Fluorescence properties of Nd3+-doped tellurite glasses

The compositional and concentration dependence of luminescence of the (4)F(3/2)-->(4)I(J) (J=13/2, 11/2 and 9/2) transitions in four Nd(3+)-doped tellurite based glasses has been studied. The free-ion energy levels obtained for 60TeO(2)+39ZnO(2)+1.0Nd(2)O(3) (TZN10) glass have been analysed using the free-ion Hamiltonian model and compared with similar results obtained for Nd(3+):glass systems. The absorption spectrum of TZN10 glass has been analysed using the Judd-Ofelt theory. Relatively longer decay rates have been obtained for Nd(3+)-doped phosphotellurite glasses. The emission characteristics of the (4)F(3/2)-->(4)I(11/2) transition, of the Nd(3+):TZN10 glass, are found to be comparable to those obtained for Nd(3+):phosphate laser glasses. The non-exponential shape of the emission decay curves for the (4)F(3/2)-->(4)I(11/2) transition is attributed to the presence of energy transfer processes between the Nd(3+) ions.     

Visible luminescence of dysprosium ions in oxyhalide lead borate glasses

Visible luminescence of Dy(3+) ions in oxyhalide lead borate glasses was examined. Luminescence spectra show two intense bands at 480 nm and 573 nm due to (4)F(9/2)→(6)H(15/2) (blue) and (4)F(9/2)→(6)H(13/2) (yellow) transitions of Dy(3+). Luminescence decays from (4)F(9/2) state and yellow-to-blue luminescence intensity ratios (Y/B) were analysed with PbX(2) (X=F, Cl) content. An introduction of PbX(2) to the borate glass results in the increasing of (4)F(9/2) lifetime and the decreasing of yellow-to-blue luminescence intensity ratio, which is due to reduction of covalency between Dy(3+) and O(2-)/X(-) ions.     

Spectroscopic properties of Dy(3+) ions in NaF-B(2)O(3)-Al(2)O(3) glasses

This paper reports the optical properties of Dy(3+) in sodium fluoroborate glasses of the type XNaF.(89-X)B(2)O(3).10 Al(2)O(3).1Dy(2)O(3) (where X=8, 12, 16, 20 and 24). Judd-Ofelt intensity parameters (Omega(2), Omega(4), Omega(6)) are derived from the absorption spectra. The Judd-Ofelt theory has been applied to interpret the local environment of Dy(3+) ions and bond covalency of RE-O bond. These parameters have been used to calculate radiative transition probabilities (A(rad)), lifetimes (tau(R)) and branching ratios (beta(R)) for the excited level (4)F(9/2). The predicted values of tau(R) are compared with the measured values for (4)F(9/2) level for five glass compositions (Glass (A-E)). The stimulated emission cross-section sigma(lambda(P)) are also evaluated for the (4)F(9/2)-->(6)H(J) (J=11/2, 13/2, and 15/2) transitions.     

The quantum cutting of Tb(3+) in Ca(6)Ln(2)Na(2)(PO(4))(6)F(2) (Ln = Gd, La) under VUV-UV excitation: with and without Gd(3+)

The VUV-vis spectroscopic properties of Tb(3+) activated fluoro-apatite phosphors Ca(6)Ln(2-x)Tb(x)Na(2)(PO(4))(6)F(2) (Ln = Gd, La) were studied. The results show that phosphors Ca(6)Gd(2-x)Tb(x)Na(2)(PO(4))(6)F(2) with Gd(3+) ions as sensitizers have intense absorption in the VUV range. The emission color of both phosphors can be tuned from blue to green by changing the doping concentration of Tb(3+) under 172 nm excitation. The visible quantum cutting (QC) via cross relaxation between Tb(3+) ions was observed in cases with and without Gd(3+). Though QC can be realized in phosphors Ca(6)La(2-x)Tb(x)Na(2)(PO(4))(6)F(2), we found that Gd(3+)-containg phosphors have a higher QC efficiency, confirming that the Gd(3+) ion indeed plays an important role during the quantum cutting process. In addition, the energy transfer process from Gd(3+) to Tb(3+) as well as (5)D(3)-(5)D(4) cross relaxation was investigated and discussed in terms of luminescence spectra and decay curves.     

Optical characterization of Eu3+ and Tb3+ ions doped cadmium lithium alumino fluoro boro tellurite glasses

This article reports on the development and spectral results of Eu(3+) and Tb(3+) ions doped cadmium lithium alumino fluoro boro tellurite (CLiAFBT) glasses in the following composition. 40TeO2-30B2O3-10CdO-10Li2O-10AlF3 (Hostglass) (40-x)TeO2-30B2O3-10CdO-10Li2O-10AlF3-xEu2O3 (40-x)TeO2-30B2O3-10CdO-10Li2O-10AlF3-xTb4O7 where x=0.25, 0.50, 0.75, 1.0, 1.25 mol%. Glass amorphous nature and thermal properties have been studied using the XRD and DSC profiles. From the emission spectra of Eu(3+):glasses, five emission transitions have been observed at 578 nm, 592 nm, 612 nm, 653 nm, 701 nm and are assigned to the transitions (5)D(0)→(7)F(0), (7)F(1,)(7)F(2), (7)F(3) and (7)F(4), respectively, with λ(exci)=392 nm ((7)F(0)→(5)L(6)). In case of Tb(3+):glasses, four emission transitions ((5)D(4)→(7)F(6,)(7)F(5), (7)F(4) and (7)F(3)) are observed at 488 nm, 543 nm, 584 nm and 614 nm, respectively, with λ(exci)=376 nm. Decay curves and energy level diagrams have been plotted to evaluate the life times and to analyze the emission mechanism.     

Spectroscopy and upconversion of Dy3+ doped in sodium zinc phosphate glass

Optical absorption and fluorescence spectra of Dy3+ doped in sodium zinc phosphate glasses have been reported. Judd-Ofelt theory has been applied to analyze the spectra and determine the optical parameters such as transition probabilities, radiative lifetime, stimulated emission cross-section, etc. The fluorescence intensity of Dy3+ corresponding to 4F9/2-->6H13/2 transition increases with increasing concentration of Dy3+ but at higher concentrations, concentration quenching is observed. The radiative lifetime of the 4F9/2 level at 1 mol% concentration of Dy3+ in this host is found to be 541 micros. Emission corresponding to 4F9/2-->6H13/2 transition (570 nm) is observed on excitation with NIR radiation due to upconversion. An attempt is made to explain this observation.     

Optical characterization of Sm3+ and Dy3+:ZnO-PbO-B2O3 glasses

Here, we present the results of the analysis of Sm(3+) or Dy(3+) (0.5 mol%) ions doped heavy metal oxide (HMO)-based zinc lead borate (ZLB) glasses. Optical measurements such as absorption, emission spectra, lifetimes, XRD, DSC profiles have been carried out. The emission spectrum of Sm(3+):ZLB has shown the emission transitions of (4)G(5/2)-->(6)H(5/2) (563 nm), (4)G(5/2)-->(6)H(7/2) (598 nm), (4)G(5/2)-->(6)H(9/2) (646 nm), (4)G(5/2)-->(6)H(11/2) (708 nm) with lambda(exc): 401 nm ((6)H(5/2)-->(4)F(7/2)). In the case of the Dy(3+):ZLB glass, emission transitions of (4)F(9/2)-->(6)H(15/2) (485 nm), (4)F(9/2)-->(6)H(13/2) (575 nm) and (4)F(9/2)-->(6)H(11/2) (664 nm) with lambda(exi): 447 nm ((6)H(15/2)-->(4)I(15/2)) have been identified. Energy level schemes relating to the emission mechanisms involved in Sm(3+) and Dy(3+) glasses have been given.     

Luminescence and microstructures of Eu(3+)-doped Ca9LiGd(2/3)(PO4)7

A red-emitting phosphor, Eu(3+)-doped Ca(9)LiGd(2/3)(PO(4))(7), was synthesized by the conventional high-temperature solid-state reaction. X-ray powder diffraction (XRD) analyses confirmed the pure crystalline phase of Whitlockite-type structure. The excitation spectra of Eu(3+) doped Ca(9)LiGd(2/3)(PO(4))(7) were measured in the VUV and UV region indicating an efficient energy transfer process from the host and Gd(3+) to Eu(3+) ions. Upon excitation with VUV and UV radiation, the phosphor showed strong red emission around 611 nm corresponding to the forced electric dipole (5)D(0)→(7)F(2) transition of Eu(3+) ions. The VUV- and UV-excited luminescence spectra of Ca(9)LiGd(2/3)(PO(4))(7):Eu(3+) together with the dependence of the integrated emission intensities on the doping levels were investigated. The Eu(3+) ions were investigated by a tunable laser as an excitation source. The excitation spectra of (7)F(0)→(5)D(0) transitions suggest that there are two families of inequivalent sites for Eu(3+) in this host. The concentration quenching and crystallographic site-occupancy of Eu(3+) ions in Ca(9)LiGd(2/3)(PO(4))(7) host were discussed on the basis of the site selective excitation and emission spectra, the luminescence decay and its crystal structure.     

A novel strategy for controllable emissions from Eu3+ or Sm3+ ions co-doped SrY2O4:Tb3+ phosphors

Trivalent rare-earth (RE) ions (Eu(3+), Tb(3+) and Sm(3+)) activated multicolor emitting SrY(2)O(4) phosphors were synthesized by a sol-gel process. The structural and morphological studies were performed by the measurements of X-ray diffraction profiles and scanning electron microscope (SEM) images. The pure phase of SrY(2)O(4) appeared after annealing at 1300 °C and the doping of RE ions did not show any effect on the structural properties. From the SEM images, the closely packed particles were observed due to the roughness of each particle tip. The photoluminescence (PL) analysis of individual RE ions activated SrY(2)O(4) phosphors exhibits excellent emission properties in their respective regions. The Eu(3+) co-activated SrY(2)O(4):Tb(3+) phosphor creates different emissions by controlling the energy transfer from Tb(3+) to Eu(3+) ions. Based on the excitation wavelengths, multiple (green, orange and white) emissions were obtained by Sm(3+) ions co-activated with SrY(2)O(4):Tb(3+) phosphors. The decay measurements were carried out for analyzing the energy transfer efficiency and the possible ways of energy transfer from donor to acceptor. The cathodoluminescence properties of these phosphors show similar behavior as PL properties except the energy transfer process. The obtained results indicated that the energy transfer process was quite opposite to the PL properties. The calculated CIE chromaticity coordinates of RE ions activated SrY(2)O(4) phosphors confirmed the red, green, orange and white emissions.     

Thermo-optical characteristics and concentration quenching effects in Nd3+ doped yttrium calcium borate glasses

In this work we present a comprehensive study of the spectroscopic and thermo-optical properties of a set of samples with composition xNd(2)O(3)-(5-x)Y(2)O(3-)40CaO-55B(2)O(3) (0 ≤ x ≤ 1.0 mol%). Their fluorescence quantum efficiency (η) values were determined using the thermal lens technique and the dependence on the ionic concentration was analyzed in terms of energy transfer processes, based on the F?rster-Dexter model of multipolar ion-ion interactions. A maximum η = 0.54 was found to be substantially higher than for yttrium aluminoborate crystals and glasses with comparable Nd(3+) content. As for the thermo-optical properties of yttrium calcium borate, they are comparable to other well-known laser glasses. The obtained energy transfer microparameters and the weak dependence of η on the Nd(3+) concentration with a high optimum Nd(3+) concentration put this system as a strong candidate for photonics applications.     

Fe(3+) ions in alkali lead tetraborate glasses--an electron paramagnetic resonance and optical study

Glass systems of composition 90R(2)B(4)O(7)+9PbO+1Fe(2)O(3) (R=Li, Na and K) and 90Li(2)B(4)O(7)+(10-x)PbO+xFe(2)O(3) (x=0.5, 1, 3, 4, 5, 7 and 9 mol %) have been investigated by means of electron paramagnetic resonance (EPR) and optical absorption techniques. The EPR spectra exhibit three resonance signals at g approximately 6.0, 4.2 and 2.0. The resonances at g approximately 6.0 and 4.2 are attributed to Fe(3+) ions in rhombic and axial symmetry sites, respectively. The g approximately 2.0 resonance signal is due to two or more Fe(3+) ions coupled together with dipolar interaction. The EPR spectra of 1 mol % of Fe(2)O(3) doped in lithium lead tetraborate glass samples have been studied at different temperatures (123-433 K). The intensity of g approximately 4.2 resonance signal decreases and the intensity of g approximately 2.0 resonance signal increases with the increase of temperature. The line widths are found to be independent of temperature. The EPR spectra exhibit a marked concentration dependence on iron content. A decrease in intensity for the resonance signal at g approximately 4.2 with increase in iron content for more than 4 mol % has been observed in lithium lead tetraborate glass samples and this has been attributed to the formation of Fe(3+) ion clusters in the glass samples. The paramagnetic susceptibility (chi) is calculated from the EPR data at various temperatures and the Curie constant (C) has been evaluated from 1/chi versus T graph. The optical absorption spectrum of Fe(3+) ions in lithium lead tetraborate glasses exhibits three bands characteristic of Fe(3+) ions in an octahedral symmetry. The crystal field parameter D(q) and the Racah interelectronic repulsion parameters B and C have also been evaluated. The value of interelectronic repulsion parameter B (825 cm(-1)) obtained in the present work suggests that the bonding is moderately covalent.     

Investigation of concentration quenching and 1.3 microm emission in Nd(3+)-doped bismuth glasses

Nd(2)O(3)-doped 70Bi(2)O(3)-20B(2)O(3)-10SiO(2)-xNd(2)O(3) (x=0.1, 0.3, 0.5, 0.7, 1.0, 1.5 mol%) bismuth glasses were prepared by the conventional melt-quenching method, and the Nd(3+):(4)F(3/2)-->(4)I(13/2) fluorescence properties had been studied for different Nd(3+) concentrations. The Judd-Ofelt analysis for Nd(3+) ions in bismuth boron silicate glasses was also performed on the base of absorption spectrum. The transition probabilities, excited state lifetimes, the fluorescence branching ratios, quantum efficiency and the stimulated emission cross-sections of (4)F(3/2)-->(4)I(13/2) transition were calculated and discussed. Based on the electric dipole-dipole interaction theory, the interaction parameters: C(DD), for the energy migration rate (4)F(3/2), (4)I(9/2)-->(4)F(3/2), (4)I(9/2) and C(DA), for cross-relaxation rate (4)F(3/2), (4)I(9/2)-->(4)I(15/2), (4)I(15/2), and/or (4)F(3/2), (4)I(9/2)-->(4)I(13/2), (4)I(15/2) in bismuth boron silicate glasses were about 18.4 x 10(-40)cm(6)/s and 3.4 x 10(-40)cm(6)/s, respectively.     

Eu3+/Tb3+和Eu3+/Pr3+共掺杂P(MMA-co-St)的荧光性能的研究

将不同荧光性能的铽(Tb)、镨(Pr)离子分别与铕(Eu)离子混合，以三异丙氧基稀土的形式掺杂P(MMA-CO-St)共聚物，研究Eu^3 ／Tb^3 和Eu^3 ／pr^3 共掺杂P(MMA-CO-St)的荧光性能的变化情况．结果表明，Eu^3 ／Tb^3 掺杂的P(MMA-CO-St)中，Tb^3 作为能量给予体，Eu^3 作为能量接受体，能量转移的结果使Eu^3 特征荧光显增强；Eu^3 ／pr^3 掺杂的P(MMA-CO-St)中，Eu^3 的能量向pr^3 转移，致使Eu^3 的特征荧光猝灭，pr^3 的荧光略为增强．     

Study of luminescence properties of novel Er3+ single-doped and Er3+/Yb3+ co-doped tellurite glasses

The novel Er(3+) single-doped and Er(3+)/Yb(3+) co-doped tellurite glasses were prepared. The effect of Yb(2)O(3) concentration on absorption spectra, emission spectra and upconversion spectra of glasses were measured and investigated. The emission intensity, fluorescence full width at half maximum (FWHM) and upconversion luminescence of Er(3+) go up with the increasing concentration of Yb(3+) ions. The maximum FWHM of (4)I(13/2) --> (4)I(15/2) transition of Er(3+) is approximate 77 nm for 1.41 x 10(21)ions/cm(3) concentration of Yb(3+)-doped glass. The visible upconversion emissions at about 532, 546 and 659 nm, corresponding to the (2)H(11/2) --> (4)I(15/2), (4)S(3/2) --> (4)I(15/2) and (4)F(9/2) --> (4)I(15/2) transitions of Er(3+), respectively, were simultaneously observed under the excitation at 970 nm. Subsequently, the possible upconversion mechanisms and important role of Yb(3+) on the green and red emissions were discussed and compared. The results demonstrate that this kind of tellurite glass may be a potentially useful material for developing potential amplifiers and upconversion optical devices.     

Cooperative processes governing formation of small pentanuclear lanthanide(III) nanoclusters and energy transport within and between them

Syntheses, lanthanide quantitative analyses, mass spectrometry and luminescence spectroscopy, and decay dynamics of crystals containing pentanuclear hetero-lanthanide(III) nanoclusters [(Ln'(5-x)Ln(x))(NO(3))(6)(mu(5)-OH)(mu(4)-L)(2)] (0 < or = x < or = 5), Ln' = Eu or Tb; Ln = La-Nd, Sm-Ho (hereafter Ln'(5-x) Ln(x)) were undertaken in search of information on factors governing self-assembly processes by which the clusters are formed and electronic interactions within and between them. The data obtained are consistent with the self-assembly of Ln'(5-x) Ln(x) nanoclusters being a concerted process featuring a profound expression of complementarity among mutually bridging [Ln(mu(4)-L](-) and [Ln(NO(3))(2)](+) components. The energy transport regime in crystals of Eu(5-x) Ln(x) is in the dynamic regime when x = 0 or Ln = La and, at 293 K, Ln = Dy, despite the presence of two crystallographically different Eu(3+) coordination environments which give rise to a doublet in the excitation and emission spectra of Eu(3+)((5)D(0)). The luminescence decay behavior of Eu(3+)((5)D(0)) in Eu(5-x) Ln(x) (Ln = Dy (for 77 K), Sm) is intermediate between the static and dynamic limits and reveals extensive electronic coupling among lanthanide ions, including many-body processes at relatively high Dy(3+) or Sm(3+) concentrations.     

A facile synthesis and photoluminescence properties of water-dispersible Re3+ doped CeF3 nanocrystals and solid nanocomposites with polymers

Water-dispersible Re(3+) doped CeF(3) colloidal nanocrystals with well controllable morphology and high crystallinity have been successfully synthesized through a solvothermal process. The TEM images illustrate that the Re(3+) doped CeF(3) nanocrystals are rectangular (or cubic) with a mean diameter of ~10 nm. The excellent dispersibility in some of the polar solvents including water is achieved by using polyethyleneimine as the capping agent. The amine groups of the polymer chains on one hand bind to the nanocrystal surface; on the other hand the free ones could link to functional materials including bio-molecules. The CeF(3) nanocrystals doped with Tb(3+) and Dy(3+) ions show the characteristic emission of Tb(3+ 5)D(4)-(7)F(J) (J = 6-3, with (5)D(4)-(7)F(5) green emission at 542 nm as the strongest one) and Dy(3+ 4)F(9/2)-(6)H(15/2) (blue-green color at 478 nm) and (4)F(9/2)-(6)H(13/2) (yellow color at 571 nm) transitions, respectively. The energy transfer from Ce(3+) to Tb(3+) and Dy(3+) was also investigated in detail. In vitro studies of Re(3+) doped CeF(3) colloidal nanocrystals on HepG2 cells confirm their excellent biological compatibility. The obtained solid CeF(3)?: Tb(3+)/PDMS nanocomposites are very stable and flexible and exhibit strong green photoluminescence upon UV excitation.     

Energy transfer between neodymium(III) and ytterbium(III) in transition-metal fluoride (TMFG) glasses

Energy transfer rates between Nd(III) and Yb(III) in glasses of the basic composition 36 PbF₂:24 ZnF₂:35 GaF₃:2 AlF₃;3 YF₃:4 LaF₃ were calculated from donor decay curves, and applied for construction of acceptor luminescence curves. The transfer rates are time dependent and the energy loss by Nd(III) is quantitatively transferred to Yb(III).     

Spectroscopic properties and thermal stability of Er3+ -doped TeO2-B2O3-Nb2O5-ZnO glass for potential WDM amplifier

A series of novel 70TeO2-(15-x)B2O3-xNb2O5-15ZnO-1wt.% Er2O3 (TBN x=0, 3, 6, 9, 12 and 15 mol%) tellurite glasses were prepared. The thermal stability, absorption spectra, emission spectra, and the lifetime of the (4)I(13/2) level of Er(3+) ions were measured and investigated. Three Judd-Ofelt intensity parameters Omega(t) (t=2, 4 and 6) (Omega(2)=(5.42-6.76)x10(-20)cm(2); Omega(4)=(1.37-1.73)x10(-20)cm(2); Omega(6)=(0.70-0.94)x10(-20)cm(2)) of Er(3+) ions were calculated by Judd-Ofelt theory. It is found that the Omega(6) first increases with the increase of Nb2O5 content from 0 to 6 mol% and then decreases, which is mainly affected by the number of non-bridging oxygen ions of the glass network. The high peak of stimulated emission cross-section (sigma(e)(peak)=(0.77-0.91)x10(-20)cm(2)) of Er(3+): (4)I(13/2)-->(4)I(15/2) transition were obtained according to McCumber theory and broad full width at half maximum (FWHM=65-73 nm) of the (4)I(13/2)-->(4)I(15/2) transition of Er(3+) ions were measured. The results indicate that these new TBN glasses can be used as a candidate host material for potential broadband optical amplifiers.     

Rare earth-doped lead borate glasses and transparent glass-ceramics: structure-property relationship

Correlation between structure and optical properties of rare earth ions in lead borate glasses and glass-ceramics was evidenced by X-ray-diffraction, Raman, FT-IR and luminescence spectroscopy. The rare earths were limited to Eu(3+) and Er(3+) ions. The observed BO(3)?BO(4) conversion strongly depends on the relative PbO/B(2)O(3) ratios in glass composition, giving important contribution to the luminescence intensities associated to (5)D(0)-(7)F(2) and (5)D(0)-(7)F(1) transitions of Eu(3+). The near-infrared luminescence and up-conversion spectra for Er(3+) ions in lead borate glasses before and after heat treatment were measured. The more intense and narrowing luminescence lines suggest partial incorporation of Er(3+) ions into the orthorhombic PbF(2) crystalline phase, which was identified using X-ray diffraction analysis.     

Metallophilic interactions in closed-shell d10 metal-metal dicyanide bonded luminescent systems Eu[Ag(x)Au(1-x)(CN)2]3 and their tunability for excited state energy transfer

We report on the heterobimetallic system, Eu[Ag(x)Au(1-x)(CN)(2)](3) (x = 0-1) in which sensitization of europium luminescence occurs by energy transfer from [Ag(x)Au(1-x)(CN)(2)](-) donor excited states. The donor states have energies which are tunable and dependent on the Ag/Au stoichiometric ratio. These layered systems exhibit interesting properties, one of which is their emission energy tunability when excited at different excitation wavelengths. In this paper, we report on their use as donor systems with Eu(III) ions as acceptor ions in energy transfer studies. Luminescence results show that the mixed metal dicyanides with the higher silver loading have a better energy transfer efficiency than the pure Ag(CN)(2)(-) and Au(CN)(2)(-) donors. The better energy transfer efficiency is due to the greater overlap between the donor emission and acceptor excitation. Additionally, more acceptor states are available in the high silver loading mixed metal Eu(III) complexes. The results from a crystal structure determination and Raman experiments are also presented in this paper and provide information about metallophilic interactions in the closed-shell d(10) metal-metal [Ag(x)Au(1-x)(CN(2)](-) dicyanide clusters.