Luminescence of Mn ions in Tb3Al5O12 garnet

The paper is dedicated to investigation of the Mn²⁺ luminescence in Tb₃Al₅O₁₂ (TbAG) garnet, as well as the processes of excitation energy transfer between host cations (Tb³⁺ ions) and activators (Mn²⁺ and Mn²⁺-Ce³⁺ pair ions) in single crystalline films of TbAG:Mn and TbAG:Mn,Ce garnets which can be considered as promising luminescent materials for conversion of LED's radiation. Due to the effective energy transfer between TbAG host and activator, Mn²⁺ ions in TbAG possess the bright orange luminescence in the bands peaked at 595 nm with a lifetime of 0.64 ms which are caused by the ⁴T₁→⁶A₁ radiative transitions. The simultaneous process of energy transfer is realized in TbAG:Mn,Ce: (i) from Tb³⁺ to Mn²⁺ ions; (ii) from Tb³⁺ cations to Ce³⁺ ions and then partly to Mn²⁺ ions through Tb³⁺ ion sublattice and Ce-Mn dipole-dipole interaction.     

Energy transfer and excitation wavelength dependent long-lasting phosphorescence in Pr activated Y3Al5O12

Long-lasting phosphorescence (LLP) was observed in Pr³⁺-doped Y₃Al₅O₁₂ (YAG:Pr) after it was excited by 240 or 290 nm light. The photoluminescence (PL) and LLP properties were studied. It is interesting that the PL and LLP spectra were different. In the PL emission spectra both the emissions of d-f and f-f transitions of Pr³⁺ ions were observed. However, in the LLP spectra of YAG:Pr the emissions of d-f transition were absent. It is deduced that the differences were due to the energy transfer process between traps and emission centers. On the other hand, significant differences were observed between the two LLP spectra after the sample was excited by 240 and 290 nm lights, respectively. The thermoluminescence (TL) properties were also studied. It is suggested that these studies will be significant for understanding the mechanism of LLP phenomenon.     

Energy transfer in Y3Al5O12:Ce, Pr and CaMoO4:Sm, Eu phosphors

Non-radiative energy transfers (ET) from Ce³⁺ to Pr³⁺ in Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and from Sm³⁺ to Eu³⁺ in CaMoO₄:Sm³⁺, Eu³⁺ are studied based on photoluminescence spectroscopy and fluorescence decay patterns. The result indicates an electric dipole-dipole interaction that governs ET in the LED phosphors. For Ce³⁺ concentration of 0.01 in YAG:Ce³⁺, Pr³⁺, the rate constant and critical distance are evaluated to be 4.5×10⁻³⁶ cm⁶ s⁻¹ and 0.81 nm, respectively. An increase in the red emission line of Pr³⁺ relative to the yellow emission band of Ce³⁺, on increasing Ce³⁺ concentration is observed. This behavior is attributed to the increase of spectral overlap integrals between Ce³⁺ emission and Pr³⁺ excitation due to the fact that the yellow band shifts to the red spectral side with increasing Ce³⁺ concentration. In CaMoO₄:Sm³⁺, Eu³⁺, Sm³⁺-Eu³⁺ transfer occurs from ⁴G_5/2 of Sm³⁺ to ⁵D₀ of Eu³⁺. The rate constant of 8.5×10⁻⁴⁰ cm⁶ s⁻¹ and the critical transfer distance of 0.89 nm are evaluated.     

Luminescence and Tb-Ce-Eu ion energy transfer in single-crystalline films of Tb3Al5O12:Ce,Eu garnet

The paper is devoted to investigation of the processes of excitation energy transfer between the host cations (Tb³⁺ ions) and the activators (Ce³⁺ and Eu³⁺ ions) in single-crystalline films of Tb₃Al₅O₁₂:Ce,Eu (TbAG:Ce,Eu) garnet which is considered as a promising luminescent material for the conversion of LED's radiation. The cascade process of excitation energy transfer is shown to be realized in TbAG:Ce,Eu: (i) from Tb³⁺ ions to Ce³⁺ and Eu³⁺ ions; (ii) from Ce³⁺ ions to Eu³⁺ ions by means of dipole-dipole interaction and through Tb³⁺ ion sublattice.     

Orange emission enhancement by energy transfer in Sr3Al2O5Cl2:Ce, Eu phosphor for solid-state lighting

Orange-emissive Ce³⁺/Eu²⁺ co-doped Sr₃Al₂O₅Cl₂ phosphors were synthesized by a solid-state reaction. The large overlap between the emission spectrum of blue Sr₃Al₂O₅Cl₂:Ce³⁺ and the excitation spectrum of orange Sr₃Al₂O₅Cl₂:Eu²⁺, and the shortening trend in lifetime of Ce³⁺ donors with increasing Eu²⁺ concentration in Sr₃Al₂O₅Cl₂:Ce³⁺, Eu²⁺ provide the strong evidence of energy transfer from Ce³⁺ to Eu²⁺ ions. It supports that the orange emission intensity of the optimal co-doped phosphor is 1.5 times stronger than that of single Eu²⁺-doped one. The Sr₃Al₂O₅Cl₂:Ce³⁺, Eu²⁺ phosphor is a promising orange-emitting phosphor for warm-white-light-emitting diode because of its effective excitation in the near ultraviolet range.     

钇复合氧化物颜料的制备与表征

通过尿素分解法,把三价铬离子掺入到钇铝石榴石Y₃Al₅O₁₂中,采用共沉淀法制备出绿色颜料。扫描电镜测试表明产物颗粒直径在200 nm左右,用XRD测试复合氧化物的结晶相行为,确定主相是钇铝石榴石相,用紫外可见漫反射光谱测试掺杂离子的配位状态和电子跃迁行为,用色度学测试氧化物颜色特征。将复合氧化物颜料颗粒与高分子聚丙烯共混,熔体纺丝,并通过北京同步辐射X射线CT对制得的纤维加以测试,结果表明复合氧化物颜料在高分子基质中得到良好的分散。这种颜料性能稳定,对环境友好,为实现无水印染技术奠定基础,减少纺织印染工业中所排放的污水。     

Energy transfer and luminescent properties of Ce, Cr co-doped Y3Al5O12

The phosphors in the system Y_3−xAl_5-yO₁₂:xCe³⁺,yCr³⁺ were synthesized by solid-state reactions and their photoluminescence properties were investigated. These phosphors have absorption in the visible light region and give luminescence in the far-red region (∼688 nm), which are suitable for the application in the device of luminescent solar concentrator (LSC). In these phosphors, Ce³⁺ located at Y³⁺ site can effectively transfer its absorbed energy to Cr³⁺ at Al³⁺ site.     

Curie temperatures of Y3Fe5O12/Gd3Fe5O12 superlattices

The magneto-optical Kerr effects (MOKE) of epitaxial Y₃Fe₅O₁₂/Gd₃Ga₅O₁₂ (YIG/GGG) garnet superlattices grown on (1 1 1)GGG previously by pulsed laser deposition (PLD) were measured. A series of superlattices were investigated with the thickness of the ferrimagnetic YIG layer varied from six unit cells to only one unit cell while keeping the Curie paramagnetic GGG fixed at one unit cell. It was demonstrated that the ellipsometric technique employing photoelastic modulators (PEM) is sensitive enough to measure the MOKE signals of these ultrathin oxide samples. The Curie temperatures, determined by MOKE, are fit with a power law, yielding a shift exponent λ = 3.1 ± 1.2.     

Eu/Tb ions co-doped white light luminescence Y2O3 phosphors

Y₂O₃:Eu³⁺, Tb³⁺ phosphors with white emission are prepared with different doping concentration of Eu³⁺ and Tb³⁺ ions and synthesizing temperatures from 750 to 950 °C by the co-precipitation method. The resulted phosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. The results of XRD indicate that the crystallinity of the synthesized samples increases with enhancing the firing temperature. The photoluminescence spectra indicate the Eu³⁺ and Tb³⁺ co-doped Y₂O₃ phosphors show five main emission peaks: three at 590, 611 and 629 nm originate from Eu³⁺ and two at 481 and 541 nm originate from Tb³⁺, under excitation of 250-320 nm irradition. The white light luminescence color could be changed by varying the excitation wavelength. Different concentrations of Eu³⁺ and Tb³⁺ ions were induced into the Y₂O₃ lattice and the energy transfer from Tb³⁺→Eu³⁺ ions in these phosphors was found. The Commission International de l’Eclairage (CIE) chromaticity shows that the Y₂O₃:Eu³⁺, Tb³⁺ phosphors can obtain an intense white emission.     

Luminescence properties of Y3Al5O12:Ce nanoceramics

Comparative analysis of the luminescent properties of Y₃Al₅O₁₂:Ce (YAG:Ce) transparent optical ceramics (OС) with those of single crystal (SC) and single crystalline film (SCF) analogues has been performed under excitation by pulsed synchrotron radiation in the fundamental absorption range of YAG host. It has been shown that the properties of YAG:Ce OC are closer to the properties of the SCF counterpart, where Y_Al antisite defects are completely absent, rather than to the properties of SC of this garnet with large concentration of Y_Al antisite defects. At the same time, the luminescence spectra of YAG:Ce OC show weak emission bands in the 200-470 nm range related to Y_Al antisite defects and charged oxygen vacancies (F⁺ and F centers). YAG:Ce ОС also possesses significantly larger contribution of slow components in the Ce³⁺ luminescence decay under high-energy excitation in comparison with SC and SCF of this garnet due to the involvement of antisite defects, charged oxygen vacancies as well as boundaries of grains in the energy transfer processes from the host to the Ce³⁺ ions.     

Comparison of Lu3Al5O12:Pr and Bi4Ge3O12 scintillators for gamma-ray detection

The scintillation properties of Lu₃Al₅O₁₂:Pr³⁺ (LuAG:Pr) single crystal grown by the Czochralski method with praseodymium concentration of 0.19 mol% were investigated. For a comparison, a good quality Bi₄Ge₃O₁₂ (BGO) single crystal grown by Bridgman method was also studied. The light yield and energy resolution were measured using photomultiplier tube (XP5200B PMT) readout. Moderate light yield of 15,900 photons per MeV was measured for the LuAG:Pr(0.19%) crystal. For 662 keV gamma rays (¹³⁷Cs source), an energy resolution of 6.5% obtained for LuAG:Pr(0.19%) is much better than that of 9.0% obtained for BGO. The light yield non-proportionality and energy resolution versus energy of gamma rays were measured and the intrinsic resolution of the crystals was determined after correcting the measured energy resolution for PMT statistics. The LuAG:Pr(0.19%) showed a good proportionality of the light yield within 5% over the energy range from 1274.5 keV down to 32 keV, which is much better than that of 14% for BGO. The photofraction was determined at 320 and 662 keV for both crystals and compared with the ratio of the cross-sections for the photoelectric effect to the total one calculated using WinXCOM program.     

Enhanced luminescence of Dy in Y3Al5O12 by Bi co-doping

In the present paper, phosphors with the composition Y_3−x−yAl₅O₁₂:Bi³⁺_x, Dy³⁺_y were synthesized with solid state reactions. The luminescence properties of Bi³⁺ and Dy³⁺ in Y₃Al₅O₁₂(YAG) and the energy transfer from Bi³⁺ to Dy³⁺ were investigated in detail. Bi³⁺ in YAG emits one broad band peaking at 304 nm which can be ascribed to the transition from excited states ³P_{0, 1} to ground state ¹S₀. Dy³⁺ in YAG emits two groups of peaks around 484 and 583 nm, respectively, which can be ascribed to the transitions from excited state ⁴F_9/2 to ground states ⁶H_15/2 and ⁶H_13/2. The co-doping of Bi³⁺ enhances the luminescent intensity of Dy³⁺ by ∼7 times because Bi³⁺ can transfer the absorbed energy to Dy³⁺ efficiently. The mechanism of energy transfer was also discussed.     

Probing of surface Eu ions present in ZnO:Eu nanoparticles by covering ZnO:Eu core with Y2O3 shell: Luminescence study

Eu³⁺ doped ZnO nanoparticles are known to have significance extent of surface Eu³⁺ ions due to a large difference in ionic radii. Effect of such Eu³⁺ ions on the luminescence properties of ZnO:Eu nanoparticles has been understood from the luminescence studies of ZnO:Eu nanoparticles covered with Y₂O₃ shell. Based on the asymmetric ratio of luminescence and extent of energy transfer, it is established that when ZnO:Eu nanoparticles are covered with Y₂O₃ shell, a part of Eu³⁺ ions present with ZnO:Eu core migrate to Y₂O₃ shell and occupy Y³⁺ lattice positions.     

Improving monochromaticity of upconversion luminescence by codoping Eu ions in Y2O3:Ho, Yb nanocrystals

Upconversion (UC) luminescence of Y₂O₃:Ho³⁺, Yb³⁺ nanocrystals codoped with different concentrations of Eu³⁺ ions were investigated to improve the monochromaticity of the UC emission. The results show that the monochromaticity, quantified by a parameter SR, increases as the concentration of Eu³⁺ ions becomes higher, which is due to the energy transfer between ⁵I₇ (Ho³⁺) and ⁷F₆ (Eu³⁺). The energy transfer accelerates the relaxation of Ho³⁺ ions from the ⁵I₇ to ⁵I₈ state and then quenches the red emission. The influence of the Eu³⁺ concentration on the pump power dependence of the red UC fluorescence in Y₂O₃:Ho³⁺, Yb³⁺, Eu³⁺ nanocrystals is verified using the steady-state rate equation theory.     

Weak field magnetic transition in Tb3Fe5O12

A jump like magnetic transition is observed at relatively weak field in Tb₃Fe₅O₁₂ when the magnetic field is applied along the hard axis and no transition is observed with the field applied along the easy axis. We believe that this evolution is related to the ”Umbrella” type magnetic structure known to exist in Tb₃Fe₅O₁₂ at low temperatures.     

Luminescence enhancement by energy transfer from Ce ions in Ba1.6Ca0.4P2O7:Ce:Tb phosphor

The optical properties of Ba_1.6Ca_0.4P₂O₇ doped with Ce³⁺ and Tb³⁺ are investigated. Under excitation at 280 nm the emission spectrum of Ba_1.6Ca_0.4P₂O₇:Ce³⁺ consists of a peak at 370 nm and a shoulder at the longer wavelength side. The emission spectra of Ba_1.6Ca_0.4P₂O₇:Tb³⁺ shows the well-known emission lines due to ⁵D₄-⁷F_J transitions of Tb³⁺. The green emissions of Tb³⁺ ions are enhanced upon UV excitation through energy transfer from Ce³⁺ to Tb³⁺ ions. The efficiency of such an energy transfer is estimated based on spectroscopic data. The dependence of photoluminescence (PL) intensities of Ce³⁺ and Tb³⁺ emissions on Ce³⁺ or Tb³⁺ concentrations in the systems (Ba_1.6Ca_0.4P₂O₇:0.04Ce³⁺,xTb³⁺ and Ba_1.6Ca_0.4P₂O₇:xCe³⁺,0.04Tb³⁺) and the temperature dependence of PL emission spectra of Ba_1.6Ca_0.4P₂O₇:0.06Ce³⁺,0.04Tb³⁺ is also investigated.     

Optical spectroscopy of Ca3Sc2Si3O12, Ca3Y2Si3O12 and Ca3Lu2Si3O12 doped with Pr

The silicates Ca₃Sc₂Si₃O₁₂, Ca₃Y₂Si₃O₁₂ and Ca₃Lu₂Si₃O₁₂, both undoped and doped with Pr³⁺ ions, have been synthesized by solid-state reaction at high temperature. The luminescence spectroscopy and the excited state dynamics of the materials have been studied upon VUV and X-ray excitation using synchrotron radiation. All doped samples have shown efficient 5d-4f emission upon direct VUV excitation of 5d levels, but only Ca₃Sc₂Si₃O₁₂:Pr³⁺ shows luminescence upon interband VUV or X-ray excitation. The VUV excited emission spectra of Ca₃Y₂Si₃O₁₂:Pr³⁺ and Ca₃Lu₂Si₃O₁₂:Pr³⁺ show features attributed to emission from two distinct sites accommodating the Pr³⁺ dopant. The decay kinetics of the Pr³⁺ 5d-4f emission in Ca₃Sc₂Si₃O₁₂:Pr³⁺ upon VUV excitation across the band gap are characterized by decay times in the range 25-28 ns with no significant rise after the excitation pulse. They appear to be faster upon X-ray irradiation than for VUV excitation. Weak afterglow components are attributed to defect luminescence.     

Solution-combustion synthesis of Tb-doped Y3Al5O12 nanoparticles

Nano-sized YAG:Tb powder phosphors were prepared by a solution-combustion method, using the general inorganic salts as starting materials. The X-ray diffraction (XRD) measurements showed that the precursor can be well-crystallized at 900 °C. As-prepared particles have sizes mostly in the range between 30 and 100 nm as obtained by scanning electron microscope (SEM) and transition electron microscope (TEM). Selected area electron diffraction (SAED) patterns proved that the larger particles are monocrystalline. The effects of annealing temperature and Tb-doping concentration on the luminescence intensity were studied.     

Luminescence properties of Cr:Y3Al5O12 nanocrystals

The Cr³⁺-doped Y₃Al₅O₁₂ (YAG) nanocrystalline powders were prepared by the Pechini method. The structural and phase evolution studies were performed using X-ray powder diffraction (XRD) method. The TEM images were taken in order to characterize the grain size and morphology of the Cr:YAG nanocrystals. Their excitation and luminescence spectra were investigated. It was found that luminescence properties of the Cr:YAG nanocrystals were strongly affected by size of the particles. With increasing the grain size the electron-phonon coupling decreases whereas the crystal-field strength increases.     

Oxide coatings on Y3Al5O12:Tb particles

A coating method with precipitating process was developed to reduce the particle size and to improve the particle dispersion of Y₃Al₅O₁₂:Tb³⁺ phosphor prepared by sol-gel method. The particle morphology was observed by using SEM and TEM; and the particle size and its dispersion was measured by using laser scattering technique. Several coating materials were tested. Among them, Al₂(SiO₃)₃ coating not only reduced the particle size from several micrometers to ∼1 μm and improved the particle dispersion, but also well kept luminescent intensities and improved the duration of the phosphor under the bombardment of cathode ray. The mechanism of the particle size reduction was proposed.