Spectroscopic studies on the luminescence properties of ternary europium complexes with different ligands

In this paper, ligand effect of several bi-dental oxygen (O) and nitrogen (N) ligands on the red luminescence properties of europium ion (Eu³⁺) was studied comprehensively. Absorption, emission, and excitation spectral properties of ternary europium complexes with different combinations of ligands including thenoyl trifluoroacetone (TTA), naphthyl trifluoroacetone (NTA), 2,2′-bipyridyl (bpy) and phenanthroline (Phen) were investigated. Efficient Eu³⁺ red emission was observed with all the combinations of the above mentioned ligands. The most intense emission was found with the all nitrogen coordinated complex Eu(bpy)₂(Phen)₂ while the longest wavelength excitation band was recorded with oxygen-nitrogen mixed NTA-bpy complex Eu(NTA)₁(bpy)₃. With change of the ligands combination and ratio, the Eu³⁺ emission peak changes slightly from 612 to 618 nm. The absorption and excitation spectra of the europium complexes were compared and analyzed referring to the individual absorption spectral properties of the ligands. The relation between ligand-to-metal charge transfer states and luminescence intensities for different complexes was studied.     

Synthesis and luminescent properties of complexes of Eu(III) with 2-thienyltrifluoroacetonate, terephthalic acid and phenanthroline

This work reports the synthesis and luminescent properties of complexes of europium(III) with 2-thienyltrifluoroacetonate (HTTA), terephthalic acid (TPA) and phenanthroline (Phen), in the solid state. The new complexes were characterized by elemental analysis, infrared (IR) spectroscopy, scanning electronic microscopy (SEM) and thermal stability analysis. Both binuclear complex Eu₂(TPA)(TTA)₄Phen₂ and polynuclear complex Eu(TPA)(TTA)Phen present better thermal stability than the mononuclear complex Eu(TTA)₃Phen does. The formation of the binuclear/polynuclear structure of the complexes appears to be responsible for the enhancement of the thermal stability. The emission spectra show narrow emission bands that arise from the ⁵D₀→⁷F_J (J=0-4) transition of the Eu³⁺ ion. The spectral data of the complexes Eu(TPA)(TTA)Phen and Eu₂(TPA)(TTA)₄Phen₂ present only one sharp peak in the region of the ⁵D₀→⁷F₀ transition indicating that only one Eu³⁺ ion species is present in each sample. In addition, the luminescence decay curves of the complexes Eu(TPA)(TTA)Phen and Eu₂(TPA)(TTA)₄Phen₂ fit a single-exponential decay law. The values of quantum efficiencies of the emitting ⁵D₀ level for the complexes Eu(TPA)(TTA)Phen and Eu₂(TPA)(TTA)₄Phen₂ are 29% and 28%, respectively.     

Role of methylene spacer in the excitation energy transfer in europium 1- and 2- naphthylcarboxylates

A series of compounds Ln(RCOO)₃·Phen (Ln=Eu, Gd, Tb; RCOO⁻-1- and 2-naphthoate, 1- and 2-naphthylacetate, 1- and 2-naphthoxyacetate anions, Phen-1,10-phenanthroline) was investigated by methods of optical spectroscopy. Compounds of composition Ln(RCOO)₃·nH₂O with the same carboxylate ligands are also considered. Results of studies of the effects of methylene spacer decoupling the π-π- or p-π-conjugation in the naphthylcarboxylate ligand on the structure of Eu³⁺ coordination centre, on the lifetime of ⁵D₀ (Eu³⁺) state, and on processes of the excitation energy transfer to Eu³⁺ or Tb³⁺ ions are presented. Introduction of the methylene bridge in the ligand weakens the influence of the steric hindrances in forming of a crystal lattice and results in lowering the distortion of the Eu³⁺ luminescence centre, and in elongation of the observed ⁵D₀ lifetime τ_obs. The latter is caused by decrease in contribution of the radiative processes rate 1/τ_r. This is confirmed by the correlation between the lifetimes τ_obs and the quantities “τ_r·const” inversely proportional to the total integral intensities of Eu(RCOO)₃·Phen luminescence spectra. The methylene spacer performs a role of regulator of sensitization of the Ln³⁺ luminescence efficiency by means of an influence on mutual location of lowest triplet states of the ligands, the ligand-metal charge transfer (LMCT) states, and the emitting states of Ln³⁺ ions. The lowest triplet state in lanthanide naphthylcarboxylate adducts with Phen is related to carboxylate anion. A presence of the methylene spacer in naphthylcarboxylate ligand increases the triplet state energy. At the same time, the energy of “carboxylic group-Eu³⁺ ion” charge transfer states falls, which can promote the degradation of excitation energy. In naphthylcarboxylates investigated a range of the carboxylate triplet state energies from 19 150 to 20 600 cm⁻¹ was demonstrated in dependence on the type of the carboxylate anion. The interligand energy transfer from Phen to carboxylate lowest triplet state was revealed in complexes with Phen ligand. The effect of OH-group inserted in 1- or 3-position of 2-naphthoate ligand on the excitation energy transfer is also analyzed.     

Assemblies, characterization, and luminescent enhancement of organized molecular films based on rare earth complexes

Langmuir-Blodgett (LB) films of different molar percentages of Eu(TTA)₃Phen (TTA=2-thenoyltrifluoroacetone; Phen=1,10-phenanthroline) with Gd(TTA)₃Phen coexisting with arachidic acid (AA) (complexes:AA=1:l, in molar ratio) were fabricated and the luminescence enhancement of Eu(III) in the films was studied in this investigation. The monolayers and LB films were characterized by π-A isotherms, fluorescence microscopy, UV-vis spectroscopy and low-angle X-ray diffraction. High-quality LB films and strongly luminescent films were obtained. It was learned from the present study that an efficient intermolecular energy transfer occurred from Gd(TTA)₃Phen to Eu(TTA)₃Phen in the films, which resulted in the luminescence enhancement effect. According to the proposed model of the “active enhancement circle” the distance of energy transfer from Gd-, Tb-, La-, and Y-complex to Eu-complex were calculated to be 1.2, 1.2, 0.7 and 1.0 nm, respectively.     

Effect of Nd concentration on structural and optical properties of Nd:Y2O3 transparent ceramic

Y₂O₃ transparent ceramics with different Nd concentration (0.1-7.0at%) were fabricated using ZrO₂ as additive. All the samples exhibit high transparency over a broad spectral region. The elements (Y, O and Nd) are uniformly distributed in the ceramic body, and the average grain size increases with Nd content. Based on the absorption spectrum, the Judd-Ofelt intensity parameters are calculated (Ω₂=4.364×10⁻²⁰ cm², Ω₄=3.609×10⁻²⁰ cm² and Ω₆=2.919×10⁻²⁰ cm²). The absorption coefficients increase linearly with Nd³⁺ doping concentration. The absorption cross-section at 804 nm and stimulated emission cross-section at 1078 nm are calculated to be 1.54×10⁻²⁰ and 7.24×10⁻²⁰ cm², respectively. All the emission bands exhibit the highest emission intensities with 1.0at% Nd³⁺ ion content, while the lifetime decreases dramatically from 321.5 μs (0.1at% Nd) to 17.9 μs (7.0at% Nd). According to the emission spectra and measured lifetime, the optimum doping concentration of Nd³⁺ ion in Y₂O₃ transparent ceramic might be around 1.0at%.     

Optical properties of Er/Yb-codoped transparent PLZT ceramic

Optical absorption and emission spectra of Er³⁺/Yb³⁺ ions in PLZT (Pb_1−xLa_xZr_yTi_1−yO₃) ceramic have been studied. Based on the Judd—Ofelt (J-O) theory, the J-O intensity parameters were calculated to be Ω₂=2.021×10⁻²⁰ cm², Ω₄=0.423×10⁻²⁰ cm², Ω₆=0.051×10⁻²⁰ cm² from the absorption spectrum of Er³⁺/Yb³⁺-codoped PLZT. The J-O intensity parameters have been used to calculate the radiative lifetimes and the branching ratios for some excited ⁴I_13/2, ⁴I_11/2, ⁴I_9/2⁴F_9/2, and ⁴S_3/2 levels of Er³⁺ ion. The stimulated emission cross-section (8.24×10⁻²¹ cm²) was evaluated for the ⁴I_13/2→⁴I_15/2 transition of Er³⁺. The upconversion emissions at 538, 564, and 666 nm have been observed in Er³⁺/Yb³⁺-codoped PLZT by exciting at 980 nm, and their origins were identified and analyzed.     

Characterization of the VUV excitation spectrum of BaZr(BO3)2:Eu

The excitation spectra of M (M=Si⁴⁺, Ti⁴⁺) and Eu³⁺ co-doped BaZr(BO₃)₂, BaZrO₃:Eu and La₂Zr₂O₇:Eu in the vacuum ultraviolet (VUV) regions of 110-300 nm are investigated and the host-lattice absorption are characterized. The result indicated that BaZr(BO₃)₂:Eu³⁺ phosphor has a strong absorption under the VUV excitation, and in the host-lattice excitation, the strong band at 130-160 nm could be due to the BO₃ atomic groups; the band at 160-180 nm is related to the excitation of Ba-O; 180-200 nm corresponds to the charge transfer (CT) transition of Zr-O. The band at 200-235 nm due to the CT band of Eu³⁺-O²⁻ and a bond valence study explained the observed weak CT band of Eu³⁺-O²⁻ in the excitation spectra of BaZr(BO₃)₂:Eu³⁺. The emission results show that Si⁴⁺ can sensitize luminescence in the host of BaZr(BO₃)₂:Eu but Ti⁴⁺ has no improvement effect on luminescence.     

Growth and spectroscopic characterization of Er: Sr3Y(BO3)3 crystal

This paper reports the growth and spectroscopic characterization of Er³⁺:Sr₃Y(BO₃)₃ crystal. Er³⁺:Sr₃Y(BO₃)₃ crystal with dimensions up to ∅20×35 mm³ has been grown by Czochralski method. The polarized spectroscopic properties of Er³⁺:Sr₃Y(BO₃)₃ crystal were investigated. Based on the Judd-Ofelt theory, the effective intensity parameters Ω_t were obtained: Ω₂=1.71×10⁻²⁰ cm², Ω₄=1.39×10⁻²⁰ cm², Ω₆=0.74×10⁻²⁰ cm² for π-polarization, and Ω₂=1.77×10⁻²⁰ cm², Ω₄=1.44×10⁻²⁰ cm², Ω₆=0.65×10⁻²⁰ cm² for σ-polarization. The emission cross-section σ_em was calculated to be 4.75×10⁻²¹ cm² for π-polarization at 1536 nm and 6.30×10⁻²¹ cm² for σ-polarization at 1537 nm. The investigated results showed that Er³⁺:Sr₃Y(BO₃)₃ crystal may be regarded as a potential laser host material for 1.55 μm IR solid-state lasers.     

Investigation of spectroscopic properties and thermal stability of Er/Yb-co-doped Bi2O3-B2O3-Ga2O3 glasses

A series of Er³⁺/Yb³⁺-co-doped 60Bi₂O₃-(40−x) B₂O₃ -xGa₂O₃ (BBGA x=0, 4, 8, 12, 16 mol%) glasses have been prepared. The absorption spectra, emission spectra, fluorescence lifetime of Er³⁺:⁴I_13/2 level and thermal stability were measured and investigated. Three Judd-Ofelt intensity parameters Ω_t (t=2,4,6) (Ω₂=(4.67-5.93)×10⁻²⁰ cm², Ω₄=(1.50-1.81)×10⁻²⁰ cm², Ω₆=(0.92-1.17)×10⁻²⁰ cm²) of Er³⁺ ions were calculated by Judd-Ofelt theory. It is found that the Ω₆ first increases with the increase of Ga₂O₃ content from 0 to 8 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 () of Er³⁺: ⁴I_13/2→⁴I_15/2 transition were obtained according to McCumber theory and broad full width at half maximum (FWHM=69-76 nm) of the ⁴I_13/2→⁴I_15/2 transition of Er³⁺ ions were measured. The results indicate that these new BBGA glasses can be used as a candidate host material for potential broadband optical amplifiers.     

Spectroscopic analysis of Er transition in Mg/Er-codoped LiNbO3 crystal

We present a Judd-Ofelt spectroscopic analysis on the Mg/Er-codoped congruent lithium niobate (LiNbO₃) crystals. The Judd-Ofelt model is applied to the room temperature unpolarized absorption intensities of Er³⁺ ions on eleven transition bands to determine their intensity parameters: Ω₂=2.36×10⁻²⁰ cm², Ω₄=0.76×10⁻²⁰ cm², Ω₆=0.30×10⁻²⁰ cm² in Er:LiNbO₃ crystal heavily codoped with MgO. The radiative lifetime of ²H_9/2 becomes longer when MgO is added into Er:LiNbO₃ crystal. The experimental lifetimes are obtained using microsecond time-resolved spectra at 400 nm femtosecond pulse excitation to predict radiative quantum efficiency. Combining higher radiative quantum efficiency with longer radiative lifetime, we conclude that Mg/Er-codoped LiNbO₃ crystals are more suitable than Er: LiNbO₃ ones in laser materials.