A vibrational spectroscopic study of the phosphate mineral churchite (REE)(PO4)���2H2O

Vibrational spectroscopy has been used to study the rare earth mineral churchite of formula (REE)(PO4)-���2H2O. The mineral contains a range of rare earth metals including yttrium depending on the locality. The Raman spectra of churchite-(REE) are characterized by an intense sharp band at 984 cm-1 assigned to the v1 (PO��-) symmetric stretching mode. A lower intensity band observed at around 1067 cm-1 is attributed to the v3 (PO��-) antisymmetric stretching mode. The (PO��-) bending modes are observed at 497 cm-1 (v2) and 565 cm-1(v4). Raman bands at 649 and 681 cm-1 are assigned to water librational modes. Vibrational spectroscopy enables aspects of the structure of churchite to be ascertained.

Lanthanum, praseodymium and neodymium chloroacetates

The monochloroacetates of lanthanum, praseodymium and neodymium of the composition M(ClCH2COO)3��2H2O have been prepared and characterised. The compounds behave as non-electrolytes in dimethylformamide. The infrared spectra are consistent with bidentate coordination of the carboxylate group and show the presence of two types of water molecules, coordinated, and free. With six oxygen atoms from the three acetato groups and one from the water bonded to the metal, a coordination number of seven has been assigned to the rare earths in these compounds. On pyrolysis, the chloroacetates lose water at ~130 ��C and yield the oxychlorides at ~500 ��C. The X-ray powder patterns of the chloroacetates have been indexed for the monoclinic system, with four molecules per unit cell.

X-ray photoelectron spectroscopy of superconducting RuSr2Eu1.5Ce0.5Cu2O10 and nonsuperconducting RuSr2EuCeCu2O10

We report x-ray photoelectron spectroscopic investigation of RuSr2Eu1.5Ce0.5Cu2O10 with ferromagnetic T-C similar to 100 K and a superconducting transition temperature of similar to 30 K compared with RuSr2EuCeCu2O10, which is a ferromagnetic (T-C similar to 150 K) insulator. Our results show that the rare earths, Eu and Ce, are in 3+ and 4+ states, respectively. Comparing the Ru core level spectra from these compounds to those from two Ru reference oxides, we also show that Ru in these ruthenocuprates is always in 5+ state, suggesting that the doped holes in the superconducting compound arising from the substitution of Ce4+ by Eu3+ are primarily in the Cu-O plane, in close analogy to all other doped high-T-C cuprates. Analysis of Cu 2p spectra in terms of a configuration interaction model provides a quantitative description of the gross electronic structures of these ruthenocuprates.

Photoluminescence of Sr(2-x)Ln(x)CeO(4+x/2) (Ln = Eu, Sm or Yb) prepared by a wet chemical method

A wet chemical route is developed for the preparation of Sr2CeO4 denoted the carbonate-gel composite technique. This involves the coprecipitation of strontium as fine particles of carbonates within hydrated gels of ceria (CeO2.xH(2)O, 40<x<75) by the addition of ammonium carbonate. During calcination, CeO2.xH(2)O dehydroxylation is followed by the reaction with SrCO3 to form Sr2CeO4 with complete phase purity. Doping of other rare-earths is carried out at the co-precipitation stage. The photoluminescence (PL) observed for Sr2CeO4 originates from the Ce4+-O2- charge-transfer (CT) transition resulting from the interaction of Ce4+ ion with the neighboring oxide ions. The effect of next-nearest-neighbor (NNN) environment on the Ce4+-O2- CT emission is studied by doping with Eu3+, Sm3+ or Yb3+ which in turn, have unique charge-transfer associated energy levels in the excited states in oxides. Efficient energy transfer occurs from Ce4+-O2- CT state to trivalent lanthanide ions (Ln(3+)) if the latter has CT excited states, leading to sensitizer-activator relation, through non-resonance process involving exchange interaction. Yb3+-substituted Sr2CeO4 does not show any line emission because the energy of Yb3+-O2- CT level is higher than that of the Ce4+-O2- CT level. Sr2-xEuxCeO4+x/2 shows white emission at xless than or equal to0.02 because of the dominant intensities of D-5(2)-F-7(0-3) transitions in blue-green region whereas the intensities of D-5(0)-F-7(0-3) transitions in orange-red regions dominate at concentrations xgreater than or equal to0.03 and give red emission. The appearance of all the emissions from D-5(2), D-5(1) and D-5(0) excited states to the F-7(0-3) ground multiplets of Eu3+ is explained on the basis of the shift from the hypersensitive electric-dipole to magnetic-dipole related transitions with the variation in site symmetry with increasing concentration of Eu3+. White emission of Sr2-x SmxCeO4+x/2 at xless than or equal to0.02 is due the co-existence of Ce4+-O2- CT emission and (4)G(4)(5/2)-H-6(J) Sm3+ transitions whereas only the Sm3+ red emission prevails for xgreater than or equal to0.03. The above unique changes in PL emission features are explained in terms of the changes in NNN environments of Ce4+. Quenching of Ce4+-O2- CT emission by other Ln(3+) is due to the ground state crossover arising out of the NNN interactions.

Comparative study of Eu3+ -activated LnOCl (Ln=La and Gd) phosphors and their Judd-Ofelt analysis

Eu3+-activated layered LnOCl (Ln=La and Gd) phosphors were synthesized by the conventional solid-state method at relatively low temperature (700 degrees C) and shorter duration of 2 h. The structural parameters were refined by the Rietveld refinement analysis and confirmed by the high resolution transmission electron microscopy (HRTEM). Both the compounds were crystallized in the tetragonal structure with space group P4/nmm (No. 129). The homogeneity of the elements were analyzed by TEM mapping and found to be uniformly distributed. The photoluminescence spectra revealed that the intensity of D-5(0)-> F-7(2) transition (619 nm) was more intense in Eu3+-activated GdOCl compared to LaOCl. This was due to the property of Gd3+ ions to act as an intermediate sublattice to facilitate the energy transfer to Eu3+ ions. Intensity parameters and radiative properties such as transition probabilities, radiative lifetime and branching ratio were calculated using the Judd-Ofelt theory. The CIE color coordinates result revealed that the Eu3+-activated GdOCl (0.641, 0.354) phosphor was close to the commercial red phosphors like, Y2O3:Eu3+ (0.645, 0.347), (Y2OS)-S-2:Eu3+ (0.647, 0.343) and National Television System Committee (NTSC) (0.67, 0.33). The results suggest that the present GdOCl:Eu3+ compound acts as a potential candidate for red phosphor materials.

Numerical Study on Flow Field and Temperature Distribution in Growth Process of 200 mm Czochralski Silicon Crystals

The melt flow and temperature distribution in a 200 mm silicon Czochralski furnace with a cusp magnetic field was modeled and simulated by using a finite-volume based FLUTRAPP ( Fluid Flow and Transport Phenomena Program) code. The melt flow in the crucible was focused, which is a result of the competition of buoyancy, the centrifugal forces caused by the rotations of the crucible and crystal, the thermocapillary force on the free surfaces and the Lorentz force induced by the cusp magnetic field. The zonal method for radiative heat transfer was used in the growth chamber, which was confined by the crystal surface, melt surface, crucible, heat shield, and pull chamber. It was found that the cusp magnetic field could strength the dominant counter-rotating swirling flow cell in the crucible and reduce the flow oscillation and the pulling-rate fluctuation. The fluctuation of dopant and oxygen concentration in the growing crystal could thus be smoothed.

Effect of humidity on microstructure and properties of YBCO film prepared by TFA-MOD method

Epitaxial YBCO superconducting films were deposited on the single crystal LaAlO3 (001) substrate by metal organic deposition method. All YBCO films were fired at 820 degrees C in humidity range of 2.6%-19.7% atmosphere. Microstructure of YBCO thin films was analyzed by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). Superconducting properties of YBCO films were measured by four-probe method. XRD results showed that the second phase (such as BaF2)and a-axis-oriented grains existed in the films prepared at 2.6% humidity condition; a-axis-oriented grains increased in the film prepared at higher than 4.2% humidity condition; almost pure c-axias-oriented grains existed in the films fired at 4.2% humidity condition. Morphologies of the YBCO films showed that all films had a smooth and crack-free surface. YBCO film prepared at 4.2% humidity condition showed J(c) value of 3.3 MA/cm(2) at 77 K in self-field.

Estudo do efeito magnetocal��rico em sistemas magn��ticos com terras raras

O efeito magnetocal��rico, base da refrigera����o magn��tica, �� caracterizado por duas quantidades: a varia����o isot��rmica da entropia (&#916;ST) e a varia����o adiab��tica da temperatura (&#916;TS); que s��o obtidas sob varia����es na intensidade de um campo magn��tico aplicado. Em sistemas que apresentam anisotropia magn��tica, pode&#8208;se definir o efeito magnetocal��rico anisotr��pico, o qual, por defini����o, �� calculado sob varia����es na dire����o de aplica����o de um campo magn��tico cuja intensidade mant��m&#8208;se fixa, e �� caracterizado por duas quantidades: a varia����o anisotr��pico&#8208;isot��rmica da entropia (&#916;San) e a varia����o anisotr��pico&#8208;adiab��tica da temperatura (&#916;Tan). O efeito magnetocal��rico e o efeito magnetocal��rico anisotr��pico foram estudados nos compostos intermet��licos formados por terras e outros materiais n��o magn��ticos: RNi2, RNi5, RZn e Gd1&#8208;nPrnAl2. Os c��lculos foram feitos partindo de hamiltonianos modelo que incluem as intera����es de troca, Zeeman, de campo cristalino e quadrupolar.

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Influence of heat treatment on spectroscopic properties of Er3+ in multicomponent ZrF4-ZnF2-AlF3-YF3-MF2 (M = Ca, Sr, Ba) based glass

Er3+ doped multicomponent fluoride based glass was prepared. These precursor fluoride glass samples were then heated using different schedules. Crystalline phase particles were successfully precipitated in the multicomponent fluoride glass samples after heat treatment. The influence of heat treatment on the spectroscopic properties of Er3+ in multicomponent fluoride based glass samples were discussed. Small changes of the Judd-Ofelt parameters Omega(i) (i = 2,4,6) were found in multicomponent fluoride glass samples before and after heat treatment compared to oxyfluoride telluride glass. Preparation conditions used to produce transparent multicomponent fluoride glass ceramics doped with rare-earth ions are discussed. (c) 2007 Elsevier B.V. All rights reserved.

Investigations on valence-change behaviors of europium ions in Eu-doped aluminate and silicate phosphors

Compounds of Sr3Al2O6: Eu, Sr4Al14O25: Eu, and BaZnSiO4: Eu were synthesized by high-temperature solid state reactions. The doping Eu3+ ions were partially reduced to Eu2+ in Sr4Al14O25: Eu and BaZnSiO4: Eu prepared in an oxidizing atmosphere, N-2 + O-2. However, such an abnormal reduction process could not be performed in Sr3Al2O6: Eu, which was also prepared in an atmosphere of N-2 + O-2. Moreover, even though Sr3Al2O6: Eu was synthesized in a reducing condition CO, only part of the Eu3+ ions was reduced to Eu2+. The existence of trivalent and divalent europium ions was confirmed by photoluminescent spectra. The different valence-change behaviors of europium ions in the hosts were attributed to the difference in host crystal structures. The higher the crystal structure stiffness, the easier the reduction process from Eu3+ to Eu2+.

Upconversion emission in Er3+ doped novel bismuthate glass

Novel Er3+-doped bismuth lead strontiam glass was fabricated and characterized, and the absorption spectrum and upconversion spectrum of the glass were studied. The Judd-Ofelt intensity parameters Omega(t)(t = 2, 4, 6) were found to be Omega(2) = 3.27 x 10(-20) cm(2), Omega(4) = 1.15 x 10(-20) cm(2), and Omega(6) = 0.38 x 10(-20) cm(2). The oscillator strength, the spontaneous transition probabilities, the fluorescence branching ratios, and excited state lifetimes were also measured and calculated. The upconversion emission intensity varies with the power of infrared excitation intensity. A plot of log I-up vs log I-IR yields a straight line with slope 1.86, 1.88 and 1.85, corresponding to 525, 546, and 657 nm emission bands, respectively, which indicates that a two-photon process for the red and green emission.

Upconversion luminescence of Ce3+ doped BK7 glass by femtosecond laser irradiation

Near-infrared to visible upconversion luminescence was observed in a multicomponent silicate (BK7) glass containing Ce3+ ions under focused infrared femtosecond laser irradiation. The emission spectra show that the upconversion luminescence comes from the 4f-5d transition of the Ce3+ ions. The relationship between the intensity of the Ce3+ emission and the pump power reveals that a three-photon absorption predominates in the conversion process from the near-infrared into the blue luminescence. The analysis of the upconversion mechanism suggests that the upconversion luminescence may come from a three-photon simultaneous absorption that leads to a population of the 5d level in which the characteristic luminescence occurs.

Valence state change and refractive index change induced by femtosecond laser irradiation in Sm³⁺ doped fluoroaluminate glass

We report femtosecond laser induced valence state and refractive index change in transparent Sin(3+)-doped fluoroaluminate glass. The effect of annealing on the induced changes was studied and the thermal stability of these changes was discussed. The results show that the femtosecond laser induced valence state change is more stable than the induced refractive index change. The observed phenomenon could be applied to design the thermally erasable or stable storage medium. (c) 2007 Elsevier B.V. All rights reserved.