Synthesis, characterization and microwave dielectric properties of nanocrystalline CaZrO3 ceramics

The energy-transfer mechanisms and frequency upconversion emissions in 0.5Er³⁺/xHo³⁺ co-doped tellurite glasses by exciting at 980 nm have been investigated. Three intense upconversion luminescence emissions are observed at around 525, 548, and 660 nm, which correspond to Er³⁺:²H_11/2 → ⁴I_15/2, Er³⁺:⁴S_3/2 → ⁴I_15/2 + Ho³⁺:⁵S₂(⁵F₄) → ⁵I₈, and Er³⁺:⁴F_9/2 → ⁴I_15/2 + Ho³⁺:⁵F₅ → ⁵I₈ transitions, respectively. The upconversion emissions reach the maximum values when Ho₂O₃ is 0.5 mol%, and the intensities of the green and red light emissions were about 4.5 and 6 times stronger than those un-doped Ho₂O₃, respectively. The possible upconversion mechanisms and energy transfer between Er³⁺ and Ho³⁺ were also estimated and evaluated. All the three emissions are based on two photon absorption processes.     

Upconversion-induced ultraviolet emission in Ho doped SrLaGa3O7 and SrLaGaO4 crystals

An analysis of the red to ultraviolet wavelength upconversion in Ho³⁺ in SrLaGa₃O₇ and SrLaGaO₄ crystals is given. Upconverted, ultraviolet emission from the ³D₃ level under cw 647 nm excitation at room temperature was observed. Excitation of the ⁵F₅ level, corresponding to the ⁵I₈→⁵F₅ transition, leads to intense emission from the ⁵I₇, ⁵I₆, ⁵F₅, ⁵S₂, ⁵F₃, ³G₅ and ³D₃ levels. Based on the energy level diagram of Ho³⁺, the pump intensity dependencies and experimental time dependencies of the observed emissions, an excitation scheme is proposed.     

Properties of ytterbium and neodymium doped alkali metal yttrium double phosphates of the M3Y1−xLnx(PO4)2 type

The spectroscopic behaviour of the Nd³⁺ and Yb³⁺ doped alkaline metal yttrium double phosphates, M₃Y_1−xLn_x(PO₄)₂ (M=Na, Rb; x=0.01–0.3) were studied for both powder and single crystal samples. The high resolution absorption and emission spectra were measured in the visible and IR regions. Spectral changes with the Nd³⁺ and Yb³⁺ concentration were interpreted. The absorption strengths of the 4f–4f transitions were analysed and used to assess the structural modifications of the two double phosphates. Based on the 4 K absorption spectra the number of metal sites occupied by the dopants was investigated.

Strong emission from Na₃Y_1−xNd_x(PO₄)₂ involving the ⁴F_3/2→⁴I_9/2,⁴I_11/2,⁴I_13/2,⁴I_15/2 transitions were observed whereas the corresponding emission from the rubidium phosphate was presumably quenched by multiphonon processes due to the water molecules absorbed in the channel-like structure.

The IR spectra were used to assign the vibronic components of the electronic transitions. The Yb³⁺ emission bands were broadened depending on the Yb³⁺ concentration (1–10 mol%). The tentative energy level scheme of the ground and excited ²F_J (J=7/2, 5/2) levels was described.     

Spectral properties of Ho:GdVO4 single crystal

Absorption and emission spectral properties of GdVO₄ single crystal doped with Ho³⁺ ions were investigated at room temperature. Polarized absorption cross section is calculated in the range of 400–2200 nm. Results were analyzed and parameters were calculated based on Judd-Ofelt theory, the emission spectrum shows that the emission intensity around the wavelength of 546 nm associated with transition ⁵S₂ → ⁵I₈ is much stronger than other bands in the observed range and potentially enable the green light output around this emission band in this crystal.     

Upconversion dynamics in Er doped nanocrystalline YAlO3

We report the luminescence and upconversion spectra of nanocrystalline YAlO₃ doped with trivalent erbium at concentrations of 5.0, 1.0 and 0.1 mol.%. The powder samples were prepared using a solution combustion reaction method, and the resulting YAlO₃ nanocrystals show, under wide-angle X-ray diffraction, a size in the range 20–40 nm. Efficient green and red emissions are observed at room temperature under continuous-wave pumping at 980 nm. A weak emission can also be detected in the blue at 410 nm. The upconversion dynamics were studied measuring the decay times and the pump-power dependence of the transitions to the ⁴I_15/2 ground state starting from the ²H_11/2, ⁴S_3/2 and ⁴F_9/2 excited states. Excited-state absorption (ESA) is found to be responsible for the higher energy (²H_11/2, ⁴S_3/2→⁴I_15/2) green transitions. On the other hand, for the ⁴F_9/2→⁴I_15/2 red transition a competing energy-transfer upconversion (ETU) mechanism is found, which accounts for the more than 100-fold increase in intensity of the red emission on passing from the lowest (0.1 mol.%) to the highest (5 mol.%) erbium concentration.     

Crystal structures and structural relationships of KFe2(SeO2OH)(SeO3)3 and SrCo2(SeO2OH)2(SeO3)2

The new phases KFe₂(SeO₂OH)(SeO₃)₃ and SrCo₂(SeO₂OH)₂(SeO₃)₂ have been synthesized under low-hydrothermal conditions and their structures were determined by single-crystal X-ray methods. Both compounds are monoclinic; KFe₂(SeO₂OH)(SeO₃)₃: space group P2, A = 9.983(4), B = 5.270(1), C = 10.614(4) Å, β = 97.42(2)°, V = 553.7 ų, Z = 2; SrCo₂(SeO₂OH)₂(SeO₃)₂: space group P2ln, A = 14.984(2), B = 5.286(1), C = 13.790(2) Å, β = 94.72(1)°, V = 1088.5 ų , Z = 4. The refinements converged to R-values of 2.9 and 3.6% respectively.

The atomic arrangement in KFe₂(SeO₂OH)(SeO₃)₃ and SrCo₂(SeO₂OH)₂(SeO₃)₂ is based on isolated MO₆ octahedra (M = Fe³⁺, Co²⁺), which are corner-linked via trigonal pyramidal selenite groups to a framework structure. Interstitials are occupied by potassium or strontium atoms in ten- or eight-coordination respectively, and by the lone-pair electrons of the Se⁴⁺ atoms. Both compounds are not isotypic but are closely related and may be interpreted as different distortions of an idealized structure type in space group P2/m, which was modelled for a theoretical compound SrFe₂(SeO₃)₄ by distance least squares refinement (program ).     

Infrared tuneable up-conversion phosphor based on Er-doped nano-glass–ceramics

Up-conversion luminescence has been studied in the Er³⁺-doped oxyfluoride glass, its daughter nano-glass–ceramics and the polycrystalline ErF₃ when excited at infrared wavelengths of either 800 or 980 nm. The mechanism of the up-conversion luminescence is shown to differ for excitations at 800 and 980 nm since the different excited levels of the Er³⁺ are involved, respectively. An order of magnitude increase of red-to-green up-conversion luminescence ratio has been observed with nano-ceramming of the precursor glass when excited at 800 nm and a full dominance of the red up-conversion luminescence has been observed in the ErF₃ at the both excitation wavelengths. Observed changes in the spectra of the up-conversion luminescence from the precursor glass to its daughter nano-glass–ceramics provide a tool for tuning the colour of the up-conversion luminescence by ceramming of the precursor glass. These changes are shown to be due to decrease of the vibration energy of phonons coupled to the Er³⁺ ions embedded to the PbF₂ nano-crystals with nano-ceramming. Hence we report for the first time that the red up-conversion luminescence from the Er³⁺-doped material can be due to the radiative transition ⁴F_5/2, ⁴F_3/2 → ⁴I_13/2 of the Er³⁺ ion, which is principally allowed only in such a low-phonon energy host as the PbF₂ nano-crystals, while such red up-conversion luminescence is almost completely non-radiatively quenched in the oxyfluoride precursor glass. The up-conversion emission spectrum of the ErF₃ is dominated by a cross-relaxation mechanism typical of hosts with a very high doping level of the Er³⁺ ions.     

Structural studies in lead fluorogermanate and fluorosilicate glasses

We report the results of structural studies by means of Eu³⁺ fluorescence line narrowing techniques in the binary systems PbF₂-GeO₂ and PbF₂-SiO₂. Several features characteristic of the europium fluorescence in lead glasses are put forward. The absence of selectively excited emission at room temperature demonstrates an unusually large homogeneous broadening of the electronic levels. A relative increase in the ⁵D₀ → ⁷F₁ (magnetic dipole) with respect to the ⁶D₀ → ⁷F₂ (electric dipole) transition is observed with time-resolved. detection. This effect shows that accidental coincidences of ⁵D₀ → ⁷F₀ energies and ⁷F₁ splitting do occur between europium sites differing only by their ⁶D₀ lifetimes and magnetic dipole: electric dipolar relative intensities. The general characteristics are interpreted with oxygen neighbours for Eu³⁺ rather than fluorine ions. The crystal field strength expressed as N_v = [∑_k,a (B_g^k)² × 4π/(2k + 1)]^1/2 (limited to k=2 parameters) is slightly higher in the germanate than in the silicate matrix.     

Magnetic circular dichroism simulations of trivalent neodymium compounds

The example of three trivalent neodymium compounds Na₃Nd(ODA)₃·2NaClO₄·6H₂O, Nd₂Mg₃(NO₃)₁₂·24H₂O and LiYF₄/Nd³⁺ is used to show how the simulation of the magnetic circular dichroism transitions in addition to the simulation of the -spectrum can provide an independent tool for checking the reliability of the wave functions and intensity parameters. The ⁴F_9/2←⁴I_9/2 transition, which is clearly observed in all three samples, is used here to illustrate the simulation procedure.     

Spectral properties of Yb ions in LiNbO3 single crystals: influences of other rare-earth ions, OH ions, and γ-irradiation

Absorption spectra have been studied in 190–3100 nm region at various temperatures from 16 to 292 K for Yb³⁺-doped and Yb³⁺/Nd³⁺-, Yb³⁺/Er³⁺- and Yb³⁺/Pr³⁺-co-doped LiNbO₃ single crystals before and after γ-irradiation with a dose of 10⁵–10⁷ Gy. Intense 400 and 500 nm absorption bands were observed after γ-irradiation, which are due to the creation of oxygen vacancy (F-type color center) and Nb⁴⁺ polaron, respectively. Different change was observed in the 2870 nm OH⁻ absorption band intensity among the various rare-earth doped crystals. These are interpreted by discrepancy of ionic radii between substituting rare earth dopant ion and Li⁺ or Nb⁵⁺ host ion. The observed temperature dependence of the hot bands is understood by electronic transition from the thermally populated ²F_7/2 Stark levels to the excited ²F_5/2 level. The position of the Yb^{3+ 2}F_7/2→²F_5/2 first resonant line was observed to be slightly different among the co-doped crystals. This is due to the perturbation of Yb³⁺ by co-doped rare earth ion which is located at the neighborhood of theYb³⁺.     

Spectroscopy, magnetism and non-radiative processes in heteronuclear Cu:Pr squarate; [Pr2Cu(C4O4)4(H2O)16]·2H2O

In the present work, the spectroscopic and magnetic properties of heteronuclear Cu:Pr squarate are reported. Single crystals of [Pr₂Cu(C₄O₄)₄(H₂O)₁₆]·2H₂O were obtained by reaction of squaric acid, praseodymium chloride and copper chloride in water solution according to the procedure described earlier. The crystals of title compound are isomorphic with [La₂Cu(C₄O₄)₄(H₂O)₁₆]·2H₂O crystal, where squarate anions participate as bridging ligands between metal ions.

The UV region of absorption spectra of the title compound is dominated by C–T band of Cu(II), f–d transition of Pr(III) and internal π–π*(A_1g→E_u) and π–π*(A_1g→E_g) ligand transitions. In visible and IR regions, t_2g–e_g of copper Cu(II) as well as ³H₄→³P_J, ¹D₂, ¹G₄, ³F_J, ³H₆ Pr(III) transitions at 293 and 4 K were recorded. At low temperature splitting given by Jahn–Teller effect can be observed. Significant anisotropy of d–d transitions intensities confirms well the Jahn–Teller effect, too. Unexpectedly high intensity of ³H₄→¹G₄ transition is probably due to the intensity borrowing from the Cu (II) d–d transition.

The ³P₀ and ¹D₂ emission of Pr(III) in the [Pr₂Cu(C₄O₄)₄(H₂O)₁₆]·2H₂O crystals is quenched even at 77 K. Whereas emission of appropriate polynuclear europium squarate was detected. The pathways of excited state quenching by e_g levels of Cu(II), multhiphonon relaxation and concentration quenching can be considered in the system under studies. Magnetic susceptibility measurements were carried out in 300–1.7 K temperature range and are discussed in relation to the structure.

Effect of the polymeric structure on spectroscopic behaviour is presented. Selectivity of polymeric europium squarate in vitro test for different tumor cells is shown.     

Optical study of praseodymium dicarboxylate [Pr(H2O)]2[O2C(CH2)3CO2]3.4H2O

Praseodymium dicarboxylate, [Pr(H₂O)]₂[O₂C(CH₂)₃CO₂]₃.4H₂O]–glutarate, Pr[glut], is synthesized by hydrothermal techniques. The title compound crystallizes in the monoclinic space group C2/c (No. 15). The rare earth cation is coordinated by nine oxygen atoms, eight oxygen atoms from the carboxylate groups and one from the water molecule. The local symmetry of Pr site is low, C_s. The absorption spectra of Pr[glut] are recorded from the visible to the far IR domain at 300, 77 and 9 K. Under various Ar⁺ laser excitations no emission is detected from ³P₀ and ¹D₂ excited levels of Pr³⁺ ion. In the low temperature absorption spectra only one electronic line is recorded for ³H₄→³P₀ transition. It confirms a unique local environment for the rare earth ion in Pr[glut]. The utility of the ‘barycenter curves’ in the attribution of electronic lines is demonstrated. Energy level scheme of 36 Stark components is deduced from the absorption spectra. The parametric calculation was performed on the whole 4f² (Pr³⁺) configuration with the starting set of crystal field parameters obtained previously for the Eu³⁺ ion in the isostructural compound. Eight free ion and nine phenomenological crystal field parameters in C_2v symmetry reproduce quite well several electronic levels of Pr³⁺ ion experimentally observed in Pr[glut]. A good r.m.s. standard deviation of 14.8 cm⁻¹ is obtained.     

Spectroscopic study of europium doped RCOB host lattices: evidence of local perturbations

The results of the high-resolution absorption, selective excitation, time-resolved emission and emission kinetics of Eu³⁺ in GdCOB and EuCOB single crystals are presented. The Eu³⁺ spectra show at least three non-equivalent centers whose static spectral characteristics were used to assign structural models. The crystal field parameters were estimated for prevailing Eu³⁺ center in EuCOB. The inhomogeneous broadening and shifts of the ⁵D₀→⁷F₀ and ⁵D₀→⁷F₁ Eu³⁺ lines in GdCOB under selective excitation in main lines were explained by J mixing of ⁷F₂ states into ⁷F₁ and ⁷F₀ by second order crystal field terms and connected to disordered structure in cationic spheres.     

The electronic structure of organometallic complexes of the f elements: XL. Crystal field strength of η-cyclopentadienyl ligand estimated on the basis of the crystal field parameters of (Me3SiC5H4)3Pr

The absorption, magnetic circular dichroism and luminescence spectra of monomeric pseudo trigonal planar (η⁵-Me₃SiC₅H₄)₃Pr^III (Cp′Pr) have been measured at room and at low temperatures. Applying the selection rules for molecular D_3h symmetry, a truncated crystal field (CF) splitting pattern (which comprises essentially excited Γ₄ and Γ₆ states) could be derived. The parameters of an empirical Hamiltonian were fitted to the energies of 24 levels to give an r.m.s. deviation of 21.4 cm⁻¹. On the basis of the CF parameters obtained, the CF strength of one Cp ligand was estimated.     

Electronic absorption and vibrational IR and Raman studies of binary phosphate β-K4Ce2P4O15

The binary phosphate K₄Ce₂P₄O₁₅ was prepared in the polycrystalline state in the solid state reaction of cerium oxide and potassium phosphate KPO₃. The phosphate fragment of this compound appears in the form of two PO₄³⁻ and one P₂O₇⁴⁻ anions occupying the sites of low symmetry. Electronic absorption, emission as well as infrared and Raman spectroscopic methods have been applied to characterise the properties and structure of the compound studied. Its electronic spectra agree with the Ce³⁺ ion spectroscopic characteristics. The ²F_5/2→²F_7/2 transition appears in the typical for this ion region: about 2000 cm⁻¹. The multiplet structure of the spectrum suggests the existence of at least two crystallographic different sites of this ion in the unit cell. The absorption bands in the range 25000–45000 cm⁻¹ have been assigned to the 4f¹→5d¹ transitions of the cerium ion and CT transition of the phosphate ligands. The vibrational spectra were discussed on the basis of correlation diagrams and factor group analysis.

The radiation-less mechanism of the return from the excited state to the ground state via CT states in the system studied is proposed.     

Structural chemistry and magnetism of dicyclopentadienidehalides of lanthanides Part 8: terbiumdicyclopentadienidebromide [Tb(C5H5)2Br]2

A single-crystal X-ray structural investigation of [Tb(C₅H₅)₂Br]₂ revealed the [Sc(C₅H₅)₂Cl]₂-type structure, space group P2₁/c, with a = 1407.6(2) pm, b = 1644.7(2) pm, c = 1370.6(9) pm, β = 93.46(3)°, V = 3167(2) × 10⁶ pm³, D_c = 2.322 g cm⁻³ and Z = 6 dimers (R = 0.036 for 4627 reflections with I > 3σ(I)). The metal centres have the pseudosymmetry C_2v. Magnetic susceptibility data show Curie-Weiss behaviour between 213 and 6 K with θ_p = −4.5(3) K and a magnetic moment μ = 9.8(1) μ_B close to the Tb³⁺ free-ion value (9.72 μ_B). Below 6 K, deviations from Curie-Weiss behaviour are observed, and at 5.3 K a maximum in the susceptibility is detected which may be caused by intradimer antiferromagnetic spin coupling. The magnetic properties are compared with the prediction of various models, starting from cubic crystal fields and isotropic intramolecular exchange interactions, followed by extension to lower crystal field symmetry (orthorhombic) and anisotropic contributions to the spin coupling. However, a reasonable agreement between the measured and calculated data was not obtained. As in [Gd(C₅H₅)₂Br]₂, the low-temperature behaviour is governed by effects which cannot be described by spin coupling models in the generally accepted form.     

Preparation and crystal structure of a new barium silicon nitride, Ba5Si2N6

Single crystals of a new ternary nitride, Ba₅Si₂N₆, were synthesized by slow cooling from 750°C using a starting mixture of Ba, Si, Na and NaN₃, where Na and NaN₃ were a flux and a nitrogen source respectively. It crystallizes with orthorhombic symmetry: space group P2₁2₁2₁ (No. 19), A = 6.159, B = 10.305, C = 15.292 Å, and Z = 4. The crystal structure was determined from single-crystal data and refined to R1 = 0.0495 for all 1637 observed reflections and 89 variables. A pair of SiN₄ tetrahedra contained in the structure forms a nitridometallate anion of [Si₂N₆]¹⁰ by edge sharing.     

Crystal fields in (La1−xGdx)OCl:Eu solid solutions

The formation of cation solid solution in the (La_1−xGd_x)OCl:Eu³⁺ (0≤x_Gd≤1; Δx_Gd=0.1) series was studied by photoluminescence spectroscopy. The luminescence from the ⁵D_0–2 to the ⁷F_0–4 levels of the Eu³⁺ ion in the (La_1−xGd_x)OCl series was recorded at 77 K by using argon ion laser excitation (457.9 nm). The interpretation of the spectra according to the C_4v site symmetry of the Eu³⁺ ion in the tetragonal PbFCl-type structure yielded nearly complete sets (18 to 19 levels) for the ⁷F_0–4 levels. Simulations of the Stark level schemes were carried out with the aid of a phenomenological c.f. theory utilizing the five non-zero c.f. B_q^k parameters (B₀², B₀⁴, B₄⁴, B₀⁶ and B₄⁶) allowed for the C_4v site symmetry. By using the calculated c.f. parameter sets a quantitative measure was obtained to monitor the formation of cation solid solutions. The strength of the c.f. effect was estimated with the c.f. strength parameters S and S^k (k=2, 4 and 6). The c.f. parameter sets reproduced the experimental ⁷F_J (J=0–4) energy level schemes with the rms deviations between 4 and 11 cm⁻¹. The individual parameters as well as the c.f. strength parameters were found to evolve in a smooth manner indicating complete solid solubility in the (La_1−xGd_x)OCl series. Some local distortions from the C_4v symmetry — probably of long range—leading to the splitting of the ⁷F₁ doubly degenerate E level were observed, however.     

Red photoluminescence and morphology of Eu doped Ca3La3(BO3)5 phosphors

Europium doped phosphors Ca₃La₃(BO₃)₅ were first synthesized by a sol–gel process technique. The reaction temperature of the sol–gel process was 300 °C lower than that of the solid-state reaction and the reaction time of the sol–gel process was shorter. The photoluminescence properties of Eu³⁺ doped Ca₃La₃(BO₃)₅ indicated that the phosphors exhibited a strong luminescence of ⁵D₀–⁷F₂ transition at 612 nm under the excitation at 237 nm. The emission intensity of the phosphors prepared by the sol–gel process was higher than those prepared by the solid-state reaction. The relationship between optical properties and morphologies were studied. In particular, Li⁺ ion doping effectively enhanced the luminescent properties of the Eu³⁺ doped Ca₃La₃(BO₃)₅ phosphors. The highest brightness was observed in the phosphor Ca₃La_2.82Eu_0.1Li_0.08B₅O_15−δ prepared by the sol–gel process.     

High pressure spectroscopy of Pr in LiNbO3

Absorption, emission, and luminescence excitation spectra of the LiNbO₃ crystal doped with 0.5% Pr³⁺ and 0.8% Yb³⁺ are presented. Additionally the photoluminescence spectra at high pressure have been measured. Hydrostatic pressures up to 135 kbar were applied with a diamond anvil cell. Absorption of the Pr³⁺:LiNbO₃ crystal is characterized by the strong threshold at about 400 nm, related to the band-to band-transitions and the sharp structure in the visible region attributed to the transitions to ³P_J and ¹D₂ levels of Pr³⁺ ion. After the 488 nm excitation the yellow emission related to the ¹D₂→³H_J transition of Pr³⁺ have been observed when the ³P₀ emission has not been detected. The excitation spectra of the ¹D₂ luminescence consist of the sharp lines related to the ³H₄→³P_J (J=0, 1, 2) transitions and two broad bands peaked at 340 and 400 nm related probably to the bound exciton. The ¹D₂→³H_J emission shifts with pressure toward the lower energies with the rate of −2.4 cm⁻¹ kbar⁻¹. Additionally, for higher pressures the ¹D₂ emission is considerably quenched. This is explained as being due to the decrease of the energy of the bound exciton with pressure which results in the higher nonradiative depopulation rate of the ¹D₂ state.