Octahedral tilt twinning and compositional modulation in NaLaMgWO6

A combination of selected-area electron diffraction (SAED), neutron powder diffraction (NPD) and high-resolution transmission electron microscopy (HRTEM) reveals a complex superstructure in the ordered perovskite NaLaMgWO6. Through indexing of SAED patterns the unit-cell dimensions are found to be 46.8 × 7.8 × 7.9 Å, which corresponds to a 12a p × 2a p × 2a p superstructure of the simple Pm\overline 3 m perovskite unit cell. HRTEM images reveal the formation of an unmistakable stripe contrast that repeats with the same periodicity. Doubling of the b and c axes is brought about by a combination of layered ordering of Na and La, rock-salt ordering of Mg and W, and octahedral tilting. The a axis repeat distance results from a one-dimensional twinning of the octahedral tilts in combination with a compositional modulation. Modeling of the NPD pattern shows that the underlying tilt system is a − a − c 0 with tilt angles of ∼ 8° about the a and b axes. The octahedral tilt-twin boundaries run perpendicular to the a axis and are separated by 6a p. Simulated HRTEM images show that octahedral tilt twinning alone cannot explain the stripes seen in the HRTEM images, rather a compositional modulation involving the A-site cations is necessary to explain the experimental images.

Microstructure Study of BaTiO3 Ceramics Using Convergent Beam Electron Diffraction

The nanoscale local structure of core-shell structured BaTiO3 grains with a nonuniform dopant distribution was studied by convergent beam electron diffraction. The direct measurements of the variation of lattice parameter in an individual BaTiO3 grain were achieved. It was found that the lattice parameter continuously increased from inside the grain core to the grain shell and there was no discontinuity at the core/shell interface. The increasing gradient of c-axes was slightly smaller than that of a-axes, suggesting that the perovskite unit cell in the grain shell has lower tetragonality.

High-Pressure Synthesis of a Novel PbFeO3

A novel perovskite-type oxide PbFeO3 was successfully synthesized under a pressure as high as 7GPa, and the crystal structure, oxidation state, thermal stability, magnetic and dielectric properties were investigated. PbFeO3 possesses an orthorhombic perovskite unit cell and there is no phase transition between room temperature and 570 K. This compound decomposes into Pb2Fe2O5 in the vicinity of 740 K in air. According to XPS, it was found that this compound includes the Pb2+, Pb4+, and Fe3+ ions.

Electron microscopy characterization of Ba(Cd1/3Ta2/3)O3 microwave dielectrics with boron additive

The microstructure of Ba(Cd1/3Ta2/3)O3 ceramics with boron additive was investigated by high-resolution and analytical electron microscopy. Superlattice reflections were present at positions of (h ± 1/3, k ± 1/3, l ± 1/3) away from the fundamental reflections in the [110] zone diffraction pattern for the pseudocubic perovskite unit cell. Lattice images showed a well-ordered structure with hexagonal symmetry. No boron segregation and amorphous phase was observed along grain boundaries. An amorphous phase rich in boron-oxide was observed to form pockets partially penetrating along multiple grain junctions.

Influence of Post-Deposition Annealing on Lattice Strain, Electrical Transport and Magnetic Properties in Epitaxial La0.8Ca0.2MnO3 CMR Films

The effect of annealing on 3-dimensional lattice strain, crystallographic domain structure, magnetic and electrical properties of both 250 Å and 4000 Å thick epitaxial La0.8Ca0.2MnO3 (LCMO(x=0.2)) thin films grown on (001) LaAlO3 substrates have been studied. While short annealing time (∼2hrs. at 950 °C in oxygen of 1 atm. pressure) leads to anomalous increase of the peak temperature (Tp) and Curie temperature (Tc) above room temperature and that of the bulk material, longer annealing time (∼10 hrs.) restores the Tp and Tc to almost the same values as that of the as-grown films. Furthermore, as the annealing time is increased, the lattice strain relaxes with film's lattice parameter approaching the bulk value. In-plane and out-of-plane lattice parameters and strain states of the as-grown and annealed films were measured directly using normal and grazing incidence x-ray diffraction. A clear correlation is observed between Tp and perovskite unit cell volume for both the films. Tp is found to increase with the decrease of perovskite unit cell volume. This is attributed to the enhancement of overlap between Mn d orbitals and oxygen p orbitals leading to increased bandwidth and conductivity. Crystalline quality of the films as determined by the full width at half maximum (FWHM) of the x-ray rocking curves, improves with the annealing time. This work highlights the importance of controlling the 3-dimensional lattice strain for optimizing the properties of CMR films.

Structural Characterization of Pulsed Laser Deposited Ktn Thin Films

The renewed interest in KTa1−xNbxO (KTN) mixed perovskite materials, especially in thin films of a high quality, is connected with their remarkable dielectric properties in the dilute compositions. Off-center Nb ions in the highly polarizable KTaO3 lattice provide a drastic increase in the dielectric peak up to 20 times in comparison with pure KTaO3 and KNbO3. We prepared KTN thin films with several Nb concentrations in the range of 0 ≤ x ≤ 1 by pulsed laser deposition from semented KTaO3, KNbO3 and KNO3 targets. The effect of the substrate and symmetry-breaking defects was studied by micro-Raman spectroscopy. An anomalous residual intensity of the forbidden first-order scattering modes in the cubic paraelectric phase of the KTN films was connected with the formation of polar microregions even far above the bulk Tc value. On the whole, the KTN film behavior shows the existence of specific defects enlarging the perovskite unit cell in the film so that the activity of off-center Nb ions increases in producing larger electric dipoles and extending the precursor phase above Tc.

Powder diffraction data of SmBa4Cu3O8.5+δ

Rietveld analysis of X-ray powder diffraction data was performed on SmBa4Cu3O8.5+δ, which was synthesized from precursors Sm2O3, BaO2, and CuO at 1000 °C in an oxygen atmosphere. SmBa4Cu3O8.5+δ has a cubic perovskite-related structure that is isostructural with YBa4Cu3O8.5+δ, and a doubled perovskite unit cell parameter of 8.177 90±0.000 04 Å.

Single crystal growth of cuprates from hydroxide fluxes

Barium and potassium hydroxide have been investigated as fluxes for the growth of cuprate single crystals. The relatively high solubility of transition metals and lanthanoids in these salt fluxes at moderate temperatures allows significant lowering of the growth temperatures required for many phases. Also, phases not stable at high temperatures become accessible. Two new cuprates have been prepared in the Ba–Ca–Cu–O and Ba–Y–Cu–O systems from a Ba(OH)2 · H2O flux. The compounds Ba3(Y0.23Cu0.77)2O5.78 and Ba3(Ca0.24Cu0.76)2O4.43 crystallize in a tetragonal (space group I4/mmm) oxygen deficient Sr3Ti2O7-type structure with lattice parameters a = 4.069(2) Å, 4.022(1) Å and c = 21.61(2) Å, 21.63(2) Å, respectively. The compound (Ba0.92Sr0.08) (Ca0.38Cu0.62)O2.1 crystallizes with a doubled perovskite unit cell along all three axes, a = 8.116(4) Å. In addition, single crystals of Ba2Ycu3O7–δ have been prepared from a KOH flux at 750 °C.

Herstellung von CuTa2O6 - von der Trirutil- zur Perowskit-Struktur / Preparation of CuTa2O6 - from the Trirutile to the Perovskite Structure

A new trirutile MTa2O6 was synthesized by thermal decomposition of a freeze dried Cu- Ta-oxalate precursor. Its formation takes place preferentially starting from Cu-rich precursor compositions. Above 1000°C decomposition leads to the already known perovskite like structure with a composition Cu1.05Ta1.98O6 . The degree of the orthorhombic distortion of the perovskite unit cell depends on the conditions during the cooling process after perovskite formation.

An Electron Microscopy study of the BaxLa1-xFeO3-x/2 (1/2≤x≤2/3) system

In a previous paper we have shown that compositional variations in BaxLa1-xFeO3-y materials prepared in air. are accommodated in a different way than in other perovskite-related ferrites probably due to the bigger size of barium.When oxidated BaxLa1-xFe3+,4+O3-y samples in the 1/2 ≤ x ≤ 2/3 range, are reduced by annealing at 1100°C for 24h. in flowing Ar-5%H2, all iron,as deduced from chemical analysis data, is found in the III state oxidation. Powder X-ray diffraction data in this range (La1/2Ba1/2FeO2.75-La1/3Ba2/3FeO2.67) can be indexed on the basis of a single cubic perovskite unit cell (ac ≃ 3.95Å)In order to elucidate the way in which anionic vacancies are accommodated in these solids an electron diffraction (ED) and microscopy study was performed, similar results being obtained in both La1/2Ba1/2 FeO2.75 and La1/3Ba2/3FeO2.67samples.