Optical second harmonic generation and ordering effects in the system of ferroelectric barium titanate nanocrystals

The temperature dependence of the optical second harmonic generation in nanocrystalline BaTiO₃:Eu³⁺ revealed a strong hysteresis in the C_4v-O_h ferroelectric phase transition region. The explanation of the effect by the ordering processes in the system of ferroelectric nanocrystals is confirmed by the experiments in an external electric field.     

Spectral-luminescent properties of Eu<Superscript>3+</Superscript> ions in inorganic D<Subscript>2</Subscript>O and POCl<Subscript>3</Subscript>-SnCl<Subscript>4</Subscript> solvents

Absorption and luminescence spectra of Eu³⁺ ions in D₂O and POCl₃-SnCl₄ inorganic solvents were measured. Oscillator strengths and spontaneous radiation transition probabilities for the most intense electron transitions in Eu³⁺ were calculated. Judd-Ofelt parameters, the radiative lifetime of the ⁵ D ₀ metastable level of Eu³⁺ in D₂O-Eu³⁺ and POCl₃-SnCl₄-Eu³⁺ solutions, and matrix elements for radiative transitions from the ⁵ D ₀ level were determined. The luminescence lifetime of the ⁵ D ₀ level of Eu³⁺ in these solutions was measured. The photoluminescence quantum yield for transitions from the ⁵ D ₀ level of Eu³⁺ in ⁵ D ₀ and POCl₃-SnCl₄-Eu³⁺ solutions was found to be 0.32 and 0.88, respectively.     

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.     

Influence of nanoenvironment on luminescence of Euactivated SnO2 nanocrystals

The emission intensity of the peak at 612 nm (⁵D₀→⁷F₂) of the Eu³⁺ ions activated SnO₂ nanocrystals (doped and coated) is found to be sensitive to the nanoenvironment. We have compared the luminescence efficiencies of the nanocrystals of SnO₂ doped by Eu₂O₃ with those of SnO₂ coated by Eu₂O₃ and we found that the intensities are significantly higher in coated nanocrystals. Furthermore, it is clear from luminescence intensity measurements that Eu³⁺ ions occupy low symmetry sites in the Eu₂O₃ coated SnO₂ nanocrystal. The analysis suggests that the radiative relaxation rate is higher in Eu₂O₃ coated SnO₂ nanocrystals than Eu₂O₃ doped SnO₂ nanocrystals due to the asymmetric environment of Eu³⁺ ions in coated samples.     

Optical absorption and photoluminescence studies of Eu-doped phosphate and fluorophosphate glasses

Phosphate (P₂O₅+K₂O+BaO+Al₂O₃+Eu₂O₃) and fluorophosphate (P₂O₅+K₂O+BaO+BaF₂+Al₂O₃+Eu₂O₃) glasses with different Eu³⁺ ion concentrations have been prepared and characterized through optical absorption, photoluminescence and decay times. An intense red luminescence is observed from the ⁵D₀ emitting level of Eu³⁺ ions in these glasses. The relative luminescence intensity ratio of ⁵D₀→⁷F₂→⁵D₀→⁷F₁ transitions has been evaluated to estimate the local site symmetry around the Eu³⁺ ions. The emission spectra of these glasses show a complete removal of degeneracy for the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions. Second and fourth rank crystal-field (CF) parameters have been calculated together with the CF strength parameter by assuming the C_2v symmetry for the Eu³⁺ ions in both the phosphate and fluorophosphate glasses. Judd-Ofelt parameters have been evaluated from the luminescence intensity ratios of ⁵D₀→⁷F_J (J=2, 4 and 6) to ⁵D₀→⁷F₁ transitions. These parameters have been used to derive radiative properties such as transition probabilities, branching ratios, radiative lifetimes and peak stimulated emission cross-sections for the ⁵D₀→⁷F_J transitions. Decay curves of the ⁵D₀ level of Eu³⁺ ions in these two Eu³⁺:glass systems have been measured by monitoring the ⁵D₀→⁷F₂ transition (611 nm) at room temperature. The experimental lifetime of the ⁵D₀ level in the title glasses is found to be higher than Eu³⁺-doped niobium phosphate glasses. The analysis indicates that the lifetime of the ⁵D₀ level is found to be less sensitive to the Eu³⁺ ion concentration and addition of BaF₂ has no significant effect on the optical properties of Eu³⁺-doped phosphate glasses.     

Study of frequency upconversion in Yb<Superscript>3+</Superscript>/Eu<Superscript>3+</Superscript> by cooperative energy transfer in oxyfluoroborate glass matrix

Oxyfluoroborate glass co-doped with Eu and Yb ions has been prepared and characterized for its optical properties through photoluminescence, absorption and lifetime measurements. An intense red upconversion is observed from the ⁵D₀ level of Eu³⁺ ions through energy transfer from Yb³⁺ to Eu³⁺ ion when excited with 980 nm. The Judd–Ofelt parameters have been evaluated to estimate the local site symmetry around the Eu³⁺ ions. These parameters have been used to derive radiative properties such as transition probabilities, branching ratios, radiative lifetimes and stimulated emission cross-sections for the ⁵D₀–⁷F_J transitions. Decay of excitation of the ⁵D₀ level has been measured by monitoring the ⁵D₀→⁷F₂ transition (613 nm) at room temperature. Quantum efficiency for this transition is found to be 73%. We also monitored the effect of temperature on the fluorescence emission of Eu³⁺. PACS 42.70.Ce; 42.70.Hj     

Radiative transitions and spectral-hole burning in MgO: Cr<Superscript>3+</Superscript> nanocrystals

Luminescence spectra of Cr³⁺ ions in nanocrystalline MgO obtained by sol-gel technology were studied. The radiative lifetime of excited ²E states of cubic and tetragonal Cr³⁺ centers was found to be considerably longer than that of bulk single crystals. This effect is caused by a modified effective refractive index of the inhomogeneous medium. Burning of long-lived spectral holes in the ⁴A₂-²E transition profile of cubic centers was observed, which sets nanocrystalline samples strongly apart from bulk crystals, where no hole burning was found.     

Luminescence of Cr<Superscript>3+</Superscript> impurity ions in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> nanocrystals and clusters embedded in lithium germanate glasses

The properties of Cr³⁺-doped Li₂Ge₇O₁₅ (LGO) lithium germanate nanocrystals produced in lithium germanate glasses under isothermal heating were studied. The samples were characterized by x-ray diffraction and small-angle scattering, as well as by transmission electron microscopy. The luminescence spectra of the impurity chromium measured in lithium germanate glasses containing LGO crystals revealed transitions in Cr³⁺ ions residing in the glass phase and in LGO crystallites starting from extremely small clusters. This provided the possibility of following the process of crystallization of the lithium germanate glass from Cr³⁺ luminescence spectra. The effects observed in the Cr³⁺ luminescence spectrum revealed a ferroelectric phase transition in LGO nanocrystals embedded in the glass.     

Multiplesite structure and photoluminescence properties of Eu3+ doped MgO nanocrystals

MgO:Eu³⁺ nanocrystals with average diameter around 15 nm were prepared via a facile combustion method under a weak reductive atmosphere at temperature as low as 300°C. The photoluminescence spectra showed that the MgO:Eu³⁺ nanocrystals emit white light, the hypersensitive transition (⁵ D ₀→⁷ F _j of Eu³⁺) emission was prominent in the emission spectra resulting from the noinversion symmetry local site at which Eu³⁺ ions were located. Two kinds of luminescence sites of Eu³⁺ are identified by means of the fluorescence decay and site-selective spectroscopy. The excitation and absorption spectra indicated that the absorption of surface state decreased with the increase of Eu³⁺ concentration, meaning that the surface defect decreased through Eu³⁺ doping for some of them located at the disordered sites near the surface or absorbed at the surface of MgO host. Meanwhile, absorptivity and CIE chromaticity coordinates of all samples were measured; the results were in accordance with the excitation and absorption spectra and photoluminescence spectra, respectively.     

Probing of inversion symmetry site in Eu-doped GdPO4 by luminescence study: Concentration and annealing effect

Eu³⁺-doped gadolinium orthophosphate (GdPO₄) (Eu³⁺ at%=0, 2, 5, 7, 10, 15, 20 and 30) nanoparticles have been prepared by ethylene glycol route and subsequently heated at 500 and 900 °C. The crystallite size increases with increasing heat-treatment temperature. Luminescence study shows that magnetic dipole transition (⁵D₀→⁷F₁) is prominent over the electric dipole transition (⁵D₀→⁷F₂), which has been attributed to occupancy of inversion symmetry site by more Eu³⁺ ions in Eu³⁺-doped GdPO₄. The luminescence intensity is enhanced as heat-treatment temperature increases from 500 to 900 °C due to the improved crystallinity. Optimum luminescence is observed for 5–7 at% Eu³⁺ in GdPO₄ nanoparticles. Above this concentration, luminescence intensity decreases due to concentration quenching effect. This is supported by lifetime study.     

Photophysics of RbCl co-doped with Eu2+ and Eu3+

Excitation and luminescence spectra of RbCl co-doped with divalent and trivalent europium ions are reported. Spectral dips appearing in the blue emission from Eu²⁺ are resulted from the radiative energy transfer from Eu²⁺ to Eu³⁺ and consequently induces the luminescence from Eu³⁺ that is responsible for the ⁵D₀→⁷F_J (J=0, 1, 2, 3, 4) transitions. The induced luminescence has been characterized as a function of temperature and a decay time. In addition, the polarized emission from RbCl doped with only Eu²⁺ is also reported.     

Lanthanide Luminescence as a Probe of Nanocrystalline Materials

The sharp lines in the optical spectra of lanthanide ions in solids are sensitive to the local environment surrounding the ion and, therefore, provide a local probe to study new materials. This paper reports the laser spectroscopic characterization of a series of Eu₂O₃ nanocrystals, which serve as a model compound for understanding the spectroscopy of lanthanides in nanocrystalline materials. The optical spectra of Eu₂O₃ particles with diameters of approximately 18 to 4 nm show an increase in inhomogeneous broadening and a transition to a very disordered phase as the particle size decreases. The ⁵D₀ fluorescence transients of the nanocrystals are shorter than in bulk material show no clear trend as a function of particle size but do become single exponential for 6- and 4-nm particles.     

Enhancement of luminescence intensity and increase of emission lifetime in Eu-doped 3CdO-Al2O3-3SiO2 amorphous system

Intense photoluminescence at room temperature was observed in amorphous cadmium aluminum silicate doped with europium prepared by the sol-gel method. The structure of the 3CdO-Al₂O₃-3SiO₂:Eu³⁺ system (CAS:Eu³⁺) has been determined by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The excitation and the emission spectra indicated that the red characteristic emission (611 nm) of CAS:Eu³⁺ under UV excitation due to ⁵D₀→⁷F₂ electric dipole transition is the strongest. Both XRD data and the emission ratio of (⁵D₀→⁷F₂)/(⁵D₀→⁷F₁) reveal that the Eu³⁺ is in a site without inversion symmetry. The maximum photoluminescence intensity has been obtained for 25 mol% concentration of Eu³⁺ in CAS, and the intensity enhancement and lifetime increase of Eu³⁺ with increasing sintering temperature were observed due to the less OH-content in the samples.     

Synthesis and properties of colloidal ternary ZnGa2O4:Eu nanocrystals

A nonhydrolytic hot solution synthesis technique was used to grow monodisperse ternary oxide nanocrystals of ZnGa₂O₄:Eu³⁺. The shape of ZnGa₂O₄:Eu³⁺ nanocrystals was a function of the type of precursor, and their size was controlled by changing the concentration ratio of Zn precursor to surfactant. The crystal structure of synthesized ZnGa₂O₄ nanocrystals was a cubic spinel with no detectable secondary phases. Photoluminescence of red-emitting ZnGa₂O₄:Eu³⁺ nanocrystals resulted in a high (⁵D₀-⁷F₂)/(⁵D₀-⁷F₁) intensity ratio, suggesting that the Eu³⁺ ions occupy tetrahedral Zn²⁺ sites or distorted octahedral Ga³⁺ sites with no inversion symmetry in ZnGa₂O₄ nanocrystals.     

Effect of concentration on the luminescence of Eu ions in nanocrystalline La2O3

Nanocrystalline powders with various Eu³⁺ concentration (from 1 to 10 mol %) doped La₂O₃ were prepared via a combustion route. Their structure and morphology were characterized using X-ray diffraction (XRD) and High-resolution transmission electron microscopy. The emission spectra of the as-synthesized samples show that the strongest emission position is centered at 626 nm corresponding to ⁵D₀→⁷F₂ transition of Eu³⁺ ions and the intensity change of 626 nm emission is considered as a function of ultraviolet (240 nm) irradiation time. The excitation spectra at 626 nm monitoring indicate that the charge transfer state band is varies with different Eu³⁺ ion concentration. These results are attributed to the surface defects of the nanocrystals.     

壳聚糖/LaF3 ∶ Eu3+纳米复合粒子的简易合成及发光特性

在水溶液中采用化学共沉淀法制备了壳聚糖/LaF₃ ∶ Eu³⁺纳米复合粒子。通过透射电子显微镜(TEM),X射线衍射(XRD),傅立叶变换近红外(FT-IR)光谱对样品进行了表征。结果表明:所得纳米复合粒子大小在 20 nm左右,粒径均匀,表面包覆的壳聚糖使其易溶于水,并具备了与生物蛋白偶联的多个基团。测量了该纳米复合粒子的激发光谱与发射光谱,详细说明了各发光峰对应能级的跃迁及其发光机理,分析了不同掺杂浓度对其相对发光强度的影响。结果表明:当 Eu³⁺离子掺杂摩尔分数为 10%时,样品的相对发光强度达到最大值。最后介绍了壳聚糖/LaF₃ ∶ Eu³⁺纳米复合粒子与荧光蛋白 FITC偶联的方法,以表明其在生物学中潜在的应用价值。     

Photoluminescence and electrical properties of Eu-doped (Na0.5Bi0.5)TiO3 ferroelectric single crystals

Eu³⁺-doped Na_0.5Bi_0.5TiO₃ (Eu:NBT) single crystals were grown by a top-seeded solution growth method. Photoluminescence emission and excitation spectra of Eu:NBT were investigated. The two transitions in ⁷F₀ → ⁵D₀ excitation spectra reveal that Eu³⁺ ions were incorporated into two adjacent crystallographic sites in NBT, i.e., Bi³⁺ and Na⁺ sites. The former has a symmetrical surrounding, while the later has a disordered environment, which was confirmed by decay curve measurements. The dielectric dispersion behavior was depressed and the piezoelectric and ferroelectric properties were improved after Eu doping.     

Calcination temperature optimization,energy transfer mechanism and fluorescence temperature dependence of KLa(MoO4)2:Eu3+ phosphors

The optimum calcination temperature for KLa(MoO₄)₂:Eu³⁺ phosphor was confirmed to be 1000 °C via checking the XRD patterns, SEM images and fluorescence spectra for the samples derived from solid state reaction. The energy transfer behavior between Eu³⁺ ions was studied. It was found that electric dipole–dipole interaction is responsible for the fluorescence quenching of ⁵D₂ and ⁵D₁ levels, but exchange interaction is in charge of ⁵D₀ fluorescence quenching. It was also observed that color coordinates of the studied phosphor can be tuned when the doping concentration is relatively low. The fluorescence thermal quenching process was investigated. It was found the thermal quenching followed well crossover model. Judd–Ofelt parameters of Eu³⁺ in KLa(MoO₄)₂ were obtained, and the optical transition properties were further discussed.     

Synthesis and luminescent properties of oleic acid (OA)-modified CaF2: Eu nanocrystals

The OA-modified CaF₂: Eu nanocrystals that can be well dispersed in chloroform to form a clear solution were synthesized and characterized. The nanocrystals have a roughly spherical shape with particle diameter of about 10 nm. Possible mechanism was proposed to explain the growth process. Upon the excitation at 395 nm, the room-temperature emission spectrum of the nanocrystals in chloroform presents the characteristic transitions ⁵D₀→⁷F_J of Eu³⁺ ions, with ⁵D₀→⁷F₂ (610 nm) transition as the most prominent group. The luminescence decay of Eu³⁺ ions in CaF₂ nanocrystals was also investigated and two luminescence lifetimes of 737 μs (11.2%) and 2.08 ms (88.8%) were obtained.     

Intramolecular Energy Transfer and Co-luminescence Effect in Rare Earth Ions (La, Y, Gd and Tb) Doped with Eu3+ β-diketone Complexes

In this paper, Eu³⁺ β-diketone Complexes with the two ligands 1-(2-naphthoyl)-3, 3, 3-trifluoroacetonate (TFNB) and 2’2-bipyridine (bpy) have been synthesized. Furthermore, we reported a systematical study of the co-fluorescence effect of Eu(TFNB)₃bpy doped with inert rare earth ions (La³⁺, Gd³⁺ and Y³⁺) and luminescence ion Tb³⁺. The co-luminescence effect can be found by studying the luminescence spectra of the doped complexes, which means that the existence of the other rare earth ions (La³⁺, Y³⁺, Gd³⁺ and Tb³⁺) can enhance the luminescence intensity of the central Eu³⁺, which may be due to the intramolecular energy transfer between rare earth ions and Eu³⁺. The efficient intramolecular energy transfer in all the complexes mainly occurs between the ligand TFNB and the central Eu³⁺. Full characterization and detail studies of luminescence properties of all these synthesized materials were investigated in relation to co-fluorescence effect between the central Eu³⁺ and other inert ions. Further investigation into the luminescence properties of all the complexes show that the characteristic luminescence of the corresponding Eu³⁺ through the intramolecular energy transfers from the ligand to the central Eu³⁺. Meantime, the differences in luminescence intensity of the ⁵D₀→⁷F₂ transition, in the ⁵D₀ lifetimes and in the ⁵D₀ luminescence quantum efficiency among all the synthesized materials confirm that the doped complex Eu_0.5Tb_0.5(TFNB)₃bpy exhibits higher ⁵D₀ luminescence quantum efficiency and longer lifetime than the pure Eu(TFNB)₃bpy complex and other materials.