Brillouin light scattering in niobium doped lead zirconate single crystal.

Brillouin light scattering experiments were performed for lead zirconate single crystals doped with niobium. Special attention was paid to the elastic mode softening near phase transition temperatures. The results are compared with data obtained by Raman light scattering experiments. We observed that the interaction between acoustic and optic modes is responsible for symmetry breaking far above TC, leading to polar regions' appearance. No changes in the acoustic mode frequency and its damping are observed at TC, where ε(T) exhibits a maximum value. The absence of these changes and the central peak observed in Raman experiments suggest that the phase transition at TC is mainly of the order-disorder type. The origin of other phase transitions is discussed as well.

Local properties and phase transitions in Sn doped antiferroelectric PbHfO3 single crystal.

Pb(Hf1-x Sn x )O3 single crystals with x = 0.23 were characterized using single-crystal x-ray diffraction in the wide temperature range. The information on the structure of two intermediate phases, situated between low temperature antiferroelectric and high temperature paraelectric phases, has been obtained. The lower-temperature intermediate AFE2 phase is characterized by incommensurate displacive modulations in the Pb sublattice. The higher temperature intermediate IM phase is characterized by rotations of oxygen octahedra, primarily in the form of anti-phase tilts, which are also present in the lower-temperature AFE2 phase. For the same crystal, 119Sn Mossbauer effect in the temperature range from 300 K to 600 K has been used to study phase transitions mechanism. Two kinds of quadruple splitting have been found. It implies that two different environments of the central Sn ion exist. The observed two kinds of quadruple splitting do not disappear in the whole investigated temperature range which confirm that even far above T C the structure of paraelectric phase is locally non-centrosymmetric.

Crystallographic and optical study of PbHfO3 crystals.

The symmetry of the intermediate high-temperature phase of PbHfO3 has been determined unambiguously to be orthorhombic using a combination of high-resolution X-ray diffraction and birefringence imaging microscopy measurements of crystal plates. While lattice parameter measurements as a function of temperature in the intermediate phase are consistent with either orthorhombic or tetragonal symmetry, domain orientations observed in birefringence imaging microscopy measurements utilizing the Metripol system are only consistent with orthorhombic symmetry with the unit cell in the rhombic orientation of the pseudocubic unit cell.

Critical scattering and incommensurate phase transition in antiferroelectric PbZrO3 under pressure.

Antiferroelectric lead zirconate is the key ingredient in modern ferroelectric and piezoelectric functional solid solutions. By itself it offers opportunities in new-type non-volatile memory and energy storage applications. A highly useful and scientifically puzzling feature of this material is the competition between the ferro- and antiferroelectric phases due to their energetic proximity, which leads to a challenge in understanding of the critical phenomena driving the formation of the antiferroelectric structure. We show that application of hydrostatic pressure drastically changes the character of critical lattice dynamics and enables the soft-mode-driven incommensurate phase transition sequence in lead zirconate. In addition to the long known cubic and antiferroelectric phases we identify the new non-modulated phase serving as a bridge between the cubic and the incommensurate phases. The pressure effect on ferroelectric and incommensurate critical dynamics shows that lead zirconate is not a single-instability-driven system.

Lattice dynamics in the paraelectric phase of PbHfO3 studied by inelastic x-ray scattering.

We report the results of an inelastic x-ray scattering study of the lattice dynamics in the paraelectric phase of the antiferroelectric lead hafnate PbHfO3. The study reveals an avoided crossing between the transverse acoustic and transverse optic phonon modes propagating along the [1 1 0] direction with [1 -1 0] polarization. The static susceptibility with respect to the generally incommensurate modulations is shown to increase on cooling for the entire Γ-M direction. We consider different approaches to the data analysis that correspond to different models for the temperature evolution of the dynamic susceptibility function. A number of similarities and differences between the lattice dynamics of PbHfO3 and PbZrO3 are described.

Absorption, fluorescence and second harmonic generation in Cr³âº-doped BiB3O6 glasses.

Synthesis, spectral properties and photoinduced nonlinear optical effects of chromium-doped BiB3O6 glass are studied in the present paper. Absorption, excitation and time resolved luminescence spectra are presented and luminescence decay behavior is discussed. Detailed analysis of the obtained spectra (assignment of the most prominent spectral features in terms of the corresponding Cr(3+) energy levels, crystal field strength Dq, Racah parameters B and C) was performed. A weak photostimulated second harmonic generation signal was found to increase drastically due to poling by proton implantation in the investigated sample.

Second-order susceptibility spectra for δ-BiB3O6 polymer nanocomposites deposited on the chalcogenide crystals.

The optimized conditions for the enhancement of the second harmonic generation in the composites of the orthorhombic δ-BiB3O6:Pr(3+) nanoparticles embedded in polyvinyl alcohol films and deposited on the AgGaGe2Se6, AgGaGe2.7Si0.3Se8 (90 mol.% AgGaGe3Se8 - 10 mol.% AgGaSi3Se8), and AgGaGe3Se8:Cu substrates were established. The highest second-order susceptibility was achieved during the Ag-Ga-Ge-Se crystalline substrates photo-illumination by nanosecond laser pulses of about 2900 nm wavelength. The effect was found to be completely reversible after the interruption of the photo-inducing stimulation. Complementary studies of Atomic Force Microscopy, AFM, X-ray Diffraction, XRD, and Fourier-Transform Infrared Spectroscopy, and DFT simulations of spectral dependences of the corresponding second-order nonlinear optical susceptibilities, were performed.

The origin of antiferroelectricity in PbZrO3.

Antiferroelectrics are essential ingredients for the widely applied piezoelectric and ferroelectric materials: the most common ferroelectric, lead zirconate titanate is an alloy of the ferroelectric lead titanate and the antiferroelectric lead zirconate. Antiferroelectrics themselves are useful in large digital displacement transducers and energy-storage capacitors. Despite their technological importance, the reason why materials become antiferroelectric has remained allusive since their first discovery. Here we report the results of a study on the lattice dynamics of the antiferroelectric lead zirconate using inelastic and diffuse X-ray scattering techniques and the Brillouin light scattering. The analysis of the results reveals that the antiferroelectric state is a 'missed' incommensurate phase, and that the paraelectric to antiferroelectric phase transition is driven by the softening of a single lattice mode via flexoelectric coupling. These findings resolve the mystery of the origin of antiferroelectricity in lead zirconate and suggest an approach to the treatment of complex phase transitions in ferroics.

Lattice dynamics and pressure-induced phase transitions in α-BaTeMo2O9.

Orthorhombic α-BaTeMo2O9 nonlinear optical single crystals were investigated at ambient pressure by micro-Raman and infrared spectroscopy with a focus on the polarization properties of the vibrational modes. These results were analyzed based on classical lattice dynamics calculations, allowing us to propose the normal-mode symmetries and assignments. In addition to the ambient-pressure studies, high-pressure Raman scattering studies were performed. These studies showed the onset of a reversible first-order phase transition near 3.5 GPa. The pressure dependence of Raman bands provides strong evidence that the phase transition involves significant distortion of the TeOx (x = 3,4) polyhedra, whereas the MoO6 octahedra are less affected. A large increase in the number of observed bands points to lower symmetry of the high-pressure phase.

Temperature-dependent IR and Raman scattering studies of phase transitions in K2MgWO2(PO4)2.

Temperature-dependent Raman scattering and IR experiments were performed on K(2)MgWO(2)(PO(4))(2), which is derived from KTP by the replacement of two Ti(4+) ions with Mg(2+) and W(6+) cations. These studies revealed significant changes in phonon properties of these materials with increasing temperature due to the onset of phase transitions at 436, 537 and 637 K. Analysis of the obtained data showed that disordering processes in the sublattice of potassium ions play a significant role in the mechanism of these phase transitions. However, these transitions are also accompanied by weak tilts of the nearly rigid PO(4), WO(6) and MgO(6) groups. Present results also provide strong arguments that the phase transition at 637 K can be classified as occurring from the normal high-temperature phase with D(4) point symmetry into a modulated or incommensurate phase with the same D(4) point symmetry. Our results also show that the order-disorder (displacive) contribution to the phase transition mechanism is significantly stronger (weaker) in K(2)MgWO(2)(PO(4))(2) when compared to KTP.

Temperature-dependent Raman scattering study of the defect pyrochlores RbNbWO6 and CsTaWO6.

Lattice dynamics calculations and temperature-dependent Raman scattering experiments were performed on RbNbWO(6) and CsTaWO(6) pyrochlore oxides. The observed bands were assigned to the respective motions of atoms in the unit cell. The spectra showed the presence of additional Raman bands not allowed for by the [Formula: see text] cubic structure. We have shown that these bands appear due to both substitutional disorder in the 16c sites and displacive disorder of the A ions. Raman studies also revealed the presence of an additional 80 cm(-1) band at room temperature for RbNbWO(6), not observed for CsTaWO(6). The presence of this band has been attributed to off-center displacement of the Nb and W ions due to structural phase transition into a tetragonal ferroelectric phase. The temperature evolution of the 80 cm(-1) band intensity revealed that it disappeared at a much higher temperature (about 650 K) than the reported phase transition temperature (about 360 K). This behavior is reminiscent of chemically disordered perovskite ferroelectrics, including relaxor ferroelectrics, and was attributed to the presence of small polar regions with local tetragonal distortion embedded in the paraelectric matrix of the [Formula: see text] structure.

Specific features of Tm3+ doped BiB3O6 glasses fluorescence spectra and their kinetics.

Synthesis and spectral fluorescent features of the thulium-doped BiB(3)O(6) glasses are presented. All spectra were recorded using a pulsed (pulse energy ca. 1µJ, pulse duration 10ns) 355nm third harmonic of 10kHz Nd:YAG laser as an excitation source. A laser beam was focused in a backscattering geometry onto about 1mm(2) spot on the surface of a sample. The Andor SR-303i spectrograph equipped with an Andor DH-501 intensified charge coupled device with spectral resolution up to 1nm was used as a spectra recorder. The time-resolution of this system can be as low as 5ns. The decay kinetics was derived from integrated time-resolved spectra. Additionally the absorption and excitation spectra were measured. The main parameters of the Judd-Ofelt analysis were calculated and comparison of the obtained results with corresponding data for other materials was carried out.

Vibrational properties of RbNd(WO4)2: high pressure Raman study, structural and phonon calculations.

RbNd(WO(4))(2) was investigated by high pressure Raman spectroscopy in the 0.1-12.3 GPa pressure interval. The assignment of modes was made based on lattice dynamics calculations and the results of these calculations helped us to also discuss the high pressure behavior of phonon spectra in this material. Our results show that a double oxygen bridge plays a fundamental role in the vibrational properties of this system. A density functional theory (DFT) calculation of hydrostatic pressure effects on RbNd(WO(4))(2) was performed in order to understand the effect of internal bond changes on the vibrational properties of RbNd(WO(4))(2). No pressure induced structural phase transition was observed in the Raman study at room temperature, and the DFT calculation (T = 0 K) is consistent with this result. The anomalous softening of the bridge stretching mode at 770 cm(-1) was attributed to the decrease of W-O1-W bond angle with increasing pressure.

Effect of U on the electronic properties of neodymium gallate (NdGaO3): theoretical and experimental studies.

We have performed a density functional calculation for the centrosymmetric neodymium gallate using a full-potential linear augmented plane wave method with the LDA and LDA+U exchange correlation. In particular, we explored the influence of U on the band dispersion and optical transitions. Our calculations show that U = 0.55 Ry gives the best agreement with our ellipsometry data taken in the VUV spectral range with a synchrotron source. Our LDA+U (U = 0.55) calculation shows that the valence band maximum (VBM) is located at T and the conduction band minimum (CBM) is located at the center of the Brillouin zone, resulting in a wide indirect energy band gap of about 3.8 eV in excellent agreement with our experiment. The partial density of states show that the upper valence band originates predominantly from Nd-f and O-p states, with a small admixture of Nd-s/p and Ga-p B-p states, while the lower conduction band prevailingly originates from the Nd-f and Nd-d terms with a small contribution of O-p-Ga-s/p states. The Nd-f states in the upper valence band and lower conduction band have a significant influence on the energy band gap dispersion which is illustrated by our calculations. The calculated frequency dependent optical properties show a small positive uniaxial anisotropy.

UV-induced nonlinear absorption in lanthanum calcium borate single crystals.

It has been revealed that lanthanum calcium borate (La2CaB10O19) crystals show two-photon absorption (TPA) induced by a UV laser field. UV-induced TPA measurements were performed in the spectral range of 475-1130 nm using as fundamental beam the third harmonics of the 28 ps Nd-YAG pulsed laser as a pumping beam for LiB3O5 optical parametrized generator using Z-scan method. Investigations performed by the Z-scan method were done during illumination by a Xe-F laser (lambda = 217 nm) as a photoinducing (pumping) beam. The pumping laser beam created a thin surface layer (about 80-90 nm) that was the source of the observed photoinduced TPA. The highest values of the TPA beta coefficients were achieved for polarization of the pumping light directed along the second-order crystallographic axis of the investigated crystals. The obtained values of the TPA coefficients were higher than those for the BiB3O6 crystals investigated earlier by us.

High-average-power femtosecond pulse generation in the blue using BiB3O6.

Efficient generation of tunable femtosecond pulses in the blue is reported in the nonlinear crystal BiB3O6. By use of fundamental pulses from a mode-locked Ti:sapphire laser at 76 MHz, single-pass second-harmonic average powers of as much as 830 mW have been generated at 50% conversion efficiency, and a tunable range of 375-435 nm in the blue is demonstrated. Temporal measurements using cross correlation of the fundamental and second-harmonic pulses in a 100-microm-thick beta-BaB2O4 crystal result in blue pulse durations of 220 fs for 130-fs fundamental pulses. Direct experimental comparison with beta-BaB2O4 confirms the superior performance BiB3O6 for second-harmonic generation of femtosecond pulses.

Subependymal giant cell astrocytoma: clinical, histologic and immunohistochemical characteristic of 3 cases.

Three cases of subependymal giant cell astrocytoma (SEGA) in the women aged 23, 26, and 36 years were reported. Two of them had no clinical evidence of tuberous sclerosis complex (TSC) and the one woman presented apparent mental retardation. All patients manifested sudden clinical onset with symptoms of elevated intracranial pressure due to tumor of lateral ventricles and obstructive hydrocephalus. At surgery, the neoplasm was removed totally in one case and resected partially in 2 cases. Histologically, the tumors were composed of large polygonal cells with vesicular nuclei, prominent nucleoli and glassy eosinophilic cytoplasm, intermingled with spindle and small cells. In addition, multinucleated and bizarre giant cells were present, but they were very numerous in one case only. The tumor cells revealed in all cases variegated immunoreactivity for glial fibrillary acidic protein (GFAP), S-100 protein, vimentin (VIM) and neuron-specific enolase (NSE), with stronger expression of VIM than GFAP in 2 cases. Immunostaining of neurofilament proteins and synaptophysin was negative. The results suggest rather astroglial incomplete or aberrant differentiation and maturation than neuronal differentiation of tumor cells. The immunohistochemical variations of SEGA in asymptomatic TSC cases and those associated with tuberous sclerosis are discussed.

Supratentorial astrocytoma associated with arteriovenous malformation. Case report.

A case of the 18-year-old boy suffering from epilepsy since 8 years and suspected of microangioma is presented. The craniotomy revealed left parietal parasagittal superficially located neoplasm and arteriovenous malformation beneath. Unexpected fibrillary astrocytoma associated with vascular tumor was the diagnostic problem, solved histologically after the operation. The problem of coexistence of various neoplasms with arteriovenous malformations is discussed.