Spectral Hole-Burning in Femtosecond Laser-Irradiated Eu<Superscript>3+</Superscript>-Doped Aluminosilicate Glasses

We studied the persistent spectral hole-burning (PSHB) of the Eu³⁺-doped Al₂O₃-SiO₂ glasses, prepared by a sol–gel process, exposed to femtosecond laser pulses. The spectral holes were burned in the excitation spectra of the ⁷F₀⁵D₀ transition of Eu³⁺ ion. The depth and width of the burned holes were 15% and 2.5 cm^–1 fwhm at 7 K, respectively. The burned hole is stable up to room temperature. Fluorescence line narrowing spectra showed that Eu³⁺ ions were located in two different sites.     

Eu<Superscript>3+</Superscript>-fluorescence properties in nano-crystallized SnO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript> glass-ceramics

Fluorescence and spectral hole burning properties of Eu³⁺ ions were studied in nanocrystals-precipitated SnO₂-SiO₂ glasses. The glasses were prepared to contain various amount of Eu₂O₃ using the sol-gel method, in which SnO₂ nanocrystals were precipitated by heating in air. In the glasses containing Eu₂O₃ less than 1%, the Eu³⁺ ions were preferentially doped in the SnO₂ nanocrystals and their fluorescence intensities were enhanced by the energy transfer due to the recombination of electrons and holes excited in SnO₂ crystals. The SnO₂ nanocrystals-precipitated glasses exhibited the persistent spectral holes with the depth of ∼25% of the total fluorescence intensities of the Eu³⁺ ions. With the increasing Eu₂O₃ concentration, the amount of SnO₂ nanocrystals decreased and the Sn⁴⁺ ions formed the random glass structure together with the silica network. This structure change induced the fluorescence intensities and the hole depth to decrease.     

Ultrasensitive mercury(II) ion detection by europium(III)-doped cadmium sulfide composite nanoparticles

With the biomolecule glutathione (GSH) as a capping ligand, Eu³⁺-doped cadmium sulfide composite nanoparticles were successfully synthesized through a straightforward one-pot process. An efficient fluorescence energy transfer system with CdS nanoparticles as energy donor and Eu³⁺ ions as energy accepter was developed. As a result of specific interaction, the fluorescence intensity of Eu³⁺-doped CdS nanoparticles is obviously reduced in the presence of Hg²⁺. Moreover, the long fluorescent lifetime and large Stoke's shift of europium complex permit sensitive fluorescence detection. Under the optimal conditions, the fluorescence intensity of Eu³⁺ at 614 nm decreased linearly with the concentration of Hg²⁺ ranging from 10 nmol L⁻¹ to 1500 nmol L⁻¹, the limit of detection for Hg²⁺ was 0.25 nmol L⁻¹. In addition to high stability and reproducibility, the composite nanoparticles show a unique selectivity towards Hg²⁺ ion with respect to common coexisting cations. Moreover, the developed method was applied to the detection of trace Hg²⁺ in aqueous solutions. The probable mechanism of reaction between Eu³⁺-doped CdS composite nanoparticles and Hg²⁺ was also discussed.     

Local structure and photoluminescent characteristics of Eu<Superscript>3+</Superscript> in ZnO–SiO<Subscript>2</Subscript> glasses

The photoluminescence properties of xZnO–(100−x)SiO₂ (x = 0, 5, 10, 20) containing 1% Eu₂O₃ prepared by a sol–gel method were systematically investigated. The results indicated that the relative proportion of f–f transitions to charge transfer (CT) absorption decreased with the increase of ZnO concentration. The intensity of ⁵D₀–⁷F_J transitions of Eu³⁺ ions was enhanced with the increase of ZnO content due to local structure changes and decreased quantities of Eu³⁺ ions clusters. The results of fluorescence line narrow (FLN) spectra indicated that Eu³⁺ ions occupied one site in SiO₂ glass and two sites in ZnO–SiO₂ glasses. The second-order crystal field parameters were calculated. B₂₀ and B₂₂ for site 1 increased with excitation energy, while ones hardly changed for site 2.     

Synthesis and characterization of Eu<Superscript>3+</Superscript> doped Lu<Subscript>2</Subscript>O<Subscript>3</Subscript> nanophosphor using a solution-combustion method

Fine Eu³⁺-doped lutetium oxide (Lu₂O₃:Eu³⁺) nanophosphor were synthesized using a low-temperature solution-combustion method in a methyl-alcohol solution. The characteristics of the nanophosphors synthesized at various sintering temperatures with different Eu³⁺ concentrations were analyzed to determine the optimum synthesis conditions. Thermogravimetry/differential thermal analysis showed that Lu₂O₃:Eu³⁺ crystallizes completely when the dry powder is sintered at 500 °C. The Lu₂O₃:Eu³⁺ crystals had a cubic structure and monoclinic phase. The peak position of the luminescence spectrum did not differ with the concentration of Eu or the sintering temperature or atmosphere, whereas the luminescence intensity was strongly dependent on the concentration and sintering conditions.     

Exploring fluorescent covalent organic frameworks for selective sensing of Fe<Superscript>3+</Superscript>

Covalent organic frameworks (COFs) have been widely applied in gas capture and separation, but the fluorescent property of COFs with large π-conjugated system tends to be underexplored. Here we report the fluorescent properties of several COFs including TaTa, DhaTab, TRITER-1 and TzDa and the effect of metal ions of Na⁺, Mg²⁺, K⁺, Ca²⁺, Cu²⁺, Zn²⁺, Pb²⁺, Ag⁺, Cd²⁺ and Fe³⁺ on the fluorescence of these COFs. The results show that only Fe³⁺ significantly quenched the fluorescence of the studied COFs. The possibility of the four COFs for selective sensing of Fe³⁺ was demonstrated. The possible mechanism of the effect of Fe³⁺ on the fluorescence of the COFs was based on the absorption competition quenching.     

Crystal structure of Eu-doped M3MgSi2O8 (M: Ba, Sr, Ca) compounds and their emission properties

Emission properties of Eu²⁺-doped M₃MgSi₂O₈ (M: Ba, Sr, Ca) are discussed in terms of the crystal structure. When Ba²⁺ ions account for over one third of M²⁺ ions, M₃MgSi₂O₈ crystallizes in glaserite-type trigonal structure, while Ba-free compounds crystallize in merwinite-type monoclinic structure. Under UV excitation, the Eu²⁺-doped glaserite-type compounds exhibit an intense blue emission assigned to 5d-4f electron transition at about 435 nm, regardless of the molar ratio of Ba²⁺, Sr²⁺ and Ca²⁺ ions. By contrast, the Eu²⁺-doped merwinite-type compounds show an emission color sensitive to the ratio. A detailed analysis of the emission spectra reveals that the emission chromaticity for the Eu²⁺-doped M₃MgSi₂O₈ is composed of two emission peaks reflecting two different sites accommodating M²⁺ ion.     

Synthesis and optical properties of novel red phosphors YNbTiO6:Eu3+ with highly enhanced brightness by Li+ doping

Highly luminescent euxenite phased YNbTiO₆:Eu³⁺ and Li⁺-doped YNbTiO₆:Eu³⁺ red phosphors have been prepared through a facile sol–gel combustion process and investigated for the first time. The introduction of Li⁺ ions into YNbTiO₆:Eu³⁺ is able to result in significant changes of the crystallinity and particle size, and bring a clear red-shift of absorption edge. A dominant red emission peak at 611 nm due to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ was observed from photoluminescence spectra of the YNbTiO₆:Eu³⁺ and Li⁺-doped YNbTiO₆:Eu³⁺ phosphors. In particular, the emission intensity of the optimal Li⁺-doped YNbTiO₆:Eu³⁺ was examined to be close to 400% of commercial Y₂O₃:Eu³⁺ phosphor. The mechanism of the enhanced emission by Li⁺ doping was discussed.     

Thermal study in Eu3+-doped boehmite nanofibers and luminescence properties of the corresponding Eu3+:Al2O3

Eu³⁺-doped boehmite nanofiber materials with different Eu³⁺ concentrations were synthesized without any surfactant, and followed by a series of characterizations. It was found that the boehmite nanofibers became coarser with the increase of Eu³⁺ concentration, which resulted in a gradual decrease of their specific surface areas. Moreover, the thermal stability of the boehmite nanofibers was studied by thermogravimetry–differential scanning calorimetry. All materials showed the phase transition from γ-Al₂O₃ to other forms. Yet the transition temperature was increased with the increase of Eu³⁺ concentration. The Eu³⁺-doped boehmite nanofibers with the maximum Eu³⁺ concentrations showed the best thermal stability. Photoluminescence spectra showed that the 2 mol% of doping concentration of Eu³⁺ ions in Eu³⁺:Al₂O₃ nanofiber was optimum.     

The New Fluorescence Enhancement System Eu<Superscript>3+</Superscript>-ARADE-HMTM-Al<Superscript>3+</Superscript> and its Analytical Application

A new bis-Schiff base ligand, N,N-bis-(4-N-aminothiourea-2-amylidene)-4,4-diaminodiphenyl ether (ARADE), was synthesized. Its complex with Eu³⁺ in DMF emits the intrinsic fluorescence of Eu³⁺. The fluorescence intensity of the Eu³⁺-ARADE system was enhanced about 60-fold by the addition of hexamethylene tetramine (HMTM) and potash alum. This is a new fluorescence enhancement phenomenon. The excitation and emission wavelengths are 375nm and 615nm, respectively. Under optimal conditions, the fluorescence intensities vary linearly with the concentration of Eu³⁺ in the range of 7.8×10^–9–1.75×10^–5mol·L^–1 with a detection limit of 5.2×10^–9mol·L^–1, or with the concentration of Al³⁺ in the range of 3.1×10^–7–9.7×10^–5mol·L^–1 with a detection limit of 2.7×10^–7mol·L^–1. The interferences of some rare earth metals and other inorganic ions were described. This method was applied to the determination of Eu³⁺ in high purity yttrium oxide and the analysis of Al³⁺ in alloy steel standard samples. The mechanism of fluorescence enhancement was also studied.     

The standard and anomalous crystal-field spectra of Eu

The crystal-field (CF) spectra of Eu³⁺ in various inorganic crystalline phases are summarized based on previous investigations. A majority of experimental results can be well interpreted using a standard CF model. However, there are cases in which the spectroscopic properties and fluorescence dynamics of Eu³⁺ cannot be interpreted within the framework of the standard model. A particularly interesting system is Eu³⁺ doped into microcrystals of a charge-unbalanced host such as BaFCl. For Eu³⁺:BaFCl, one Eu³⁺ site (Site I) exhibits normal CF splitting and its energy levels and fluorescence intensity are similar to most other normal systems ever reported. A standard CF fitting has been performed for Site I. However, Eu³⁺ at a distorted site (Site II) is of anomalous fluorescence dynamics and CF splitting which are significantly different from those of Site I. In the metastable state of ⁵D₀, Eu³⁺ ions at Site II also exhibit unusual temperature-dependent lifetime.     

Photoreduction of Europium (III) in Sol-Gel Derived Inorganic-Organic Hybrid Materials

Eu²⁺-doped inorganic-organic hybrid materials, which are potentially suitable for a tunable laser in the near ultra violet and blue region, were prepared through the photoreduction of Eu³⁺ ions in the materials under the irradiation of the fourth harmonic wave light (266 nm) of the Nd:YAG laser. The hybrid materials doped with Eu³⁺ ions were prepared from Si(OCH₃)₄, CH₃Si(OCH₃)₃, EuCl₃ and chloropropyltrimethoxysilane (CPTM). After the prehydrolized silica sol was added to the Eu³⁺-containing solution, Eu³⁺-doped transparent inorganic-organic hybrid material was obtained by drying at 50°C. The emission peak around 450–475 nm due to the charge transfer transition (5d-4f) of Eu²⁺ ions increased with the laser irradiation time. Eu³⁺ ions were effectively photoreduced to Eu²⁺ ions in pore-free materials prepared at high CPTM to Eu³⁺ ratios. Eu²⁺ ions were generated by the photodecomposition of the bond between Eu³⁺ and Cl (Cl^– or Cl(CH₂)₃ in CPTM).     

Eu<Superscript>3+</Superscript>-doped LaPO<Subscript>4</Subscript> and LaAlO<Subscript>3</Subscript> nanosystems and their luminescence properties

Eu³⁺ ion-doped LaPO₄ nanowires or nanorods have been successfully synthesized by a simple hydrothermal method. The influence of varying the hydrothermal and subsequent sintering conditions on the morphology and structure of the LaPO₄ host has been investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). For comparison, the Eu³⁺ ions were also doped into monoclinic monazite LaPO₄ nanoparticles and perovskite LaAlO₃ nanoparticles. The relative intensities of the emission lines of the LaPO₄:Eu³⁺ nanosystems were essentially independent of their shape. The optimal doping concentrations in the monoclinic LaPO₄ and perovskite LaAlO₃ nanosystems were determined to be about 5.0 and 3.5 mol%, respectively. Under appropriate UV-radiation, the red light emitted from LaAlO₃:Eu³⁺ (3.5 mol%) was brighter than that from LaPO₄:Eu³⁺ (5.0 mol%) nanomaterial, resulting from differences in their spin-orbit couplings and covalence, which indicates that the nanoscale LaAlO₃ is a promising host material for rare earth ions. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. Supported by the National Natural Science Foundation of China (Grant Nos. 20873039 & 90606001), Hunan Provincial Natural Science Foundation (No. 07jj4002), and the Students Innovation Training Fund of Hunan University     

Synthesis and luminescence properties of Eu(III)-doped silica nanorods based on the sol–gel process

Uniform Eu³⁺-doped SiO₂ nanorods were synthesized through a simple sol–gel method using cetyltrimethylammonium bromide (CTAB) as surfactant template and tetraethylorthosilicate as silicon source. X-ray diffraction, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectrum, scanning electron microscope (SEM), transmission electron microscopy, and photoluminescence spectra were employed to characterize the products in detail. The nanorods have good uniformity and their diameters and lengths are in the range of 200–300 and 500–700 nm through the SEM images, respectively. The formation of the nanorods was studied by taking SEM images after different aging time. The experimental results indicate that CTAB plays a crucial role in the formation of the silica nanorods. The luminescence of Eu³⁺-doped SiO₂ nanorods is dominated by red-emission around 612 nm due to intra-atomic 4f → 4f (⁵D₀ → ⁷F₂₎ transition of Eu³⁺ ions. Furthermore, the effect of doping concentrations of Eu³⁺ ions on the luminescence was investigated.     

Hydrothermal synthesis and characterization of In<Superscript>3+</Superscript> modified BiVO<Subscript>4</Subscript> nanoparticles with enhanced photocatalytic activity

In³⁺-doped BiVO₄ nanoparticles with enhanced visible light activity have been successfully synthesized by a hydrothermal method. The synthesized materials were characterized by X-ray diffraction, Raman, X-ray photoelectron spectroscopy, scanning electron microscopy, BET surface areas analysis, and ultraviolet–visible diffuse reflectance spectra. In comparison with pure BiVO₄, the In³⁺-doped BiVO₄ displayed greater photocatalytic activity in the degradation of methyl blue under visible light illumination. All samples possessed a single monoclinic structure. The introduction of In ions resulted in structural distortion and the decreased band gap energy, producing more electrons and holes for photocatalytic reaction. In the meantime, the doping In ions entails a red shift in the absorption edge and an increase in the intensity of light absorption. The best photocatalytic performance was obtained with the BiVO₄ sample containing 5.0 mol% In ions.     

Novel 1,8-naphthalimide dye for multichannel sensing of H<Superscript>+</Superscript> and Cu<Superscript>2+</Superscript>

A novel 1,8-naphthalimide dye with simple structure has been produced by a facile synthetic method for colorimetric and fluorescent sensing of H⁺ and Cu²⁺. In CH₃CN/H₂O (1/1, v/v), the dye could monitor H⁺ using dual channels (ratiometric absorbance and fluorescence intensity change) from pH 6.2 to 12.0. Meanwhile, in the pH range of 1.9–5.2, the dye could also be used to detect Cu²⁺ using triple channels [ultraviolet–visible (UV–Vis) absorption, fluorescence intensity reduction, as well as fluorescence blueshift]. The detection limits for Cu²⁺ evaluated by colorimetric and fluorescent titration were 6.10 × 10^?7 and 2.62 × 10^?7 M, respectively. The dye exhibited specific selectivity and sensitivity for H⁺ and Cu²⁺ over various coexisting metal ions. Moreover, the sensing mechanism of the dye for H⁺ and Cu²⁺ was carefully examined.     

Kinetic aspects of the ion-exchange reactions of Cs<Superscript>+</Superscript>, Na<Superscript>+</Superscript>, Sr<Superscript>2+</Superscript>and Eu<Superscript>2+</Superscript> ions on the H<Superscript>+</Superscript> form of chromium hexacyanoferrate(II)

Summary This paper reports the radiochemical study of the ion-exchange of Cs⁺, Na⁺, Sr²⁺ and Eu³⁺ ions with H⁺ by chromium hexacyanoferrate(II) which was prepared in a granular form using a gel method. The slow steps which determine the rate of exchange of these ions are directly proportional to the particle diameter and this is confirmed from the linearity test of Bt vs. t plots at different particle diameters. Boyed’s equation and Reichenberg’s tables were used for evaluating all the kinetic parameters. The results reveal that the effective particle radii are unchanged for both chromium hexacyanoferrate(II) dried at 60 and 120 °C. The obtained data were analyzed using McKay plots and Arrhenius equation and the kinetic and thermodynamic parameters, e.g., effective diffusion coefficient, activation energies and entropies of activation have been evaluated. The mobility of these ions inside the particles of chromium hexacyanoferrate(II) decrease in the order of Eu³⁺>Sr²⁺>Na⁺⊃Cs⁺.     

A selective colorimetric and fluorescence chemosensing sensor for Cr<Superscript>3+</Superscript> based on a rhodamine base derivative

A rhodamine-conjugated coumarin (L) was used in designing a selective fluorescence chemosensor for the determination of trace amounts of Cr³⁺ ions in acetonitrile–water (MeCN/H₂O (90:10, %v/v) solutions. The intensity of the fluoresce emission of the chemosensor is intensified upon addition of Cr³⁺ ions in MeCN/H₂O (90:10, %v/v) solutions, due to the formation of a selective 1:1 complex between L and Cr³⁺ ions. The fluorescence enhancement versus Cr³⁺ concentration has been found to be linear from 1.0?×?10^?7 to 1.8?×?10^?5 M and a detection limit of 7.5?×?10^?8 M. The proposed fluorescent probe proved to be highly selective towards Cr³⁺ ions as compared to other common metal ions and could be successfully applied to the determination of Cr³⁺ concentrations in some water and wastewater samples.     

Physicochemical Investigation of HDDP Azomethine Dye as Turn-On Fluorescent Chemosensor for High Selectivity and Sensitivity of Al<Superscript>3+</Superscript> Ions

4-[(2-Hydroxy-naphthalen-1-ylmethylene)-amino]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-one (HDDP) was synthesized by the reaction of 4-amino-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one with 2-hydroxy-l-naphthaldehyde. The structure was confirmed by the IR, ¹H-NMR, ¹³C-NMR, and EI-MS spectra and elemental analysis. Physicochemical parameters of the HDDP such as extinction coefficient, oscillator strength, transition dipole moment, Stokes shift, and fluorescence quantum yield in different solvents were studied on the basis of polarities. The interactions of various metal ions with HDDP were also studied using steady state fluorescence measurements. The emission profile reveals that it acts as off–on type fluorescent chemosensor for selective and sensitive detection of Al³⁺ ions. Complexation stoichiometry and mechanism of enhancement were determined from a Benesi–Hildebrand plot.     

Effects of boric acid on structural and luminescent properties of BaAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:(Eu<Superscript>2+</Superscript>, Dy<Superscript>3+</Superscript>) phosphors

Eu²⁺/Dy³⁺-codoped BaAl₂O₄ phosphors were prepared by conventional solid-state reaction with boric acid flux. The effects of boric acid on structural and luminescent properties of BaAl₂O₄:(Eu²⁺, Dy³⁺) were investigated. The crystallinity of BaAl₂O₄ improved with increasing amount of H₃BO₃. Incorporation of Eu²⁺ and Dy³⁺ ions into effective lattice sites was promoted by H₃BO₃ addition. As a result, Eu²⁺ emission in BaAl₂O₄ was greatly enhanced by H₃BO₃, and the duration of persistent luminescence increased with the amount of H₃BO₃. However, the decay lifetime of persistent luminescence was not strongly influenced by the amount of H₃BO₃.