theoretical relative density as determined by Archimedes method. Dielectric and ferroelectric measurements of these ceramics were performed. Measurements of the ferroelectric properties show that, above the depolarization temperature T_d, the shape of the hysteresis loops approaches that of linear dielectrics. The dielectric study results correlate with the hysteresis loops measurements. The relaxor-like behavior of the investigated materials was revealed.     

Effect of uniaxial stress on the dielectric properties of BaTiO3+0.1wt.%Eu2O3 ceramics

ABSTRACT

BaTiO₃+0.1wt.%Eu₂O₃ ceramics were prepared by a solid-state reaction method. The dielectric behavior of these ceramics as a function of uniaxial pressure has been systematically studied. The external stress showed obvious effects on these properties. An increase of the Curie point (T_c) and decrease of the Curie–Weiss temperature (T₀) was observed with increasing pressure, resulting in an increase in the first-order nature of the phase transformation (T_c–T₀ increases). Broadening and flattening of the permittivity versus temperature curves near their maximum was found. The pressure behavior of thermal hysteresis and the ??/?T vs. T plot suggests that the phase transition changes to second-order type with increasing pressure. Furthermore, the Curie–Weiss constant obtained from a modified Curie–Weiss law strongly decreases with increasing pressure, suggesting that the mechanism of phase transition is going to order–disorder type.     

Dielectric properties of [(CH3)2NH2]3CuCl5 crystal in external electric field

Dielectric properties of [(CH₃)₂NH₂]₃CuCl₅ under the influence of external electric field was studied. At constant values of electric field intensity, the characteristic temperatures T _m and T _c are distinguished, where the maximum value of permittivity and the jump-like decrease of permittivity are observed, respectively. The splitting of the transition is connected with the presence of a defect density wave. Observed in the sinusoidal field, the hysteretic behaviour of permittivity is connected with the slow transition to the ferroelectric phase and the coexistence of the phases in the range (T _m–T _c). The experimentally observed behaviour was explained qualitatively using the Holakovský–Dvo?ák theoretical model.     

Factory-roof-shaped phase front at the paraelectric-ferroelectric transition in KD PO : an incoherent interface

The phase front during the 218 K transition in KD₂PO₄ crystals under a thermal gradient perpendicular to the c ferroelectric axis is observed to have a factory-roof shape. This shape is studied versus the magnitude of G_e in samples cut with faces in (100), (010), (001) planes or in ( 0), (110), (001) ones. A geometric approach as well as the calculation of the elastic-strain energy caused by lattice misfits along the phase front demonstrate the incoherent interface nature of the phase front. Furthemore, the results and their interpretation allow to predict the sign of the lattice deformation u _xx ( > 0). Received 25 April 2002 Published online 29 November 2002     

Size effects on Curie temperature of ferroelectric particles

A model for the size dependence of the Curie temperature T_c of perovskite ferroelectric particles without any free adjustable parameters has been developed. The model predicts that T_c decreases with decreasing particle size. The predictions of the model are in agreement with experimental results for PbTiO₃ and BaTiO₃. PACS 61.46.+w; 77.80.Bh; 77.84.Dy     

Dielectric relaxation in the weak ferroelectric Li2Ge7O15 near the ferroelectric phase transition

The dielectric permittivity of Ni-doped Li₂Ge₇O₁₅ crystals was studied in the vicinity of the ferroelectric phase transition. Introduction of Ni has been shown to suppress the dielectric anomaly and to reduce substantially the transition temperature. A temperature hysteresis in ɛ (T) has been observed in nominally pure and Ni-doped Li₂Ge₇O₁₅ crystals near the transition point. Measurements performed under cooling from the paraphase reveal dispersion of dielectric permittivity at Debye relaxation frequencies of the order of 10⁴–10⁵ Hz at T _c . It is proposed that the hysteresis phenomena and the low-frequency dispersion are caused by residual defects (of the type of random local fields), which become polarized in the ferroelectric phase and become disordered above T _c . Fiz. Tverd. Tela (St. Petersburg) 40, 2198–2201 (December 1998)     

The effect of hydrostatic pressure on the ferroelectric phase transition in [NH2(CH3)2]3[Sb2Cl9]

The effect of hydrostatic pressure on the ferroelectric phase transition temperature in [NH₂(CH₃)₂]₃[Sb₂Cl₉] (DMACA) has been studied by electric permittivity measurements at pressures up to 400 MPa. The pressure-temperature phase diagram is given. The phase transition temperature (T_c) increases with increasing pressure up to 150 MPa, passes through a maximum and then decreases with a further increase of pressure. The unexpected nonlinear decrease in T_c with pressure increasing above 150 MPa suggests that the mechanism of ferroelectric phase transition in DMACA is different from hitherto assumed.     

Optical second harmonic generation and ordering effects in the system of ferroelectric barium titanate nanocrystals

The temperature dependence of the optical second harmonic generation in nanocrystalline BaTiO₃:Eu³⁺ revealed a strong hysteresis in the C_4v-O_h ferroelectric phase transition region. The explanation of the effect by the ordering processes in the system of ferroelectric nanocrystals is confirmed by the experiments in an external electric field.     

Ferroelectric properties of SrTiO3-PbTiO3 solid solutions

Dielectric properties of ceramic samples of Sr_1−x Pb_xTiO₃ solid solutions for x varying from 0 to 0.3 have been studied. The ferroelectric phase transition in this system has been established to persist down to x=0.005. Within the x values of 0.002 to 0.05, the ferroelectric transition temperature is shown to follow the relation T _c=A(x−x _c)^1/2, with A=440 K and x _c=0.002. Fiz. Tverd. Tela (St. Petersburg) 39, 714–717 (April 1997)     

Decoupling of the order-disorder and displacive contributions to the phase transition in NH4H(ClH2CCOO)2

The effects of hydrostatic pressure and substitution of Rb⁺for the ammonium cations on the ferroelectric phase transition temperature in NH₄H(ClH₂CCOO)₂ have been studied by electric permittivity measurements. The transition temperature (T_c) decreases with increasing pressure up to 800 MPa and the pressure coefficient dT_c/dp=−1.4×10⁻² [K/MPa] has been experimentally determined. The substitution of Rb⁺ for the ammonium cations has been shown to considerably lower the ferroelectric phase transition temperature T_c. In mixed crystals, additional electric permittivity anomaly has been clearly evidenced. The results are discussed assuming a model, which combines polarizability effects, related to the heavy ion units, with the pseudo-spin tunnelling.     

Influence of cubic anisotropy in dipole-dipole interactions on structural phase transitions using the renormalization group transformation

The critical behaviour of ferroelectrics is studied forT>T _c and for zero electric field, by the renormalization group techniques ind=3 dimensions. The model hamiltonian we used contains an isotropic exchange coupling and a dipolar interaction with strong cubic anisotropy. A quadratic anisotropic fixed point is found to be stable for the cubic anisotropic scale field. Experiments on BaTiO₃ and KTaO₃ are compared with our results.Work supported by N.F.W.O.     

Spontaneous reorientation of the electric polarization in Eu1 − x Ho x MnO3 multiferroics

The magnetic, dielectric, and ferroelectric properties of Eu_{1 ? x} Ho _x MnO₃ single crystals (0 < x ≤ 0.5), where magnetic ordering can be varied from the canted antiferromagnetic phase to modulated spin structures, have been studied. It has been found that a ferroelectric state appears at x ≥ 0.2 and low temperatures. As the temperature decreases and the holmium content increases, the electric polarization in this state is reoriented from the a axis to the c axis. It has been shown that the polarization is reoriented owing to a change in the spin rotation plane in the cycloidal phase from the ab to cb plane because of the stabilization of the latter upon an increase in the rare-earth contribution to the anisotropy energy. The T-x phase diagram of magnetic and ferroelectric states has been constructed.