An infrared spectroscopic study of the low-spin to intermediate-spin state ((1)A(1)-T-3(1)) transition in rare earth cobaltates, LnCoO(3) (Ln = La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO(3) (Ln = La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoo(3) and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition. (C) 2001 Published by Elsevier Science B.V.

Magnetic order of the hexagonal rare-earth manganite Dy(0.5)Y(0.5)MnO(3)

Hexagonal Dy(0.5)Y(0.5)MnO(3), a multiferroic rare-earth manganite with geometrically frustrated antiferromagnetism, has been investigated with single-crystal neutron diffraction measurements. Below 3.4 K magnetic order is observed on both the Mn (antiferromagnetic) and Dy (ferrimagnetic) sublattices that is identical to that of undiluted hexagonal DyMnO(3) at low temperature. The Mn moments undergo a spin reorientation transition between 3.4 K and 10 K, with antiferromagnetic order of the Mn sublattice persisting up to 70 K; the antiferromagnetic order in this phase is distinct from that observed in undiluted (h) DyMnO(3), yielding a qualitatively new phase diagram not seen in other hexagonal rare-earth manganites. A magnetic field applied parallel to the crystallographic c axis will drive a transition from the antiferromagnetic phase into the low-temperature ferrimagnetic phase with little hysteresis.

Complexes of rare-earth perchlorates with ditbutyl amides of di, tri and tetraglycolic acids

New complexes of lanthanide perchlorates with di-t-butyl amides of di, tri and tetraglycolic acids have been synthesised. The complexes have the general formula Ln(DiGA)3(ClO4)3; Ln(TriGA)2 (ClO4)3 and Ln(TetGA)2 (C1O4)3, where Ln = La-Yb and Y and DiGA = N,N′, di-t-butyl diglycolamide, TriGA N,N′, di-t-butyl triglycolamide and TetGA = N,N′ di-t-butyl tetraglycolamide, respectively. The complexes have been characterized by analysis, electrolytic conductance, infrared,1H and13C nuclear magnetic resonance and electronic spectral data.Infrared spectra indicate the coordination of all the available ether oxygens and the amide carbonyls in each of the ligands, to the metal ions. IR and conductance data show that the perchlorate groups in all the complexes are ionic.1H and13C NMR data support the IR data regarding the mode of coordination of ligands to the metal ions. Electronic spectral shapes have been interpreted in terms of nine, eight and ten coordination in DiGA, TriGA and TetGA complexes respectively.

Gibbs energies of formation of rare earth MPt5 compounds

The Gibbs energies of formation of MPt5 (MNd, Dy, Ho, Er) intermetallic compounds were determined in the temperature range 900–1100 K using the solid state cell Ta,M+MF3¦CaF2¦MPt5+Pt+MF3,Ta For M ≡ Sm, a mixture of Gd + GdF3 was used as the reference electrode. In the case of Eu, a mixture of Eu + EuF2 served as the reference electrode. The trifluorides of Sm and Eu are not stable in equilibrium with the metal. The fluoride phase coexisting with a SmPt5 + Pt mixture is SmF3, whereas EuF2 is the equilibrium phase in contact with EuPt5 + Pt. All the MPt5 compounds studied (except EuPt5) exhibit similar stability. Europium is divalent in the pure metal and trivalent in EuPt5. The energy required for the promotion of divalent Eu to the trivalent state accounts for the less negative Gibbs energy of formation of EuPt5. The enthalpies of formation of all the MPt5 compounds obtained in this study are in good agreement with Miedema's model.

Study of surface oxidation of rare-earth-metals by photoelectron-spectroscopy

Surface oxidation of La, Ce, Sm and Tb metals has been investigated by He(II) ultraviolet photoelectron spectroscopy (u.p.s.) and X-ray photoelectron spectroscopy (X.p.s.). Oxidation of La gives rise to La2O3 on the surface. While Ce2O3 appears to be the stable oxide on the surface, we find evidence for formation of CeO2 at high oxygen exposure. Valence band of Sm clearly shows the presence of both divalent and trivalent states due to interconfigurational fluctuation. Exposure of Sm to oxygen first depletes the divalent Sm at the surface. While Sm2O3 is the stable oxide on the surface of Sm, Tb2O3 is the stable oxide on the surface of Tb (and not any of the higher oxides).

Rare-earth carboxylates, Ln(2)(III)(mu(3)-OH)(C4H4O5)(2)(C4H2O4)]center dot 2H(2)O Ln = Ce, Pr and Nd]: synthesis, structure and properties

A new series of inorganic-organic hybrid framework compounds, Ln(2)(mu(3)-OH)(C4H4O5)(2)(C4H2O4)]center dot 2H(2)O, (Ln = Ce, Pr and Nd), have been prepared employing a hydrothermal method. Malic acid and fumaric acid form part of the structure. The malate units connect the lanthanide centers forming Ln-O-Ln two-dimensional layers, which are cross-linked by the fumarate units forming the three-dimensional structure. Extra framework water molecules form a dimer and occupy the channels. The water molecules can be reversibly adsorbed. The dehydrated structure did not show any differences in framework structure/ connectivity. The presence of lattice water provides a pathway for proton conductivity. Optical studies suggest an up-conversion behavior involving more than one photon for a neodymium compound.

Infrared-to-visible upconversion emissions in Er3+ doped TeO2-based oxyhalide glasses

The fluorescence and up-conversion spectral properties of Er3+-doped TeO2-ZnO and TeO2-ZnO-PbCl2 glasses suitable for developing optical fiber amplifier and laser have been fabricate and characterized. Strong green (around 527-550 nm) and red (around 661 nm) up-conversion emissions under 977 nm laser diode excitation were investigated, corresponding to H-2(11/2), S-4(3/2), --> I-4(15/2) and F-4(9/2) --> I-4(15/2) transitions of Er3+ ions respectively, have been observed and the involved mechanisms have been explained. The dependence of up-converted fluorescence intensity versus laser power confirm that two-photons contribute to up-conversion of the green-red emissions. The novelty of this kind of optical material has been its ability in resisting devitrification, and its promising optical properties strongly encourage for their further development as the rare-earth doped optical fiber amplifiers and upconversion fiber laser systems.

Experimental study on a nonlinear photonics process of Er(0.5)Yb(3): FOV oxyfluoride nanophase vitroceramics

We study the nonlinear photonics of rare-earth-doped oxyfluoride nanophase vitroceramics (FOV), oxyfluoride glass (FOG), and ZBLAN fluoride glass. We found that an interesting fluorescence intensity inversion phenomenon between red and green fluorescence occurs from Er(0.5)Yb(3):FOV The dynamic range Sigma of the intensity inversion between red and green fluorescence of Er(0.5)Yb(3):FOV is about 5.753 x 10(2), which is 100 to 1000 times larger than those of other materials. One of the applications of this phenomenon is double-wavelength fluorescence falsification-preventing technology, which is proved to possess the novel antifriction loss and antiscribble properties. (c) 2007 Optical Society of America.

Intense frequency upconversion fluorescence of Er3+/Yb3+ co-doped lithium-strontium-lead-bismuth glasses

Infrared-to-visible upconversion fluorescence of Er(3+)/Yb(3+) co-doped lithium-strontium-lead-bismuth (LSPB) glasses for developing potential upconversion lasers has been studied under 975-nm excitation. Based on the results of energy transfer efficiency and upconversion spectra, the optimal Yb(3+)-Er(3+) concentration ratio is found to be 5:1. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions 2H_(11/2)-->4I_(15/2), 4S_(3/2)-->4I_(15/2), and 4F_(9/2)-->4I_(15/2), respectively, were observed. The quadratic dependence of the 525-, 546-, and 657-nm emissions on excitation power indicates that a two-photon absorption process occurs under 975-nm excitation. The high-populated 4I_(11/2) level is supposed to serve as the intermediate state responsible for the upconversion processes. The intense upconversion luminescence of Er(3+)/Yb(3+) co-doped LSPB glasses may be a potentially useful material for developing upconversion optical devices.

Upconversion properties of TM3+/Yb3+ codoped fluorophosphate glasses with low phonon density of states

Fluorophosphate glasses codoped with Tm3+ and Yb3+ were prepared and their thermal stability, phonon states, and upconversion properties were studied. It is found that the increment of phosphate content is good for the thermal stability but increases the phonon density of states. However, the phonon density of states of these fluorophosphate glasses is very low due to the low phosphate content in their composition. The upconversion luminescence spectra were measured under excitation of 970 nm laser diode, and the intense blue (476 nm) and near infrared (794 nm) emission were simultaneous obtained at room temperature. The sensitizing mechanisms of Yb3+ to Tm3+ for blue and red emission contain both sequential and cooperative sensitization. The near infrared emission is a two-photon upconversion process. These researches suggest that when the phosphate content in the composition is low enough, fluorophosphate glass can be suitable host material of Tm3+ codoped with Yb3+ for blue and near infrared upconversion luminescence. (c) 2005 Elsevier B.V All rights reserved.

CW-pumped evanescent amplification based on side-polished fiber with heavily Er3+-doped glass overlay

A novel diffractive-pumping scheme is proposed to improve the evanescent amplification using blazed fiber grating for the first time. We also investigate the cw-pumped-evanescent amplification at 1.55 mu m wavelength with the relative optical gain pumped at 1480 nm of around 2 dB based on side-polished fiber with the effective interaction length as long as 16 mm and with a heavily Er3+-doped (N-Er(3+) > 1.19 x 10(21) ions/cm(3)), low refractive index (n(1550) < 1.47) glass overlay, which has no concentration quenching (tau(f) = 9.0 ms).