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.     

Ground state and properties of ferroelectric superlattices based on crystals of the perovskite family

The crystal structure of the ground state of ten free-standing ferroelectric superlattices based on crystals with the perovskite structure (BaTiO₃/SrTiO₃, PbTiO₃/SrTiO₃, PbTiO₃/PbZrO₃, SrZrO₃/SrTiO₃, PbZrO₃/BaZrO₃, BaTiO₃/BaZrO₃, PbTiO₃/BaTiO₃, BaTiO₃/CaTiO₃, KNbO₃/KTaO₃, and KNbO₃/NaNbO₃) was calculated from first principles within the density functional theory taking into account criteria for stability of the structures with respect to acoustic and optical distortions. It was shown that the ground state in all the considered superlattices corresponds to the ferroelectric phase. It was found that the polarization vector has a tendency toward a tilt to the plane of the superlattice layers, which makes it possible to decrease the electrostatic and elastic energy in the superlattices consisting of materials with different ferroelectric properties. The importance of the inclusion of structural distortions due to unstable phonons at the Brillouin zone boundary, which, in a number of cases, lead to significant changes in ferroelectric and dielectric properties of the superlattices, was demonstrated.     

Ferroelectricity in SrTiO3 nanocrystalline disks

SrTiO₃ and CaTiO₃ conventional bulk materials are incipient ferroelectrics. In this note, we report for the first time that ferroelectricity could occur in SrTiO₃ nanocrystalline disks even at room temperature. The peak in the temperature dependence of permittivity for a CaTiO₃ nanocrystalline disk at a low temperature is also observed. The observed ferroelectricity (or permittivity peak) in SrTiO₃ (or CaTiO₃) nanocrystalline disks could be attributed to the strain effect.     

XAFS studies of the local environment of Pb impurity atoms in barium,strontium, and calcium titanates

The local environment of Pb impurity atoms in BaTiO₃, SrTiO₃, and CaTiO₃ crystals was studied by XAFS technique. It is shown that, in both polar and nonpolar phases of BaTiO₃ and in SrTiO₃, the Pb atoms are displaced from the A lattice sites by ～0.15 Å; in CaTiO₃ this displacement is absent. Large values of Debye-Waller factors (0.05–0.10 Ų) for the atoms in the first shell of Pb observed in all the three crystals indicate the distortion of the oxygen environment of Pb atoms. The appearance of these features was explained by the fact that the Pb-O chemical bond has a noticeable covalent component and a Pb atom can form strong bonds only with four of the 12 surrounding oxygen atoms. The obtained data were used to determine the main factors responsible for the occurrence of ferroelectric phase transition in SrTiO₃ and CaTiO₃ and for the increase of the Curie temperature of BaTiO₃ when it is doped with Pb.     

Probing the Ba 5d states in BaTiO3 and BaSO4: A resonant x-ray emission study at the Ba-L3 edge

We have directly probed the Ba 5d states in the ferroelectric barium titanate BaTiO₃ using two bulk-sensitive spectroscopic probes, resonant x-ray emission spectroscopy (RXES) and x-ray absorption spectroscopy in the partial fluorescence mode (PFY-XAS) at the Ba-L₃ edge. The results are compared with those of the non-ferroelectric barium sulfate BaSO₄. While the RXES spectra point to a localized character for the Ba 5d states in both compounds, the main peak of the PFY-XAS spectrum, corresponding to the dipolar transitions from 2p to 5d, is found to be significantly broader for BaTiO₃ than for BaSO₄. On the basis of band structure calculations, this broadening is ascribed to strong hybridization between the unoccupied Ba 5d and O 2p states in the ferroelectric. This suggests that the hybridization between the conduction states of the Ba²⁺ and O^2? ions, and not only Ti⁴⁺ and O^2?, plays a central role in determining the electronic structure of BaTiO₃, and is therefore likely to be indirectly correlated with the occurrence of ferroelectricity in this material.     

Ferroelectric behaviour of 30nm BaTiO3 ceramics prepared by high pressure assisted sintering

Dense nanocrystalline BaTiO3 ceramics with a homogeneous grain size of 30 nm was obtained by pressure assisted sintering. The ferroelectric behaviour of the ceramics was characterized by the dielectric peak at around 120 ℃, the P-E hysteresis loop and some ferroelectric domains. These experimental results indicate that the critical grain size for the disappearance of ferroelectricity in nanocrystalline BaTiO3 ceramics fabricated by pressure assisted sintering is below 30 nm. The ferroelectric property decreasing with decreasing grain size can be explained by the lowered tetragonality and the ＇dilution＇ effect of grain boundaries.     

Magnetic field influence on ferroelectric phase transitions in BaTiO3-type systems

The effect of an external magnetic field on ferroelectric characteristics of BaTiO₃-type crystals is discussed and estimated in the framework of the vibronic theory of ferroelectricity.     

Percolative effects and giant dielectric tunability of BaTiO3–LuFe2O4 composites

We report on exotic dielectric properties of composite materials consisting of traditional ferroelectric BaTiO₃ and electronic ferroelectric LuFe₂O₄. The composites were synthesized by a simple ceramic processing method with properties that can be tailored by adjusting LuFe₂O₄ concentration. A percolative effect was observed at the volume fraction of ～0.26, which led to an abrupt increase in the dielectric permittivity. For composites with high LuFe₂O₄ fractions, a giant dielectric tunability was observed over a broad temperature interval, which is in strong contrast to traditional ferroelectrics.     

The phase transitions and ferroelectric behavior of dense nanocrystalline BaTiO3 ceramics fabricated by pressure assisted sintering

Dense nanocrystalline BaTiO₃ ceramics with uniform grain sizes of 30 nm was obtained by pressure assisted sintering. The phase transitions were investigated by Raman scattering at temperatures ranging from −190 to 200 °C. With increasing temperature, similar to 3 μm BaTiO₃ normal ceramics, the successive phase transitions from rhombohedral to orthorhombic, orthorhombic to tetragonal, tetragonal to cubic were also observed in 30 nm BaTiO₃ ceramics. Especially, the coexistence of ferroelectric tetragonal and orthorhombic phases was found at room temperature. The ferroelectric behavior was further characterized by P-E hysteresis loop. The experimental results indicate that the critical grain size of the disappearance of ferroelectricity in nanocrystalline BaTiO₃ ceramics fabricated by pressure assisted sintering is below 30 nm.     

Aspects of symmetry in the problem of phase transitions in improper ferroelectrics

The term ‘improper’ ferroelectrics has recently come to be used for ferroelectrics in which the spontaneous polarizationP _s is not a transition parameter. From the standpoint of symmetry therefore, the new (polar) symmetry group is no longer the highest common sub-group of the crystal symmetry and the spontaneous polarization symmetry (polar vector symmetry group ∞mm). The concept of an improper ferroelectric has therefore been revised to include transitions from polar to polar groups. It is shown that in the general cases where other parameters are permissible, the problem has to be solved using the symmetry of directions. The present analysis on the bases of irreducible representation of polar crystals establishes all the possible cases where spontaneous polarization is accompanied by spontaneous magnetisation, optical activity and more complex phenomena. The symmetry changes and the polarization configurations in Gd(MoO₄)₃, boracites, (NH₄)₂BeF₄, alkali trihydrogen selenite family have been discussed in the light of the extended concept of an ‘improper’ ferroelectric.     

Orientation dependence of the electrocaloric effect of ferroelectric bilayer thin films

An analytical thermodynamic theory is applied to investigate the electrocaloric effect of ferroelectric BaTiO₃/SrTiO₃ bilayer thin films with different orientations at room temperature. Theoretical analysis indicates that the strong electrostatic coupling between the layers results in the suppression of ferroelectricity at a critical relative thickness which occurs approximately at 50%, 23%, and 12% of SrTiO₃ fraction in the (001), (110), and (111) bilayer thin films, respectively. The ferroelectric bilayer thin films are respected to have the largest electrocaloric effect at this critical relative thickness. Moreover, the electrocaloric effect strongly depends on the orientation and the (110) oriented bilayer thin films have the largest electrocaloric effect. Consequently, control of the orientation and the relative thickness of SrTiO₃ layer can be used to adjust the electrocaloric effect of ferroelectric bilayer thin films, which may provide the potential for practical application in refrigeration devices.     

Lead-free ferroelectric BaTiO3 doped-(Na0.5Bi0.5)TiO3 thin films processed by pulsed laser deposition technique

The difficulties in synthesizing phase pure BaTiO₃ doped-(Na_0.5Bi_0.5)TiO₃ are known. In this work, we reporting the optimized pulsed laser deposition (PLD) conditions for obtaining pure phase 0.92(Na_0.5Bi_0.5)TiO₃-0.08BaTiO₃, (BNT-BT_0.08), thin films. Dielectric, ferroelectric and piezoelectric properties of BNT-BT_0.08, thin films deposited by PLD on Pt/TiO₂/SiO₂/Si substrates are investigated in this paper. Perovskite structure of BNT-BT_0.08 thin films with random orientation of nanocrystallites has been obtained by deposition at 600 °C. The relative dielectric constant and loss tangent at 100 kHz, of BNT-BT_0.08 thin film with 530 nm thickness, were 820 and 0.13, respectively. Ferroelectric hysteresis measurements indicated a remnant polarization value of 22 μC/cm² and a coercive field of 120 kV/cm. The piezoresponse force microscopy (PFM) data showed that most of the grains seem to be constituted of single ferroelectric domain. The as-deposited BNT-BT_0.08 thin film is ferroelectric at the nanoscale level and piezoelectric.     

Thermoelectric transport coefficients of n-doped CaTiO3, SrTiO3 and BaTiO3: A theoretical study

Boltzmann transport equations and density functional theory calculations were employed to calculate the thermoelectric transport coefficients of CaTiO₃, SrTiO₃ and BaTiO₃. It was found that BaTiO₃ has the largest Seebeck coefficient and power factor. Then the transport coefficients were analyzed using the ‘Tight Binding Model’. The band narrowing, caused by the increasing lattice constants from CaTiO₃ to BaTiO₃, was the main reason for the increasing Seebeck coefficients and the decreasing electrical conductivity. The calculated electrical conductivity and electronic thermal conductivity were in line with the Wiedemann-Franz law and the Lorenz factor was determined to be 2.45 for these oxides as degenerate semiconductors. Our theoretical results are helpful for seeking high performance thermoelectric oxides.     

Effects of the depolarization field in a perforated film of the biaxial ferroelectric

The domain structure in a biaxial ferroelectric layer perforated by cylindrical channels has been investigated using the numerical simulation based on the phenomenological theory of ferroelectricity and the equations of electrostatics in the framework of the Gauss-Seidel iterative method. Both polar axes lie in the plane of the film, which is characteristic of thin epitaxial films of BaTiO₃ and (Ba_{1 ? x} Sr _x )TiO₃ on a MgO substrate. The calculations have been performed using the parameters of BaTiO₃, which does not matter because of the qualitative character of the results: the electrostatic problem is two-dimensional and formally applies to infinitely thick layers rather than to thin layers. The primary attention has been paid to the systems containing sixteen channels. Two different orientations of the polar axes with respect to the lattice channels have been considered. It has been shown that, for these orientations, the domain structure has a different character: when the line with the minimum distance between the channels is perpendicular to the bisector of the angle between the polar axes, this structure contains a single channel in the repeating motif and a polarization vortex; when one of the polar axes is perpendicular to the line with the minimum distance between the channels, the situation is less clear. There are indications that the repeating motif of the domain structure in a system of many channels contains two channels and does not contain vortices. The strong influence of the electrodes on the domain structure in this case has been noted.     

‘Dirty’ displacive ferroelectrics

Using the powder Raman technique we have measured most of the lattice vibrational modes in the Pb_1?xLa_xTi_1?x/4O₃ perovskite solid solution series. From the data for these disordered systems the clamped dielectric constant at zero frequency, ?_m, was determined and compared with the clamped dielectric constant, ?_cap, measured by standard capitance techniques. We find that ?_cap/?_m exceeds one, and increases as the transition temperature is approached from below. Strikingly, we also find similar behavior for the ‘classical’ ferroelectrics BaTiO₃, LiNbO₃ and LiTaO₃, as well as for ferroelectrics with the tungsten bronze crystal structure.     

Optical properties of cubic and tetragonal KTa0.5Nb0.5O3 by density functional theory

Using density functional methods, optical properties of KTa_0.5Nb_0.5O₃ (KTN) are investigated. The imaginary part of dielectric function ε₂(ω), the optical absorption coefficient I(ω) and the reflectivity R(ω) of KTN in the cubic (paraelectric) and tetragonal (ferroelectric) phases are calculated. The origin of the different behavior of the optical spectra between the two phases is discussed.     

Properties of BaTiO3/BaZrO3 ferroelectric superlattices with competing instabilities

Properties of (BaTiO₃)₁/(BaZrO₃) _n ferroelectric superlattices (SLs) with n = 1?7 grown in the [001] direction are calculated from first principles within the density functional theory. It is revealed that the quasi-two-dimensional ferroelectricity occurs in these SLs in the barium titanate layers with a thickness of one unit cell; the polarization is oriented in the layer plane and weakly interacts with the polarization in neighboring layers. The ferroelectric ordering energy and the height of the barrier separating different orientational states of polarization in these SLs are sufficiently large to provide the formation of an array of independent polarized planes at 300 K. The effect of the structural instability on the properties of SLs is considered. It is shown that the ground state is a result of simultaneous condensation of the Γ₁₅ polar phonon and phonons at the M point (for SLs with even period) or at the A point (for SLs with odd period); it is a polar structure with out-of-phase rotations of the octahedra in neighboring layers, in which highly polarized layers are spatially separated from the layers with strong rotations. The competition between the ferroelectric and structural instabilities in biaxially compressed SLs manifests itself in that the switching on of the octahedra rotations leads to an abrupt change of the polarization direction and can cause an improper ferroelectric phase transition to occur. It was shown that the experimentally observed z-component of polarization in the SLs can appear only as a result of the mechanical stress relaxation.     

The shape of inhomogeneously broadened resonant lines due to nonlinear contributions

A theory of the shape of inhomogeneously broadened resonant lines is developed for the case where the shifts of the spin-packet resonance frequencies are determined by nonlinear (in particular, quadratic) random-field contributions. It is shown that the line shape I(ω) is described by a narrow δ-type curve with broad wings. Homogeneous broadening reduces the intensity I _max(ω) and broadens the line. A comparison is made of the calculated and measured 93Nb NMR line shapes for PbMg_1/3Nb_2/3O₃ (PMN) at T=430 K and KTa_0.988Nb_0.012O₃ (KTN). The theory describes well the observed resonant-line shape anomalies. Specific features in the structure of the disordered ferroelectrics PMN and KTN are discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 1313–1320 (July 1998)     

Role of electrodes materials in determining the interfacial and magnetoelectric properties in BaTiO<Subscript>3</Subscript>-based multiferroic tunnel junctions

Using the first-principles calculations based on density functional theory, the important role of electrode materials in determining the interfacial, ferroelectric stability and magnetoelectric properties in BaTiO₃-based multiferroic tunnel junctions (MFTJs) have been investigated comparatively. It is found that the SrO–TiO₂ interface of MFTJs with oxide electrode SrRuO₃ is the most favorable interfacial structure. The average ferroelectric polarizations of MFTJs with electrode Co, FeCo and SrRuO₃ are 25, 36 and 0 μC/cm², respectively. The using of alloy electrode FeCo is more contributed to ferroelectric stability and the enhancement of magnetoelectric coupling of BaTiO₃-based MFTJs. We expect our findings can provide an essential evaluation for the selection of electrode materials in spintronic storage devices.