Eu3+- and Ho3+-doped Ba3Al2O6- and MgAl2O4-type phosphors and their photoluminescent properties

Journal of Thermal Analysis and Calorimetry - The aluminate hosts were basically activated with the Eu3+- and Ho3+-ions which were prepared by solid-state reaction in this study. The DTA/TG results...     

Thermal study in Eu3+-doped boehmite nanofibers and luminescence properties of the corresponding Eu3+:Al2O3

Eu³⁺-doped boehmite nanofiber materials with different Eu³⁺ concentrations were synthesized without any surfactant, and followed by a series of characterizations. It was found that the boehmite nanofibers became coarser with the increase of Eu³⁺ concentration, which resulted in a gradual decrease of their specific surface areas. Moreover, the thermal stability of the boehmite nanofibers was studied by thermogravimetry–differential scanning calorimetry. All materials showed the phase transition from γ-Al₂O₃ to other forms. Yet the transition temperature was increased with the increase of Eu³⁺ concentration. The Eu³⁺-doped boehmite nanofibers with the maximum Eu³⁺ concentrations showed the best thermal stability. Photoluminescence spectra showed that the 2 mol% of doping concentration of Eu³⁺ ions in Eu³⁺:Al₂O₃ nanofiber was optimum.     

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.     

Judd-Ofelt intensity parameters and spectral properties of Gd2O3:Eu3+ nanocrystals

Three nonequivalent centers of Cs (A, B, and C) in monoclinic phase and C2 and S6 centers in cubic phase were identified in the Gd2O3:Eu3+ nanocrystals with spectral techniques. Size dependence in the spectra indicated that the excitations from both host and charge-transfer band (CTB) for the 5D0 --> 7F2 transition of Eu3+ ions were nearly equal for a larger size of 135 nm of the cubic phase; however, with decreasing the size to or less than 23 nm, the excitations by the CTB dominated. The variation of excitation leading to the symmetry and energy change in the C2 and S6 sites was also observed for larger particle sizes. The Judd-Ofelt intensity parameters Omega(lambda) (lambda = 2, 4) for Gd2O3:Eu3+ nanoparticles were experimentally determined. The parameters Omega(lambda) were found to significantly change with the sizes of Gd2O3:Eu3+ from nanoparticles to bulk material. With decreasing the size from 135 to 15 nm, the quantum efficiencies for 5D0 reduced from 23.6% to 4.6% due to the increasing ratio of surface to volume.     

Thermoluminescence study of persistent luminescence materials: Eu2+- and R3+-doped calcium aluminates, CaAl2O4:Eu2+,R3+

Thermoluminescence properties of the Eu2+-, R3+-doped calcium aluminate materials, CaAl2O4:Eu2+,R3+, were studied above room temperature. The trap depths were estimated with the aid of the preheating and initial rise methods. The seemingly simple glow curve of CaAl2O4:Eu2+ peaking at ca. 80 degrees C was found to correspond to several traps. The Nd3+ and Tm3+ ions, which enhance most the intensity of the high-temperature TL peaks, form the most suitable traps for intense and long-lasting persistent luminescence, too. The location of the 4f and 5d ground levels of the R3+ and R2+ ions were deduced in relation to the band structure of CaAl2O4. No clear correlation was found between the trap depths and the R3+ or R2+ level locations. The traps may thus involve more complex mechanisms than the simple charge transfer to (or from) the R3+ ions. A new persistent luminescence mechanism presented is based on the photoionization of the electrons from Eu2+ to the conduction band followed by the electron trapping to an oxygen vacancy, which is aggregated with a calcium vacancy and a R3+ ion. The migration of the electron from one trap to another and also to the aggregated R3+ ion forming R2+ (or R3+-e-) is then occurring. The reverse process of a release of the electron from traps to Eu2+ will produce the persistent luminescence. The ability of the R3+ ions to trap electrons is probably based on the different reduction potentials and size of the R3+ ions. Hole trapping to a calcium vacancy and/or the R3+ ion may also occur. The mechanism presented can also explain why Na+, Sm3+, and Yb3+ suppress the persistent luminescence.     

APTES-modified RE2O3:Eu3+ luminescent beads: structure and properties

Europium-doped lanthanide oxide RE(2)O(3):Eu(3+) (RE = Y or Gd) luminescent beads, with a spherical shape and a diameter of 150 ± 15 nm, have been modified by reaction with 3-aminopropyltriethoxysilane (APTES), in order to introduce reactive amine groups at their surfaces. The direct silanation has resulted in the formation of a nanometric layer at the surface of the beads, with an optimum grafting rate of 0.055 ± 0.005 mol APTES/mol RE(2)O(3). Fourier transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopies confirmed the condensation of an organosilane layer, made of cross-linked -O-Si-O-Si- and of groups -O-Si-R (with R = (CH(2))(3)NH(2) or O-Et). Titration of the accessible amine groups has been performed by simultaneously measuring the luminescence of grafted fluorescein isothiocyanate and that of core particles: there are about 2.3 × 10(4) (2.8 × 10(4)) -NH(2) per Y(2)O(3):Eu(3+) (Gd(2)O(3):Eu(3+)) bead. The isoelectronic point was shifted by one pH unit after APTES modification. The surface modification by APTES at least preserved (for Gd(2)O(3):Eu(3+)) or improved (for Y(2)O(3):Eu(3+)) the red emission of the beads.     

Studies on the persistent luminescence of Eu2+ and Dy3+-doped SrAl2O4 phosphors: a review

This review includes research papers on different methods of preparation of Eu²⁺ and Dy³⁺-doped SrAl₂O₄ phosphors and papers reporting luminescence studies of the materials. The methods of preparation were compared and it was concluded that solid state reaction is the best method. Papers on characterization of these phosphors by X-ray diffraction and scanning electron microscopy are also discussed. The review ends with a few important conclusions.     

晶场效应和化学键性质对Eu^2+光谱结构的影响

合成了掺Eu^2+的单一氟化物五种和复合氟化物六种; 研究了Eu^2+在基质中的跃迁发射随晶场、化学键性质变化的规律。 在一些低配位数、强晶场的体系中观察到了Eu^2+的f→f跃迁发射, 首次在室温下,观察到单一氟化物AlF3:Eu^+中的f→f跃迁发射。     

Characterization and properties of Eu3+-doped CdWO4 prepared by a hydrothermal method

Eu³⁺-doped CdWO₄ was prepared for the first time by a hydrothermal method. The structure, morphology, and luminescence of the Eu³⁺-doped CdWO₄ were characterized. TEM results revealed that the pure CdWO₄ was a nanorod with a width of about 50 nm. The photoluminescent properties of Eu³⁺-doped CdWO₄ complexes indicated energy transfer from WO₄ ^2? groups to Eu³⁺ and suggested effective doping of Eu³⁺ into the lattice of CdWO₄. The photocatalytic activity of CdWO₄ and Eu³⁺-doped CdWO₄ was investigated by the photodegradation of methyl orange (MO). Eu³⁺-doped CdWO₄ had enhanced photocatalytic activity in the photodegradation of MO. The hydroxyl radical was detected by the terephthalic acid photoluminescence (TA-PL) method, and the regular change revealed that the hydroxyl radical may be the active species.     

Photoluminescence spectral change in layered titanate oxide intercalated with hydrated Eu3+

A number of interesting photoluminescence properties of titanate layered oxide intercalated with hydrated Eu3+ have been demonstrated. Photoluminescence intensity of Eu3+ decreased rapidly with time during irradiation by UV light having energy higher than the band gap energy of the host TiO (Ti(1.81)O4) layer. This is presumably due to the decrease in energy transfer from the host TiO layer to Eu3+ as a result of the change in the hydration state of water molecules surrounding Eu3+, which is caused by the hole produced in the TiO valence band. When irradiation was discontinued, the emission intensity gradually recovered. The recovery time increased when the water in the interlayer is removed by heat treatment. This indicates that the state of interlayer water changes during irradiation and returns to its initial state after discontinuation of irradiation. The excitation spectra changed drastically at any given wavelength upon irradiation with UV light. A comparison of the excitation spectra before and after irradiation reveals that only the excitation peak at around the irradiation wavelength decreased upon irradiation, as in the case of spectral hole burning. The hydration state of water molecules surrounding Eu3+ presumably changes depending on the irradiation wavelength, leading to the above spectral change because the Eu/TiO film has a superlattice structure producing holes with different energies.     

CaAl12O19基质中Eu2+-Cr3+的能量传递与发光性质

在还原气氛下高温固相法合成了CaAl12O19:Eu2+,Cr3+荧光粉.样品光谱显示:Eu2+发射带与Cr3+吸收带有重叠,具备Eu2+-Cr3+之间发生能量传递必要条件.在290 nm近紫外光激发下,单掺杂Eu2+和Cr3+时样品均无691 nm发射,仅在Eu2+,Cr3+共掺时才出现691 nm发射,这证明Eu2+和Cr3+之间发生了能量传递,且监测691 nm时样品的激发光谱也证实了这一点.CaAl12O19:1%Eu2+,x%Cr3+样品组的发射光谱研究表明:增大x能提高Cr3+红光与Eu2+蓝紫光发射强度之比及Eu2+-Cr3+之间能量传递效率.CaAl12O19:2%Cr3+,x%Eu2+样品组的激发光谱分析表明:x>2时,Cr3+在415 nm处的吸收效率相对于565 nm有显著提高.还对样品CaAl12O19:1%Eu2+,1%Cr3+荧光寿命和能量传递速率进行了简单分析.     

Phase structure and luminescence properties of Eu3+-doped TiO2 nanocrystals synthesized by Ar/O2 radio frequency thermal plasma oxidation of liquid precursor mists

Eu3+-doped TiO2 luminescent nanocrystals have been synthesized in this work via Ar/O2 thermal plasma oxidizing mists of liquid precursors containing titanium tetra-n-butoxide and europium(III) nitrate, with varied O2 input in the plasma sheath (10-90 L/min) and Eu3+ addition in the precursor solution (Eu/(Ti + Eu) = 0-5 atom%). The resultant nanopowders are mixtures of the anatase (30-36 nm) and rutile (64-83 nm) polymorphs in the studied range, but the rutile fraction increases steadily at a higher Eu3+ addition, as revealed by X-ray diffraction (XRD) and Raman spectroscopy, because of the creation of oxygen vacancies in the TiO2 gas clusters by substitutional Eu3+ doping. The amount of Eu3+ that can be doped into a TiO2 lattice was limited up to 0.5 atom%, above which Eu2Ti2O7 pyrochlore was formed in the final products. High resolution transmission electron microscopy (HRTEM) observation indicates that the particles are dense and have sizes ranging from several nanometers up to 180 nm. Efficient nonradiative energy transfer from the TiO2 host to Eu3+ ions, which was seldom reported in the wet-chemically derived nanoparticles or thin films of the current system, was confirmed by combined studies of excitation, UV-vis (ultraviolet-visible), and PL (photoluminescence) spectroscopy. As a consequence of this, bright red emissions were observed from the plasma-generated nanopowders either by exciting the TiO2 host with UV light shorter than 405 nm or by directly exciting Eu3+ at a wavelength beyond the absorption edge (405 nm) of TiO2.     

Preparation, characterization and photoluminescence properties of BaB2O4: Eu3+ red phosphor

A new red emitting BaB2O4: Eu3+ phosphor was synthesized by solid-state reaction method. X-ray powder diffraction (XRD) analysis confirmed the monoclinic formation of BaB2O4. Field-emission scanning electron-microscopy (FE-SEM) observation indicated that the microstructure of the phosphor consisted of irregular grains with heavy agglomerate phenomena. Upon excitation with 394 nm light, the BaB2O4: Eu3+ phosphor shows bright red emissions with the highest photoluminescence (PL) intensity at 611 nm due to 5D0→7F2 transitions of Eu3+ ions. The CIE chromaticity coordinates are calculated from the emission spectrum to be x=0.64, y=0.35. The effects of the Eu3+ concentration on the PL were investigated. The results showed that the optimum concentration of Eu3+ in BaB2O4 host is 6 mol% and the dipole-dipole interaction plays the major role in the mechanism of concentration quenching of Eu3+ in BaB2O4: Eu3+ phosphor. The effect of charge compensation on the emission intensity was also studied. The charge compensations of Li+, Na+ and K+ anions all increased the luminescent intensity of BaB2O4: Eu3+. K+ anion gave the best improvement to enhance the intensity of the emission, indicating K+ is the optimal charge compensator. All properties show that this phosphor could serve as a potential candidate for application as a red phosphor for NUV chip LED.     

Synthesis and Photoluminescence Properties of Uniform Y2O3:Eu3+ Hollow Spheres with Tunable Shell Thickness

Y2O3:Eu3+ hollow spheres were successfully prepared with melamine formaldehyde(MF) spheres as template. The MF spheres played a significant role in directing the formation of the hollow shells which are composed of numerous primary nanoparticles. Furthermore, the shell thickness of these hollow spheres could be readily tailored by adjusting the dosage of MF template. Based on the photoluminescence(PL) investigation, the red emission intensities(613 nm) of these Y2O3:Eu3+ hollow spheres are greatly influenced by their shell thickness and it was found that hollow spheres with thin shell thickness and intact hollow structures permit a better PL performance.     

SrMgB6O11:Eu3+纳米材料的水热法制备及发光性能研究

采用水热法制备了Eu3+掺杂SrMgB6O11纳米发光材料.利用X射线粉末衍射仪(XRD)、场发射扫描电子显微镜(FESEM)和荧光光谱对SrMgB6O11:Eu3+样品进行表征.结果表明:采用水热法可以成功地合成粒度均匀、结晶完好的SrMgB6O11:Eu3+纳米发光粉.深入研究了反应温度和pH值对SrMgB6O11:Eu3+纳米材料的晶体结构及形貌的影响.结果表明,在120℃时形成了尖锐且强度最强的衍射峰,同时FESEM也表明此时所得材料为纳米棒组成的规则扇形形貌,此后随着温度的升高,XRD图中衍射峰的位置和强度发生变化,说明荧光粉的晶体结构发生变化,FESEM也表明该荧光粉已变为球形颗粒.归属了发射光谱和激发光谱中各激发峰所对应的能级跃迁.荧光光谱也显示:反应温度和pH值影响着Eu3+在晶格中的对称性,且反应温度为120℃及pH值为9时,Eu3+在晶格中的对称性较好.另外,还初步探讨了纳米粒子的生长机制.     

Ab initio theoretical study of luminescence properties of Pr3+-doped Lu2O3

Ab initio embedded cluster calculations have been performed on $\hbox{Pr}^{3+}$ -doped $\hbox{Lu}_2\hbox{O}_3$ , in order to investigate the mechanism responsible for the highly efficient $^3P_0\rightarrow^1D_2$ non-radiative relaxation experimentally observed. $(\hbox{PrO}_6)^{9-}$ embedded clusters representing the C ₂ and S ₆ substitutional sites of Pr³⁺:Lu₂O₃ have been studied using wave function-based methods. It is found that an outward relaxation of the first coordination sphere around the impurity takes place upon doping. At the relaxed geometry of the lowest spin triplet 4f5d state, all the 4f5d states lie much higher in energy than all 4f ² states (except the ¹S multiplet). This result is in opposition to the interpretation of intersystem crossing through a low-lying 4f5d excited state of Pr³⁺ as the mechanism for the fast non-radiative ³ P ₀????¹ D ₂ relaxation proposed in the literature. Absorption to the lowest spin triplet 4f5d state is calculated to be around 4,800?cm^?1 higher for the C ₂ site than for the S ₆ site, supporting the assignment of bands in the excitation spectrum previously reported.     

Eu3+/Tb3+-doped La2O2CO3/La2O3 nano/microcrystals with multiform morphologies: facile synthesis, growth mechanism, and luminescence properties

LaCO(3)OH nano/microcrystals with a variety of morphologies/sizes including nanoflakes, microflowers, nano/microrhombuses, two-double microhexagrams sandwichlike microspindles, and peach-nucleus-shaped microcrystals have been synthesized via a facile homogeneous precipitation route under mild conditions. A series of controlled experiments indicate that the pH values in the initial reaction systems, carbon sources, and simple ions (NH(4)(+) and Na(+)) were responsible for the shape determination of the LaCO(3)OH products. A possible formation mechanism for these products with diverse architectures has been presented. After annealing at suitable temperatures, LaCO(3)OH was easily converted to La(2)O(2)CO(3) and La(2)O(3) with the initial morphologies. A systematic study on the photoluminescence and cathodoluminescence properties of Eu(3+)- or Tb(3+)-doped La(2)O(2)CO(3)/La(2)O(3) samples has been performed in detail. The excitation and site-selective emission spectra were recorded to investigate the microstructure, site symmetry, and difference in the (5)D(0) → (7)F(2) transition of Eu(3+) ions in La(2)O(2)CO(3) and La(2)O(3) host lattices. In addition, the dependence of the luminescent intensity on the morphology for the as-prepared La(2)O(2)CO(3)/La(2)O(3):Ln(3+) (Ln = Eu, Tb) samples has been investigated. The ability of generating diverse morphologies and multiemitting colors for different rare-earth activator ion (Ln = Eu, Tb) doped La(2)O(2)CO(3)/La(2)O(3) nano/microstructures provides a great opportunity for the systematic evaluation of morphology-dependent luminescence properties, as well as the full exploration of their application in many types of color display fields.     

Photoluminescence properties of rare earths (Eu3+, Tb3+, Dy3+ and Tm3+) activated NaInW2O8 wolframite host lattice

The photoluminescence (PL) studies on NaIn_1?xRE_xW₂O₈, with RE=Eu³⁺, Tb³⁺, Dy³⁺ and Tm³⁺ phases have shown that the relative contribution of the host lattice and of the intra-f–f emission of the activators to the PL varies with the nature of the rare earth cation. In the case of Dy³⁺ and Tm³⁺ activators, with yellow and blue emission, respectively, the energy transfer from host to the activator plays a major role. In contrast for Eu³⁺, with intense red emission, the host absorption is less pronounced and the intra-f–f transitions of the Eu³⁺ ions play a major role, whereas for Tb³⁺ intra-f–f transitions are only observed, giving rise to green emission.     

Eu2+和Pb2+离子在Sr4Si3O8Cl4中发光的研究

本文研究了Sr₄Si₃O₈Cl₄基质的物理化学性质和以Eu^<2+、Ph²⁺离子为激活剂的荧光体的发射光谱、激发光谱、反射光谱及激活剂浓度对发光性能的影响。     

Novel dumbbell-like LaVO4:Eu3+ nanocrystals and effect of Ba2+ codoping on luminescence properties of LaVO4:Eu3+ nanocrystals

Journal of Sol-Gel Science and Technology - LaVO4:Eu3+ nanocrystals with different morphologies were synthesized via a simple hydrothermal method in a wide pH range. The as-synthesized samples were...