Energy transfer from the singlet levels of diketones and dyes to lanthanide ions in nanoparticles consisting of their diketonate complexes

The energy transfer from the S ₁ levels of p-phenylbenzoyltrifluoroacetone (PhBTA) and dyes to different Ln³⁺ ions is studied in nanoparticles (NPs) composed of complexes of this diketone with Ln³⁺ and 1,10-phenanthroline (phen) and doped with dye molecules. The quenching rate constants in the NPs consisting from complexes of Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Ho³⁺, Er³⁺, and Tm³⁺ are determined from the data on the quenching of sensitized (cofluorescence) and ordinary fluorescence of coumarin 30 (C30) and rhodamine 6G (R6G). The quenching rate constants vary from ≤5 × 10¹¹ to 10¹³ s^?1 for the fluorescence quenching of PhBTA by different Ln³⁺ ions, while the quenching of dye fluorescence occurs at rates of the order of 10⁹ s^?1. In the case of complexes with the Pr³⁺ ions, the fluorescence quenching of PhBTA in NPs composed of its complexes is accompanied by sensitized luminescence of Pr³⁺. The quenching observed is due to a nonradiative energy transfer from the S ₁ states of ligands and dyes to these ions. It is shown that in NPs composed of complexes with Eu³⁺, Yb³⁺, and Sm³⁺ the cofluorescence of C30 is quenched via the electron-transfer mechanism. The study of quenching of cofluorescence and fluorescence of dyes in NPs composed of mixed complexes of La³⁺ and Nd³⁺ (Ho³⁺) shows that the observed quenching of fluorescence and cofluorescence is governed mainly by the quenching of the S ₁ state of dyes when the Nd³⁺ (Ho³⁺) content does not exceed 5–10% and by the quenching of the S ₁ state of a ligand when the Nd³⁺ (Ho³⁺) content exceeds 50%. It is assumed that the high rate constant of energy transfer from the S ₁ level of ligands to ions Pr³⁺, Nd³⁺, Ho³⁺, Er³⁺, and Tm³⁺ in NPs composed of beta-diketonate complexes is caused by exchange interactions.     

NIR-luminescence from ternary lanthanide [Ho, Pr and Tm] complexes with 1-(2-naphthyl)-4,4,4-trifluoro-1,3-butanedionate

The ligand 1-(2-naphthyl)-4,4,4-trifluoro-1,3-butanedionate (Htfnd) has been employed to synthesize six novel ternary-lanthanide complexes in which the synergic ligands were 1,10-phenanthroline-5,6-dione (dione) and 4,5-diazafluoren-9-one (dafone), respectively. Two series of complexes Ln(tfnd)₃dione and Ln(tfnd)₃dafone (Ln=Ho, Pr, Tm) were obtained. These complexes were characterized by elemental analysis, Fourier Transform Infrared spectra and diffused reflectance. After ligand-mediated excitation, Ln(tfnd)₃dione and Ln(tfnd)₃dafone all show the characteristic NIR luminescence of the corresponding Ln³⁺ ions (Ln=Ho, Pr, Tm). This can be attributed to the efficient energy transfer from ligands to central Ln³⁺ ions, via an antenna effect. The indirect energy transfer in the complexes has been investigated and the differences in the luminescence intensity between Ln(tfnd)₃dione and Ln(tfnd)₃dafone were discussed in detail. The excellent luminescent performances enable these NIR-luminescent complexes to have potential applications in optical amplification operating at 1300 or 1500 nm.     

Electronic excitation dynamics and energy transfer in lithium-gadolinium borates doped by rare earths

This paper reports on luminescence studies of lithium borate Li₆Gd(BO₃)₃ doped with Eu³⁺ and Ce³⁺ and Li₆Eu(BO₃)₃ crystals upon selective excitation by synchronous radiation in the pump energy region 3.7–27 eV at temperatures of 10 and 290 K. The effective energy transfer between the rare-earth ions Gd³⁺ → Ce³⁺ and Gd³⁺ → Eu³⁺ is found to operate by the resonant mechanism, as well as through electron-hole recombination. A study is made of the fast decay kinetics of the Ce³⁺-center activator luminescence under intracenter photoexcitation and excitation in the interband transition region. The mechanisms underlying luminescence excitation and radiative relaxation of electron states of rare-earth ions are analyzed and energy transfer processes active in these crystals are discussed.     

A cross-relaxation mechanism of fluorescence quenching in complexes of lanthanide ions with organic ligands

For the first time, direct experimental evidence of a new mechanism for the quenching of fluorescence of organic ligands (L) in complex compounds with lanthanide ions (Ln³⁺) is obtained. By analogy with the mechanism of luminescence quenching upon pair interactions of Ln³⁺ ions in inorganic systems, this mechanism is called the cross-relaxation mechanism. The experiments are performed with complexes of Tb³⁺ with dianions of halogen-substituted fluoresceins (HSFs): 4,5-dibromo-and 4,5-diiodofluorescein, eosin B, eosin, erythrosin, and Rose Bengal in dimethyl sulfoxide. In accordance with this mechanism—exchange energy transfer, L^2?(*S ₁), Tb³⁺(⁷ F ₆)→L^2?(T ₁), Tb³⁺(⁷ F _{5, 4}), allowed by the spin selection rules—an increase in the quantum yield of formation of the triplet state (Φ_T) of a ligand L^2? and a decrease in the quantum yield of fluorescence (Φ_fl) are found to take place upon complexation. The efficiency of this process amounts to ～1 in accordance with the equality Φ_fl+Φ_T=1, valid for solutions of HSFs. The possibility of other processes leading to a similar effect, specifically, recharging of the system (as for complexes of HSFs with Eu³⁺ and ³⁺) is considered. An example of inductive resonance interactions in complexes of HSFs with Pr³⁺ is given. The manifestation of equilibrium between outer-sphere and inner-sphere complexes in the photophysics of complexes of metals with HSFs is discussed.

     

Photoinduced energy transfer from the triplet state of naphthalene moiety in the Tb/Eu complexes of a specially designed naphthalene cryptand

The paper reports time-resolved emission and energy transfer (ET) studies of metal ion complexes of a specially designed rigid macrocyclic naphthalene cryptand (L) under different conditions. Complex formation of L with Li⁺ and H⁺ causes an appreciable increase in singlet state quantum yield and lifetime of L implying photoinduced electron transfer (PET) from the cryptand moiety to naphthalene unit in the free L. The system exhibits photoinduced ET at 77 K in its Tb³⁺ and Eu³⁺ complexes with either NO₃⁻¹ or Cl⁻¹ as counter-anion. The extent of ET is higher for the Tb³⁺ complex as compared to that for the Eu³⁺ complex. In both Tb³⁺ and Eu³⁺ complex, the NO₃⁻¹ ions influence the relative orientation of donor (L) and acceptor (Ln³⁺) more in favour of ET than the Cl⁻¹ ions. The rate constants for the ET from the naphthalene moiety of L to the acceptor (Ln³⁺) have been evaluated at 77 K. The results suggest ET from the triplet state of naphthalene using an exchange mechanism. The ground state geometries of the system L and its complexes with Li⁺, Cs⁺ and Tb³⁺ have been determined using DFT methods to interpret our results.     

Luminescence VUV spectroscopy of cerium-and europium-doped lithium borate crystals

The paper reports on a study of the luminescence of lithium borate crystals (Li₆Gd(BO₃)₃ doped by Eu³⁺ and Ce³⁺ ions, Li_5.7Mg_0.15Gd(BO₃)₃: Eu, and Li₆Eu(BO₃)₃) initiated by selective excitation by synchrotron radiation at excitation energies of 3.7–27 eV at 10 and 290 K. Efficient energy transfer between the rare-earth ions Gd³⁺ → Ce³⁺ and Gd³⁺ → Eu³⁺ was found to proceed by the resonance mechanism, as well as by electron-hole recombination. Fast decay kinetics of luminescence of the Ce³⁺ activator centers was studied under intracenter photoexcitation and excitation in the interband transition region. The mechanisms involved in luminescence excitation and radiative relaxation of electronic states of rare-earth ions are analyzed, and the energy transfer processes operating in these crystals are discussed.     

Ln(III)-cored complexes based on 2-thenoyltrifluoroacetone ligand for near infrared emission: Energy transfer pathway and transient absorption behavior

Lanthanide(III)-cored complexes based on 2-thenoyltrifluoroacetone (TTA) ligand for near infrared (NIR) emission have been developed to investigate the energy transfer pathway from the antenna ligand to the Ln³⁺ ion. Their photophysical studies indicate the sensitization of Ln³⁺ luminescence by energy transfer through the excited triplet state of β-diketone ligand. Nanosecond (ns) transient absorption behavior of Ln³⁺-[TTA]₃(terpy) complexes at room temperature is explored. The triplet-triplet absorption spectrum for Gd³⁺-[TTA]₃(terpy) is observed under degassed condition, whereas it is hardly observed in Er³⁺-[TTA]₃(terpy) complex. The sensitizing process in Er³⁺-[TTA]₃(terpy), through the triplet state of TTA ligand to Er³⁺ ion, is also independent on the presence of oxygen. It indicates that the energy transfer rate through the excited triplet state of β-diketone ligand to Er³⁺ ion occurs approximately faster than that of the oxygen quenching rate.     

Luminescence of Ln3+ and WO 2 2+ ions in wolframylphosphate glasses

We investigate the luminescent properties of potassium wolframylphosphate glasses doped with Eu³⁺, Tb³⁺, and Dy³⁺ ions whose luminescence is excited by donor-acceptor interaction between the active WO ₂ ²⁺ and Ln³⁺ ions, as well as the migration of energy in the subsystems of each type of the active ions. Comparison of the obtained data with the results of investigation of the spectroscopic properties of Ln³⁺ in uranylphosphate materials shows that a sufficiently high degree of the ionicity of bonds of Ln³⁺ with the atoms of its first coordination sphere is preserved in wolframylphosphate matrices. We show that three stages of the decomposition of electron excitations are typical of the WO ₂ ²⁺ ions in wolframylphosphate glasses doped with Ln³⁺ and two stages in nonactivated glasses. The electron excitation energy transfer in the WO ₂ ²⁺ −Ln³⁺ system occurs due to induction-resonance interaction. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 620–625, September–October, 1997.     

Energy transfer phenomena in ordered perovskites of the type Sr2Na0.5Ln3+0.5X6+O6

We have investigated perovskites with composition Sr₂Na_0.5Ln³⁺_0.5WO₆ and Sr₂Na_0.5Ln³⁺_0.5 UO₆ (Ln = La, Gd, Eu). Their luminescence gives information on crystallographic details of the crystal structure and on a number of different energy transfer phenomena in these compounds. For Ln = La the Na⁺ and La³⁺ ions are disordered; for Ln = Gd(Eu) they are ordered. Single-step energy transfer is observed for the couples U⁶⁺ -Eu³⁺ and W⁶⁺ - Eu³⁺; energy migration occurs within the uranium and the europium sublattices.     

Optical spectroscopy of lanthanides doped in wide band-gap semiconductor nanocrystals

Currently, tripositive lanthanide (Ln³⁺) ions doped wide band-gap semiconductor nanocrystals (NCs) have been the focus of research interest due to their distinct optical properties and potential applications in optical devices and luminescent biolabels. Because of the low absorptions of parity-forbidden 4f-4f transitions for Ln³⁺, it is highly anticipated that the luminescence of Ln³⁺ ions embedded in wide band-gap NC lattices can be sensitized efficiently via exciton recombination in the host. For this purpose, the successful incorporation of Ln³⁺ into the lattices of semiconductor NCs is of utmost importance, which still remains intractable via conventional wet chemical methods. Here, the most recent progress in the optical spectroscopy of Ln³⁺ ions doped wide band-gap semiconductor NCs is discussed. Much attention was focused on the optical properties including electronic structures, luminescence dynamics, energy transfer as well as the up-conversion emissions of Ln³⁺ ions in ZnO, TiO₂, SnO₂ and In₂O₃ NCs that were synthesized in our laboratory using wet chemical methods.     

Photophysics of the triple state of metal complexes of 9-anthracenecarboxylic acid

The triplet-triplet (T-T) absorption spectra and the T-T absorption decay kinetics are measured for solutions of 9-anthracenecarboxylic acid (ACA) and its complexes with metal ions (Cd³⁺ and Ln³⁺=Y³⁺, La³⁺, Ce³⁺, Eu³⁺, Gd³⁺, and Tb³⁺) in dimethylsulfoxide (DMSO) by the methods of flashlamp and laser pulse photolysis. The rate constants k _T of intracomplex quenching of the triplet state are measured for ACA complexes with ions Gd³⁺, Ce³⁺, Tb³⁺, and Eu³⁺. Larger values of k _T in complexes of ACA with paramagnetic ions Ce³⁺, Tb³⁺, and Eu³⁺, which have low-lying energy levels, compared to the values of k _T for complexes with other ligands (pyrene-3-sulfonate, pyrene-1,3,6,8-tetrasulfonate, and benzo[ghi]perylene-1,2-dicarboxylate) were explained by the lower energy of the triplet state of ACA (14400 cm^?1). For a complex with a paramagnetic ion Gd³⁺, which has no low-lying energy levels, the value of k _T is close to that measured by us earlier for the inner-sphere complex of pyrene-1,3,6,8-tetrasulfonate with the same ion. These results confirm our earlier assumption about the inner-sphere complexing of ACA with Ln³⁺ ions in DMSO.     

Energy transfer from Tb3+ to Eu3+ ions sorbed on SrTiO3 surface

The energy transfer at room temperature between Tb³⁺ and Eu³⁺ ions sorbed onto SrTiO₃ powders is investigated, using Time-Resolved Laser-induced Fluorescence Spectroscopy (TRLFS). Several published works deal with the energy transfer between two lanthanide ions in co-doped matrices but it is the first time that transfer processes between two lanthanide ions sorbed on a solid surface is reported. The results show that the energy transfer between sorbed Tb³⁺ and Eu³⁺ ions on strontium titanate is a non-radiative process and follows a dipole–dipole type interaction. Moreover, the higher the acceptor ions Eu³⁺ concentration, the more efficient the energy transfer.It is shown that no energy migration between the Tb³⁺ donor ions occurs. A formalism based on the model of Inokuti–Hirayama is used and allows one to fit the non-exponential Tb³⁺ fluorescence decay. It is thus possible to evaluate the critical radius (R₀) of the influence sphere of the sorbed Tb³⁺ ions. According to the previous works, two sorption sites are considered for the sorbed rare-earth. The calculated radii are similar to those obtained for other couples of donor–acceptor lanthanide ions reported in the literature.     

Luminescence properties of Y2O3:Bi3+, Ln3+ (Ln=Sm,Eu, Dy,Er, Ho) and the sensitization of Ln3+ by Bi3+

The spectroscopic characterization of yttria, singly and doubly doped with Ln³⁺ (Ln=Sm, Eu, Dy, Er, Ho) and Bi³⁺ ions, is performed through excitation spectra, emission spectra and decay time measurements. The obtained spectroscopic data clearly indicate that energy transfer takes place from Bi³⁺ to Ln³⁺ ions. The energy transfer efficiency of Bi³⁺→Ln³⁺ and quantum efficiency of Ln³⁺ were calculated. Upon excitation of 370 nm (Bi³⁺ excitation band), the quantum efficiency of Ln³⁺ varies from ～4% to ～44%. The energy transfer efficiency increases continuously with increasing Ln³⁺ concentrations, whereas the variation of the quantum efficiency of Ln³⁺ is complicated. The quantum efficiency of Ln³⁺ is discussed in terms of electron transfer and cross relaxation.     

Quantum cutting abilities of sol-gel derived LiGdF4:Eu powders

Optical properties of europium doped LiGdF₄ (LGF) powders synthesized by the sol-gel process were investigated in the VUV range. Emission of two visible photons (due to ⁵D₀→⁷F_J transitions on two Eu³⁺ ions) per absorbed VUV photon was demonstrated indicating that a quantum cutting phenomenon takes place. This mechanism is explained by a two-step energy transfer when exciting Gd³⁺ ions in their ⁶G_J high energy level. Best luminescence efficiency was recorded at room temperature for samples with a doping rate of 5 mol% in europium ions. Effect of rare-earth concentration on internal quantum cutting efficiency was studied. Temperature dependence was also investigated and showed that the down-conversion process upon excitation at 202 nm becomes inefficient at low temperature since energy transfer from Gd³⁺ ions to Eu³⁺ ions is not effective any more. Such a result was connected with the thermal population at room temperature of Eu³⁺⁷F₁ state which is involves in the first step of the energy transfer.     

Trapping mechanism in the afterglow process of the rare-earth activated Y2O2S phosphors

Phosphorescence properties are investigated in Y₂O₂S phosphors doped with rare-earth (lanthanoid, Ln) ions. Luminescence afterglow with a decay time of several ten milliseconds is observed at room temperature in the phosphors activated by Nd, Sm, Eu, Dy, Ho, Tm, Er, and Yb. The depths (thermal activation energies) of the traps causing the afterglow are measured with the transient luminescence method.It is concluded that the excited electron and the hole in the conduction and valence bands are trapped separately in the states (impurity levels) located in the vicinity of the Ln³⁺ ion. The trapping depths of the level range from 0.3 to 1.1 eV and are dependent on the electron affinity of the Ln³⁺ ion estimated from the energy difference between the 4fⁿ⁺¹ and the 4fⁿ configurations in the 4f shell of the ion.     

Potential PDP phosphors with strong absorption around 172 nm: Rare earth doped NaLaP2O7 and NaGdP2O7

NaLaP₂O₇ and NaGdP₂O₇ powder samples are prepared by solid-state reactions at 750 and 600 °C, respectively, and the VUV-excited luminescence properties of Ln³⁺ (Ln=Ce, Pr, Tb, Tm, Eu) in both diphosphates are studied. Ln³⁺ ions in both hosts show analogous luminescence. For Ce³⁺-doped samples, the five Ce³⁺ 5d levels can be clearly identified. As for Pr³⁺ and Tb³⁺-doped samples, strong 4f-5d absorption band around 172 nm is observed, which matches well with Xe-He excimer in plasma display panel (PDP) devices. As a result, Pr³⁺ can be utilized as sensitizer to absorb 172 nm VUV photon and transfer energy to appropriate activators, and Tb³⁺-doped NaREP₂O₇(RE=La, Gd) are potential 172 nm excited green PDP phosphors. For Tm³⁺ and Eu³⁺-doped samples, the Tm³⁺-O²⁻ charge transfer band (CTB) is observed to be at 177 nm, but the CTB of Eu³⁺ is observed at abnormally low energy position, which might originate from multi-position of Eu³⁺ ions. The similarity in luminescence properties of Ln³⁺ in both hosts indicates certain structural resemblance of coordination environment of Ln³⁺ in the two sodium rare earth diphosphates.     

Study of lanthanide liquid-crystalline complexes by Photoacoustic and luminescence spectroscopy

Lanthanide complexes Ln(bta)₃L₂ (Ln³⁺: Eu³⁺, Tb³⁺ and Ho³⁺; bta: benzoyltrifluoroacetonate; L: N-octadecyl-2-hydroxy-4-tetradecyloxybenzal- dimine) are synthesized. Their photoacoustic (PA) spectra are reported and interpreted. In the region of ligand absorption, PA intensity increases for Eu(bta)₃L₂, Tb(bta)₃L₂ and Ho(bta)₃L₂, respectively. It is found that the PA intensity of the ligand bears a relation to the intramolecular energy transfer process. By comparison with luminescence spectra, the energy transfer process and phase transition of lanthanide complexes are studied from two aspects: radiative and nonradiative processes.     

The luminescence enhancement of Eu3+ ion and SnO2 nanocrystal co-doped solben gel SiO2 films

SnO₂ nanocrystal and rare-earth Eu³⁺ ion co-doped SiO₂ thin films are prepared by sol-gel and spin coating methods. The formation of tetragonal rutile structure SnO₂ nanocrystals with a uniform distribution is confirmed by X-ray diffraction and transmission electron microscopy. Fourier transform infrared spectroscopy is used to investigate the densities of the hydroxyl groups, and it is found that the emission intensity from the ⁵D₀-⁷F₂ transitions of the Eu³⁺ ions is enhanced by two orders of magnitude due to energy transfer from the oxygen-vacancy-related defects of the SnO₂ nanocrystals to nearby Eu³⁺ ions. The influences of the amounts of Sn and the post-annealing temperatures are systematically evaluated to further understand the mechanism of energy transfer. The luminescence intensity ratio of Eu³⁺ ions from electric dipole transition and magnetic dipole transition indicate the different probable locations of Eu³⁺ ions in the sol-gel thin film, which are further discussed based on temperature-dependent photoluminescence measurements.     

Dependence of the mechanism and regularities of energy transfer in binuclear lanthanide complexes in solutions on the nature of the anion and solvent

The effect of anions contained in solutions on the energy transfer from Tb(III) and Dy(III) ions to different Ln(III) ions is investigated in aqueous and alcohol solutions. It is shown that the regularities revealed in the energy transfer are completely determined by the ratio between the dissociation rate of the binuclear complex and the rate of energy transfer in it. The rate constant k _t of energy transfer in solutions in which labile binuclear complexes of Ln(III) ions are linked through the strong acid anions Cl^?, NO ₃ ^? , and HSO ₄ ^? depends on the nature of ions in the pairs. It is demonstrated that the energy transfer in all the systems predominantly occurs through the induction-resonance mechanism. The rate constants k _t in aqueous solutions of weak (acetic, salicylic, and carbonic) acids also depend on the nature of ions interacting in pairs but do not correlate with the Förster overlap integral of the spectra. In labile binuclear complexes, the interaction between these ions proceeds by the exchange-resonance mechanism at a distance of ≈0.4 nm. It is established that the constants k _t in alcohol solutions of Ln(III) ions are virtually independent of the nature of the pairs of the ions interacting through the acetate bridge. A comparison of the dissociation rate constants for Ln-anion complexes in alcohol solutions and the expected intracomplex rates of energy transfer in the binuclear complexes offers a satisfactory explanation of the obtained results and makes it possible to determine the association constants for binuclear lanthanide complexes in these solutions.     

Charge transfer transitions in the transition metal oxides ABO4:Ln and APO4:ln (A=La, Gd, Y, Lu, Sc; B=V, Nb, Ta; Ln=lanthanide)

We have compiled and analyzed optical and structural properties of lanthanide doped non-metal oxides of the form APO₄:Ln³⁺ with A a rare earth and of transition metal oxides with formula ABO₄:Ln³⁺ with B a transition metal. The main objective is to understand better the interrelationships between the band gap energy, the O²⁻→Ln³⁺ charge transfer energy, and the Ln³⁺→B⁵⁺ inter-valence charge transfer energy. Various models exist for each of these three types of electron transitions in inorganic compounds that appear highly related to each other. When properly interpreted, these optically excited transitions provide the locations of the lanthanide electron donating and electron accepting states relative to the conduction band and the valence band of the hosting compound. These locations in turn determine the luminescent properties and charge carrier trapping properties of that host. Hence, understanding the relationship between the different types of charge transfer processes and its implication for lanthanide level location in the band gap is of technological interest.