Raman scattering study on ferroelectric (Ba0.32Sr0.68)2Nb2O7 ceramics

Raman scattering technique was applied to examine the Ba-doping effect to the two low temperature phase transitions of Sr₂Nb₂O₇ (SN) in the temperature range from −190 to 600 °C. The line shape of Raman spectra can be well fitted by multidamped harmonic oscillator model. We did not observe any soft mode related to the two low temperature phase transitions corresponding to those of the pure SN. It is correlated to the disappearance of the incommensurate phase in (Ba_0.32Sr_0.68)₂Nb₂O₇ ceramics. However, the temperature dependence behavior of the three low frequency modes indicates another new structural phase transition around 270 °C. It is considered that the reduction of the interlayer interaction caused by partial replacement of Sr-site by Ba-site, whose ionic radius is larger than that of Sr, may be the reason for the disappearance of the incommensurate phase transition in (Ba_0.32Sr_0.68)₂Nb₂O₇ ceramics.     

Investigation of the temperature dependence of electron and phonon Raman scattering in single crystal YBa2Cu3O6.952

Detailed Raman-scattering measurements have been performed on high-quality YBa₂Cu₃O_6.952 single crystal (T _c =93 K, T _c =0.3 K). A sharp (FWHM 7.2 cm^–1 at 70 K and 10.0 cm^–1 at 110 K) 340 cm^–1phonon mode has been observed inB _1g polarization. An electronic scattering peak at 500 cm^–1 in theB _1g polarization extends down to 250 cm^–1. These FWHM values determine the upper limit of the homogeneous linewidth of the phonon and electronic excitations. The start of the electronic spectral function renormalization and of the 340 cm^–1 mode anomalies (frequency softening, linewidth sharpening, and intensity increase) have been observed to occur approximately 40 K aboveT _c . The 340 cm^–1 mode Fano shape analysis has been performed and the temperature dependences of the Fano shape parameters have been estimated. All 340 cm^–1 mode anomalies have been explained by the electronic spectral function renormalization.This work was supported by Swedish Natural Sciences Research Council (G.B. and L.B.) and by the National Science Foundation (DMR 91-20000) through the Science and Technology Center for Superconductivity (G.B. and M.V.K.).     

Oxygen pressure dependent VO2 crystal film preparation and the interfacial epitaxial growth study

High quality VO₂ crystal films have been prepared on sapphire substrates by pulsed laser deposition method and the effects of oxygen pressure on the crystal phase structure are investigated. Results indicate that the phases and microstructures of VO₂ films are strongly sensitive to oxygen pressure. High oxygen pressure tends to form coarse B-VO₂ nanocrystals while low pressure favors a flat M1-VO₂ film epitaxial growth. X-ray diffraction φ-scan patterns confirm the [020] epitaxial growth orientation of the M1-VO₂ film and the in-plane lattice epitaxial relationship at the interface is also examined. Raman spectra indicate that M1-VO₂ phase has much stronger Raman scattering modes than B-VO₂, and the clear phonon modes further confirm the idea stoichiometry of VO₂ crystal film. Infrared transmittance spectra as the function of temperature are recorded and the results show that M1-VO₂ crystal films undergo a distinct infrared transmittance variation across metal insulator transition boundary, while B-VO₂ exhibits negligible thermochromic switching properties in the temperature range concerned. The pronounced phase transition behavior of the M1-VO₂ crystal film makes it a promising candidate for optical filter/switch and smart window applications in the future.     

Photoinduced changes in Raman spectra of YBa2Cu3O6.4 films

The evolution of Raman spectra with illumination has been studied in YBa₂Cu₃O_6.4 films at temperatures between 5–300 K. Low laser power has always been used to avoid local overheating, which was controlled by measuring the local temperature by the Stokes/anti-Stokes ratio. Three important photoinduced effects have been found: (i) the enhancement of the intensity of the observed phonon modes: (Cu(2) at 141 cm^–1, O(2)-O(3) at 338 cm^–1, and O(4) at 488 cm^–1), which may be related to the ordering of oxygen vacancies, (ii) the increase of the electronic scattering background for low Raman frequencies, which is in agreement with the enhancement of the static conductivity(0) after illumination, and (iii) the suppression of the intensity of the two-magnon band, which may be caused by the increase of charge carriers due to photodoping.     

Electronic Raman scattering in YBa2Cu4O8

We report on the electronic Raman scattering in YBa₂Cu₄O₈ and find that, In contrast to the other superconducting cuprates, the continuum in the normal state is strongly temperature pendent in all polarizations. This temperature dependence is found to follow a Bose-Einstein-like form. We conclude that the absence of the Bose-Einstein factor in the electronic continuum is not essential to high-T_c superconductivity, as is sometimes implied. Additionally, we report on the rearrangement of the continuum which occurs belowT _c.     

High pressure Raman spectroscopy of ferrite MgFe2O4

An in situ Raman spectroscopic study was conducted to explore the pressure-induced phase transformation of ferrite MgFe₂O₄ to 51.6 GPa. Results indicate that MgFe₂O₄ transforms to a high pressure polymorphism at a pressure of 27.7 GPa, which was assigned to an orthorhombic structure. Upon release of pressure to ambient conditions, this high pressure polymorphism of MgFe₂O₄ remains stable. The crystallization of high pressure phase of MgFe₂O₄ is dominated by a diffusionless crystallizing mechanism.     

Orthorhombic (LiNbGeO5): efficient stimulated Raman scattering and tunable near-infrared laser emission from chromium doping

The structural, optical, spectroscopic, and laser properties of pure and chromium-doped lithium–niobium germanate (LiNbGeO₅) single crystals are discussed in this paper. Efficient stimulated Raman scattering (SRS), investigated with the one-micron fundamental and second harmonic wave of a picosecond Nd³⁺:Y₃Al₅O₁₂ laser, reveals the potential of this new cubic non-linear susceptible (χ⁽³⁾) optical material for realizing effective solid state Raman shifters. The data are analyzed and compared with spectroscopic data from spontaneous Raman scattering. Pulsed tunable laser action of chromium-doped LiNbGeO₅ crystals was demonstrated in the spectral range between 1.3 and 1.52 μm at cryogenic temperature and around 1.4 μm at room temperature. Due to its excellent crystalline and optical properties, LiNbGeO₅ is a promising material for tunable near-infrared lasers with integrated frequency converters.     

Enhanced performance of sandwich structure Pb0.8La0.1Ca0.1Ti0.975O3 thin film for pyroelectric applications

Using the advantages of low-temperature crystallization and high orientation in Pb_0.8La_0.1Ca_0.1Ti_0.975O₃ (PLCT) film, a dense PLCT/porous PLCT/dense PLCT sandwich structure was obtained in the present study. It is found that dense PLCT layer can both sustain the porous density in the core layer and also lead to better preferential orientation of the sandwich structure. In the sandwich structure, low dielectric constant (ε_r = 43) and leakage current density (J < 9 × 10^− 5A/cm²) are simultaneously achieved. Because of high orientation in sandwich structure, the pyrocoefficient (p > 185 µC/m² K) is still keeping a relatively large value. The resulting high figure of merit (F_V′ = 4.5 µC/m² K, F_d′ = 228 µC/m² K) make the sandwich structure films good candidate for pyroelectric thin-film devices.     

Temperature evolution of structure and magnetic properties in the perovskite Sr2MnSbO6

The structural and magnetic properties of the perovskite Sr₂MnSbO₆ have been studied. Combining neutron and X-ray powder diffraction data, the temperature evolution of the structural parameters was investigated with the Rietveld method between 2 and 1000 K. The crystal structure is tetragonal (space group I4/m) within the temperature interval of 2-750 K and cubic (space group Fm-3m) above 750 K. Both octahedral B-site positions were found to be partially occupied by Mn and Sb, but with different Mn/Sb ratios. The magnetic susceptibilities showed irreversibility between field cooled and zero-field cooled (ZFC) conditions and spin glass like magnetic dynamics including aging and memory phenomena at temperatures below 30 K; all appearing well above a broad maximum at 13 K in the ZFC susceptibility curves. This suggests that the material reaches an unconventional spin-glass state at low temperatures, possibly arising from a competitive situation between the double exchange (ferromagnetism) and the super-exchange (antiferromagnetism). Neutron diffraction patterns showed no evidence of a long-range magnetic ordering at 2 K which is consistent with spin glass behavior. The factors governing the observed structural and magnetic properties of Sr₂MnSbO₆ are discussed and compared with those of other quaternary Mn- and Sb-containing perovskites. Graphs of the temperature of magnetic phase transitions as functions of the cation size were constructed and are discussed for the AB³⁺_1/2B⁵⁺_1/2O₃ series with isomorphous substitution of B³⁺ and B⁵⁺ cations. Possible influence of the A-cation sublattice on magnetic properties is also shortly considered.     

High temperature-induced phase transitions in Sr2GdRuO6 complex perovskite

The crystal structure behavior of the Sr₂GdRuO₆ complex perovskite at high-temperature has been investigated over a wide temperature range between 298 K ≤ T ≤ 1273 K. Measurements of X-ray diffraction at room-temperature and Rietveld analysis of the experimental patterns show that this compound crystallizes in a monoclinic perovskite-like structure, which belongs to the P2₁/n (#14) space group and 1:1 ordered arrangement of Ru⁵⁺ and Gd³⁺ cations over the six-coordinate M sites. Experimental lattice parameters were obtained to be a =5.8103(5) Å, b =5.8234(1) Å, c =8.2193(9) Å, V = 278.11(2) Å³ and angle β = 90.310(5)°. The high-temperature analysis shows the occurrence of two-phase transitions on this material. First, at 573 K it adopts a monoclinic perovskite-type structure with I2/m (#12) space group with lattice parameters a = 5.8275(6) Å, b = 5.8326(3) Å, c = 8.2449(2) Å, V = 280.31(3) Å³ and angle β = 90.251(3)°. Close to 1273 K it undergoes a complete phase-transition from monoclinic I2/m (#12) to tetragonal I4/m (#87), with lattice parameters a = 5.8726(1) Å, c = 8.3051(4) Å, V = 286.39(8) Å³ and angle β = 90.0°. The high-temperature phase transition from monoclinic I2/m (#12) to tetragonal I4/m (#87) is characterized by strongly anisotropic displacements of the anions.     

Raman scattering studies of ultrathin-layer YBa2Cu3O7/PrBa2Cu3O7 superlattices

We present Raman scattering studies ofc-oriented ultrathin-layer superconducting (YBa₂Cu₃O₇) _m /(PrBa₂Cu₃O₇) _n superlattices. For the superlattice with (m=2,n=1) sequence, Raman spectra reveal a new line in the spectral region around 320 cm^–1. It is interpreted as a mode representing a combination of IR optical phonons of the Y-sublayers with an admixture of aB _1g type Raman active vibration in the Pr sublayers. This new line, which is similar to those from the interior of the Brillouin zone of the original lattice, does not exhibit superconductivity-induced self-energy effects, although its counterpart in the pure substance does. No additional line is found in the (m=1,n=2) superlattice in the same region, supporting our interpretation for the (m=2,n=1) sample.     

Effect of SBA-15 microporosity on the inserted TiO2 crystal size determined by Raman spectroscopy

The effect of SBA-15 microporosity on the crystal size of TiO₂ was investigated employing SBA-15 materials with high (SBA-15-HM) and low (SBA-15-LM) microporosities (14.2% and 4.7% of microporous volume, respectively). TiO₂ phase was incorporated inside SBA-15 using internal hydrolysis method over a wide range of loadings (7–63 wt%). At all loadings, TiO₂ inside SBA-15 pores was in the form of anatase nanocrystals as found in characteristic Raman spectra. The crystal size of TiO₂ anatase phase was determined by Raman spectroscopy using a correlation between Raman peak position and peak width and TiO₂ crystal size. The correlation was established based on the set of unsupported TiO₂ samples with the crystals size in the range 5–120 nm (BET and XRD). Using this correlation, it was found that the crystal size of TiO₂ inside SBA-15 with high microporosity was lower than inside SBA-15 with low microporosity. This is a direct proof of the effect of wall microporosity on the dispersion of TiO₂ inside SBA-15. Due to the higher TiO₂ dispersion, TiO₂/SBA-15-HM adsorbed more vanadia than TiO₂/SBA-15-LM at the same TiO₂ loadings. As a result, V₂O₅/TiO₂/SBA-15-HM displayed higher activity than V₂O₅/TiO₂/SBA-15-LM in NO SCR with ammonia.     

Optical properties of rare-earth doped epitaxial Sr0.5Ba0.5Nb2O6 thin films grown by pulsed laser deposition

Optical quality rare-earth (RE) (Nd³⁺, Eu³⁺, Gd³⁺ and Yb³⁺) doped Sr_0.5Ba_0.5Nb₂O₆ (SBN) epitaxial films of ~ 170 nm thick have been successfully grown on MgO (100) single crystal substrates using pulsed laser deposition technique. Strong residual stress in these films has been revealed by Raman spectroscopic studies. Two kinds of in-plane orientations with respect to the MgO substrate co-exist. All the film samples show high transparency in the visible wavelength. Their band-gap energies appear to be independent of the types of dopant. Photoluminescence (PL) spectra of RE-doped SBN ceramics show a strong and broad emission band at around 600 nm (2.07 eV). The peak position of this emission band changes slightly with different RE-dopants. Thin film samples, however, yield a broad PL band at around 385 nm (3.22 eV). This UV emission shows no observable shift in the peak position for different dopants. Apart from these broad emission bands, conspicuous emission lines from Eu³⁺ and Nd³⁺ ions are also noted. The origins of these PL spectra are discussed.     

Raman spectroscopic study of structure of WO3La2O3B2O3 glasses with no color and crystallization of LaBWO6

Glasses with the nominal compositions of xWO₃25La₂O₃(75 − x)B₂O₃ (mol%) with x = 15, 25, and 50 were prepared using a conventional melt quenching method, and their structure and crystallization behavior were examined from Raman scattering spectra and X-ray diffraction analyses. The glasses are colorless in the visible light region and give the optical band gap energy of 3.49-3.61 eV. The glass transition and crystallization temperatures and the thermal stability against crystallization decrease with increasing WO₃ content. The strong Raman bands at 840 and 940-960 cm⁻¹ suggest that the main coordination state of W⁶⁺ ions in the glasses is isolated (WO₄)²⁻ tetrahedral units. The formation of WO₆ octahedral units is also suggested in the glasses with high WO₃ contents. The main crystallization mechanism in the glasses is the surface crystallization, and the glass of 50WO₃25La₂O₃25B₂O₃ shows the crystallization of LaBWO₆ single phase. The present study proposes that WO₃La₂O₃B₂O₃ glasses and crystallized glasses are very interesting as optical functional materials.     

Inhomogeneous electronic properties of epitaxial La2/3Ca1/3MnO3 thin films

In this paper, we have reported on epitaxial fully strained La_2/3Ca_1/3MnO₃ films grown on single-crystalline SrTiO₃ substrates, with thicknesses ranging from 6 to 108 nm. ⁵⁵Mn NMR experiments, combined with magnetization data, show that the films have non-homogeneous magnetoelectronic properties and that non-ferromagnetic insulating regions are present close to the interface with the SrTiO₃. This observation may account for the repeatedly described disruption of the performance of manganite-based tunneling devices with increasing temperature and may help to better identify the possible causes of the modification of the La_2/3Ca_1/3MnO₃/SrTiO₃ interface properties.     

Raman scattering characterization of bismuth based mixed oxides with Bi2O3 related structures

Orthorhombic Bi₁₇Ln₇O₃₆ (=Bi_0.708Ln_0.292O_1.5) and triclinic BiLnO₃ (=Bi_0.5Ln_0.5O_1.5) with Ln = Tm, Yb and Lu, as well as a cubic δ-type Bi_0.7Yb_0.3O_1.5, have been characterized at room temperature by Raman scattering spectrometry. The Raman spectrum deconvolution of the δ-Bi₂O₃ type cubic form allowed us to establish a correlation between the different phases of these mixed metallic oxides for the lattice modes as well as for the internal species. Using the empirical relation from Hardcastle, the BiO bond lengths have been estimated from the stretching frequency value observed at 635, 597 or 639 cm⁻¹ for cubic, orthorhombic or triclinic forms, respectively. A comparison with the X-ray results is discussed. The peritectoïdic transformation BiTmO₃ → δ + Tm₂O₃ has also been characterized by Raman spectroscopy.     

Thermomechanical processing and transport current density of Ag-sheathed (Tl,Cr)Sr2(Ca0.9,Pr0.1)Cu2O7 superconductor tapes

Powders with nominal composition (Tl,Cr_0.15)Sr₂(Ca_0.9,Pr_0.1)Cu₂O₇ (Tl-1212) and T_c90 K were used to fabricate Ag-sheathed superconducting tapes employing the powder-in-tube (PIT) method. The tapes were subjected to intermediate mechanical rolling or pressing. Conditions that enhance the transport critical current density (J_c) of the tapes were investigated. Optimum annealing temperature and period together with uniaxial pressing are necessary to increase J_c of the Tl-1212/Ag tapes. Annealing at 910 °C for 0.5–1 h enhanced the 1212 phase formation and improved intergranular connectivity between grains, as well as to provide healing for the fractured structure caused by deformation process. A relatively longer annealing time at higher temperature gave rise to secondary phases and resulted in the decrease of J_c. Mechanical uniaxial pressing greatly densified the tapes core and thus led to closer contact between grains. At liquid nitrogen temperature and zero field, J_c of the pressed tapes annealed at 910 °C for 1 h is 3060±127 A cm⁻². The initial drastic drop of J_c in low fields (<0.06 T) indicates the performance of the tapes is limited by weak links. No significant anisotropic transport properties were observed in applied magnetic field. This is due to the absence of texturing in the tapes as the grains are randomly oriented revealed through SEM micrographs.     

Solubility of SrAl2O4 in CaAl2O4—a high resolution powder diffraction study

The solid solubility of the SrAl₂O₄-CaAl₂O₄ system has been investigated using high resolution synchrotron powder diffraction methods. Analysis of the patterns shows there is a limited composition range at which single phase samples can be obtained, x<0.25 and x>0.75 for the series Ca_1−xSr_xAl₂O₄. At intermediate compositions up to three phases are observed, two monoclinic and one hexagonal. The temperature dependence of the structures is also described.     

First-Principles Study on the Stability and Electronic Properties of Bi-Doped Sr3Ti2O7

The electronic and crystal structural properties of Bi-doped Sr_3Ti_2O_7are studied using the first principles density functional theory(DFT)based on pseudopotentials basis and plane-wave method.Our results show that the formation energy of Bi doping in Site-1 and Site-2 of Sr_3Ti_2O_7increases with increasing doping concentration.And at the same doping concentration,the formation energy of Bi doping in Site-2 is lower than that in Site-1.The undoped Sr_3Ti_2O_7is found to be an insulator and its Fermi level stays at the top of the valence band.While the Fermi level of the Bi-doped Sr_3Ti_2O_7moves into the bottom of conduction band,the system undergoes an insulator-to-metal phase transition.Furthermore,our calculation results demonstrated that the Fermi level of the Bi-doped Sr_3Ti_2O_7goes deeper into the bottom of conduction band with increasing doping concentration.     

Low-temperature synthesis,phonon and luminescence properties of Eu doped Y3Al5O12 (YAG) nanopowders

This contribution presents two simple and cost-effective routes for the low-temperature and large-scale production of pure and Eu-doped Y₃Al₅O₁₂ (yttrium aluminum garnet YAG) nanopowders. The proposed methodologies combine a mechanically assisted metathesis reaction or coprecipitation from solution followed by crystallization of the obtained precursors from molten sodium nitrate/nitrite. Both procedures allow obtaining pure and/or doped YAG nanopowders at remarkably low temperatures, i.e. already at 350 °C although firing at 500 °C is needed in order to get single phase and fully crystalline materials. As-obtained samples were characterized by XRD, TEM, Raman, IR and luminescence methods. These methods showed that the mean crystallite size is near 23–31 and 51 nm, when crystallization is performed from the amorphous precursor obtained by a mechanically assisted metathesis reaction and coprecipitation, respectively. Raman and IR spectra indicated better crystallinity of the powders prepared at 500 °C. The emission study showed that the intensity ratio between hypersensitive ⁵D₀ → ⁷F₂ and magnetic-dipole ⁵D₀ → ⁷F₁ transitions of Eu³⁺ is significantly larger than expected for well-crystallized YAG. Origin of this behavior is discussed.