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.     

Luminescence spectroscopy of Eu in Ca3Sc2Si3O12

Ca₃Sc₂Si₃O₁₂ doped with 1 mol% Eu³⁺ and having a cubic garnet structure was prepared by a solid state reaction. The low temperature luminescence spectrum shows no measurable ⁵D₀→⁷F₀ band, in agreement with the location of the lanthanide dopant in a site of D₂ symmetry, i.e. with a Ca²⁺ substitution. On the other hand, the spectrum is clearly dominated by the ⁵D₀→⁷F₄ band, which is significantly stronger than that for the other transitions originating from the ⁵D₀ level. This unusual behavior is explained on the basis of a model describing the distortion of the EuO₈ coordination polyhedron from a cubic geometry to the actual D₂ one.     

Investigation of host-to-activator energy transfer and surface losses in SrY2O4:Eu under VUV excitation

We have completed a study of the optical properties of SrY₂O₄:Eu³⁺ under vacuum ultraviolet (VUV) excitation. Reflectance measurements on the undoped material yield a calculated band gap of about 6.1 eV. Studies on the doped material indicate that Eu³⁺ occupies the Y(1) and Y(2) sites in this host. Host-to-activator energy transfer calculations indicate a preference for transfer to Eu³⁺ at the Y(2) site. Modeling of the transfer efficiency data leads us to estimate that about 35% of absorbed radiation is lost to the surface under excitation near the band edge.     

Processes of the excitation energy migration and transfer in Ce-doped alkali gadolinium phosphates studied with time-resolved photoluminescence spectroscopy technique

Spectral-kinetic characteristics of Gd³⁺ and Ce³⁺ luminescence from a series of Ce³⁺-doped alkali gadolinium phosphates of MGdP₄O₁₂ type (M=Li, Na, Cs) have been studied within 4.2-300 K temperature range using time-resolved luminescence spectroscopy techniques. The processes of energy migration along the Gd³⁺ sub-lattice and energy transfer between the Gd³⁺ and Ce³⁺ ions have been investigated. Peculiarities of these processes have been compared for MGdP₄O₁₂ phosphate hosts with different alkali metal ions. A contribution of different levels from the ⁶P_j multiplet of the lowest Gd³⁺ excited state into the energy migration and transfer processes has been clarified. The phonon-assisted occupation of high-energy ⁶P_{5/2, 3/2} levels by Gd³⁺ in the excited ⁶P_j state has been revealed as a shift of Gd³⁺⁶P_j→⁸S_7/2 emission into the short-wavelength spectral range upon the temperature increase. The relaxation of excited Gd³⁺ via phonon-assisted population of Gd³⁺⁶P_5/2 level (next higher one to the lowest excited ⁶P_7/2) is supposed to be responsible for the rise in probability of energy migration within the Gd³⁺ sub-lattice initiating the Gd³⁺→Ce³⁺ energy transfer at T<150 K, whereas further intensification of Gd³⁺→Ce³⁺ energy transfer at T>150 K is explained by the increase in probability of Gd³⁺ relaxation into the highest ⁶P_3/2 level of the ⁶P_j multiplet. An efficient reversed Ce³⁺→Gd³⁺ energy transfer has been revealed for the studied phosphates at 4.2 K.     

Luminescence efficiency of aromatic carboxylates of europium and terbium when methylene bridges and nitro groups are present in the ligands

We discuss the possibility of optimizing the brightness of luminescence for phenylcarboxylates, naphthylcarboxylates, and indolylcarboxylates of europium and terbium and their adducts with 1,10-phenanthroline and 2,2′-bipyridine by modifying the ligands. We have studied the efficiency of luminescence and luminescence excitation. We consider the effect of blocking energy transfer from the ligands to the Eu³⁺ and Tb³⁺ ions by methylene (-CH₂-) bridges dividing the π-electron system of the ligands into two parts and by the electronacceptor nitro group (-NO₂). We have analyzed the pathways for transfer and degradation of the excitation energy at 77 K and 300 K. From the phosphorescence spectra of gadolinium salts, we have determined the energies of the lowest excited triplet states of the ligands. We consider the effect of the relative positions of the triplet levels of the ligands and the excited levels of the Eu³⁺ and Tb³⁺ ions on the luminescence efficiency. We found channels for dissipation of the excitation energy via the ππ* and nπ* states of the aromatic system of the carboxylate and the NO₂ group. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 48–54, January–February, 2007.     

Relationship between structural characteristics and photoluminescent properties of (La1−xEux)2M2O7 (M=Zr, Hf, Sn) pyrochlores

Eu-doped pyrochlores, La₂M₂O₇ (M=Zr, Hf, Sn), were synthesized by solid-state reaction at a temperature range of 1473 and 1673 K, and their structures and optical properties were characterized by X-ray Rietveld analysis, field emission scanning electron microscope (FE-SEM), and photoluminescent spectroscopy. The Rietveld analysis indicated that the distortion of the (EuO₈)ⁿ⁻ scalenohedra increased with decreasing ionic radii of the M⁴⁺ ion, and the crystallinity increased with the sintering temperature. The splitting width of ⁵D₀-⁷F₁ transition of Eu³⁺ ions increased with the distortion of the (EuO₈)ⁿ⁻ scalenohedra. The luminescent intensity ratio of magnetic dipole transitions to electronic dipole transitions decreased with the crystallinity, and the chromaticity changed from deep-red to orange-red. The relationship between the chromaticity of phosphors and the crystallinity was clarified, and the control of crystallinity is an important factor that provides phosphors with required chromaticity.     

Electronic energy relaxation and luminescence decay dynamics of Eu in Zn2SiO4:Eu phosphors

Electronic energy relaxation and decay dynamics of Eu³⁺ in Zn₂SiO₄:Eu³⁺ phosphors display evidence of intra-ion energy transfer from the ⁵D₁ to the ⁵D₀ manifold. The energy transfer timescale does not depend on Eu³⁺ concentration, or the addition of Mn²⁺ as a co-dopant and is estimated to be about 11 μs in Zn₂SiO₄. Evidence for intra-ion Eu³⁺ electronic energy transfer has also been observed in Eu-doped MgS as well as Eu³⁺ encapsulated in zeolite-Y. The energy transfer timescale in these other materials is shorter than in Zn₂SiO₄, most likely due to differences in Eu³⁺ surroundings or site symmetry.     

Some studies of BF2 and B+F implanted Silicon

Ion-implanted shallow junctions have been investigated using BE₂ (molecular ions) by the anodic oxidation method coupled with a four-point probe technique. BF₂ ions were implanted through screen oxide at doses of 3–5 × 10¹⁵ ions/cm² and energies of 25 and 45 keV which is equivalent to 5.6 keV and 10 keV of boron ions. The effect of energy, dose and annealing temperature on shallow junctions is presented in this paper. The shallow junctions in the range of 0.19 μm to 0.47 μm were fabricated.

The effect of fluorine on sheet resistivity of boron implanted silicon at various doses, treated with two-step and three-step annealing, is also presented for comparison in the paper.     

Fluorescence and persistent spectral hole burning of Eu in Ge-Ga-S-KBr glasses

Fluorescence and efficient persistent spectral hole burning of Eu³⁺ at 77 K were observed in chalcohalide glasses. The depth of the hole was approximately 30% after a burning process of 1 min with 50 mW power, and it was completely erased with Ar⁺ laser irradiation. The hole survived room temperature heat treatment and showed good thermal stability. The hole-burning mechanism was most probably the photo-reduction of Eu³⁺→Eu²⁺. Fluorescence from Eu³⁺ decreased with increasing temperature and disappeared at the temperature above ∼130 K.     

Emission properties of Eu, Mn in MAl2Si2O8 (M=Sr, Ba)

The emission properties of Eu²⁺ and Mn²⁺ in monoclinic SrAl₂Si₂O₈ (M-SAS) and hexagonal BaAl₂Si₂O₈ (H-BAS), both of which have only one alkaline-earth site, were studied. The emission peaks of both Eu²⁺ (405 nm) and Mn²⁺ (564 nm) in SrAl₂Si₂O₈, are located at longer wavelengths, compared with those in H-BAS (373 nm for Eu²⁺ and 518 nm for Mn²⁺), because of the stronger crystal field strength at the Sr site. EPR spectra showed that the g values of Mn²⁺ are 4.5065 in M-SAS:Mn and 2.0247 in H-BAS:Mn. Magnetic measurements proved that Mn²⁺ was at high-spin state in both hosts. The large g value of Mn²⁺ in M-SAS was ascribed to the mixing of the first excitation state to the ground state, both of which have lower d orbital degeneracy due to the lower symmetry of Mn²⁺ site. The transfer efficiency from Eu²⁺ to Mn²⁺was about 10% in M-SAS, higher than that in H-BAS (5%). This was probably because Eu²⁺ emission overlaps the relatively low excitation level of Mn²⁺ in M-SAS. In order to obtain high transfer efficiency, it was necessary for the Eu²⁺ emission to overlap the lowest excitation level of Mn²⁺. The results obtained in this work may be helpful to design the new white or red phosphors for white-light emitting diode (w-LED) applications.     

Luminescent properties of (Y,Gd)BO3:Bi,RE (RE=Eu, Tb) phosphor under VUV/UV excitation

Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors were prepared and their luminescent properties under vacuum ultraviolet (VUV)/UV excitation were investigated. Strong red emission for (Y,Gd)BO₃:Bi³⁺,Eu³⁺ and strong green emission for (Y,Gd)BO₃:Bi³⁺,Tb³⁺ are observed under VUV excitation from 147 to 200 nm with a much broader excitation region than that of single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃ phosphor. Strong emissions are also observed under UV excitation around 265 nm where as nearly no luminescence is observed for single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃. The luminescence enhancement of Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors is due to energy transfer from Bi³⁺ ion to Eu³⁺ or Tb³⁺ ion not only in the VUV region but also in the UV region. Besides, host sensitization competition between Bi³⁺ and Eu³⁺ or Tb³⁺ is also observed. The investigated phosphors may be preferable for devices with a VUV light 147-200 nm as an excitation source such as PDP or mercury-free fluorescent lamp.     

Energy transfer between Sm and Er in orthophosphate YPO4

The energy transfer between Sm³⁺ and Er³⁺ ions in yttrium orthophosphate is studied. This choice of ions is based on the possibility of quantum cutting processes and the host material is selected according to the position of the 5d bands of the Sm³⁺ ion. The Sm³⁺ and Er³⁺ doped and Sm³⁺, Er³⁺ co-doped YPO₄ have been synthesized. Spectroscopic studies were done in the ultraviolet and vacuum ultraviolet ranges. The energy transfer between Sm³⁺ and Er³⁺ is very efficient but it does not lead to Er³⁺ visible emission. Whatever the excitation wavelength, the emission of co-doped samples mainly occurs in the infrared range.     

Eu2+,Mn2+在BaZnP2O7中的发光及Eu2+→Mn2+能量传递

采用高温固相法合成了BaZnP₂O₇:Eu²⁺,Mn²⁺荧光粉,并对其发光性质及Eu²⁺对Mn²⁺的能量传递机理进行了研究.Eu²⁺和Mn²⁺在380 nm和670nm的发射峰分别由Eu²⁺的5d—4f跃迁和Mn²⁺的⁴T₁(^{4关键词： 磷酸盐 2+}')" href="#">Eu²⁺ 2+')" href="#">Mn²⁺ 能量传递     

Eu2+,Mn2+在BaZnP2O7中的发光及Eu2+→Mn2+能量传递

采用高温固相法合成了BaZnP₂O₇:Eu²⁺,Mn²⁺荧光粉，并对其发光性质及Eu²⁺对Mn²⁺的能量传递机理进行了研究.Eu²⁺和Mn²⁺在380 nm和670nm的发射峰分别由Eu²⁺的5d—4f跃迁和Mn²⁺的⁴T₁(^{4相似文献}   

Eu2+, Cr3+共掺杂的MAl12O19 (M=Ca, Sr, Ba) 的发光性质及能量传递

三基色荧光粉中, 红色荧光粉性能较差, 为获得性能优良的红色荧光粉, 本文采用高温固相法合成了Eu²⁺, Cr³⁺单掺杂及共掺杂的碱土金属多铝酸盐MAl₁₂O₁₉ (M =Ca, Sr, Ba) 发光体. 实验表明, 在以上三种基质中均存在Eu²⁺→Cr³⁺的能量传递, 利用能量传递可以有效将Eu²⁺的蓝光或绿光转换为红光. 三种碱土金属多铝酸盐基质的晶体结构相似,但Eu²⁺, Cr³⁺发光受晶体场影响,导致在不同的基质中Eu²⁺, Cr³⁺间能量传递效率不同.通过光谱分析及能量传递效率计算发现, 相同掺杂浓度下,CaAl₁₂O₁₉中Eu²⁺→Cr³⁺的能量传递效率最高,SrAl₁₂O₁₉次之, BaAl₁₂O₁₉最低.红光转换率在CaAl₁₂O₁₉中最高.     

Photophysical properties of highly efficient red-emitting CaTiO3:Eu phosphors under near ultra-violet excitation

The photophysical properties of europium-doped calcium titanate for near ultra-violet excitation were studied in order to investigate whether it is applicable to white light-emitting diodes. CaTiO₃:Eu³⁺ phosphors were synthesized by using the solid-state reaction method. The structures and basic properties of the phosphors were characterized by using X-ray diffractometer, scanning electron microscope, UV-visible spectrophotometer, and X-ray photoelectron spectrometer. The photophysical properties were examined by taking excitation and emission spectra. A strong red luminescence corresponding to ⁵D₀ → ⁷F₂ transition of Eu³⁺ under near ultra-violet excitation was observed. It was found that CaTiO₃:Eu³⁺ was a red-emitting phosphor and had higher efficiency for operation under near ultra-violet excitation.     

Energy transfers between Sm and Eu in YPO4, LaP5O14 and LaP3O9 phosphates. Potential quantum cutters for red emitting phosphors

This work concerns the studies of energy transfers between Sm³⁺ and Eu³⁺ ions in some phosphates as new luminescent materials emitting in the orange-red color. The choose of ions is based on the possibility of quantum cutting process and the matrices are selected according to the 5d bands position of Sm³⁺ ion. The Sm³⁺ and Eu³⁺ doped YPO₄, LaP₅O₁₄ and LaP₃O₉ are synthesized and spectroscopic studies in ultraviolet and vacuum ultraviolet ranges have been achieved.     

Photoluminescence of Eu in SrGa2S4

A photoluminescence (PL) study of the green-emitting SrGa₂S₄:Eu²⁺ phosphor is reported. Diffuse reflectance, excitation, and emission spectra were examined with the aim to enlarge the fundamental knowledge about the emission of the Eu²⁺ ion in this lattice. The thermal dependence of the radiative properties was investigated. In particular, the Stokes shift, the crystal field splitting and the activation energy of the thermal quenching were determined. By combining these results with the information presented in literature, we discussed the location of the Eu²⁺ levels relative to the valence and conduction bands of SrGa₂S₄.     

A potential reddish orange emitting phosphor Ca2BO3Cl:Eu for white light-emitting diodes

A series of phosphors Ca₂BO₃Cl:Eu³⁺ were synthesized by using a high-temperature solid-state reaction technique, and their UV–vis luminescence properties were investigated. The f–f transitions of Eu³⁺ in the host lattice were assigned and discussed. The excitation and emission spectra indicate that this phosphor can be effectively excited by ultraviolet (394 nm), and exhibit reddish orange emission corresponding to the ⁵D₀→⁷F_J (J=0, 1, 2) transitions of Eu³⁺. The influence of the doping concentration and charge compensators on the relative emission intensity of Eu³⁺ was investigated, and the optimum doping concentration is 0.04. The critical distance R_c was estimated to be 17.1 Å in terms of the concentration quenching data. The present study suggests that Ca₂BO₃Cl:Eu³⁺ can be a potential candidate as an UV-convertible phosphor for white light-emitting diodes (LEDs).     

Europium-Activated Orthophosphate Phosphors For Energy-Efficient Solid-State Lighting: A Review

As a new class of inorganic phosphor, orthophosphate phosphors materials have received great interest because of their potential applications in solid-state lightings and displays. In this article, we focus on current developments in the synthesis, crystal structure and luminescence properties of orthophosphate phosphors for solid-state lightings. We discuss the synthesis of a family of orthophosphate phosphor doped with europium (Eu²⁺ and Eu³⁺) by traditional and novel methods. In the fluorescent lamp, phosphor materials convert UV radiation into visible radiation. Lamp phosphors are mostly white in color and they should not absorb the visible radiation. New phosphors that can absorb excitation energy from blue or near ultraviolet (n-UV) LEDs and generate visible emissions efficiently are desired. The criteria of choosing the best phosphors, for blue (450–480 nm) and n-UV (380–400 nm) LEDs, strongly depends on the absorption and emission of the phosphors. Here, we will review the status of phosphors for solid-state lightings and prospect the future development. The impacts of doping of europium and photoluminescence properties on orthophosphate phosphors were investigated and we propose a feasible interpretation.