A new electron diffraction approach for structure refinement applied to Ca3Mn2O7.

The digital large-angle convergent-beam electron diffraction (D-LACBED) technique is applied to Ca3Mn2O7 for a range of temperatures. Bloch-wave simulations are used to examine the effects that changes in different parameters have on the intensity in D-LACBED patterns, and atomic coordinates, thermal atomic displacement parameters and apparent occupancy are refined to achieve a good fit between simulation and experiment. The sensitivity of the technique to subtle changes in structure is demonstrated. Refined structures are in good agreement with previous determinations of Ca3Mn2O7 and show the decay of anti-phase oxygen octahedral tilts perpendicular to the c axis of the A21am unit cell with increasing temperature, as well as the robustness of oxygen octahedral tilts about the c axis up to ∼400°C. The technique samples only the zero-order Laue zone and is therefore insensitive to atom displacements along the electron-beam direction. For this reason it is not possible to distinguish between in-phase and anti-phase oxygen octahedral tilting about the c axis using the [110] data collected in this study.

Magnetic resonance study of bulk and thin film EuTiO3.

Magnetic resonance spectra of EuTiO3 in both bulk and thin film form were taken at temperatures from 3-350 K and microwave frequencies from 9.2-9.8 and 34 GHz. In the paramagnetic phase, magnetic resonance spectra are determined by magnetic dipole and exchange interactions between Eu2+ spins. In the film, a large contribution arises from the demagnetization field. From detailed analysis of the linewidth and its temperature dependence, the parameters of spin-spin interactions were determined: the exchange frequency is 10.5 GHz and the estimated critical exponent of the spin correlation length is ≈0.4. In the bulk samples, the spectra exhibited a distinct minimum in the linewidth at the Néel temperature, T N ≈ 5.5 K, while the resonance field practically does not change even on cooling below T N. This is indicative of a small magnetic anisotropy ~320 G in the antiferromagnetic phase. In the film, the magnetic resonance spectrum is split below T N into several components due to excitation of the magnetostatic modes, corresponding to a non-uniform precession of magnetization. Moreover, the film was observed to degrade over two years. This was manifested by an increase of defects and a change in the domain structure. The saturated magnetization in the film, estimated from the magnetic resonance spectrum, was about 900 emu cm-3 or 5.5 µ B/unit cell at T = 3.5 K.

Spectroscopic studies of the ferroelectric and magnetic phase transitions in multiferroic Sr1-xBaxMnO3.

Dielectric response of perovskite Sr1-xBaxMnO3 (x = 0.43 and 0.45) ceramics was investigated using microwave, THz and infrared spectroscopic techniques in order to study the ferroelectric and antiferromagnetic phase transitions with critical temperatures TC ≈ 350 K and TN ≈ 200 K, respectively. The two lowest-frequency polar phonons are overdamped above TN and they exhibit pronounced softening on heating towards TC. Nevertheless, permittivity ε' in the THz range shows only a small anomaly at TC because the phonon contribution to ε' is rather small. The phonons are coupled with a central mode which provides the main contribution to the dielectric anomaly at TC. Thus, the ferroelectric phase transition has characteristics of a crossover from displacive to order-disorder type. At the same time, the intrinsic THz central peak is partially screened by conductivity and related Maxwell-Wagner relaxation, which dominates the microwave and lower-frequency spectra. Below TN, the ferroelectric distortion markedly decreases, which has an influence on the frequencies of both the central and soft modes. Therefore, ε' in the THz range increases at TN on cooling. In spite of the strong spin-phonon coupling near TN, surprisingly no magnetodielectric effect was observed in the THz spectra upon applying magnetic field of up to 7 T, which is in contradiction with the theoretically expected huge magnetoelectric coupling. We explain this fact as due to the insensitivity of TN to magnetic field.

Lattice modes in paraelectric La1/2Na1/2TiO3 by infrared and Raman spectroscopy.

The lattice dynamics of La(1/2)Na(1/2)TiO(3) single crystal have been investigated by far-infrared and Raman scattering spectroscopy. Far-IR reflectivity spectra revealed Slater, Last and Axe modes near 140, 190 and 555 cm(-1), respectively. The frequency of the Slater mode decreases by about 10% on cooling, which is enough to account for the observed increase of the low-frequency permittivity. The results allowed us to discuss the reasons for the suppressed ferroelectricity of the material. Temperature evolution of the Raman scattering intensity of an oxygen octahedra bending mode near 455 cm(-1) suggests a second-order phase transition towards the perovskite aristotype phase near 870 K.

Soft-mode-driven lattice instabilities in Cs2HgCl4 crystal: phenomenological treatment and far-infrared spectroscopy of the structurally modulated phases.

This paper reports a comprehensive phenomenological description and experimental infrared (IR) investigations of the soft-mode-driven lattice instabilities into various commensurately and incommensurately modulated phases of Cs(2)HgCl(4) crystals. Our theoretical analysis shows that the lattice instabilities along the a and c crystallographic directions are related to low-frequency transverse optical (TO) phonon branches of Σ(2) and Λ(3) symmetry, respectively, which merge together in the center of the Brillouin zone at the point of B(3g) symmetry. As the temperature decreases both branches fall down, leading first to the direct condensation of the soft TO Σ(2) mode in the symmetric Σ direction (k is parallel to a*). On the other hand, coupling of the TO and transverse acoustic (TA) modes of Λ(3) symmetry causes, at somewhat lower temperatures, a series of frozen modulated commensurate and incommensurate states developing along the symmetric Λ direction (k is parallel to c*). Polarized far-infrared (FIR) reflectivity spectra (15-600 cm(-1)) of Cs(2)HgCl(4) crystals were measured in a broad temperature region, 10-297 K. Despite a rich sequence of structurally modulated phases existing above 163 K we observed rather moderate temperature evolution of IR spectra where only a few new modes of different polarizations have been activated. However, the commensurately modulated phases occurring below 163 K made an essential impact on the spectra of all three polarizations. The process of activation of both the Raman- and the IR-active phonons in the structurally modulated phases is subjected to the phenomenological analysis.

Dielectric, magnetic and structural properties of novel multiferroic Eu(0.5)Ba(0.5)TiO(3) ceramics.

Dielectric properties of Eu(0.5)Ba(0.5)TiO(3) ceramics were investigated between 10 and 300 K in the frequency range of 1 MHz-100 THz. Permittivity exhibits a strong peak near the ferroelectric phase transition at 215 K. This is mainly due to softening of the lowest frequency polar phonon revealed in THz and infrared spectra. Dielectric relaxation was observed also below the ferroelectric soft mode frequency in the whole investigated temperature region, but it is probably caused by some defects such as Eu(3 + ) cations or oxygen vacancies. This implies that the ferroelectric phase transition has predominantly a displacive character. Raman scattering spectra revealed a lowering of crystal symmetry in the ferroelectric phase and XRD analysis indicated orthorhombic A2mm symmetry below 215 K. The magnetic measurements performed at various frequencies in the field cooled and field heating regime after cooling in zero magnetic fields excluded spin glass behavior and proved an antiferromagnetic order below 1.9 K in Eu(0.5)Ba(0.5)TiO(3).

Infrared phonon spectroscopy of a compressively strained (001) SrTiO3 film grown on a (110) NdGaO3 substrate.

Polarized infrared reflectivity was measured between 5 and 300 K on a 17 nm thick, 1.1% compressively strained epitaxial (001) SrTiO(3) film and the orthorhombic (110) NdGaO(3) substrate upon which it was grown. A strong in-plane infrared anisotropy of the NdGaO(3) substrate was observed and polar modes with B(1u)-and a mixture of B(2u) + B(3u)-symmetry were seen. At low temperatures three new modes arose in the 90-130 cm( - 1) range, which we assigned to 4f Nd electronic transitions. The in-plane SrTiO(3) film phonons showed strong stiffening compared to the phonon frequencies of bulk unstrained SrTiO(3), particularly the soft mode, and the in-plane phonon peaks were found to split. No anomalies were detected as a function of temperature in either the infrared response or lattice parameters of the compressively strained SrTiO(3) film, providing an absence of evidence for the out-of-plane ferroelectric phase transition predicted by theory.

A multiferroic material to search for the permanent electric dipole moment of the electron.

We describe the first-principles design and subsequent synthesis of a new material with the specific functionalities required for a solid-state-based search for the permanent electric dipole moment of the electron. We show computationally that perovskite-structure europium barium titanate should exhibit the required large and pressure-dependent ferroelectric polarization, local magnetic moments and absence of magnetic ordering at liquid-helium temperature. Subsequent synthesis and characterization of Eu(0.5)Ba(0.5)TiO(3) ceramics confirm the predicted desirable properties.

Bulk dielectric and magnetic properties of PFW-PZT ceramics: absence of magnetically switched-off polarization.

We investigated ceramics samples of solid solutions of [PbFe(2/3)W(1/3)O(3)](x)-[PbZr(0.53)Ti(0.47)O(3)](1 - x) (PFW(x)-PZT(1 - x), x = 0.2 and 0.3) by means of broad-band dielectric spectroscopy, differential scanning calorimetry and SQUID magnetometry. We did not confirm the observations of Kumar et al (2009 J. Phys.: Condens. Matter 21 382204), who reported on reversible suppression of ferroelectric polarization in polycrystalline PFW(x)-PZT(1 - x) thin films for magnetic fields above 0.5 T. We did not observe any change of ferroelectric polarization with external magnetic fields up to 3.2 T. Pirc et al (2009 Phys. Rev. B 79 214114) developed a theory explaining the reported large magnetoelectric effect in PFW(x)-PZT(1 - x), taking into account relaxor magnetic and relaxor ferroelectric properties of the system. Our data revealed classical ferroelectric properties below 525 K and 485 K in samples with x = 0.2 and 0.3, respectively. Moreover, paramagnetic behavior was observed down to 4.5 K instead of previously reported relaxor magnetic behavior. It seems that the reported switching-off of ferroelectric polarization in PFW(x)-PZT(1 - x) thin films is not an intrinsic property, but probably an effect of electrodes, interlayers, grain boundaries or second phases presented in polycrystalline thin films.

The negative phonon confinement effect in nanoscopic sodium nitrite.

A nanocomposite of porous glass and a NaNO(2) ferroelectric (channels of approximately 7 nm diameter) was studied using infrared reflectivity, THz transmission and Raman spectroscopy as a function of temperature in the range of 300-500 K, including the ferroelectric transition. From the infrared and THz response the effective dielectric function was calculated and compared with the dielectric functions calculated from the Bruggeman and Lichtenecker models of the effective medium, using the known data on the polar phonon modes of the NaNO(2) single crystals. The results show good qualitative agreement, indicating that the stiffening of the effective modes is due to local depolarization fields on the glass-ferroelectric interfaces. The nonpolar Raman modes show no substantial modification compared to those of the bulk NaNO(2). Some signatures of the ferroelectric transition were even seen. The results indicate that the intrinsic size effect (phonon confinement) is negligible in this nanocomposite.

Anisotropic dielectric function in polar nanoregions of relaxor ferroelectrics.

The Letter suggests treating the infrared reflectivity spectra of single crystal perovskite relaxors as fine-grained ferroelectric ceramics: locally frozen polarization makes the dielectric function strongly anisotropic in the phonon frequency range and the random orientation of the polarization at nanoscopic scale requires taking into account the inhomogeneous depolarization field. Employing a simple effective medium approximation (the Bruggeman symmetrical formula) turns out to be sufficient for reproducing all principal features of room temperature reflectivity of Pb(Mg(1/3)Nb(2/3))O3. One of the reflectivity bands is identified as a geometrical resonance entirely related to the nanoscale polarization inhomogeneity. The approach provides a general guide for systematic determination of the polar mode frequencies split by the inhomogeneous polarization at the nanometer scale.

Soft and central mode behaviour in PbMg(1/3)Nb(2/3)O(3) relaxor ferroelectric.

The relaxor ferroelectric PbMg(1/3)Nb(2/3)O(3) (PMN) is investigated by means of dielectric and Fourier transform far infrared transmission spectroscopy in the frequency range from 10 kHz to 15 THz at temperatures between 20 and 900 K using mostly thin films on infrared transparent sapphire substrates. While the thin film relaxors display reduced dielectric permittivity at low frequencies, their high frequency lattice response is shown to be the same as for single-crystal/ceramic specimens. In contrast to the results of inelastic neutron scattering, the optic soft mode is found to be underdamped at all temperatures. On heating, the TO1 soft phonon follows the Cochran law with an extrapolated critical temperature of 670 K near to the Burns temperature. Above 450 K the soft mode frequency levels off near 50 cm(-1) and above the Burns temperature it slightly hardens. Central-mode-type dispersion assigned to the dynamics of polar nanoclusters appears below the Burns temperature at frequencies near to but below the soft mode and slows down and broadens dramatically on cooling, finally, below the freezing temperature of 200 K, giving rise to frequency independent losses from the microwave range down. A new explanation of the phonon 'waterfall' effect in inelastic neutron scattering spectra is proposed.

Origin of the "waterfall" effect in phonon dispersion of relaxor perovskites.

We have undertaken an inelastic neutron scattering study of the perovskite relaxor ferroelectric Pb(Zn(1/3)Nb(2/3))O3 with 8% PbTiO3 (PZN-8%PT) in order to elucidate the origin of the previously reported unusual kink on the low frequency transverse phonon dispersion curve (known as the "waterfall effect"). We show that its position (q(wf)) depends on the choice of the Brillouin zone and that the relation of q(wf) to the size of the polar nanoregions is highly improbable. The waterfall phenomenon is explained in the framework of a simple model of coupled damped harmonic oscillators representing the acoustic and optic phonon branches.

[A case of malignant fibrous histiocytoma of the cecum].

A case of primary malignant fibrous histiocytoma (MFH) of the cecum was reported. Patient was a 52-year-old female, and complained of right lower abdominal pain. The barium enema and abdominal computed tomography demonstrated a localized mass involving the entire circumference of the cecum. Right hemicolectomy was performed and the resected specimen revealed a tumor of 8 X 6 X 5 cm in size extending to the entire circumference of the cecum. The histopathological examination revealed a storiform pattern, which was diagnostic of MHF. The tumor proliferated chiefly in the subserous tissue and partially infiltrated the tunica muscularis propria. The postoperative course was uneventful and she showed no sign of recurrence at 15 months after operation. This is the ninth reported case of primary MFH in digestive organs.

[A case of dumbbell neurogenic tumor in the posterior mediastinum].

We have recently experienced a dumbbell tumor that developed in the posterior mediastinum in a 64-year-old male. The patient suffered from dorsalgia one year and a half previously. Chest X-ray examinations revealed a well-defined boundary in the right posterior mediastinum. Myelography followed by computerized tomographic scanning (CT) revealed that the tumor developed in a paravertebral area linked with a vertebral canal through an intervertebral foramen and destructed a rib in growing in the paraspinal muscular layer. Longitudinal incision of about 10 cm was made downward from immediately above the first thoracic spinous process, and the chest was opened by posterolateral incision extending into the muscles of the back in an arc shape. The tumor was entirely excised by additional laminectomy. Since malignant schwannoma was diagnosed histologically, Linac X-ray of 50 Gray was given. The patient is now enjoying his healthy daily life with no postoperative complication 2 years after operation. Myelography followed by CT was proved to be quite useful in evaluating a relationship between the tumor and the spinal cord in the diagnosis of this disease.