Gadolinium(Gd) doped ferroelectric lead lanthanum zirconate titanate (PLGZT 6/2/65/35) thin films were prepared by sol-gel spin coating technique. Fused silica and platinized silicon were used as substrates. Two-step pre-annealing heat treatment was employed to prepare crack free films. Annealing temperature was optimized though the x-ray diffraction studies to prepare films in single perovskite phase. Effects of Pb concentration and the seeding layer on the crystallization were studied. Optical transmission spectra were recorded and from this, refractive index, extinction coefficient and thickness were calculated for amorphous films on fused silica annealed at 400°C. In addition, the resultant films showed more than 60% transmission in the visible region. The electrical measurements were conducted on metal-ferroelectric-metal (MFM) capacitors. Ferroelectric properties of crystalline films were studied by plotting the P-E hysteresis loop.

We present and discuss main results of the calculations for the surface relaxation and rumpling of SrTiO3 surfaces with TiO2 and SrO terminations using a wide variety of methods of modern computational physics and chemistry, including the shell model (SM) and ab initio methods based on Hartree-Fock (HF) and Density Functional Theory (DFT). The HF and DFT formalisms with different exchange-correlation functionals are implemented into Crystal-98 computer code using a Gaussian-type basis set. We demonstrate that a hybrid B3PW formalism gives the best results for the bulk SrTiO3 properties. Results are compared with previous ab initio plane-wave LDA calculations and LEED experiments. Our calculations demonstrate an increase of the covalency effects between Ti and O atoms near the surface.

Dielectric properties and microstructure were investigated in BaTiO3 ceramics with various additives, Ho2O3, MgO, Ho2O3/MgO, and La2O3. The dielectric constants were increased up to ∼4000 and ∼3000 at 25°C in the 1 mol% Ho-doped and 0.5 mol% Mg-doped BaTiO3 materials, respectively. The BaTiO3 material codoped with 3 mol% Ho + 1.5 mol% Mg led to increase dielectric constant up to ∼6000 at 25°C and the dielectric constant peak around Curie temperature was suppressed at temperature range of from 25°C to 125°C. The size of BaTiO3 grains depended on the content and kind of an additive. Core-shell grains and secondary phase were also dependent on an additive. Core-shell grains were formed completely in Ho-doped BaTiO3 except for 0.5 mol%, but the structure was little observed in Mg- and La-doped BaTiO3 material. Codoped BaTiO3 also formed the core-shell grains.

The current theoretical and experimental knowledge of new polaronic-type excitons in ferroelectric oxides - charge transfer vibronic excitons (CTVE) is discussed. It is shown that quantum chemical Hartree-Fock-type calculations using a semiempirical Intermediate Neglect of Differential Overlap (INDO) method (modified for ionic/partly ionic solids) as well as photoluminescence studies in ferroelectric oxygen-octahedral perovskites confirm the CTVE existence. Our INDO calculations for KTaO3 and KNbO3 have demonstrated that the triplet exciton is a triad centre containing one active O atom and two Ta atoms sitting on the opposite sites from this O atom. The total energy of a system is lowered by the combination of Coulomb attraction between electron and hole and the vibronic effect in this charge transfer vibronic exciton. It is shown by means of our INDO calculations that polaronic-type CTVE in ferroelectric oxides could lead to the formation of a new crystalline phase. The ground state energy of this phase consisting of strongly correlated CTVEs lies within an optical gap of a pure crystal, and is characterized by a strong tetragonal lattice distortion, as well as by the ferroelectric ordering.

Magnesium rich (Mg1-x,Fex perovskite is thought to be the most abundant mineral in the earth's lower mantle between 660 km and 2900 km depth. We discuss (mg,Fe) solid solutions and their elastic properties at lower mantle pressures. The diffrences of the elastic constants between the Mg-endmember and the iron bearing perovskite with x=0.25 are used to predict the compositional contribution to lateral variations of elastic wave-velocities at high pressures. These predictions are compared and discussed in the context of seismic observations.

MgSiO3 - rich perovskite is expected to dominate the Earth's lower mantle (pressures > 25 GPa), with iron and aluminum as significant substituents. The incorporation of trivalent ions, M3+, may occur by two competing mechanisms: MgA+ SiB = MA + MB and SiB = AlB + 0.5 VO. Phase synthesis studies show that both substitutions do occur, and the nonstoichiometric or defect substitution is prevalent along the MgSiO3 - MgAlO2.5 join. Oxide melt solution calorimetry has been used to compare the energetics of both substitutions. The stoichiometric substitution, represented by the reaction 0.95 MgSiO3 (perovskite) + 0.05 Al2O3 (corundum) = Mg0.95Al0.10Si0.95O3 (perovskite), has an enthalpy of -0.8±2.2 kJ/mol. The nonstoichiometric reaction, 0.90 MgSiO3 (perovskite) + 0.10 MgO (rocksalt) + 0.05 Al2O3 (corundum) = MgSi0.9Al0.1O2.95 (perovskite) has a small positive enthalpy of 8.5±4.6 kJ/mol. The defect substitution is not prohibitive in enthalpy, entropy, or volume, is favored in perovskite coexisting with magnesiowüstite, and may significantly affect the elasticity, rheology and water retention of silicate perovskite in the Earth.

While phase transition pressures and zero temperature thermodynamic properties can be accurately determined from electronic structure calculation, transition temperatures are more problematic because of the need to sample phase space and quantise vibrations. The quasiharmonic method has proved extremely accurate for calculating thermodynamic properties up to 90% of the melting point without explicit phase space sampling for most materials, but has low temperature divergences for soft mode materials such as perovskites. Here we present a modified quasiharmonic method which avoids these difficulties. Using a simple model system, we demonstrate trends of behaviour in both the classical and quantum limits showing the importance of phonon quantisation in soft-mode behavior.

Development of high performance dielectric materials is required to facilitate the trend towards miniaturization of microwave communications circuits. A novel two-step sintering process has been found that enhances the value of (Q-factor) (frequency) (QF)product of Ba(Mg ⅓ Ta ⅔)O3 (BMT). Detailed examination of samples densified in this way gives not only details of the grain size, defect content and state of order of the ordered perovskite grains but also reveals the presence of a number of previously unreported phases. These new phases have been examined by TEM using energy dispersive X-ray analysis to give them approximate chemical composition and convergent beam electron diffraction to determine their crystallography. Large unit cells are found which are evidently related to compounds studied previously in the x 3 BaMnO - system. The results will be discussed in relation to the enhanced performance of the materials.

The synthesis, structure and preliminary magnetic characteristics of the new layered manganese oxide chlorides, Sr2MnO3Cl and Sr4Mn3O8-yCl2 are reported. Sr2MnO3Cl adopts a K2NiF4 type structure with sheets of MnO5 square based pyramids linked through oxygen and separated by SrCl layers; it is the end member of a new family of Ruddlesden-Popper type manganese oxide halides which includes the 3-layer member Sr4Mn3O8-yCl2. Magnetic susceptibility measurements reveal antiferromagnetic transitions at 95 K and 90 K for Sr2MnO3Cl and Sr4Mn3O8-yCl2 respectively. These materials demonstrate the extension of mixed anion chemistry to manganese and will increase flexibility in designing and controlling oxidation states of new GMR materials.

The oxygen vacancy ordering process and displacive transitions have been characterised in the system CaTiO3-CaFeO2.5 as a function of composition and temperature at atmospheric pressure using X-ray diffraction, Mössbauer spectroscopy, infrared spectroscopy, transmission electron microscopy, electron energy loss spectroscopy, neutron diffraction and electrical conductivity methods. With increasing concentration of vacancies the following sequence is observed: isolated defects → short defect chains → infinite chains in layers. Similar experiments at high pressures and temperatures have been conducted to determine the nature of oxygen vacancies in the lower mantle phases (Mg,Fe)(Si,Al)O3-σ and Ca(Si,Fe)O3-σ perovskite.

We present a comprehensive model of ferroelectricity in oxygen perovskite crystals that account quantitatively for both displacive like and order-disorder like properties. The model assumes that in the paraelectric phase, the system has a soft mode, interacting with spontaneous disordered off-center displacements. The resulting theory is shown to quantitatively explain the properties of two representative perovskites: KNbO3 and PbTiO3. We have further extended this theory to explain the properties of mixed incipient ferroelectrics with small concentrations of ferroelectricity inducing ions such as KTa1-xNbxO3. The model quantitatively reproduces the basic experimental data in the quantum regime: the temperature dependence of the inverse dielectric function, the impurity and temperature dependence of the renormalized soft mode vibrational frequency and the impurity concentration dependence of the transition temperature Tc. In particular we show that, the critical concentration for Tc=0 is determined by the ion tunneling frequency, the bare soft mode parameters and the pseudospin - phonon coupling constant.

We develop phase diagrams for single domain epitaxial barium strontium titanate films on cubic substrates as a function of the misfit strain based on a Landau-Devonshire phenomenological model similar to the one developed by Pertsev et al. [Phys. Rev. Lett. 80, 1988 (1998)]. Unusual ferroelectric phases that are not possible in single crystals and bulk ceramics are demonstrated in epitaxially constrained BST films. The misfit strain is correlated with the film thickness quantitatively by taking into account the formation of misfit dislocations that relieve epitaxial stresses during deposition. Theoretical estimation of the dielectric constant of (001) Ba0.7Sr0.3TiO3 and Ba0.6Sr0.4TiO3 films grown on Si, MgO, LaAlO3, and SrTiO3 substrates as a function of film thickness is provided. It is shown that the selection of the substrate and the film thickness can be chosen as design parameters to manipulate the internal stress level in the film to achieve enhanced dielectric response.

Cubic strontium manganese oxide is an end-member of the colossal magnetoresistive (CMR) family of manganese-based perovskites, Ln1-xAExMnO3. Because normal synthesis conditions lead to the 4-H hexagonal polymorph, high-pressure conditions are typically used to obtain the cubic perovskite polymorph. In this work, we describe the synthesis and structural/physical characterization of the cubic perovskite form of the high-alkaline-earth containing phases of Y1-xSrxMnO3 (x ≥ 0.7) as epitaxial thin films. Thin films of various stoichiometries were grown on single-crystal perovskite substrates SrTiO3, NdGaO3, and LaAlO3 using pulsed laser deposition. After optimizing deposition conditions, the perovskite polymorph is obtained using PLD at 800°C and 10-100 mTorr O2 for x=1, 0.9, 0.8, and 0.7, as demonstrated by x-ray diffraction. Epitaxial growth was determined to be cube-on-cube. Electrical property measurements demonstrated insulating behavior and no metal-insulator transition or magnetoresistive behavior, similar to related stable compounds.