Effective lattice stabilization of gadolinium aluminate garnet (GdAG) via Lu3+ doping and development of highly efficient (Gd,Lu)AG:Eu3+ red phosphors

Abstract

The metastable garnet lattice of Gd₃Al₅O₁₂ is stabilized by doping with smaller Lu³⁺, which then allows an effective incorporation of larger Eu³⁺ activators. The [(Gd_1?xLu_x)_1?yEu_y]₃Al₅O₁₂ (x = 0.1–0.5, y = 0.01–0.09) garnet solid solutions, calcined from their precursors synthesized via carbonate coprecipitation, exhibit strong luminescence at 591 nm (the ⁵D₀ → ⁷F₁ magnetic dipole transition of Eu³⁺) upon UV excitation into the charge transfer band (CTB) at ～239 nm, with CIE chromaticity coordinates of x = 0.620 and y = 0.380 (orange-red). The quenching concentration of Eu³⁺ was estimated at ～5 at.% (y = 0.05), and the quenching was attributed to exchange interactions. Partial replacement of Gd³⁺ with Lu³⁺ up to 50 at.% (x = 0.5) while keeping Eu³⁺ at the optimal content of 5 at.% does not significantly alter the peak positions of the CTB and ⁵D₀ → ⁷F₁ emission bands but slightly weakens both bands owing to the higher electronegativity of Lu³⁺. The effects of processing temperature (1000–1500 °C) and Lu/Eu contents on the intensity, quantum efficiency, lifetime and asymmetry factor of luminescence were thoroughly investigated. The [(Gd_0.7Lu_0.3)_0.95Eu_0.05]₃Al₅O₁₂ phosphor processed at 1500 °C exhibits a high internal quantum efficiency of ～83.2% under 239 nm excitation, which, in combination with the high theoretical density, favors its use as a new type of photoluminescent and scintillation material.     

Recent progress in advanced optical materials based on gadolinium aluminate garnet (Gd3Al5O12)

This review article summarizes the recent achievements in stabilization of the metastable lattice of gadolinium aluminate garnet (Gd₃Al₅O₁₂, GAG) and the related developments of advanced optical materials, including down-conversion phosphors, up-conversion phosphors, transparent ceramics, and single crystals. Whenever possible, the materials are compared with their better known YAG and LuAG counterparts to demonstrate the merits of the GAG host. It is shown that novel emission features and significantly improved luminescence can be attained for a number of phosphor systems with the more covalent GAG lattice and the efficient energy transfer from Gd³⁺ to the activator. Ce³⁺ doped GAG-based single crystals and transparent ceramics are also shown to simultaneously possess the advantages of high theoretical density, fast scintillation decay, and high light yields, and hold great potential as scintillators for a wide range of applications. The unresolved issues are also pointed out.     

Recent progress in advanced optical materials based on gadolinium aluminate garnet (Gd3Al5O12)

Abstract

This review article summarizes the recent achievements in stabilization of the metastable lattice of gadolinium aluminate garnet (Gd₃Al₅O₁₂, GAG) and the related developments of advanced optical materials, including down-conversion phosphors, up-conversion phosphors, transparent ceramics, and single crystals. Whenever possible, the materials are compared with their better known YAG and LuAG counterparts to demonstrate the merits of the GAG host. It is shown that novel emission features and significantly improved luminescence can be attained for a number of phosphor systems with the more covalent GAG lattice and the efficient energy transfer from Gd³⁺ to the activator. Ce³⁺ doped GAG-based single crystals and transparent ceramics are also shown to simultaneously possess the advantages of high theoretical density, fast scintillation decay, and high light yields, and hold great potential as scintillators for a wide range of applications. The unresolved issues are also pointed out.     

Eu3+掺杂Lu3Al5O12球形荧光颗粒的合成及性能研究

以尿素为沉淀剂, 通过均匀沉淀技术制备前驱体颗粒, 经后续煅烧获得分散性能良好的球形(Lu_0.95Eu_0.05)₃Al₅O₁₂((Lu_0.95Eu_0.05)AG)荧光颗粒。通过调整尿素浓度实现了球形荧光颗粒尺寸的可控合成。在此基础上, 采用 FT-IR、TG/DTA、XRD、FE-SEM、TEM和PLE/PL对材料的合成、物相形成及荧光性能等进行一系列表征。分析结果表明: 前驱体经较低的温度1100℃煅烧即可获得(Lu_0.95Eu_0.05)AG球形荧光颗粒, 且该荧光颗粒具有高的理论密度, 适于闪烁体材料的应用。在235 nm电荷迁移带(CTB)的激发下, (Lu_0.95Eu_0.05)AG石榴石于592 nm (Eu³⁺的⁵D₀→⁷F₁磁偶极子跃迁)处呈现优异的橙红光发射, 其色坐标为(0.63, 0.37)。该荧光颗粒的发光强度随颗粒尺寸的增大而增强, 荧光寿命随颗粒尺寸的增大而缩短。球形(Lu_0.95Eu_0.05)AG石榴石颗粒有望成为一类新型荧光材料, 广泛应用于照明及显示领域。     

Controlled processing of (Gd,Ln)2O3:Eu (Ln = Y,Lu) red phosphor particles and compositional effects on photoluminescence

Synthesis of (Gd_0.95−xLn_xEu_0.05)₂O₃ (Ln = Y and Lu, x = 0–0.95) powders via ammonium hydrogen carbonate (AHC) precipitation has been systematically studied. The best synthesis parameters are found to be an AHC/total cation molar ratio of 4.5 and an ageing time of 3 h. The effects of Y³⁺ and Lu³⁺ substitution for Gd³⁺, on the nucleation kinetics of the precursors and structural features and optical properties of the oxides, have been investigated. The results show that (i) different nucleation kinetics exist in the Gd–Y–Eu and Gd–Lu–Eu ternary systems, which lead to various morphologies and particle sizes of the precipitated precursors. The (Gd,Y)₂O₃:Eu precursors display spherical particle morphologies and the particle sizes increase along with more Y³⁺ addition. The (Gd,Lu)₂O₃:Eu precursors, on the other hand, are hollow spheres and the particle sizes increase with increasing Lu³⁺ incorporation, (ii) the resultant oxide powders are ultrafine, narrow in size distribution, well dispersed and rounded in particle shape, (iii) lattice parameters of the two kinds of oxide solid solutions linearly decrease at a higher Y³⁺ or Lu³⁺ content. Their theoretical densities linearly decrease with increasing Y³⁺ incorporation, but increase along with more Lu³⁺ addition and (iv) the two kinds of phosphors exhibit typical red emissions at ∼613 nm and their charge-transfer bands blue shift at a higher Y³⁺ or Lu³⁺ content. Photoluminescence/photoluminescence excitation intensities and external quantum efficiency are found to decrease with increasing value of x, and the fluorescence lifetime mainly depends on the specific surface areas of the powders.     

Shaped single crystal growth and scintillating application of Yb:(Gd,Lu)3(Ga,Al)5O12 solid solutions

Shaped single crystals of (Yb_0.05Lu_xGd_0.95−x)Ga₅O₁₂ (0.0x0.9) and Yb_0.15Gd_0.15Lu_2.7(Al_xGa_1−x)O₁₂ (0.0x1.0) were grown by the modified micro-pulling-down method. Continuous solid solutions with garnet structure and a linear compositional dependency of crystal lattice parameter in the system Yb:(Gd,Lu)₃(Ga,Al)₅O₁₂ are formed. Measured optical absorption spectra of the samples show 4f–4f transitions related to Gd³⁺ ion at 275 and 310 nm, and also an onset of charge transfer transitions from oxygen ligands to Gd³⁺ or Yb³⁺ cations below 240 nm. A complete absence of Yb³⁺ charge transfer luminescence under X-ray excitation in any of the investigated samples was explained by the overlapping of charge transfer absorption of Yb³⁺ by that of Gd³⁺ ions. For specific composition of Lu_1.5Gd_1.5Ga₅O₁₂ an intense defect––host lattice-related emission, which achieve of about 40% integrated intensity compared with Bi₄Ge₃O₁₂, was found.     

(Y3-x-yREx)Al5O12:Cey(RE=Tb,Gd)荧光粉晶体结构与光致发光

采用化学共沉淀法合成具有Tb、Gd稀土掺杂的Y3Al5O12:Ce3 荧光粉,通过XRD和荧光光谱研究其晶体结构和光致发光.结果表明,(Y2.95-xTbx)Al5O12:Ce3 和(Y2.95-xGdx)Al5O12:Ce3 系列荧光粉具有与Y3Al5O12:Ce3 相同的石榴石晶体结构,但晶胞参数随Tb、Gd取代Y而略有增加;随Tb、Gd掺杂量增加,荧光粉发射波长逐渐红移,当x=2.95时,发射波长λmax分别从532nm红移至551和542nm;根据晶体场理论解释了荧光粉发射波长红移现象.这种发射波长红移的荧光粉能够显著地增强蓝光LED芯片与荧光粉组合形成的白光中红光成分,进而改善白光LED光源质量.     

微波均相沉淀法制备Ce:(Y,Gd)_3Al_5O_(12)荧光粉

以Y2O3,Gd2O3,Ce(NO3)3·6H2O,Al(NO3)3·9H2O为原料,采用微波均相沉淀法制备了Ce:(Y,Gd)3Al5O12前驱体,经1100℃煅烧得到粒径在100nm左右的近球形粉体。测试结果表明:该粉具有良好的荧光性能,呈现宽带激发和宽带发射,激发主峰在456nm,半高宽约为60nm,在460nm入射光的激发下,发射峰在566nm左右,半高宽约为125nm。由于Gd3+的掺入改变了基体的晶场结构,致使发射光谱发生了红移。     

Sol-gel synthesis of yellow-emitting La4Ca(SiO4)3O:Ce phosphors for white-light emitting diodes

Ce³⁺ doped La₄Ca(SiO₄)₃O phosphors with silicate oxyapatite structure were synthesized by the sol-gel process. The X-ray diffraction (XRD) patterns showed that a pure phase was formed when sintering temperature was higher than 1300°C. The optical properties of La₄Ca(SiO₄)₃O:Ce³⁺ phosphors with varying sintering temperature and concentration were investigated by examining their excitation and emission spectroscopy. The phosphors exhibited a broad emission band centered at 550nm which could be attributed to the 5d-4f transition of Ce³⁺ and a stronger excitation peak around 467nm as well as several shoulder bands, nicely matching with the widely applied blue LED chips. Higher emission intensity was observed when firing temperature above 1300°C, due to increasing crystallinity of the powders. When Ce³⁺ concentration was equal to 5 at%, the sample exhibited the optimum excitation and emission efficiency. The results indicate that La₄Ca(SiO₄)₃O:Ce³⁺ is a promising candidate in the application of blue chip excited white light emitting diodes (LEDs).     

Luminescence properties and gamma-ray response of the Ce and Ca co-doped (Gd,Y)F3 single crystals

The Ca0.5% and Ce1%, 3%, 7%, 10% co-doped Gd_0.5Y_0.5F₃ single crystals were grown by the μ-PD method. In the Ca0.5% and Ce3% co-doped sample, Ce³⁺-perturbed luminescence at 380 nm was observed with 32.4 ns photoluminescence decay time. The energy transfer in the sequence of the regular Ce³⁺→ (Gd³⁺)_n→ the perturbed Ce³⁺ sites was evidenced through observation of decay time shortening of the regular Ce³⁺ and Gd³⁺ centers and the change between the Gd³⁺ and Ce³⁺-perturbed emission intensity. The gamma-ray excited scintillation response of the Ca0.5%, Ce7% co-doped Gd_0.5Y_0.5F₃ sample was investigated with the help of the pulse height spectra and the light yield, energy resolution and non-proportionality was evaluated in the interval of energies of 59.4-1274 keV.     

Novel blue-emitting phosphor NaMg4(PO4)3:Eu, Ce with energy transfer

A blue-emitting phosphor of NaMg₄(PO₄)₃:Eu²⁺, Ce³⁺ was prepared by a combustion-assisted synthesis method. The phase formation was confirmed by X-ray powder diffraction measurement. Photoluminescence excitation spectrum measurements show that the phosphor can be excited by near UV light from 230 to 400 nm and presents a dominant luminescence band centered at 424 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions at room temperature. Effective energy transfer occurs in Ce³⁺/Eu²⁺ co-doped NaMg₄(PO₄)₃ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺-Eu²⁺ co-doped NaMg₄(PO₄)₃ powders can possibly be applied as blue phosphors in the fields of lighting and display.     

LuxY1-xAl 3:Ce晶体中伴生(Lu,Y3 Al5O12:Ce相成因研究

采用提拉法制备了LuxY1-xAlOa:Ce晶体样品,通过XRD物相分析和成分分析,并结合Lu2O3-Al2O3二元体系相图以及LuxY1-xAlO3:Ce 结构稳定性方面的分析与讨论,结果表明:随着熔体中Lu元素含量的增加,熔体分层加剧,析晶LuxY1-xAlO3:Ce相的熔体组成区间将向富Lu一侧偏移,这使得晶体上部易伴生(Lu,Y)3Al5O12:Ce相;而随着Lu元素含量的提高, LuxY1-xAlO3:Ce晶体的热稳定性降低,氧空位的存在则使晶体的热稳定性进一步降低,在接种过程中籽晶表面易发生相分解反应生成(Lu,Y)3Al5O12:Ce和(Lu,Y)4Al2O9:Ce,籽晶表面相分解产物(Lu,Y)3Al5O12:Ce提供了诱导析晶(Lu,Y)3Al5O12:Ce相所需的晶核,这使得晶体的外表面处易伴生(Lu,Y)3Al5O12:Ce相.调整配料组成使n((Lu,Y)2O3):n(A12O3)=1.17～100,加大熔体内部和固液界面处的温度梯度以改善熔体对流、抑制熔体分层以及籽晶表面处的相分解等有助于高Lu元素含量LuxY1-xAlO3:Ce晶体的获得.     

Synthesis and luminescent characteristic of Eu-doped (Gd,Lu)2O3 nanopowders

Eu³⁺ doped (Gd,Lu)₂O₃ nanopowders with particle sizes ranging from 20 to 70 nm were synthesized by the co-precipitant method using mixed precipitants, namely the mixture of ammonium hydroxide (NH₃⋅H₂O) and ammonium hydrogen carbonate (NH₄HCO₃). The precipitate precursor prepared by this method was believed to possess a basic carbonate composition and its thermal decomposition of the (Gd,Lu)₂O₃:Eu³⁺ powders were investigated by Thermogravimetric analysis and differential thermal analysis (TG-DTA). This preparation was followed by a calcination process at 800-1100 °C and corresponding phosphor structure were examined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Photoluminescence measurement of the (Gd,Lu)₂O₃:Eu³⁺ particles show typical red emission at the 612 nm corresponding to the ⁵D₀ → ⁷F₂ transition. We found that the optimal Eu³⁺ molar doping concentration, calcined temperature and reaction time were 7 mol%, 1000 °C, and 2 h, respectively, which is helpful to obtain the final transparent ceramics with excellent properties.     

溶胶-凝胶法合成Y3Al5O12:Ce3+,Tb3+稀土荧光粉的研究

采用溶胶-凝胶法在低温下合成了Y3Al5O12:0.08Ce^3 ,0.12Tb^3 稀土荧光粉。通过X射线衍射（XRD）分析及激发、发射光谱测试结果表明：合成的粉末为YAG晶体结构,粉体的最大激发峰为273nm,最大发射峰为545nm,色坐标为：x=0.331,y=0.558,在273nm的紫外光激发下发出明亮的绿光。     

Optical properties and gamma-ray response of Czochralski grown Pr:Lu3Al5O12 scintillating garnet crystals with different Pr content

Pr:LuAG single crystalline scintillators with different Pr³⁺ concentration, 0.1, 0.18, and 0.22 mol% were grown by the Czochralski method. The crystals were cut to dimensions of 2.2 × 2.2 × 15 mm³ and polished, simulating sensors for Positron Emission Tomography (PET). Their absorption coefficients were examined, and the absorption strength was found to be proportional to the Pr concentration. The α-ray induced emission spectra of the samples demonstrated two emission lines peaking at 310 and 370 nm. The emission intensities in the radio luminescence spectra were also proportional to the Pr content. The absolute light yields and intrinsic energy resolution under γ-ray irradiation were evaluated at +20, 0, and −20 °C using avalanche photodiode as a photodetector. Pr 0.22% doped crystal had strongest light output of 16 400 ph/MeV, and its intrinsic energy resolution was around few % at several hundred keV. When coupled with PMT, the decay time was around 25 ns, and it was almost independent on concentration.     

Synthesis of high efficient nanosized Y(V,P)O4:Eu red phosphors by a new technique

A new synthesis technique (liquid-phase precursor method) has been employed to synthesize nanosized Y(V,P)O₄:Eu³⁺ red phosphor particles of size 10-35 nm. X-ray diffraction analysis confirmed the synthesis of single phase Y(V,P)O₄:Eu³⁺ nanoparticles with tetragonal structure. The surface treatment with the KOH ionic solution at room temperature enhanced the grain growth (40-70 nm) of the nanoparticles. The possible grain growth mechanism is explained on the basis of formation of more OH⁻ groups in the solid solution after KOH introduction. The photoluminescence spectra obtained from the nanophosphors showed strong red luminescence due to ⁵D₀ → ⁷F_2,4 forced electric dipole transition. The luminescence intensity of the KOH-treated nanophosphors is comparable (about 70%) with the commercial sample.     

Growth,Optical Absorption,and Photoluminescence of Epitaxial (Pb,Gd)3(Al,Ga)5O12:Ce3+,Eu3+ Films

Inorganic Materials - (Pb,Gd)3(Al,Ga)5O12:Ce3+,Eu3+ films have been grown by liquid-phase epitaxy from a supercooled high-temperature solution based on the PbO–B2O3 system. We have measured...     

Preparation and characterization of Eu<Superscript>3+</Superscript> activated CaSiO<Subscript>3</Subscript>, (CaA)SiO<Subscript>3</Subscript> [A = Ba or Sr] phosphors

Eu³⁺ activated CaSiO₃, (Ca, Ba) SiO₃ and (Ca, Sr) SiO₃ have been prepared by sol-gel technique. Residual solvent and organic contents in the gel were removed by firing at 100°C for 3–4 h at 300 and 600°C for 2 h. Small exothermic shoulder around 850 to 875°C, as observed in DTA curve, corresponds to crystallization temperature of the doped calcium silicate. Influence of firing temperature on the luminescence of Eu³⁺ shows the maximum emission intensity in gel fired at 850°C. Photoluminescence emission peak is observed at 614 nm due to⁵D₀ →⁷F₂ transition of Eu³⁺ ion in (Ca, Ba) SiO₃ and (Ca, Sr) SiO₃ phosphors, when excited by 254 nm. The (Ca, Ba) SiO₃ material is proposed as an efficient red phosphor.     

Mg共掺杂Gd3(Al,Ga)5O12:Ce晶体快发光的作用机理

Gd₃(Al,Ga)₅O₁₂:Ce (GAGG:Ce)闪烁体综合性能优异, 应用前景广阔。为加快GAGG的发光衰减速度, 本研究通过提拉法生长了Mg共掺的Gd₃(Al,Ga)₅O₁₂:Ce单晶。测试结果显示, 随着Mg²⁺掺杂浓度增加, 晶体的闪烁衰减速度加快, 光输出降低。传统解释认为, Mg²⁺通过电荷补偿作用将部分Ce³⁺转换成Ce⁴⁺, 后者的发光速度更快。本研究尝试从缺陷的形成与抑制的角度来讨论Mg改善GAGG:Ce晶体闪烁性能的作用机理。由于Ce的离子半径比Gd大, Ce离子掺入将导致发光中心Ce_Gd附近的晶格发生畸变。畸变结果为近邻的八面体格位空间变大, 反位缺陷将更容易在这些变大的八面体格位形成。最终每个发光中心Ce_Gd被四个反位缺陷Gd_Al包裹, 后者捕获载流子, 延缓从基体到发光中心的能量传递, 导致发光速度变慢。由于Mg的离子半径介于Gd和Al之间, Mg_Al将更容易在上述畸变的八面体格位形成, 这会抑制反位缺陷Gd_Al在发光中心Ce_Gd附近形成(或富集), 最终降低(甚至消除)反位缺陷对发光中心的不良影响。XEL测试结果显示, 随着Mg掺杂量增大, 与反位缺陷相关的发射峰强度变弱, 这可以证明Mg对反位缺陷有抑制作用。     

Photoluminescence and radioluminescence of pure and Ce activated Na3Gd(PO4)2

The spectroscopic properties of Na₃Gd(PO₄)₂ and Na₃Gd(PO₄)₂:Ce³⁺ phosphors in the VUV-UV spectral range were investigated. Five excitation bands of Ce³⁺ ions at Gd³⁺ sites are observed at wavelengths of 205, 246, 260, 292, and 321 nm. Doublet Ce³⁺ 5d → 4f emission bands are observed at 341 and 365 nm with a decay constant τ_1/e around 26 ns. The X-ray excited luminescence of Na₃Gd_0.99Ce_0.01(PO₄)₂ at room temperature shows a photon yield of ∼17,000 photons/MeV of absorbed X-ray energy.