Relative Stabilities of Layered Perovskite and Pyrochlore Structures in Transition Metal-Oxides Containing Trivalent Bismuth

In order to investigate the factors determining the relative stabilities of layered perovskite and pyrochlore structures of transition metal oxides containing trivalent bismuth, several ternary and quaternary oxides have been investigated. While d0 cations stabilize the layered perovskite structure, cations containing partially-filled d orbitals (which suppress ferroelectric distortion of MO6 octahedra) seem to favor pyrochlore-related structures. Thus, the vanadium analogue of the layered perovskite Bi4Ti3O12 cannot be prepared; instead the composition consists of a mixture of pyrochlore-type Bi1.33V2O6, Bi2O3, and Bi metal. The distortion of Bi1.33V2O6 to orthorhombic symmetry is probably due to an ordering of anion vacancies in the pyrochlore structure. None of the other pyrochlores investigated, Bi2NbCrO7, Bi2NbFeO7, TlBiM2O7 (M = Nb, Ta), shows evidence for cation ordering in the X-Ray diffraction patterns, as indeed established by structure refinement of TlBiNb2O7.

Influence of Geometrical Factors on the Physico-Chemical Properties of Perovskite and Layered Perovskite Oxides

A brief qualitative comparison is made of perovskite ABO sub 3 and layered perovskite ABO sub 3 and layered perovskite A sub 2 BO sub 4 oxides with special emphasis on the influence of geometrical factors on certain physico-chemical properties. The layered perovskite oxides are distinguished from three-dimensional oxides by a looser packing, frustration in three-dimensional interactions, more internal pressure on B--O bonds for small tolerance factors, and by different values of site-percolation thresholds. Their influence on electronic configurations of metal ions, stabilities and syntheses of compounds is discussed. The influence of increased anisotropy in layered oxides on localisation of charge carriers and in suppressing the onset of long-range ferromagnetic ordering is also discussed.

K1-xLaxCa2-xNb3O10, a Layered Perovskite Series with Variable Interlayer Cation Density, and LaCaNb3O10, a Novel Layered Perovskite Oxide with No Interlayer Cations

A series of layered perovskite oxides of the formula K1-xLaxCa2-xNb3O10 for 0 < x ≤ 1.0 have been prepared. All the members are isostructural, possessing the structure of KCa2Nb3O10. The interlayer potassium ions in the new series can be ion-exchanged with protons to give H1-xLaxCa2-xNb3O10. The latter readily forms intercalation compounds of the formula (CnH2n+1NH3)1-x LaxCa2-xNb3O10, just as the parent solid acid HCa2Nb3O10. The end member LaCaNb3O10 containing no interlayer cations is a novel layered perovskite oxide, being a n = 3 member of the series An-1BnX3n+1.

Synthesis of Layered Perovskite Oxides, ACa2-xLaxNb3-xTix010 (A = K, Rb, Cs), and Characterization of New Solid Acids, HCa2-xLaxNb3-xTixOlo (0 < x d 2), Exhibiting Variable Bronsted Acidity?

Layered perovskite oxides of the formula ACa~,La,Nb3-,Ti,010 (A = K, Rb, Cs and 0 < x d 2) have been prepared. The members adopt the structures of the parent ACazNb3010. Interlayer alkali cations in the niobium-titanium oxide series can be ion-exchanged with Li+, Na+, NH4+, or H+ to give new derivatives. Intercalation of the protonated derivatives with organic bases reveals that the Bronsted acidity of the solid solution series, HC~ ~ , L ~ ,N~ ~ , T ~ ,dOep~eOnd, s on the titanium content. While the x = 1 member (HCaLaNbzTiOlo) is nearly as acidic as the parent HCazNb3010, the x = 2 member (HLazNbTizOlo) is a weak acid hardly intercalating organic bases with pKa - 11.3. The variation of acidity is probably due to an ordering of Nb/Ti atoms in the triple octahedral perovskite slabs, [Ca~,La,Nb~,Ti,0~0], such that protons are attached to NbO6 octahedra in the x = 1 member and to Ti06 octahedra in the x = 2 member.

ChemInform Abstract: Slicing the Perovskite Structure into Layers: Synthesis of Novel Three- Dimensional and Layered Perovskite Oxides, ALaSrNb2M(II)O9 (A: Na, Cs)

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

A[Bi3Ti4O13] and A[Bi3PbTi5O16] (A = K, Cs): New n=4 and n=5 members of the layered perovskite series, A[A ' n-1B nO3n+1], and their hydrates

We describe the synthesis and structural characterization of new layered bismuth titanates, A[Bi3Ti4O13] and A[Bi3PbTi5O16]for A = K, Cs, corresponding to n = 4 and 5 members of the Dion-Jacobson series of layered perovskites of the general formula, A[A'n-1BnO3n+1]. These materials have been prepared by solid state reaction of the constituents containing excess alkali, which is required to suppress the formation of competitive Aurivillius phases. Unlike the isostructural niobates and niobium titanates of the same series, the new phases reported here are spontaneously hydrated-a feature which could make them potentially useful as photocatalysts for water splitting reaction. On hydration of the potassium compounds, the c axis expands by ca. 2 Angstrom and loses its doubling [for example, the tetragonal lattice parameters of K[Bi3Ti4O13] and its dihydrate are respectively a = 3900(1)Angstrom c 37.57(2) Angstrom; a 3.885(1) Angstrom, c = 20.82(4) Angstrom]; surprisingly, the cesium analogues do not show a similar change on hydration.

Electronic structure of the ferroelectric layered perovskite SrBi2Ta2O9

The band structure of the layered perovskite SrBi2Ta2O9 (SBT) was calculated by tight binding and the valence band density of states was measured by x-ray photoemission spectroscopy. We find both the valence and conduction band edges to consist of states primarily derived from the Bi-O layer rather than the perovskite Sr-Ta-O blocks. The valence band maximum arises from O p and some Bi s states, while the conduction band minimum consists of Bi p states, with a wide band gap of 5.1 eV. It is argued that the Bi-O layers largely control the electronic response whereas the ferroelectric response originates mainly from the perovskite Sr-Ta-O block. Bi and Ta centered traps are calculated to be shallow, which may account in part for its excellent fatigue properties. © 1996 American Institute of Physics.

In situ intercalation dynamics in inorganic-organic layered perovskite thin films.

The properties of layered inorganic semiconductors can be manipulated by the insertion of foreign molecular species via a process known as intercalation. In the present study, we investigate the phenomenon of organic moiety (R-NH3I) intercalation in layered metal-halide (PbI2)-based inorganic semiconductors, leading to the formation of inorganic-organic (IO) perovskites [(R-NH3)2PbI4]. During this intercalation strong resonant exciton optical transitions are created, enabling study of the dynamics of this process. Simultaneous in situ photoluminescence (PL) and transmission measurements are used to track the structural and exciton evolution. On the basis of the experimental observations, a model is proposed which explains the process of IO perovskite formation during intercalation of the organic moiety through the inorganic semiconductor layers. The interplay between precursor film thickness and organic solution concentration/solvent highlights the role of van der Waals interactions between the layers, as well as the need for maintaining stoichiometry during intercalation. Nucleation and growth occurring during intercalation matches a Johnson-Mehl-Avrami-Kolmogorov model, with results fitting both ideal and nonideal cases.

Phase behavior of BaLn(2)Mn(2)O(7) (Ln = rare earth) with a layered perovskite structure

Many phases appear in BaLn(2)Mn(2)O(7) family (Ln = rare earth) belonging to one of the Ruddlesden-Popper type compounds, depending upon the experimental conditions such as heating conditions when prepared and composition. Some of these phases were characterized by powder X-ray diffraction method using Rietveld analysis. These phases have only a little difference in crystal structure which has fundamentally K2NiF4 type structure, although the X-ray diffraction patterns are clearly different: a little deformation or tilting of the oxygen octahedron surrounding a central manganese ion composing the main frame of this structure induce these different diffraction patterns. Phase behavior of these compounds, mainly the detailed relation between various phases in BaTb2Mn2O7, was refined including the data of high temperature X-ray diffractometry.

Structural phase transition in the layered perovskite compound BaTb2Mn2O7

A distorted layered perovskite compound BaTb2Mn2O7 was synthesized by the solid state reaction in pure argon. There is a structural phase transition in the BaTb2Mn2O7 compound. The phase transition was characterized by the DSC and high temperature Xray diffraction. The heat capacity of BaTb2Mn2O7 was calculated. The thermal anomaly corresponding to the phase transition was observed at about 740K. The lattice parameters were calculated by the CELL program for BaTb2Mn2O7, It has Tb-type orthorhombic symmetry with a = 0.3908 nm, b = 0.3866 nm, c = 2.0163 nm, and space group Immm at room temperature. With the increase of temperature, the lattice parameters gradually increase until 673K. From 723K to 973K, the compound translates to tetragonal with a = 0.39078 nm, c = 2.0277 nm and S.G. I4/mmm. This result is fairly in accordance with that of heat capacity.

Ferroelectricity in epitaxial pulsed laser deposited bismuth-layered perovskite thin films of different crystallographic orientations

Epitaxial thin films Of various bismuth-layered perovskites SrBi(2)Ta(2)O(9), Bi(4)Ti(3)O(12), BaBi(4)Ti(4)O(15), and Ba(2)Bi(4)Ti(5)O(18) were deposited by pulsed laser deposition onto epitaxial conducting LaNiO(3) or SrRuO(3) electrodes on single crystalline SrTiO(3) substrates with different crystallographic orientations or on top of epitaxial buffer layers on (100) silicon. The conductive perovskite electrodes and the epitaxial ferroelectric films are strongly influenced by the nature of the substrate, and bismuth-layered perovskite ferroelectric films with mixed (100), (110)- and (001)-orientations as well as with uniform (001)-, (116)- and (103)- orientations have been obtained. Structure and morphology investigations performed by X-ray diffraction analysis, scanning probe microscopy, and transmission electron microscopy reveal the different epitaxial relationships between films and substrates. A clear correlation of the crystallographic orientation of the epitaxial films with their ferroelectric properties is illustrated by macroscopic and microscopic measurements of epitaxial bismuth-layered perovskite thin films of different crystallographic orientations.

Investigation of Ferroelectric Layered Perovskite Barium Bismuth Tantalate Prepared by Solid-State Reaction

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electronic structure of the layered ferroelectric perovskite SrBi2Ta2O9

The band structure of the Bi layered perovskite SrBi2Ta2O9 (SBT) has been calculated by the tight binding method. We find both the valence and conduction band edges to consist of states primarily derived from the Bi-O layer rather than the perovskite Sr-Ta-O block. The valence band maximum arises from O p and some Bi s states, while the conduction band minimum consists of Bi p states, with a band gap of 5.1 eV. It is argued that the Bi-O layers largely control the electronic response of SBT while the ferroelectric response originates from the perovskite Sr-Ta-O block. Bi and Ta centered traps are calculated to be shallow, which may account in part for the excellent fatigue properties of SBT.

AILaNb2O7:A new series of layered perovskites exhibiting ion exchange and intercalation behaviour

A new series of layered perovskite oxides, AILaNb2O7 (A = Li, Na, K, Rb, Cs, NH4) constituting n = 2 members of the family A A′n−1BnO3n+1, has been prepared. Their structure consists of double perovskite slabs interleaved by A atoms. Hydrated HLaNb2O7 is formed by topotactic proton exchange of the A atoms in ALaNb2O7 (A = K, Rb, Cs). The hydrate readily loses water to give anhydrous HLaNb2O7 which is isostructural with RbLaNb2O7. HLaNb2O7 exhibits Bronsted acidity forming intercalation compounds with bases such as n-octylamine and pyridine.