Suppression of inner energy dissipation in Yb-doped NaErF4 upconversion nanocrystals through an energy cycling strategy

Suppression of the inner energy dissipation,related to the lattice phonons and inner defects,in lanthanide doped upco nversion luminescent materials remains a formidable challenge.Herein,we reveal an energy cycling strategy capable of suppressing the inner energy dissipation in lanthanide doped upconversion nanocrystals.Yb³⁺ ions were introduced in Er³⁺ heavily doped nanocrystals as an energy reservoir to compete with the inner energy dissipation.The detailed energy cycling...     

Visible luminescence of lanthanide ions in Ca3Sc2Si3O12 and Ca3Y2Si3O12

The crystalline materials Ca₃Sc₂Si₃O₁₂ and Ca₃Y₂Si₃O₁₂ were characterized by different crystal structures, as the former is a cubic garnet, while the latter is an orthorhombic compound. We investigated the optical spectroscopy of these materials doped with several trivalent lanthanide ions and compared the results for the two hosts. Polycrystalline samples were prepared by solid state reaction, both undoped and doped with the trivalent lanthanide ions Eu³⁺, Tb³⁺ and Sm³⁺. Emission, excitation and Raman spectra of these materials were measured at temperatures ranging from 300 to 10 K. The optical spectra were assigned and discussed, and the effects of the crystal structure of the host on the spectroscopic behaviour were addressed. The technological potential of these compounds in the field of optical materials and devices was discussed.     

Luminescent characterization of rare earth Dy3+ ion doped TiO2 prepared by simple chemical co-precipitation method

Pure and rare-earth ion (Dy³⁺) doped TiO₂ nanomaterials were prepared through a chemical co-precipitation method. The chemical composition, microstructure and optical properties were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy and photoluminescence (PL). XPS analysis reveals that Dy³⁺ ions are preferentially occupied in the TiO₂ crystallite lattices. Both the XRD and TEM analyses confirm that both the pure and Dy doped TiO₂ are in pure anatase phase and in nano size range, respectively. Also it is found that the maximum solubility limit for Dy³⁺ ions is found to be 0.4% in TiO₂ matrix, above which it occupies interstitials and/or crystallite surface of TiO₂ nanocrystals. From the UV-Vis spectroscopy studies it is found that Dy doping induces blue shift in TiO₂. From the PL analysis it is found that doping Dy³⁺ improves the luminescence behavior in comparison with the pure TiO₂ nanoparticles. Overall, doping very low concentrations of Dy³⁺ greatly alters the structural morphology and directly increases the luminescence behavior of TiO₂ suitable for advanced optoelectronic applications.     

Structural and luminescence enhancement properties of Eu3＋/Ag nanocrystallites doped SiO2-TiO2 matrices

We reported here the structural and optical characterisation of silver nanocrystallites/Eu3+ :SiO2-TiO2 matrices synthesised through sol-gel route. Structural characterisations were done by using energy dispersive spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), atomic force microscope (AFM) and transmission electron microscopy (TEM) measurements and optical characterisations were performed by absorption and emission spectroscopy. The TEM and XRD measurements confirmed the presence of nanocrystals. A broad absorption band was observed due to surface plasmon resonance of silver nanocrystals. The effect of silver nanocrystals on the emission spectrum of Eu3+ doped SiO2-TiO2 matrices was discussed. An attempt was made to explain this fluorescence enhancement by invoking phenomena such as energy transfer, asymmetry ratio, surface plasmon, surface roughness, crystallinity and grain boundary. Our analysis, based on the experimental results, suggested that all the phenomena except crystallinity and grain boundary had favourable effects on fluorescence enhancement. We also estimated the relevant parameters associated with the phenomena that affected the fluorescence emission from the Eu3+ ions in the matrix. It was seen that the theoretical estimate of fluorescence enhancement agreed well with the experimental estimate.     

Study of erbium (III) doped titanium dioxide nanoparticles by photoacoustic spectroscopy

Nanocrystalline titania as photocatalyst has attracted considerable attention for its potential use in environmental cleaning. Recently, lanthanide ions doped titania samples have been shown to increase the photocatalytic efficiency of selected reactions. In this work, TiO₂ nanoparticles doped with Er³⁺ were prepared via an ultrasonic assisted sol-gel method. The optical properties of the samples were determined by photoacoustic (PA) spectroscopy. It was found that the absorption edge shifted to lower wavelength when the particle size fell into nanometer range, which is the evidence of a quantum size effect. The nature of ligand bonding to Er³⁺ and the structural properties were investigated with the PA absorptions of the f-f transitions of Er³⁺, which are sensitive to the local environment. The results showed that TiO₂ gel heated at 70 °C still contained abundant trapped water and ethanol, and the environment around Er³⁺ was similar to the one in the aqueous ion. The “degree of covalency” for Er³⁺ bonding increased continuously during the gel-to-anatase transition. For the sample calcined at 1100 °C, however, the f-f transitions of Er³⁺ showed blue shifts and the intensity of the hypersensitive transition decreased, indicating an increase of ionicity in the Er³⁺ bonding. This can be attributed to the segregation of Er³⁺ ions to the external surface, forming Er₂Ti₂O₇ during the anatase-to-rutile transition, which was confirmed with XRD and TEM measurements.     

Infrared to ultraviolet upconversion luminescence in Nd doped nano-glass-ceramic

Nd^3＋ doped transparent oxyfiuoride glass ceramic containing β-YF3 nanocrystals was prepared and the upconversion luminescence behaviors of Nd^3＋ in the precursor glass and glass ceramic were investigated. Under 796 nm laser excitation, ultraviolet upconversion emissions of Nd^3＋ ions at 354 nm （^4D3/2→^4I11/2） and 382 nm （^4D3/2→^4I11/2） were observed at room temperature. Power dependence analysis demonstrated that three-photon upconversion processes populated the ^4D3/2 excited state. In comparison with those of the precursor glass, the ultraviolet emissions were enhanced by a factor of 500 in the glass ceramic, which was attributed to the change in the ligand field of Nd^3＋ ions and the decrease in phonon energy because of the partition of Nd^3＋ ions into the β-YF3 nanocrystals after crystallization.     

Structural and photoluminescence studies of Eu3+ doped zinc oxide nanorods prepared by precipitation method

Trivalent europium doped zinc oxide (ZnO:Eu3+) nanocrystals were synthesized via room temperature chemical co-precipitation and they were systematically characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and photoluminescence (PL) spectroscopy. The as-synthesized samples were found to have hexagonal wurtzite coexisted with the intermediate Zn5(OH)8Cl2·H2O phase, while the single hexagonal phase was facilitated due to the calcinations. The as obtained samples were broadly composed of nanoflakes while the highly crystalline nanorods were formed due to low temperature annealing of the as-synthesized samples. The crystallite size of the nanoflakes and nanorods (40-90 nm) were extracted from the XRD pattern which was found to be consistent with scanning electron microscopy (SEM) measurements. The photolumi-nescence (PL) spectra of nanophosphors showed bright red and orange emissions at 618 and 594 nm respectively with efficient broad blue green emission spectrum due to ZnO lattice. Further, a good energy transfer process from ZnO host to Eu3+ was observed in PL emission and excitation spectra of Eu3+ doped ZnO ions. In all, the present nanophosphors were found to have great potentiality for bio-applications.     

Preparation and luminescence properties of Eu3+ doped oxyfluoride borosilicate glass ceramics

Oxyfluoride borosilicate glass with the molar composition of 60SiO2-15B2O3-15Na2O-8CaF2-2NaF-0.25Eu2O3 was synthesized by a traditional glass melting method. Glass ceramics containing CaF2 nanocrystals were prepared by heat treating the glass samples at a tem-perature in the range of 620-680 °C. The results of X-ray diffraction (XRD) indicated that the average crystallite size and the lattice constant of CaF2 nanocrystals increased with the heat treatment temperature increasing. The luminescence spectra showed that the emission intensity of Eu3+ doped glass ceramics was stronger than that of the glass matrix, and increased with the heat treatment temperature increasing. The left edge of excitation band shifted to shorter wavelength in the glass ceramics. The local environments of Eu3+ ions in the glass and glass ceram-ics were different.     

Photoluminescent properties of Eu3＋ and Tb3＋ codoped Gd2O3 nanowires and bulk materials

In this paper, the Gd2O3：Eu3＋,Tb3＋phosphors with different doping concentrations of Eu3＋and Tb3＋ions were prepared by a hydrothermal method for nanocrystals and the solid-phase method for microcrystals. The interaction of the doped ions with different concentrations and the luminescent properties of the nanocrystals and microcrystals were studied systematically. Their structure and morphology of Gd2O3：Eu3＋,Tb3＋phosphors were analyzed by means of X-ray powder diffraction （XRD）, transmission electron mi-croscopy （TEM） and scanning electron microscopy （SEM）. The photoluminescence （PL） properties of Gd2O3：Eu3＋,Tb3＋phosphors were also systematically investigated. The results indicated that when the concentration of doped Eu3＋was fixed at 1 mol.%, the emis-sion intensity of Eu3＋ions was degenerating with Tb3＋content increasing, while when the Tb3＋content was fixed at 1 mol.%, the emission intensity of Tb3＋ions reached a maximum when the concentration of Eu3＋was 2 mol.%, implying that the energy transfer from Eu3＋to Tb3＋took place. In addition, Tb3＋could inspire blue-green light and the Eu3＋could inspire red light. Therefore co-doping systems by controlling the doping concentration and the hosts are the potential white emission materials.     

Synthesis, characterization and enhanced luminescence of terbium complexes with 2-pyrazinecarboxylic acid and butanedioic acid by inert-fluorescent lanthanide ions

Ten solid terbium complexes with 2-pyrazinecarboxylic acid (Hpyca) and butanedioic acid (BDAH) were synthesized via coprecipitation method and characterized by elemental, EDTA titration, inductively coupled plasma (ICP), thermogravimetry-differential scanning calorimetry (TG-DSC) and infrared (IR) analyses. The results showed that the complexes had the compositions of Tb(pyca)(BDA)·2H2O, Tb0.5Y0.5(pyca)(BDA)·2H2O, Tb0.5La0.5(pyca)(BDA)·3H2O, Tb0.5Gd0.5(pyca)(BDA)·2H2O, Tb0.7Y0.3(pyca)(BDA)·3H2O, Tb0.7La0.3(pyca)(BDA)·0.5H2O, Tb0.7Gd0.3(pyca)(BDA)·H2O, Tb0.6Y0.4(pyca)(BDA)·2.5H2O, Tb0.6La0.4 (pyca)(BDA)·2.5H2O and Tb0.6Gd0.4(pyca)(BDA)·3H2O. IR spectra indicated that the rare earth ions coordinated with the carboxylic oxygen atoms of Hpyca and BDAH. Luminescence spectra showed that the doped La3+, Y3+ or Gd3+ ions did not affect the luminescence emission peak positions, but remarkably increased the luminescent intensities of terbium complexes. Furthermore, the doped lanthanide complexes showed longer luminescence lifetimes and higher quantum yields than pure terbium complex. The enhanced luminescence efficiencies of Tb3+ ions in the doped complexes might result from the antenna effect of the two carboxylate ligands as well as the decrease of the self-quench of the Tb3+ ions induced by the doped lanthanide ions.     

Luminescence properties of dysprosium doped YVO4 phosphor

Trivalent dysprosium(Dy~(3+)) activated nanocrystalline yttrium vanadate(YVO_4) phosphor was synthesized via co-precipitation method. The prepared samples were characterized by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM), optical absorption and photo luminescence(PL) techniques. The XRD patterns reveal the tetragonal crystalline phase. SEM images reveal that Dy doped YVO_4 nanocrystals are agglomerated. EDAX confirms the formation of YVO_4:Dy. FTIR spectrum shows two strong absorption bands at 459 and 761 cm~(-1). Optical absorption spectrum showed the surface defects in the as-prepared samples. The PL emission spectrum shows two characteristic emission bands at 485 and 575 nm. The strong yellow emission peak at 575 nm is assigned to ~4 F_(9/2)→~6 H_(13/2) hyper sensitive transition of Dy~(3+) ions, Study of CIE chromaticity diagram indicates the suitability of the phosphor for the development of yellow-green LEDs.     

Synthesis and luminescence of Eu3+ doped nanocrystalline TiO2 spheres

Eu~(3+) doped TiO_2 anatase spheres were obtained by modified sol-gel approach.Spheres(110—250 nm) are composed of smaller(5-15 nm) nanocrystals and exhibit red emission under UV light excitation.Materials were synthesized by multi-step method from glycolated titania alkoxides.Europium doped(1.0 mol%) and non-doped spheres were synthesized.Their optical and structural properties were compared by materials characterization methods,such as X-ray powder diffraction,transmission electron microscopy and PL spectroscopy.Doped TiO_2 spheres are crystalline phase pure and exhibit high luminescence intensity.     

Removal of organic pollutants by lanthanide-doped MIL-53(Fe) metal-organic frameworks:Effect of dopant type in magnetite precursor

A series of undoped and lanthanide doped MIL-53(Fe)/Ln-Fe₃O₄(Ln=La,Nd,or Gd) metal-organic frameworks(MOFs) were prepared by the solvothermal method.All prepared samples were characterized by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),Brunauer-Emmett-Teller(BET) measurements,scanning electron microscopy(SEM),and thermal analysis.XRD and FT-IR results ascertain the successful MOF formation for all prepared samples.MIL-53(Fe)/La-Fe₃O_...     

Synthesis and optical properties of LiNd(PO_3)_4 nanocrystals dispersion in DMSO/TBE

Lanthanide doped nanocrystals with strong fluorescence, long lifetime at high doping concentrations have great potential application in bio-imaging and liquid gain medium. LiNd(PO_3)_4(LNP) crystal was reported to be one of the most excellent laser crystals with high Nd3+ concentration, and their nanocrystals synthesized via improved combustion method for the first time had strong emission intensity and long fluorescence lifetime of 122 μs. Besides,LiNd(PO_3)_4 nanocrystals can be dispersed in mixed solvents of DMSO/TBE(CHBr2 CHBr2) to form a transparent colloidal dispersion, and Judd-Ofelt theory was used to evaluate their optical parameters. In summary, LiNd(PO_3)_4 nanocrystals possess long lifetime(116 μs), low solvents quenching rate(4.9%), large emission cross section(7.63 × 10~(-20) cm~2) and high quantum yield(35.2%) under high Nd3+ ions concentration(1×10~(20) cm~(-3)), which would be the most competitive colloidal gain medium of optical amplification and laser with LD pump and potential biomaterial with low particles concentration.     

Organolanthanide Compounds Containing Methanesulfonate and Pyrazinamide Ligand in Styrene Polymerization

The synthesis of organolanthanide compounds identified as LnCp*(MS)2PzA, Ln=Sm, Tb, Yb (MS=methanesulfonate, Cp*=pentamethylcyclopentadienyl, and PzA=pyrazinamide), by the reaction of coordination compounds Ln(MS)3(PzA)4 with NaCp in THF was reported. The complexes were formulated according to elemental analyses, complexometric titration with EDTA (%Ln), and 1H NMR. IR spectroscopy revealed that PzA coordinates with lanthanide(Ⅲ) ions and methanesulfonate coordinates via oxygen atoms in a non-equivalent manner. In preliminary catalytic studies, these compounds were active in styrene polymerization that used MAO as a cocatalyst with an activity of 12.3 kg PS mol Sm-1h-1. Differential scanning calorimetry (DSC) of polystyrene showed that the polymer was mainly atactic.     

Shape control over microwave hydrothermally grown Y2O3:Eu by europium concentration adjustment

Two-step synthesis of Y2〇3:Eu nanostructures was performed. It includes microwave driven hydrothermal and calcination stages. Performed route results in crystallization of Y4〇(OH)g(N〇3):Eu crystals initially, then Y2〇3:Eu crystals after calcination. Arranged Eu contents in relation to overall cation quantity were set to 2 mol%, 10 mol% and 20 mol%. Varying europium concentrations influence habit of obtained Y4〇(OH)g(N〇3):Eu crystals from needle-like to plate-like and as a result, also shapes of final Y2〇3:Eu nanostructures. Additionally, certain amount of Eu2+ ions was detected in as-grown material using laser spectroscopy and decay kinetics measurements. Obtained material was calcined at 1200 °C in the air, which results in oxidation of Eu2+ ions and crystallization of small number of cubic EU2 O3 nanocrystals. Characterization of obtained materials was performed using XRD, SEM, TEM, EDX, CL,Raman and photoluminescence spectroscopy.     

Lanthanide complexes-functionalized ordered mesoporous TiO2: Multicolor emission (visible and near-infrared luminescence) based on visible-light sensitization

Recently, much attention has been paid to the lanthanide luminescent materials based on the visible-light sensitization for their potential applications in the fields of bio-imaging and optical devices. In this work, the lanthanide complexes have been covalently bonded to the ordered mesoporous titania (OMT) matrix, and the resulting titania-based hybrid ordered mesoporous materials (named as LnDB-OMT, Ln = Eu, Sm, Yb, Nd) were characterized by using Fourier-transform infrared (FT-IR) spectroscopy, small-angle X-ray powder diffraction (SAXD), N₂ adsorption–desorption isotherms, transmission electron microscopy (TEM), fluorescence spectroscopy, and thermogravimetric analysis. Generally, exciting with visible light is advantageous over UV excitation. Of importance here is that, under excitation with visible light, the LnDB-OMT all show characteristic visible (Eu³⁺, Sm³⁺) as well as near-infrared (Sm³⁺, Yb³⁺, Nd³⁺) luminescence of the corresponding Ln³⁺ ions (multicolor emission covered from 500 to 1400 nm spectral region), which is attributed to the energy transfer from the ligands to the Ln³⁺ ions via an antenna effect.     

Construction of NIR luminescent nanoscale lanthanide complexes with new flexible Schiff base ligands

Four mono-and bi-nuclear lanthanide complexes [LnL~1(No_3)(H_2O)DMF](Ln=Nd(1) and Yb(2)) and[Ln_2(L~2)_2(OAc)_2](Ln=Nd(3) and Yb(4)) were synthesized by using two new Schiff base ligands with long(CH_2)_2 NH(CH_2)_2 backbone.The lengths of the Schiff base ligands are about 1.8 nm.The bi-nuclear lanthanide complexes 3 and 4 have nanoscale structures with sizes of approximately 0.7 nm×1.1 nm×1.6 nm.For 3,the molar ratio of Nd:Br:O obtained by the energy dispersive X-ray spectroscopy analysis is in agreement with the crystal structure.The chromogenic Schiff base ligands in1-4 can efficiently transfer energy to lanthanide ions,thus,these complexes exhibit the typical NIR luminescence of lanthanide ions.Interestingly,3 and 4 have higher NIR emission quantum yields(Φ_(em))than 1 and 2,respectively.     

Simulation of f-d transition using the extended crystal-field model: parameter dependent study for Er3+ in various hosts

The 4f-5d transitions of Er³⁺ ions doped in crystals were widely studied due to their potential applications in quantum cutting phosphors and VUV lasers, etc. The theory to do the calculations of 4f-5d transitions and various related aspects, such as the ways to determining various parameters, were summarized. The impacts of various interactions on the spectra were also demonstrated clearly with Er³⁺ ions in crystals CaF₂ and LiYF₄. Predicted results were compared with measured spectra.     

Thermal stability and optical properties of a novel Tm~(3+) doped fluorotellurite glass

A series of fluorotellurite glasses based on（81–x）Te O2-（10＋x）KF-9La2O3（TKL）, where x=0 mol.%, 5 mol.%, 10 mol.%, 15 mol.%, doped with 2000 ppm Tm2O3, were prepared by the conventional melt quenching method.The influence of KF content on the thermal stability and optical spectroscopic properties of the Tm3＋ doped fluorotellurite glasses were investigated by differential scanning calorimetry（DSC）, X-ray diffraction（XRD）, density measurement, Fourier transform infrared spectroscopy（FTIR）, UV-VIS-NIR optical spectroscopy and fluorescence spectroscopy.Judd-Ofelt intensity parameters of Tm3＋ in as-prepared glasses were determined and used to calculate the spontaneous emission probabilities and the radiative lifetime for the 4f-4f transitions of the Tm3＋ ions.Stimulated emission cross sections in the 1470 nm region（σse） were evaluated by Füchtbauer-Ladenburg formula.The results showed that KF substitution of Te O2 was beneficial to improving the thermal stability, decreasing glass density and reducing the content of OH related groups for the investigated fluorotellurite glasses.The glass with composition of 66 Te O2-25KF-9La2O3（named TKL25） had the longest radiative lifetime of the 3H4（361 μs） and the largest FWHM×σse value（420.07×10–28 cm3）, which made it a promising material for S-band fiber amplifiers.