Ligand-rare-earth ion energy transfer in coordination compounds. A theoretical approach

A theoretical approach to the energy transfer process that occurs between a ligand and a rare-earth ion in luminescent complexes is presented. A discussion on the energy transfer mechanisms involved and on the associated selection rules is made. Numerical estimates are also presented.

Ytterbium-induced energy-transfer upconversion enhancement in Nd3+/Pr3+-codoped PbGeO3-PbF2-CdF2 glass excited at 810nm

The effect of ytterbium ions upon energy transfer (ET) excited upconversion emission in Nd3+/Pr3+ -codoped PbGeO3-PbF2-CdF2 glass under 810 nm diode laser excitation is investigated. The results revealed that the presence of Yb3+ ions in the Nd3+/Pr3+-doped sample yields a fourfold enhancement in the visible and near infrared upconversion luminescence. The dependence of the upconversion process upon the excitation power, Nd3+, and Yb3+ concentrations is examined. The results indicated that ytterbium plays a major role in the ET upconversion process by bridging the 810nm neodymium excitation to praseodymium ions. The population of the Pr3+ ions P-3(0) emitting level was accomplished through a multi-ion interaction involving ground-state and excited-state absorption of pump photons at 810 nm by the Nd3+ followed by successive ET involving the Nd3+-Yb3+ and Yb3+-Pr3+ pairs. There is also direct ET Nd3+-Pr3+. (c) 2005 Elsevier B.V. All rights reserved.

Energy-transfer mechanisms and emission quantum yields in Eu3+-based siloxane-poly(oxyethylene) nanohybrids

We report the energy-transfer mechanisms and emission quantum yield measurements of sol-gel-derived Eu3+-based nanohybrids. The matrix of these materials, classified as diureasils and termed U(2000) and U(600), includes urea cross-links between a siliceous backbone and polyether-based segments of two molecular weights, 2000 and 600, respectively. These materials are full-color emitters in which the Eu3+ (5)Do --> F-7(0-4) lines merge with the broad green-blue emission of the nanoscopic matrix's backbone. The excitation spectra show the presence of a large broad band (similar to 27000-29000 cm(-1)) undoubtedly assigned to a ligand-to-metal charge-transfer state. Emission quantum yields range from 2% to 13.0% depending on the polymer molecular weight and Eu3+ concentration. Energy transfer between the hybrid hosts and the cations arises from two different and independent processes: the charge-transfer band and energy transfer from the hybrid's emitting centers. The activation of the latter mechanisms induces a decrease in the emission quantum yields (relative to undoped nanohybrids) and permits a fine-tuning of the emission chromaticity across the Comission Internacionalle d'Eclairage diagram, e.g., (x, y) color coordinates from (0.21, 0.24) to (0.39, 0.36). Moreover, that activation depends noticeably on the ion local coordination. For the diureasils with longer polymer chains, energy transfer occurs as the Eu3+ coordination involves the carbonyl-type oxygen atoms of the urea bridges, which are located near the hybrid's host emitting centers. on the contrary, in the U(600)-based diureasils, the Eu3+ ions are coordinated to the polymer chains, and therefore, the distance between the hybrid's emitting centers and the metal ions is large enough to allow efficient energy-transfer mechanisms.

Thermally enhanced cooperative energy-transfer frequency upconversion in terbium and ytterbium doped tellurite glass

Infrared-to-visible frequency upconversion through cooperative energy-transfer and thermal effects in Tb3+/Yb3+-codoped tellurite glasses excited at 1.064 mum is investigated. Bright luminescence emission around 485, 550, 590, 625 and 65 nm, identified as due to the D-5(4) --> F-7(J) (J= 6, 5, 4, 3, and 2) transitions of the terbium ions, respectively, was recorded. The excitation of the D-5(4) emitting level of the Tb3+ ions is assigned to cooperative energy-transfer from pairs of ytterbium ions.. The effect of temperature on the upconversion process was examined and the results revealed a fourfold upconversion enhancement in the 300-500 K interval. The enhancement of the upconversion process is due to the temperature dependence of the Yb3+-sensitizer absorption cross-section under anti-Stokes excitation. A rate-equation. model using multiphonon-assisted absorption for the ytterbium excitation combined with the energy migration effect between Yb-Yb pair, and Tb3+ ground-state depopulation via multiphonon excitation of the F-7(J) excited states describes quite well the experimental results. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Dynamics of Tm-Ho energy transfer and deactivation of the F-3(4) low level of thulium in fluorozirconate glasses

The mechanism involved in the Tm3+ (F-3(4))-->Ho3+ (I-5(7)) energy transfer and Tm3+ (H-3(4), H-3(6))-->Tm3+ (F-3(4), F-3(4)) cross relaxation as a function of the donor and acceptor concentrations was investigated in Tm-Ho-codoped fluorozirconate glasses. The experimental transfer rates were determined for the Tm-->Ho energy transfer from the best fit of the acceptor luminescence decay using an expression which takes into account the Inokuti-Hirayama model and localized donor-to-acceptor interaction solution. The original acceptor solution derived from the Inokuti-Hirayama model fits well the acceptor luminescence transient only for low-concentrated systems. The results showed that a fast excitation diffusion that occurs in a very short time (t<transfer rates were always much bigger than the one predicted by the diffusion model, in which the energy transfer process is assisted by excitation migration among donors state, reinforces the existence of a fast excitation diffusion among donor ions before the energy transfer to acceptor already observed in Yb:Er:ZBLAN. The fast excitation diffusion effect was observed to dominate both the Tm-->Tm cross relaxation and Tm-->Ho energy transfer ions from H-3(4) and F-3(4) thulium states, respectively. (C) 2004 American Institute of Physics.

Energy-transfer frequency upconversion in neodymium-sensitized praseodymium-doped PbGeO3-PbF2-CdF2 glass excited at 810 nm

Visible frequency upconversion emission through resonant energy-transfer involving neodymium and praseodymium ions in PbGeO3-PbF2-CdF2 glass excited by a semiconductor laser at 8 10 nm is investigated. Luminescence emission centered around 485, 530, 610, and 645 nm, which correspond to the P-3(0) -> H-3(4), P-3(1) + I-1(6) -> H-3(5), P-3(0) -> H-3(6) and P-1(0) -> F-3(2) transitions of praseodymium ions, respectively, are observed. The upconversion excitation of the Pr3+ ions excited-state emitting levels was accomplished by means of an ion-pair interaction involving ground-state absorption, multiphonon relaxation, and excited-state absorption of pump photons at 8 10 nm by the Nd3+ (I-4(9/2) -> H-2(9/2), F-4(5/2); F-4(3/2) -> P-2(1/2)) and direct energy-transfer to Pr3+ ((4)G(11/2) + K-2(11/2), H-3(4) -> I-4(9/2), P-3(1) + I-1(6)). The dependence of the upconversion emission intensity upon the excitation power, and neodymium concentration are also examined. (c) 2004 Elsevier B.V. All rights reserved.

Energy transfer and frequency upconversion in Yb3+-Er3+-doped PbO-GeO2 glass containing silver nanoparticles

We report the infrared-to-visible frequency upconversion in Er3+-Yb3+-codoped PbO-GeO2 glass containing silver nanoparticles (NPs). The optical excitation is made with a laser at 980 nm in resonance with the F-2(5/2)-> F-2(7/2) transition of Yb3+ ions. Intense emission bands centered at 525, 550, and 662 nm were observed corresponding to Er3+ transitions. The simultaneous influence of the Yb3+-> Er3+ energy transfer and the contribution of the intensified local field effect due to the silver NPs give origin to the enhancement of the whole frequency upconversion spectra.

Enhanced frequency upconversion in Er3+ doped fluoroindate glass due to energy transfer from Tm3+

Energy transfer processes between Er3+ and Tm3+ were investigated examining the frequency upconversion emissions in a fluoroindate glass pumped at 790 nm. A 60-fold enhancement in the emission at ≈670 nm originating from Er3+ was observed when Tm3+ at concentration of 2% was introduced in a sample containing 2% of Er3+. The results are explained considering the influence of cross-relaxation processes between the active ions. © 2002 Elsevier Science B.V. All rights reserved.

Room temperature visible/infrared emission and energy transfer in Nd3+-based organic/inorganic hybrids

The photoluminescence features and the energy transfer processes of Nd3+-based siloxanepoly(oxyethylene) hybrids are reported. The host matrix of these materials, classed as di-ureasils, is formed by a siloxane backbone covalently bonded to polyether chains of two molecular weights by means of urea cross-links. The room-temperature photoluminescence spectra of these xerogels show a wide broad purple-blue-green band (350-570 nm), associated with the emitting centres of the di-ureasil host, and the typical near infrared emission of Nd3+ (700-1400 nm), assigned to the 4F3/2 → 4I9/2,11/2,13/2 transitions. Self-absorptions in the visible range, resonant with intra-4f3 transitions, indicate the existence of an energy conversion mechanism of visible di-ureasil emission into near infrared Nd3+ luminescence. The existence of energy transfer between the di-ureasil's emitting centres and the Nd3+ ions is demonstrated calculating the lifetimes of these emitting centres. The efficiency of that energy transfer changes both with the polymer molecular weight and the Nd3+ concentration.

Phonon-assisted cooperative energy transfer and frequency upconversion in a Yb3+/Tb3+ codoped fluoroindate glass

Phonon-assisted cooperative energy transfer and frequency upconversion (UC) in Yb3+/Tb3+ codoped fluoroindate glass were investigated. Anti-Stokes quasiresonant excitation of Yb3+ ions was used to study the influence of multiphonon transitions in the UC process. A rate equation model was used to describe the temperature dependence of the UC emission intensities and the theoretical results are in good agreement with the experimental data.

Optical properties and energy-transfer frequency upconversion of Yb 3+-sensitized Ho3+- And Tb3+-doped lead-cadmium-germanate glass and glass ceramic

In this report we investigate the optical properties and energy-transfer upconversion luminescence of Ho3+- and Tb3+/Yb 3+-codoped PbGeO3-PbF2-CdF2 glass-ceramic under infrared excitation. In Ho3+/Yb 3+-codoped sample, green(545 nm), red(652 nm), and near-infrared(754 nm) upconversion luminescence corresponding to the 4S 2(5F4) → 5I8, 5F5 → 5I8, and 4S2(5F4) → 5I 7, respectively, was readly observed. Blue(490 nm) signals assigned to the 5F2,3 → 5I8 transition was also detected. In the Tb3+/Yb3+ system, bright UV-visible emission around 384, 415, 438, 473-490, 545, 587, and 623 nm, identified as due to the 5D3(5G6) → 7FJ(J=6,5,4) and 5D4→ 7FJ(J=6,5,4,3) transitions, was measured. The comparison of the upconversion process in glass ceramic and its glassy precursor revealed that the former samples present much higher upconversion efficiencies. The dependence of the upconversion emission upon pump power, and doping contents was also examined. The results indicate that successive energy-transfer between ytterbium and holmium ions and cooperative energy-transfer between ytterbium and terbium ions followed by excited-state absorption are the dominant upconversion excitation mechanisms herein involved. The viability of using the samples for three-dimensional solid-state color displays is also discussed.

Energy transfer and frequency upconversion involving triads of Pr3+ ions in (Pr3+, Gd3+) doped fluoroindate glass

Blue and ultraviolet luminescence in (Pr3+, Gd3+) doped fluoroindate glass is studied for excitation in the red region (≈590 nm). Frequency upconversion (UC) is observed due to energy transfer (ET) among three Pr3+ ions initially excited to the D21 state corresponding to the ET process D21 + D21 + D21 → S01 + H53 + H53. Additionally, UC luminescence from states P 72 6 and I 72 6 of Gd3+ is observed for an excitation wavelength resonant with transitions of the Pr3+ ions. The characterization of the luminescence signals allowed to determine ET rate among the Pr3+ ions and provides evidence of interconfigurational ET between Gd3+ and Pr3+ ions. © 2006 American Institute of Physics.

Chaotic Dynamics in a Low-Energy Transfer Strategy to the Equilateral Equilibrium Points in the Earth-Moon System

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Low-energy muon-transfer reaction from hydrogen isotopes to helium isotopes

Direct muon transfer in low-energy collisions of the muonic hydrogen H-mu and helium (He++) is considered in a three-body quantum-mechanical framework of coordinate-space integro-differential Faddeev-Hahn-type equations within two- and six-state close coupling approximations. The final-state Coulomb interaction is treated without any approximation employing appropriate Coulomb waves in the final state. This procedure of treating Coulomb interaction leads to much improved results for low-energy transfer rates. The present results agree reasonably well with previous semiclassical calculations. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Optical properties and frequency upconversion fluorescence in a Tm3+-doped alkali niobium tellurite glass

Optical spectroscopic properties of Tm3+-doped 60TeO(2)-10GeO(2)-10K(2)O-10Li(2)O-10Nb(2)O(5) glass are reported. The absorption spectra were obtained and radiative parameters were determined using the Judd-Ofelt theory. Characteristics of excited states were studied in two sets of experiments. Excitation at 360 nm originates a relatively narrow band emission at 450 nm attributed to transition D-1(2)-->F-3(4) of the Tm3+ ion with photon energy larger than the band-gap energy of the glass matrix. Excitation at 655 nm originates a frequency upconverted emission at 450 nm (D-1(2)-->F-3(4)) and emission at 790 nm (H-3(4)-->H-3(6)). The radiative lifetimes of levels D-1(2) and H-3(4) were measured and the differences between their experimental values and the theoretical predictions are understood as due to the contribution of energy transfer among Tm3+ ions. (C) 2003 American Institute of Physics.