Theoretical Study of the Structural,Electronic, Chemical Bonding and Optical Properties of the A2<Subscript>1</Subscript><Emphasis Type="Italic">am</Emphasis> Orthorhombic SrBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript>

The structural parameters, density of states, electronic band structure, charge density, and optical properties of orthorhombic SrBi₂Ta₂O₉ have been investigated using the plane-wave ultrasoft pseudopotential technique based on the first-principle density functional theory (DFT). The calculated structural parameters were in agreement with the previous theoretical and experimental data. The band structure showed an indirect (S to Γ) band gap with 2.071 eV. The chemical bonding along with population analysis has been studied. The complex dielectric function, refractive index, and extinction coefficient were calculated to understand the optical properties of this compound, which showed an optical anisotropy in the components of polarization directions (100), (010), and (001).     

Microstructures and impedance studies of Bi<Subscript>3.15</Subscript>Nd<Subscript>0.85</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

Microstructures and impedance characteristics of chemical-solution-derived Bi_3.15Nd_0.85Ti₃O₁₂ thin films were studied as functions of temperature. A dielectric anomaly was found at around 450°C, corresponding to the paraelectric to ferroelectric transition. Via complex impedance studies, grain and grain boundary contributions to the impedance were separated. The resistance of grain and grain boundaries is found governed by the same kind of space charge with an activation energy around 1.1 eV, close to that of oxygen vacancies in perovskite ferroelectrics. The low temperature ac conductance of BNdT thin films shows a frequency dispersion, which can also be ascribed to space charges mainly due to oxygen vacancies. The results were compared with SrBi₂Ta₂O₉ in terms of oxygen vacancy conductivity.     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Statistical mechanics of cation ordering in 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

A model Hamiltonian for B cation ordering (Sc-Nb(Ta)) in PbSc_1/2Nb_1/2O₃ and PbSc_1/2Ta_1/2O₃ solid solutions is constructed. The parameters of the model Hamiltonian are determined from the ab initio calculation within the ionic crystal model with allowance made for the deformability and the dipole and quadrupole polarizabilities of the ions. The temperatures of the phase transition due to the ordering of the B cations are calculated by the Monte Carlo method in the mean-field and cluster approximations. The phase transition temperatures calculated by the Monte Carlo method (1920 K for PbSc_1/2Ta_1/2O₃ and 1810 K for PbSc_1/2Nb_1/2O₃) are consistent with the experimental data (1770 and 1450 K, respectively). The thermodynamic properties of the cation ordering are investigated using the Monte Carlo method.     

Impedance spectroscopy of vanadium modified BaBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

In recent years a wide range of Aurivillius layered materials have been introduced. These novel materials are produced in many various forms such as fibers, thin films as well as bulk by using a number of processing routes. As advanced materials they are they have many interesting properties which include a number of useful electrical properties related to separated grain and grain boundary conductivity, impedance, activation energies, etc. In this paper these properties are described and discussed in detail. The electrical properties of the vanadium doped BaBi₂Nb₂O₉ ceramic was measured over a wide range of temperatures by impedance spectroscopy (IS). The separated grain activation energy, calculated from Arrhenius characteristics at temperatures between room temperature and 600 °C, was 1 eV for 0 at.% of vanadium dopant and 1.2 eV for 10 at.%, whereas the activation energies in the grain boundary region were 0.97 and 1.15 eV, respectively. The obtained results suggest the significant role of vanadium dopant, causing ordering the crystalline structure.     

Study of ferroelectric phase transitions in disordered PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

Ferroelectric phase transitions and thermodynamic properties of disordered PbSc_1/2Ta_1/2O₃ and PbSc_1/2Nb_1/2O₃ solid solutions have been investigated by the Monte Carlo method. The parameters of the effective Hamiltonian were calculated within the generalized Gordon-Kim model. The obtained values of the phase-transition temperatures and spontaneous polarization are in satisfactory agreement with the experimental data.     

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.     

Effects of LaNiO<Subscript>3</Subscript> on the structures and properties of SrBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript> thin films

SrBi₂Ta₂O₉(SBT)/LaNiO₃(LNO)/Si and SBT/Pt/TiO₂/SiO₂/Si multilayers were fabricated by pulsed laser deposition. With Pt top electrodes, the measured remanent polarization (2P_r) of Pt/SBT/LNO/Si and Pt/SBT/Pt/TiO₂/SiO₂/Si capacitors was 6.5 C/cm² and 5.2 C/cm², respectively. Using LNO as both bottom electrodes and buffer layers, enhanced non-c-axis crystalline SBT films were induced, which resulted in a 2P_r greater than that of the Pt/SBT/Pt/TiO₂/SiO₂/Si capacitor. The hysteresis loop of the Pt/SBT/LNO/Si capacitor showed a great external-field-dependent horizontal shift. Using an electron-injection model, this dependence was addressed. The fatigue-free property of the Pt/SBT/LNO/Si capacitor was experimentally established, in that the non-volatile polarization decreased by less than 5% of the initial value after 1.44×10⁹ switching cycles . PACS 77.84.Dy; 68.65.+g     

Dielectric properties,ionic conductivity and phase transitions in La<Subscript>2</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

The dspersion dielectric permeability and ion conductivity of La₂Mo₂O₉ ceramics was studied. It was established that the observed low-frequency dielectric dispersion is due to relaxation effects related to high ion conductivity. It is shown that the phase transition in La₂Mo₂O₉ has characteristic features of a superionic phase transition.     

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.     

Dielectric dispersion and magnetic properties of Ba-modified Pb(Fe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript>

The polycrystalline samples of Ba-modified Pb(Fe_1/2Nb_1/2)O₃ (i.e., (Pb_1-xBa_x)(Fe_1/2Nb_1/2)O₃ PBFN, with x=0,0.05,0.07) were synthesized by a mechanosynthesis (i.e., high-energy ball milling) route followed by a mixed oxide method. Structural analysis provides the information on formation of single-phase orthorhombic structure on substitution of a small amount (x=0.07) of Ba at the Pb-site of Pb(Fe_0.50Nb_0.50)O₃ (PFN). The ferroelectric–paraelectric phase transition in PFN was observed at 383 K, which decreases on increasing Ba-concentration in PBFN. Detailed studies of dielectric properties of PBFW show the following: (i) diffuse phase transition, (ii) low loss tangent, (iii) low activation energy, and (iv) low frequency dielectric dispersion. An anomaly in the ac conductivity was found very close to phase transition temperature. The activation energy is found to decrease from 0.19 to 0.01 eV on increasing Ba-concentration to 7% (x=0.07). Temperature field-dependent magnetization measurements of all the samples showed antiferromagnetic transition at ∼15 K (for x=0.07). PBFN sample showed a slight increase in the coercivity (i.e., from 400 Oe (PFN) to 500 Oe (PBFN, for x=0.07) at 2 K. PACS 61.10.Nz; 68.37.Hk; 75.50.Ss; 75.60.Ej; 77.22.Ch; 77.22.Gm     

Properties of the ferroelectric ceramics PbSc<Subscript>0.5</Subscript>Ta<Subscript>0.5</Subscript>O<Subscript>3</Subscript> fabricated from an ultradispersed powder

The relaxor ceramics PbSc_0.5Ta_0.5O₃ produced from an ultradispersed powder is studied by X-ray diffraction and dielectric measurements. Before sintering, the powder was subjected to treatment in Bridgman anvils in combination with shear deformation. This method is shown to affect the order parameter and dielectric properties of the ceramics without using long-term high-temperature annealing.     

Investigations of dielectric enhancement in (Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>)<Subscript>1-x</Subscript>(TiO<Subscript>2</Subscript>)<Subscript>x</Subscript> ceramics prepared by laser-sintering technique

The maximum dielectric permittivity of Ti-doped Ta₂O₅ ceramics may reach 450 by a laser-sintering technique. The aim of this study is to investigate the mechanisms of the dielectric enhancement based on the unique structural and morphological properties of the laser-sintered ceramics. The reason for the dielectric enhancement is due to the crystal structure distortion in the high-temperature phase, the oriented grain growth taking place in a direction deviating from [001] in the laser-sintered ceramics. The concurrent nature of quenching effects, a sharp temperature gradient and mass transfer in liquid phase originated from laser high energy irradiation with strict directivity leads to the structural and morphological properties. PACS 81.40.Tv; 61.80.Ba; 77.22.-d; 77.22.Ch     

Electronic structure,ferroelectricity and optical properties of CaBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript>

Using first-principles calculations based on density-functional theory in its local-density approximation, we investigated the Electronic structure, ferroelectricity and optical properties of CaBi₂Ta₂O₉ (CBT) for the first time. It is found that CBT compound has an indirect band gap of 3.114 eV and the O 2s and 2p states are strongly hybridized with the 6s states of Bi which belong to the (Bi₂O₂)²⁺ planes. The quite strong Ta–O and Bi–O hybridization is the primary source for ferroelectricity. Our results imply that the interaction between Bi and O is highly covalent. The anisotropy occurs mainly above 4 eV in the optical properties. The different optical properties have been discussed.     

Manifestation of a ferroelectric-antiferroelectric phase transition in Li<Subscript>0.12</Subscript>Na<Subscript>0.88</Subscript>Ta<Subscript>0.4</Subscript>Nb<Subscript>0.6</Subscript>O<Subscript>3</Subscript> in its Raman scattering spectra

The ferroelectric-antiferroelectric phase transition in the Li_0.12Na_0.88Ta_0.4Nb_0.6O₃ ceramic solid solution has been studied by the Raman scattering technique. As the temperature approached the transition point from below, we observed an appreciable broadening of the lines associated with the vibrations of the cations occupying octahedral and cubooctahedral cavities of the structure and with the oxygen network vibrations (which implies a substantial increase in disorder on the cation sublattices), as well as a decrease to zero intensity of the 875-cm^?1 line corresponding to stretch vibrations of the bridging oxygen in the BO₆ octahedral anion in the vicinity of the transition. The temperature dependence of the 875-cm_?1 line intensity near the transition was used to study the behavior of the phase transition order parameter η. The behavior of η was found to disagree markedly with the Landau theory of second-order phase transitions. It is shown that discrepancies originate from the increase in disorder in the niobium and tantalum sublattices in the Li_0.12Na_0.88Ta _y Nb_1-y O₃ solid solution system with increasing y. The order of the transition is lowered.     

Effect of Ba-substitution on the structure and properties of Pb<Subscript>0.8</Subscript>Ba<Subscript>0.2</Subscript>[(In<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)<Subscript>1-x</Subscript>Ti<Subscript>x</Subscript>]O<Subscript>3</Subscript> ceramics

Ferroelectric ceramics with formula Pb_0.8Ba_0.2[(In_1/2Nb_1/2)_1-xTi_x]O₃ (PBINT) (x=0.0,0.1,0.2,0.3,0.4 and 0.5) were prepared via a two-step solid state reaction method. It was found that ceramics with compositions in the range of x=0.0∼0.3 showed a pseudo-cubic structure, whereas the ceramic with x=0.5 displayed a tetragonal structure. All compositions showed significant frequency dispersion in their dielectric properties. The remanent polarization P_r as well as the coercive field E_c, measured at room temperature, increases with the Ti content. The experimental results obtained in this system are summarized into a phase diagram, with the morphotropic phase boundary (MPB) located at x=0.4. Compared with the Pb[(In_1/2Nb_1/2)_1-xTi_x]O₃ solid solution system, incorporating Ba in the A-site leads to a significant decrease in the dielectric maximum temperature T_max, a suppression of the dielectric relaxation parameter γ, and a shift of the MPB composition to a higher Ti content. PACS 77.84.Dy; 77.80.Bh; 77.22.Ch     

Phase transition and electrical properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)(Nb<Subscript>1-x</Subscript>Ta<Subscript>x</Subscript>)O<Subscript>3</Subscript> lead-free piezoelectric ceramics

(K_0.5Na_0.5)(Nb_1-xTa_x)O₃ lead-free piezoelectric ceramics have been prepared by an ordinary sintering technique. The results of X-ray diffraction reveal that Ta⁵⁺ diffuses into the K_0.5Na_0.5NbO₃ lattices to form a solid solution with an orthorhombic perovskite structure. Because of the high melting temperature of KTaO₃, the (K_0.5Na_0.5)(Nb_1-xTa_x)O₃ ceramics can be sintered at higher temperatures. The partial substitution of Ta⁵⁺ for the B-site ion Nb⁵⁺ decreases both paraelectric/cubic–ferroelectric/tetragonal and ferroelectric/tetragonal–ferroelectric/orthorhombic phase transition temperatures, T_C and T_O-T. It also induces a relaxor phase transition and weakens the ferroelectricity of the ceramics. The ceramics become ‘softened’, leading to improvements in d₃₃, k_p, k_t and ε_r and a decease in E_c, Q_m and N_p. The ceramics with x=0.075–0.15 become optimum, having d₃₃=127–151 pC/N, k_p=0.43–0.44, k_t=0.43–0.44, ε_r=541–712, tanδ=1.75–2.48% and T_C=378–329 °C. PACS 77.65.-j; 77.84.Dy; 77.84.-s     

Electronic structures and ferroelectric properties of ABi2Ta2O9 (A=Ca, Sr, and Ba)

The electronic structures of ABi₂Ta₂O₉ (A=Ca, Sr, and Ba) were calculated by using first-principles under optimized structure. As the size of A-site cation decreases from that of Ba²⁺ to Ca²⁺, the band-gap between O 2p and Ta 5d increases from 2.0 to 2.9 eV, which responses to the stronger orbital hybridizations between Ta 5d and O 2p orbits favoring improvement of the ferroelectric property, decrease in leakage current, and increase in both spontaneous polarization and Curie temperature by the structural distortion. In contrast to CaBi₂Ta₂O₉ and SrBi₂Ta₂O₉, the hybridization between Ba 5p orbits and O 2p orbits in BaBi₂Ta₂O₉ has better structural stability.     

Ferroelectric phase transition of Nb-doped Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ceramics

Bi_3.25La_0.75Ti_3-yNb_yO₁₂ (y=0.0, 0.03, 0.09, 0.15, 0.21) were synthesized using the solid-state reaction method. The effects of Nb doping on ferroelectric properties were studied through dielectric and P-E measurements. The value of P_r increases with increasing Nb content. Bi_3.25La_0.75Ti_3-yNb_yO₁₂ ceramics exhibit a maximum remanent polarization of P_r=27 μC/cm² at an Nb content of y=0.09. These results indicate that Nb doping can improve the ferroelectric properties of BLT ceramics. The Curie temperature, T_c, decreased with increasing Nb-content, and the ferroelectric phase transition of BLTNy is a second-order transition without thermal hysteresis. PACS 77.55.+f; 77.80.-e; 77.22.Jp     

C-oriented SrBi2Nb2O9 films grown on YBa2Cu3O7−δ /SrTiO3 and NdGaO3

Epitaxial SrBi₂Nb₂O₉ films were grown by laser ablation on (001)YBa₂Cu₃O_7?δ /(100)SrTiO₃ and (001)NdGaO₃, with c axis normal to the substrate plane. The SrBi₂Nb₂O₉ films were grown in a layer-by-layer regime on NdGaO₃ substrates in 25-Å steps at a condensation temperature of 700 °C. Microinclusions of secondary phases and a-oriented grains were observed to exist on the surface of (001)SrBi₂Nb₂O₉ films grown on (001)YBa₂Cu₃O_7?δ /(100)SrTiO₃. The dielectric permittivity of the SrBi₂Nb₂O₉ films measured along the c axis is 123 (T=300 K, f=100 kHz), and tan δ≈0.04.