Structure and Polarization Relaxation of Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript>/(001)Si Films

The structure and dielectric characteristics of strontium barium niobate thin films deposited on single-crystalline silicon substrates without buffer layers are studied. It is found that the c axis in these heterostructures runs largely normally to the substrate surface and the a and b axes are randomly oriented in the plane of the substrate. The polarization relaxation in such heterostructures is investigated. It is shown that the film–substrate interface in the heterostructures grown by rf cathode sputtering may contain a low amount of long-lived charged defects.     

Dielectric investigations in Sr<Subscript>0.75</Subscript>Ba<Subscript>0.25</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> relaxor ferroelectric thin films

The dielectric properties of Sr_0.75Ba_0.25Nb₂O₆ relaxor ferroelectric thin films were carefully analyzed. In contrast to bulk samples which present three distinct dielectric relaxation phenomena Sr_0.75Ba_0.25Nb₂O₆ thin films present only two of them. The suppression of the third anomaly can be mainly attributed to the narrow grain size distribution of nanograins and weak tensile strains imposed to the film from the substrate. The whole set of results point to the interpretation of a dielectric response characteristic of mesoscopic structure, which is composed of clusters and nanodomains.     

Specific features in the ferroelectric properties of Sr<Subscript>0.75</Subscript>Ba<Subscript>0.25</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> crystals

The dielectric properties of strontium-barium niobate crystals with a strontium concentration of 0.75, which corresponds to the most smeared ferroelectric phase transition, were measured. The dielectric hysteresis loops and the polarization relaxation are shown to exhibit clearly pronounced features characteristic of crystals with structural disorder and a broad distribution of a random internal electric field. The measurements were performed in dc, slowly varying (quasi-static), and pulsed electric fields. The experimental data obtained are used to construct the distribution function for the coercive field in the crystal bulk.     

Formation of nanodomain ensembles during polarization reversal in Sr<Subscript>0.61</Subscript>Ba<Subscript>0.39</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript>: Ce single crystals

The results of the study of nano- and microdomain structure evolution in single crystals of relaxor ferroelectric strontium barium niobate Sr_0.61Ba_0.39Nb₂O₆ doped by cerium are presented. It was shown that the initial nanodomain structure represents a self-similar three-dimensional maze. The fractal dimension and average period were revealed. It was demonstrated that application of series of alternating electric field pulses makes it possible to produce a single-domain state in the surface layer. The features of the growth and “merging,” as well as the shape of ensembles of isolated nanodomains formed during switching from the single-domain state, were investigated. The formation of the nanodomain ensembles was considered as a result of the self-organized discrete switching controlled by determined nucleation.     

Electro-optic properties of epitaxial Sr<Subscript>0.6</Subscript>Ba<Subscript>0.4</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> films grown on MgO substrates using Li<Subscript>x</Subscript>Ni<Subscript>2-x</Subscript>O buffer layer

Textured Li_xNi_2-xO (LNO) thin films have been fabricated on (001)MgO substrates by pulsed laser deposition technique. The as-deposited LNO films shows a conductivity of 2.5×10^-3 Ω m and possess a transmittance of about 35% in the visible region. Subsequent deposition of Sr_0.6Ba_0.4Nb₂O₆ (SBN60) thin film on these LNO-coated MgO substrates resulted in a textured SBN layer with a 〈001〉 orientation perpendicular to the substrate plane. Phi scans on the (221) plane of the SBN layer indicated that the films have two in-plane orientations with respect to the substrate. The SBN unit cells were rotated in the plane of the film by ± 8.2° as well as ± 45° with respect to the LNO/MgO substrate. Besides the highly (00l)-orientation, the SBN films also exhibited a dense microstructure as shown by scanning electron microscopy. The electro-optic coefficient (r₃₃) of the SBN film was measured to be 186 pm/V. On the basis of our results, we have demonstrated that the LNO film can be used as a buffer layer as well as a transparent bottom electrode for waveguide applications. The SBN/LNO heterostructure is also a suitable candidate for integrated electro-optics devices. PACS  42.79.Gn; 42.82.Et; 78.20.Ci     

Long-time relaxation phenomena in Pb<Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>Sc<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (PBSN-6) single crystals

Long-time polarization relaxation in the temperature range where PBSN-6 single crystals reside in the relaxor state was studied. An analysis of the time dependence of the permittivity ε′(t) performed at measuring frequencies from 1 Hz to 1 kHz in weak electric fields E₀ showed that the relaxation (or freezing) times derived by extrapolating relations of the type ε′(t) ～ log(t/t₀) and ε′(t) ～ exp{?[ln(t/t₀)]_β} range from 10⁸ to 10¹¹ min and depend substantially on the bias voltage applied to the sample. A study of the pattern of the dielectric response in moderate and strong infralow-frequency fields revealed that, after a sample was maintained under a bias lower than the coercive force, it no longer exhibited the additional anomalies in the amplitude dependences of the effective loss tangent tan_eff(E₀) than were observed in a thermally recuperated sample.     

Nonlinear dielectric response of epitaxial Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript> TiO<Subscript> 3</Subscript> thin films

Based on Landau-Devonshire (LD)-type phenomenological thermodynamic theory, the electric field dependence of the dielectric properties of tetragonal single-domain barium strontium titanate(Ba_1-xSr_xTiO₃) films on cubic substrates is theoretically investigated by taking into account the high order terms of the polarization. At room temperature, the nonlinear dielectric responses of epitaxial Ba_0.6Sr_0.4TiO₃ films are provided by adjusting the film thickness and growth temperature. The strong nonlinearity of relative dielectric constant and pyroelectric coefficient are attained around critical film thickness on MgO (69 nm) and LaAlO₃ (132 nm) substrates or critical growth temperature on MgO (337 °C) substrate with respect to epitaxy-induced lattice misfit and thermal stresses during deposition. This can be explained that small compressive stresses are effective to support high nonlinearity of dielectric constant and pyroelectric coefficient for Ba_0.6Sr_0.4TiO₃ films irrespective of whether they are on compressive substrate or tensile substrate. It is also predicted that a large tunability may be achieved by altering processing conditions, such as the film thickness and growth temperature for different substrates. Our theoretical results are in good agreement with the experimental data reported in literature.     

Phase transition behavior of highly (100) textured sol-gel-derived Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> thin films

We have investigated the relations between microstructure and dielectric properties in order to fabricate sol-gel-derived highly (100) oriented Ba_0.5Sr_0.5TiO₃ (BST 50/50) thin films with properties comparable to those of the bulk material. For the first time, we were able to fabricate BST thin films which exhibited the orthorhombic-to-tetragonal transition in addition to the commonly observed tetragonal-to-cubic transition. We were successful in explaining the commonly observed degradation of the dielectric behavior of BST thin films, when compared to that of the bulk material, in terms of grain size, compositional inhomogeneity (measured in terms of Sr/Ba ratio) between the grain bulk and grain boundary, and mechanical stresses. PACS 77.55.+f; 77.22Gm; 77.80.Bh; 77.80.Dj     

Optical studies of delayed relaxation in Pb<Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>Sc<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (PBSN-6) solid solutions

The temperature dependences of the permittivity, birefringence, optical transmittance, and small-angle light scattering and their variations with time are studied for single crystals of the Pb_0.94Ba_0.06Sc_0.5Nb_0.5O₃ relaxor (PBSN-6) in the heterophase region of coexistence of different phases. It is shown that an electric field induces a phase transition to the ferroelectric state, which manifests itself within some time (delay time τ) after application of the electric field to the crystal. The observed dependence of the temperature of this transition on the heating rate of the sample and the changes in the birefringence and small-angle light scattering intensity with time confirm the kinetic character of the induced transition. Temperature dependences of the delay time τ for different electric fields are constructed. It is revealed that, at low temperatures, the delay time τ decreases with increasing temperature. This agrees with the behavior of τ in classical relaxors. At the Vogel-Fulcher temperature, however, one observes that dτ/dT reverses sign and τ increasing as the temperature continues to increase. This anomalous behavior of τ in the heterophase region is accounted for by the coexistence of the cubic relaxor and rhombohedral macrodomain phases.     

Nanostructured multiferroic PbFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> and its physical properties

Polycrystalline multiferroic PbFe_0.5Nb_0.5O3 (PFN) fabricated by a solid-phase method is studied. Before sintering, a synthesized PFN powder is processed in Bridgman anvils via a force action in combination with shear deformation (FASD) at room temperature. The electrophysical properties and structural parameters of processed samples and a reference sample are compared. Point defects are shown to play a key role in the formation of the physical properties beginning from an FASD of 200 MPa.     

Study on the spin-states of cobalt-based double-layer perovskite Sr<Subscript>2</Subscript>Y<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>Co<Subscript>2</Subscript>O<Subscript>7</Subscript>

The spin-states of cobalt based perovskite compounds depend sensitively on the valence state and local crystal environment of Co ions and the rich physical properties arise from strong coupling among charge, spin, and orbital degrees of freedom. While extensive studies have been carried out in the past, most of them concentrated on the isotropic compound LaCoO₃. In this paper, using the unrestricted Hartree-Fock approximation and the real-space recursion method, we have investigated the competition of various magnetically ordered spin-states of anisotropic double-layered perovskite Sr₂Y_0.5Ca_0.5Co₂O₇. The energy comparison among these states shows that the nearest-neighbor high-spin-intermediate-spin ferromagnetically ordered state is the relevant magnetic ground state of the compound. The magnetic structure and sizes of magnetic moments are consistent with the recent experimental observation.     

Manganese doping effects on interband electronic transitions,lattice vibrations,and dielectric functions of perovskite-type Ba<Subscript>0.4</Subscript>Sr<Subscript>0.6</Subscript>TiO<Subscript>3</Subscript> ferroelectric ceramics

The Ba_0.4Sr_0.6−x Mn _x TiO₃ (BSMT) ceramics with different Mn composition (from 1% to 10%) have been prepared via the conventional solid-state reaction sintering. The X-ray diffraction analysis shows that the ceramics are polycrystalline with the single perovskite phase. The lattice vibrations and optical properties have been investigated using Raman scattering, spectroscopic ellipsometry (SE), and infrared reflectance spectra. It was found that the optical bandgap for the BSMT ceramics is varied between 3.40 and 3.65 eV. The three first-order Raman-active phonon modes can be observed, and the frequency of the A ₁(LO₃)/E(LO) mode shows a blue shift of 8 cm⁻¹ with the Mn composition, which can be attributed to the distortion of the TiO₆ octahedron. With increasing Mn composition, the frequency of the infrared-active TO₄ mode decreases from 532 to 520 cm⁻¹, owing to the local variation of the lattice constant induced by the Mn incorporation. Moreover, the optical functions of the ceramics from the far-infrared to ultraviolet region are obtained based on the SE and reflectance spectra, which is useful for the potential applications in ferroelectric-based optoelectronic devices.     

Evolution of the optical properties of Pb<Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>Sc<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (PBSN-6) solid solution single crystals caused by a static electric field

The electric-field-induced variation of the optical properties (small-angle light scattering, birefringence) of PBSN-6 solid solutions was studied. It was found that in the absence of an electric field, the cubic nonpolar matrix contains, at temperatures below the dielectric permittivity maximum, spontaneously polarized regions of the ferroelectric phase not less than 10⁴ Å in size. It was shown that a weak electric field (～0.4 kV/cm) is capable of inducing a kinetic phase transition to the ferroelectric state, with the temperature of this transformation depending on the sample heating rate. The destruction of the induced state was accompanied by a sharp peak in the temperature dependence of the small-angle light scattering intensity (indicating the percolation nature of the transition) and was independent of the sample heating rate. The boundaries of stability of the induced state in various modes of application of an external electric field were determined, and the E-T phase diagram was constructed.     

Physical properties of Ba<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>TiO<Subscript>3</Subscript> thin films

The behavior of material constants in ferroelectric Ba_0.8Sr_0.2TiO₃ thin films is studied depending on the misfit strain at room temperature in the context of nonlinear thermodynamic potential of the phenomenological theory. Some constants are found to undergo drastic changes with the alternating strain at the interfaces. The gathered results allow one to evaluate the material constants for a specific film and to outline the direction in searching the ways to synthesize films with the needed properties.     

Structural and magnetic phase transformations in the BiFeO<Subscript>3</Subscript>-CaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Bi_{1 ? x} Ca _x Fe_{1 ? x/2}Nb _x/2O₃ system were studied. It is shown that, at x ≤ 0.15, the unit-cell symmetry of solid solutions is rhombohedral (space group R3c). Solid solutions with x ≥ 0.3 have an orthorhombic unit cell (space group Pbnm). The rhombohedral compositions are antiferromagnetic, while the orthorhombic compositions exhibit a small spontaneous magnetization due to Dzyaloshinski?-Moriya interaction. In CaFe_0.5Nb_0.5O₃, the Fe³⁺ and Nb⁵⁺ ions are partially ordered and the unit cell is monoclinic (space group P2₁/n). In the concentration range 0.15 < x < 0.30, a two-phase state (R3c + Pbnm) is revealed.     

Electrical properties of Sr<Subscript>3</Subscript>Bi<Subscript>4</Subscript>Ti<Subscript>6</Subscript>O<Subscript>21</Subscript> thin films

Highly c-axis-oriented Sr₃Bi₄Ti₆O₂₁ (SBTi) thin films were fabricated on Pt-coated Si substrates by pulsed laser deposition (PLD). The structures were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM). No peaks of SrTiO₃ (STO) could be detected in the XRD pattern, indicating the existence of the SBTi single phase. Good ferroelectric hysteresis loops of the films with Pt electrodes were obtained. With an applied field of 400 kV/cm, the measured remanent polarization (P_r) and coercive field (E_c) values were 4.1 C/cm² and 75 kV/cm respectively. The films showed little fatigue after 2.22×10⁹ switching cycles: the nonvolatile polarizations decreased by less than 5% of the initial values. The dielectric constant and the loss tangent of the films were measured to be 363 and 0.04 at 100 kHz. These results might be advantageous for nonvolatile ferroelectric random access memory (NVFRAM) and dynamic random access memory (DRAM). PACS 77.84.Dy; 77.22.-d; 68.55.Jk     

Controlling the physical properties of PbIn<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> ferroelectric ceramics by intense mechanical action with shear

PbIn_0.5Nb_0.5O₃ (PIN) ferroelectric relaxer ceramics obtained by the solid-phase method is studied. Prior to sintering, the synthesized charge is subjected to mechanical action in Bridgman anvils at room temperature. The electrophysical properties of the reference sample and test samples are compared. It is concluded that mechanical treatment of the material at the stage of preparation allows one to control the physical properties of ferroelectric ceramics. Starting from a certain amount of the action, the electrophysical properties of PIN ceramics vary nonmonotonically.     

Structural characteristics of a single-crystalline Sr<Subscript>0.75</Subscript>Ba<Subscript>0.25</Subscript>NbO<Subscript>3</Subscript> electro-optic material

Sr_0.75Ba_0.25NbO₃ (SBN-75) has the tungsten-bronze structure with a tetragonal unit cell and exhibits electro-optic properties that are important for sensors. Due to its quaternary nature, its structural uniformity, integrity, and homogeneity become important for these applications. In this paper, we present high-resolution X-ray diffraction studies of the crystalline quality and lattice parameter variation across the surface of single crystals of SBN-75. Using rocking curves, topographs, and point-wise measurements of lattice parameters, we show that these crystals have a high degree of crystalline quality and microscopic homogeneity for any electro-optic application.     

Electronic Structure of Oxygen Vacancies in the Orthorhombic Noncentrosymmetric Phase Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript>

The electronic structure of stoichiometric and oxygen-depleted Hf_0.5Zr_0.5O₂ in the orthorhombic noncentrosymmetric phase has been studied by X-ray photoelectron spectroscopy and quantum-chemical simulation based on the density functional theory. It has been established that the ion-etching-induced peak in the photoelectron emission spectrum with the energy above the top of the o-Hf_0.5Zr_0.5O₂ valence band is due to oxygen vacancies. A method of estimating the density of oxygen vacancies from the comparison of the experimental and theoretical photoelectron spectra of the valence band has been proposed. It has been established that oxygen polyvacancies in o-Hf_0.5Zr_0.5O₂ are not formed: the energetically favorable spatial arrangement of oxygen vacancies in a crystal corresponds to noninteracting oxygen vacancies distant from each other.     

Memory effect in Ba<Subscript>0.85</Subscript>Sr<Subscript>0.15</Subscript>TiO<Subscript>3</Subscript> ferroelectric films on silicon substrates

Ba_0.85Sr_0.15TiO₃ ferroelectric films on single-crystal silicon wafers were grown and studied. X-ray diffraction and electron microscopy studies showed that the films are characterized by a limited texture with a perovskite structure. It was shown that the grown films can be used as recording media for nonvolatile rerecorded data carriers in kinematic-type external memory devices. A possible mechanism of data recording and storage in the structures was considered.