Nanostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles: polyol-mediated synthesis and luminescent properties

Nano-submicrostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles were prepared by polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT-IR), thermogravimetry-differential thermal analysis (TG-DTA), photoluminescence (PL), cathodo-luminescence (CL) spectra and PL lifetimes. The results of XRD indicate that the as-prepared samples are well crystallized with the scheelite structure of CaWO4. The FE-SEM images illustrate that CaWO4 and CaWO4 : Pb2+ and CaWO4 : Tb3+ powders are composed of spherical particles with sizes around 260, 290, and 190 nm respectively, which are the aggregates of smaller nanoparticles around 10-20 nm. Under the UV light or electron beam excitation, the CaWO4 powders exhibits a blue emission band with a maximum at about 440 nm. When the CaWO4 particles are doped with Pb2+, the intensity of luminescence is enhanced to some extent and the luminescence band maximum is red shifted to 460 nm. Tb(3+)-doped CaWO4 particles show the characteristic emission of Tb3+ 5D4-7FJ (J = 6 - 3) transitions due to an energy transfer from WO4(2-) groups to Tb3+.     

Nanostructured CaWO4, CaWO4:Eu3+ and CaWO4:Tb3+ particles: sonochemical synthesis and luminescent properties

Nanostructured CaWO4, CaWO4:Eu3+, and CaWO4:Tb3+ phosphor particles were synthesized via a facile sonochemical route. X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, photoluminescence, low voltage cathodoluminescence spectra, and photoluminescence lifetimes were used to characterize the as-obtained samples. The X-ray diffraction results indicate that the samples are well crystallized with the scheelite structure of CaWO4. The transmission electron microscopy and field emission scanning electron microscopy images illustrate that the powders consist of spherical particles with sizes from 120 to 160 nm, which are the aggregates of even smaller nanoparticles ranging from 10 to 20 nm. Under UV light or electron beam excitation, the CaWO4 powder exhibited a blue emission band with a maximum at 430 nm originating from the WO4/2- groups, while the CaWO4:Eu3+ powder showed red emission dominated by 613 nm ascribed to the 5D0 --> 7F2 of Eu3+, and the CaWO4:Tb3+ powders showed emission at 544 nm, ascribed to the 5D4 --> 7F5 transition of Tb3+. The PL excitation and emission spectra suggest that the energy is transferred from WO4/2- to Eu3+ CaWO4:Eu3+ and to Tb3+ in CaWO4:Tb3+. Moreover, the energy transfer from WO4/2- to Tb3+ in CaWO4:Tb3+ is more efficient than that from WO4/2- to EU3+ in CaWO4:Eu3+. This novel and efficient pathway could open new opportunities for further investigating the novel properties of tungstate materials.     

CaWO_4粉体和CaWO_4一维阵列的制备及光致发光特性

采用溶胶-凝胶法及辅助氧化铝模板法分别制备CaWO4粉体和CaWO4一维阵列,研究合成CaWO4粉体和一维陈列的光致发光特性。结果表明,制备的样品是纯CaWO4粉体;CaWO4粉体的强发光峰是位于410 nm的宽带谱,而CaWO4一维阵列的强发光峰在450 nm处,其光致发光曲线呈现宽化和强发光峰位的红移,这是样品和模板的光致发光光谱耦合的结果。     

Patterning of red, green, and blue luminescent films based on CaWO4:Eu3+, CaWO4:Tb3+, and CaWO4 phosphors via microcontact printing route

The multicolor patterned luminescent films of CaWO(4):Eu(3+) (red), CaWO(4):Tb(3+) (green), and pure CaWO(4) (blue) on quartz substrates were fabricated by the facile and low-cost microcontact printing (μCP) method combining with the Pechini sol-gel route. On the basis of the μCP process, a hydrophobic self-assembled monolayer (SAM) was first created on the hydrophilic surface of quartz substrates by poly(dimethylsiloxane) (PDMS) mold printing, and then, the multicolor patterned luminescent films were selectively deposited on the hydrophilic regions via a spin coating process and heating treatment. The X-ray diffraction, optical microscopy, scanning electron microscopy, and photoluminescence (PL) spectra were used to characterize the structure and fluorescence properties of the corresponding samples. The results demonstrate that the μCP process can be used for patterning the inorganic phosphor materials and have potential for fabricating rare-earth luminescent pixels for the applications of display devices.     

Microwave measurements of dielectric constants of Snl2 and Snl4

The bulk dielectric parameters at microwave frequencies (8.95 GHz) for tin-di-iodide (Snl₂) and tin-tetra-iodide (Snl₄) have been determined using Looyenga's formula. It has also been investigated under different conditions such as particle size, packing fraction and temperature of the powders. It has been observed that the dielectric constant of Snl₂ is greater than that of Snl₄ materials. The temperature dependence of dielectric parameters in these materials indicated the presence of dissociation processes causing the fall in dielectric constants. An attempt has been made to understand these results and the implications are discussed.     

Phonon Raman scattering of R2CuO4 (R = Pr, Nd, Sm, and Gd)

For Gd₂CuO₄, a new symmetry-forbidden phonon for the tetragonal T structure is observed. This implies that oxygen in the CuO₂ plane is locally distorted along the CuO₂ plane. Such distortion has never been observed for other T-type superconductors, which show superconductivity by Ce doping. The disappearance of superconductivity for Gd can be correlated with the appearance of the distortion due to oxygen in the CuO₂ plane.     

Sub-nanosecond Nd:Lu0.61Gd0.39VO4 microchip laser

We report the fabrication and operation of a single-to-three-mode, sub-nanosecond passively Q-switched Nd:Lu_0.61Gd_0.39VO₄/Cr⁴⁺:YAG microchip laser, which exhibits changes in mode structure with increasing incident pump power. The laser exhibits longitudinal mode oscillations with a partial transverse mode overlap. The shortest pulse duration, highest pulse energy and peak power observed are 646 ps, 8.7 μJ and 13.5 kW, respectively.     

The effect of stress on the dielectric constants of Bi4Ti3O12 films

Both experiment and theory have shown that the stress has a notable impact on the polarization of Nd-doped Bi₄Ti₃O₁₂ films. In this paper, thermodynamic theory is used to study the effect of stress on the dielectric constants of Bi₄Ti₃O₁₂ films at room temperature with a two-dimensional model. Results indicate that the change of the dielectric constant for a-phase induced by the lattice distortion is far greater than that for c-phase. Considering the domain reorientation, the external tensile stress may lead to an obvious decrease in the effective dielectric constant of Bi₄Ti₃O₁₂ films.     

Mössbauer effect of SrLnFeO4 (Ln=La,Pr, Nd,Sm, Eu,Gd)

The Mössbauer effect has been studied in SrLnFeO₄ compounds (Ln=La, Pr, Nd, Sm, Eu, Gd) with K₂NiF₄ structure in the temperature range between 80K and 459K. The N?el temperture was determined to be 330±5K for SrLaFeO₄, 250±5K for SrPrFeO₄, 270±5K for SrNdFeO₄ and 400±10K for SrSmFeO₄. The results of the combined magnetic and quadrupole interactions indicated that the direction of internal magnetic field is perpendicular to the Z-axis of the EFG tensor and parallel to the c-axis of the crystal structure.     

Phonon Raman scattering of R2CuO4 (R = Pr,Nd, Sm,and Gd)

For Gd₂CuO₄, a new symmetry-forbidden phonon for the tetragonal T′ structure is observed. This implies that oxygen in the CuO₂ plane is locally distorted along the CuO₂ plane. Such distortion has never been observed for other T′-type superconductors, which show superconductivity by Ce doping. The disappearance of superconductivity for Gd can be correlated with the appearance of the distortion due to oxygen in the CuO₂ plane.     

Properties of Nd3+-doped and undoped tetragonal PbWO4, NaY(WO4)2, CaWO4, and undoped monoclinic ZnWO4 and CdWO4 as laser-active and stimulated raman scattering-active crystals

Spectroscopic, laser, and chi((3)) nonlinear optical properties of tetragonal PbWO(4), NaY(WO(4))(2), CaWO(4), and monoclinic CdWO(4) and ZnWO(4) were investigated. Particular attention was paid to Nd(3+)-doped and undoped PbWO(4) and NaY(WO(4))(2) crystals. Their absorption and luminescence intensity characteristics, including the peak cross sections of induced transitions, were determined. Pulsed and continuous-wave lasing in the two 4F(3/2)-->4I(11/2) and 4F(3/2)-->4I(13/2) channels was excited. For these five tungstates, highly efficient (greater than 50%) multiple Stokes generation and anti-Stokes picosecond generation were achieved. All the observed scattered laser components were identified. These results were analyzed and compared with spectroscopic data from spontaneous Raman scattering. A new crystalline Raman laser based on PbWO(4) was developed for the chi((3)) conversion frequency of 1-microm pump radiation to the first Stokes emission with efficiency up to 40%. We classify all the tungstates as promising media for lasers and neodymium-doped crystals for self-stimulated Raman scattering lasers.     

Effect of Mixing Nd, Eu, and Gd Rare Earth Elements on RE-Cuprate High-Tc Superconductors

The extent of the relationship between rare earth radius, peritectic decomposition temperature (T _p), and lattice dimensions within mixed rare earth (Nd, Eu, Gd) barium cuprate 123 superconductors has been investigated. The peritectic decomposition temperature of compositions within the ternary (Nd _x Eu _y Gd _z )Ba₂Cu₃O_{7 –} (x + y + z = 1) material, while maintaining a constant average rare earth cationic radius of 1.076 Å, was observed to be uniform. Powder X-ray diffraction analysis of processed materials also showed the lattice parameters to be uniform with these compositional changes. These results indicate a uniform mixing of the RE elements in the RE 123 phase. In contrast, the mixing of such RE elements leads to the formation of an inhomogeneous distribution of both Nd422 and RE211 second-phase particles in the matrix subsequent to melt processing.     

Ba4Nd2Ti4Ta6O30 dielectric ceramics modified by Bi substitution for Nd

Modification of dielectric properties for Ba₄Nd₂Ti₄Ta₆O₃₀ ceramic was investigated through Bi partial substitution for Nd. The dielectric constant increased and the dielectric loss decreased with increasing concentration of Bi, and the dielectric constant reached 142, combined with a low dielectric loss of 10^–4 (at 1 MHz) for the composition Ba₄(Nd_0.975Bi_0.025)₂Ti₄Ta₆O₃₀. The temperature coefficient () can be slightly improved.     

Phase transition characteristics and dielectric properties of rare-earth (La,Pr, Nd,Gd) doped Ba(Zr0.09Ti0.91)O3 ceramics

A-site deficient rare-earth doped barium zirconate titanate (BZT) ceramics (Ba_1−yLn_2y/3)Zr_0.09Ti_0.91O₃ (Ln = La, Pr, Nd, Gd) are obtained by a modified solid-state reaction method. Perovskite-like single-phase compounds were confirmed from X-ray diffraction data. Morphological analysis on sintered samples shows that the addition of rare-earth ions inhibits the growth of the grain and remarkably changes the grain morphology. The effect of rare-earth addition to BZT on phase transition and dielectric properties is analyzed. A dramatic fall in the transition temperature occurs when BZT ceramic is doped with rare-earths. Moreover, diffusivity degree of the phase transition increases and a relaxor-type behaviour is induced due to both the increment of the lanthanide content and the increase of the ionic radius of the dopant element. High values of dielectric tunability are obtained for lanthanum doped BZT. A direct relation between transition temperature and tunability is discussed. Conclusively, low permittivity and high tunability materials can be obtained by the adequate substitution of rare-earths into BZT ceramics.     

The dielectric constants of current-blackened single crystral yttria-stabilized zirconia

The dielectric constants of 8 mol % single crystal yttria-stabilized zirconia have been measured, using both radio-frequency and microwave methods, before and after blackening by high temperature electrolysis. For as-grown material = 38±4 and tan = 0.004. After electrolysis both the dielectric constant and loss tangent of the current-blackened material increased; this experimental data has been compared with theoretical predictions for composite dielectrics. The dielectric behaviour in the current-blackened material was consistent with the formation of metallic particles; these initially appeared to be spherical but elongated as electrolysis proceeded.     

Flux growth and habit modification of CaWO4 crystals

The poor quality of natural scheelite necessitates growing these crystals in the laboratory. The flux growth method has been modified to obtain crystals of better quality. Various habits of the grown crystals are reported. The effect of the growth conditions like temperature, cooling rate, charge composition, etc. to yield different morphology has been investigated.     

Identification of elastic, dielectric, and piezoelectric constants in piezoceramic disks

Three-dimensional modeling of piezoelectric devices requires a precise knowledge of piezoelectric material parameters. The commonly used piezoelectric materials belong to the 6mm symmetry class, which have ten independent constants. In this work, a methodology to obtain precise material constants over a wide frequency band through finite element analysis of a piezoceramic disk is presented. Given an experimental electrical impedance curve and a first estimate for the piezoelectric material properties, the objective is to find the material properties that minimize the difference between the electrical impedance calculated by the finite element method and that obtained experimentally by an electrical impedance analyzer. The methodology consists of four basic steps: experimental measurement, identification of vibration modes and their sensitivity to material constants, a preliminary identification algorithm, and final refinement of the material constants using an optimization algorithm. The application of the methodology is exemplified using a hard lead zirconate titanate piezoceramic. The same methodology is applied to a soft piezoceramic. The errors in the identification of each parameter are statistically estimated in both cases, and are less than 0.6% for elastic constants, and less than 6.3% for dielectric and piezoelectric constants.     

Magnetic order in the Nd,Gd, Er,and Yb trifluoromethane sulfonates

We have observed magnetic order, apparently dipolar in origin, in the hexagonal trifluoromethane sulfonate salts of Nd, Gd, Er, and Yb. With the exception of Yb, their magnetic properties are all very similar to the corresponding isostructural rare earth ethyl sulfates. The Yb salt is unique in having a different ionic ground state, and may not haveC _3h symmetry.     

Theoretical and experimental study on passive mode-locking composite Nd:GdVO4/Nd:GdVO4/Nd:GdVO4 lasers

Stable passive mode-locking multi-segment composite Nd:GdVO₄ lasers with a semiconductor saturable absorber mirror were demonstrated for the first time. For the composite crystals, the output power increased linearly with the increase of the incident pump power, showing excellent thermo-mechanical performances. While for the conventional crystal, power saturation was observed when the incident pump power exceeded 8.79 W. The maximum average output power of 1.465 W was achieved by Nd(0.1%):GdVO₄/Nd(0.5%):GdVO₄/Nd(1%):GdVO₄ composite crystal at an incident pump power of 9.28 W. The largest pulse energy of 14.90 nJ and the highest peak power of 0.53 kW with a pulse duration of 28.0 ps were also obtained by using the same composite crystal, revealing that the multi-segment composite crystal with a proper combination of Nd³⁺-doped concentrations could obtain the optimal laser performance.