Understanding the influence of nanoenvironment on luminescence of rare-earth ions

This paper presents an overview of the recent results on upconversion and photoluminescence of rare-earth ions in nanoenvironments. The role of the rare-earth ion concentration, crystal size and crystal phase on the up and downconversion emission of rare-earth ions in oxide nanocrystals and their underlying mechanisms are discussed. It is also found that the luminescence lifetime of the excited state rare-earth ions is sensitive to the particle crystalline phase and size. The analysis suggests that the modifications of radiative and nonradiative relaxation mechanisms are due to local symmetry structure of the host lattice and crystal size respectively     

Luminescence properties of solid solutions of borates doped with rare-earth ions

The structural and luminescence properties of Lu _x Y_{1 ? x} BO₃ solid solutions doped with Ce³⁺ or Eu⁺³ have been investigated. It has been found that the solid solutions crystallize in the vaterite phase with a lutetium concentration x < 0.5. For a higher lutetium concentration x, the solid solutions contain an additional calcite phase with a content less than 5 wt %. The luminescence spectra are characterized by intensive impurity emission under excitation with the synchrotron radiation in the X-ray and ultraviolet spectral ranges. It has been shown that, as the lutetium concentration x in the Lu _x Y_{1 ? x} BO₃: Ce³⁺ solid solutions increases, the emission intensity smoothly decreases, which is associated with a gradual shift of the Ce³⁺ 5d(1) level toward the bottom of the conduction band, as well as with a decrease in the band gap. It has been established that, in the Lu _x Y_{1 ? x} BO₃: Eu³⁺ solid solutions with intermediate concentrations x, the efficiency of energy transfer to luminescence centers increases. This effect is explained by the limited spatial separation of electrons and holes in the solid solutions. It has been demonstrated that the calcite phase adversely affects the luminescence properties of the solid solutions.     

Intrinsic luminescence of rare-earth oxyorthosilicates

The spectra and decay kinetics of luminescence and the excitation and reflection spectra of the luminescence of orthosilicates A ₂SiO₅ (A = Y, Lu, Sc, Gd), both nominally pure and doped with cerium, are measured using time-resolved VUV spectroscopy in the ranges of energies ?ν = 1.5–16 eV and temperatures T = 8–3000 K. The band structure of the crystals is calculated in the local electron density approximation (LDA). The origin of the intrinsic luminescence in the crystals studied is established, and the assumption regarding the existence of self-trapped excitons and their structure is made.     

Energy transfer from uranyl nitrate hexahydrate to rare-earth ions in frozen solutions

Energy transfer phenomena have been studied from uranyl nitrate hexahydrate to rare-earth ions in methanol, water, ether and nitric acid. A Stern-Volmer type of kinetics is suggested since the probability of energy transfer has a linear dependence on the concentration of acceptor ions. Energy transfer has been found more efficient from UNH to Nd³⁺ in ether and nitric acid.     

The effect of Ce3+ ions on the spectral and decay characteristics of luminescence phosphate-borate glasses doped with rare-earth ions

The luminescent characteristics of Li₂O-B₂O₃-P₂O₅-CaF₂ (LBPC) glasses doped with Gd³⁺ and Tb³⁺ ions and codoped with Ce³⁺ are studied by pulsed optical spectrometry under electron beam excitation. It is found that in glass with Ce³⁺ and Gd³⁺ ions a decrease in the decay time of gadolinium luminescence in the 312-nm band (⁶ P _J → ⁸ S _7/2) was observed. It is shown that in the glass LBPC: Tb, Ce, an increase in the emission intensity in the main radiative transitions in terbium ion was observed. In the kinetics of luminescence band 545 nm of LBPC: Tb, Ce glasses, is present stage of buildup, the character of which changes with the doped of Ce³⁺ ions. The mechanism of energy transfer in LBP glasses doped with rare elements is discussed.     

Dynamic polarization of 7Li nuclei in solutions containing radical ions

Dynamic nuclear polarization parameters, obtained at 75 G, are reported for ⁷Li ions in collision with several radical anions and with one radical cation. All systems show large negative ⁷Li N.M.R. enhancements indicative of weak scalar relaxation. However, radical induced relaxation rates derived from ⁷Li T ₁ measurements suggest stronger complexing of lithium ions with radical anions than with the radical cation as would be expected from simple coulombic considerations. Translational modulation of the dipolar interaction best accounts for proton and radical cation dipolar relaxation rates while rotational modulation best accounts for the corresponding radical anion rates; this supports the interpretation above. A model for the lithium radical collision is proposed which implies that, for radical anions, scalar coupling is only apparently weak and that the low ⁷Li scalar relaxation rates observed result from scalar correlation times (τ_c = 10^-8-10^-9 s) longer than any yet observed by this technique. The model predicts that, for certain ranges of τ_c, increasing strength of complex formation should lead to smaller scalar relaxation rates and more negative enhancements, in contrast with the behaviour of fluorocarbons where the reverse was true. The predicted dependence of enhancement upon τ_c also suggests that ⁷Li enhancements should be extremely sensitive to variations in the chemical properties of the system.     

Synchronous fluorescence determination of ciprofloxacin in the pharmaceutical formulation and human serum based on the perturbed luminescence of rare-earth ions

A simple, rapid and sensitive synchronous fluorescence method was developed for the determination of ciprofloxacin (CPFX) in the pharmaceutical formulation and human serum. The results show that when Y³⁺ is added into the CPFX solution, the characteristic fluorescence of Y³⁺ is not emitted whereas the fluorescence intensity of CPFX is significantly enhanced. The synchronous fluorescence technology is employed in this method to directly determine trace amount of CPFX in human serum. A linear relationship between the fluorescence intensity and the CPFX concentration is obtained in the range of 1.0×10⁻⁹ ∼5.0×10⁻⁶ mol L⁻¹. The limit of detection (LOD) of this method attains as low as 2.0×10⁻¹⁰ mol L⁻¹ (S/N=3). The selectivity of this method is also very good. Common metal ions, rare-earth ions and some pharmaceuticals, which are usually used together with CPFX in the clinic, do not interfere with the determination of CPFX under general conditions.     

Two-particle configuration interaction in rare-earth ions

Summary The two-particle configuration interaction by way of Coulomb field in rare-earth ions is considered and the interaction energy matrices for the commonly studied cases off ⁿ (n=2, 3, 4) are calculated in terms of three parameters.     

Potential and limitations of rare-earth luminescence in inverse opals

Inverse opals exhibiting strong photonic effects can cooperate with luminescent materials imbedded in their voids. While this has been demonstrated for dye molecules in the past, inspection of the literature reveals only few experiments on the potential of rare earths in this context. The efforts described focus on the spectral and spatial modification of emissive properties, whereas we here pursue the study of corresponding absorption properties. However, arbitrary incorporation of the luminescent species disturbs the photonic effects, therefore, principal preparative efforts need to be conducted to preserve both, the photonic properties of the opaline hosts and the luminescence efficiency of the guests. In this paper, we describe issues regarding the morphology and efficiency of inverse opal-incorporated rare-earth fluorides and oxifluorides and present an interior coating method for efficiency improvement. In addition, we were in this context, able to demonstrate the feasibility of energy transfer from Tb³⁺ modified host walls to Eu³⁺ guest species.     

Evolution of polarization in an inhomogeneous isotropic medium

The depolarization and rotation of the polarization plane of radiation propagating in a two-dimensional graded-index medium is investigated on the basis of the quantum-mechanical method of coherent states. It is shown that the degree of polarization of both linearly and circularly polarized radiation decreases with increasing distance as a result of interaction between the polarization (spin) and the path (orbital angular momentum) of the beam. The wave nature of the depolarization is emphasized. The depolarization decreases as the radiation wavelength decreases. It is found that the degree of polarization exhibits oscillations of pure diffraction origin during the propagation of light in a single-mode optical fiber. It is shown that the rotation of the polarization plane is nonuniform in character and depends on the offset and the tilt angle of the incident-beam axis relative to the fiber axis. The Berry phase is found to undergo oscillations of a wave nature during the propagation of radiation in an inhomogeneous medium. It is shown that the spread in the angle of rotation of the polarization plane increases with distance and can be determined from measurements of the degree of polarization of the radiation. Zh. éksp. Teor. Fiz. 112, 1985–2000 (December 1997)