Defect states in Lu 3 Al 5 O 12 :Ce crystals

Wavelength-resolved TSL measurements after x-ray irradiation at room temperature were performed on undoped, Ce- and (Ce, Zr)-doped Lu 3 Al 5 O 12 crystals. Several glow peaks were observed in the 20-450 v C temperature region, whose intensities and emission spectra are influenced by doping. Namely, the TSL spectra are governed by defect and trace impurity-related emissions in the undoped crystal, while only the Ce 3+ emission is detected in the doped crystals. Moreover, EPR measurements performed at 12 v K revealed typical spectra of Ce 3+ (4f 1 , S =1/2) occupying Lu 3+ substitutional positions. In situ light irradiation (250-330 v nm) of the crystals results in a step-like decrease of the Ce 3+ EPR intensity. Such a behaviour can reflect a creation of Ce 4+ ions under UV irradiation or an increase of the Ce 3+ population in the excited (5d) state.     

Photoluminescence of Lu3Al5O12:Bi and Y3Al5O12:Bi single crystalline films

Single crystalline films of Lu₃Al₅O₁₂:Bi and Y₃Al₅O₁₂:Bi have been studied at 4.2–450 K by the time-resolved luminescence spectroscopy method. Their emission spectrum consists of two types of bands with strongly different characteristics. The ultraviolet band consists of two components, arising from the electronic transitions which correspond to the ³P₁ → ¹S₀ and ³P₀ → ¹S₀ transitions in a free Bi³⁺ ion. At T < 80 K, mainly the lower-energy component with the decay time ～10^?3 s is observed, arising from the metastable ³P₀ level. At T > 150 K, the higher-energy component prevails, arising from the thermally populated emitting ³P₁ level. The visible emission spectrum consists of two dominant strongly overlapped broad bands with large Stokes shifts. At 4.2 K, their decay times are ～10^?5 s and ～10^?4 s and decrease with increasing temperature. Both of the visible emission bands are assumed to be of an exciton origin. The lower-energy band is ascribed to an exciton, localized near a single Bi³⁺ ion. The higher-energy band, showing a stronger intensity dependence on the Bi³⁺ content, is assumed to arise from an exciton, localized near a dimer Bi³⁺ center. The structure of the corresponding excited states is considered, and the processes, taking place in these states, are discussed.     

Distortion of the Ligand Environment of Gd3+ and Eu2+ Ions in Garnets: Y3Al5O12, Lu3Al5O12, and Y3Ga5O12

Physics of the Solid State - Using experimental second-rank&nbsp;parameters of the spin Hamiltonian of the rhombic centers Gd3+ and Eu2+ in three garnets and the superposition approximation...     

Y3Al5O12:Ce3+的余辉和热释光特性

高温固相法合成了Ce3+掺杂的Y3Al5O12(YAG)样品,研究了样品的结构、光致发光和热释发光性质.X射线衍射分析结果表明合成样品为YAG纯相,稀土离子的少量掺杂不改变基质YAG的结构.荧光光谱测试表明在高温空气气氛下Y2.95Al5O12:Ce4+0.05制备过程中存在Ce4+的自还原现象,一部分Ce4+被自还原为Ce3+,导致531nm黄光宽带发射.弱还原气氛下制备的Y2.95Al5O12:Ce3+0.05在紫外光照射后具有黄色长余辉,余辉时间长达35 min.热释光测试表明在Ce3+掺杂的YAG样品中存在热释发光,在弱还原气氛下制备的样品Y2.95Al5O12:Ce3+0.05的热释光随温度变化曲线上有112℃和256℃两个明显的热释光峰;而在空气气氛下制备的样品Y2.95Al5O12:Ce4+0.05的热释光随温度变化曲线上只有128℃一个明显的热释光峰.通过对比研究,热释发光主要来源于YAG基质中缺陷能级所陷俘的Ce3+.     

Lu2SiO5∶Ce荧光粉的热释光特性研究

采用溶胶-凝胶(Sol-Gel)技术,分别在空气中和石墨提供的弱还原气氛下制备出Lu2SiO5∶Ce0.006荧光粉。通过分析样品的结构,光致激发、发射谱和热释光谱等特性,发现弱还原气氛下制备的样品不仅光致发光强度比空气中的强,而且热释光曲线中598K处的高温热释光峰也得到了抑制。进一步考察空气中制备的Lu2SiO5∶Ce0.006,Kx(x=0.01～0.08)荧光粉,结果表明就光致发光和热释光特性而言,K+共掺杂具有与还原气氛类似的作用。综合以上两方面分析结果,可认为598K处热释光峰是由与Ce4+相关的缺陷引起的,并对K+共掺杂LSO∶Ce发光增强的原因给出了合理解释。     

不同方法制备Y3 Al5 O12∶Ce3＋黄色荧光粉的对比研究

分别以高温固相法、溶胶-凝胶法和水热-热解法制备了Ce3+掺杂的YAG黄色荧光粉,通过X-射线衍射（XRD）、场发射扫描电镜（FESEM）及荧光光谱（PL）进行表征,考察YAG∶Ce3+黄色荧光粉的晶相、形貌及发光性能对制备方法的依赖性。实验表明,三种方法都实现了Ce3+取代Y3+的位置进入晶格,Ce3+掺杂的YAG荧光粉在晶体结构上都保持立方晶体结构。高温固相法所得样品为不规则球形,粒径尺寸较大;溶胶-凝胶法所得样品为纳米尺度范围,细小颗粒团聚严重,水热-热解法所得样品形貌为球形结构且分散性较好,粒度在10μm左右。荧光光谱显示,三种样品都可被460 nm蓝光有效激发,在550 nm处产生宽带发射,但样品发光强度及量子效率差异较大,该现象主要是由样品形貌及粒径尺寸的差异引起的。     

Yb:Y3Al5O12/Y3Al5O12复合晶体的制作和光谱性能

采用热键合技术,制作中运用不同的工艺参量制作出12片Yb:Y3Al5O12/Y3Al5O12(Yb:YAG/YAG)复合.晶体.利用偏光显微镜对其键合界面进行了观察,研究了样品的透射光谱,从而确定出复合晶体合适的制作工艺.通过透射光谱的形状和透射率来表征复合晶体键合界面的质量.研究表明Yb:YAG/YAG复合晶体键合质量较好,可实现一体化.     

Magnetic-field-controlled polarized luminescence of Y3Al5O12-Tb and Y3Al5O12-Ho garnets

The circularly polarized luminescence spectra of Y₃Al₅O₁₂-Tb and Y₃Al₅O₁₂-Ho garnets are analyzed in the wavelength ranges of the ⁵ D ₄ → ⁷ F ₅ transition in the Tb³⁺ ion and the ⁵ S ₂ → ⁵ I ₈ transition in the Ho³⁺ ion. It is found that the intensities of the orthogonal circularly polarized components of the series of luminescence lines attributed to the studied garnets differ substantially. The results obtained are interpreted in terms of the mixing of the Tb³⁺ and Ho³⁺ electronic states in an external magnetic field.     

Scintillation response of Y3Al5O12:Pr3+ single crystal scintillators

In this paper we present the photoluminescence (PL) and scintillation response of Pr³⁺-doped Y₃Al₅O₁₂ (YAG:Pr) single crystals grown by the Czochralski method with different Pr³⁺ concentrations of 0.16, 0.33, and 0.65 mol%. PL spectra and decay curves were measured for both the fast 5d → 4f and slow 4f → 4f emissions. The PL decay times were evaluated which evidence concentration quenching especially in ¹D₂ → ³H₄ emission for the highest Pr³⁺ concentration. Light yield (LY) of 15,600 photons per MeV and energy resolution of 6.4% at 662 keV γ-rays were obtained with the YAG:Pr (0.33%) crystal. The LY non-proportionality and energy resolution versus γ-ray energy were measured and the intrinsic resolution was calculated. A good proportionality of the LY was found within 7% over the energy range from 1274.5 keV down to 32 keV. The estimated photofraction in the pulse height spectra of 320 and 662 keV γ-rays was also determined and compared with the theoretical one calculated using WinXCom program.     

Timing characteristics of the scintillation response of Gd3Al2Ga3O12:Ce and Gd3Al2.6Ga2.4O12:Ce single crystal scintillators

The timing characteristics of scintillation response of Czochralski-grown Gd₃Al₂Ga₃O₁₂:Ce and Gd₃Al_2.6Ga_2.4O₁₂:Ce single crystals were compared. The photoelectron yield, scintillation decay times, and coincidence time resolution were measured. At 662 keV γ-rays, the photoelectron yield of 6200 phe MeV⁻¹ obtained for Gd₃Al₂Ga₃O₁₂:Ce is higher than that of 4970 phe MeV⁻¹ obtained for Gd₃Al_2.6Ga_2.4O₁₂:Ce, while an inferior energy resolution of the former (7.2% vs. 5.6%) is observed. Scintillation decays are approximated by sum of exponentials with the dominant fast component decay time and its relative intensity of 89 ns (73%) for Gd₃Al₂Ga₃O₁₂:Ce and 136 ns (69%) for Gd₃Al_2.6Ga_2.4O₁₂:Ce. The coincidence time resolution obtained for Gd₃Al₂Ga₃O₁₂:Ce is superior than that of Gd₃Al_2.6Ga_2.4O₁₂:Ce. The normalized time resolution was also discussed in terms of a number of photoelectrons and decay characteristics of the light pulse.     

Dy3+和Ce3+共掺Y3Al5O12荧光粉的制备及发光性质

用高温固相法制备了YAG:5%Dy^3+以及(Ce 0.01 Dy y Y 0.99-y)3A15O12(y=0%,1%,3%,5%,7%,9%)荧光粉。XRD结果表明,NH 4Cl、LiCl、H3BO3三种助熔剂比较,添加H3BO3可有效降低YAG晶体的结晶温度,有效阻止中间相YAlO 3的形成。H3BO3做助熔剂在1450℃煅烧6 h制备的Dy^3+和Ce^3+掺杂Y 3Al 5O 12荧光粉具有单一YAG立方相结构,且随Dy^3+掺杂浓度增加,(420)衍射峰逐渐向小角度偏移。在583 nm监测下;与单掺1%Ce^3+样品比较,Ce^3+与Dy^3+共掺样品在342 nm处的吸收均减弱;与单掺5%Dy^3+样品比较,Ce^3+与Dy^3+共掺样品在351 nm处的吸收明显增强。351 nm激发下,随Dy^3+掺杂浓度增加,Ce^3+与Dy^3+共掺样品中Ce^3+在526 nm处的发射强度逐渐减小,而在583 nm处的发射强度先增加后减弱,这说明351 nm激发下,Ce^3+与Dy^3+共掺样品中存在Ce^3+向Dy^3+的部分能量传递。465 nm激发下,Ce^3+与Dy^3+共掺杂样品中只出现Ce^3+的发射峰,且随Dy^3+浓度增加,Ce^3+发光减弱。当Dy^3+离子浓度为3%时,Ce^3+与Dy^3+共掺样品中Dy^3+相对光强达到最大,此时Ce^3+→Dy^3+能量传递效率为15.7%。405 nm激发下,随Dy^3+掺杂浓度增加,合成粉体中Ce^3+的寿命逐渐减小。经计算,Ce^3+→Dy^3+能量传递临界距离为3.464 nm,为电四极-电四极相互作用的共振能量传递。     

Y3Al5O12：Ce^3＋的合成及真空紫外发光性质

采用高温固相反应及共沉淀法合成Y3-xAl5O12:Ce3 x(x=0.01,0.03,0.05,0.07,0.09)黄色系列粉末状发光材料.经X射线衍射分析产物为单相,属立方晶系,其结果与JCPDS标准卡(88-2047)相符.分析了两种方法合成的粉末样品的SEM照片,发现共沉淀法不仅能降低合成温度,对细化粉体晶粒粒度也有较大作用.检测了材料的真空紫外激发光谱和发射光谱.发现,Y3Al5O12:Ce3 的真空紫外激发光谱,在100~300 nm范围内呈三个带状峰,峰值分别在126,177,230 nm附近.随着Ce3 含量x由0.01增加到0.05,YAG:Ce3 发射强度逐渐增加到最大值,之后随着x继续增加其发射强度逐渐下降,呈现明显的浓度猝灭现象.     

Studies of the spin-Hamiltonian parameters and defect structures for the trigonal Mo 3+ centers in Y 3Al 5O 12 and Lu 3Al 5O 12 crystals

The complete diagonalization (of energy matrix) method (CDM) and the perturbation theory method (PTM) are applied to calculate the spin-Hamiltonian (SH) parameters (electron paramagnetic resonance g factors g _//, g _⊥ and zero-field splitting D) of the trigonal Mo ³⁺ centers in Y ₃Al ₅O ₁₂ and Lu ₃Al ₅O ₁₂ crystals. Both methods are based on the cluster approach in which the covalence effect due to the admixture between the d orbitals of central d ⁿ ion and p orbitals of ligands is considered. The g factors calculated by both methods are close to each other and agree with the experimental values. However, the calculated zero-field splittings D from PTM for both crystals are about 84% those from CDM. The reasons that the CDM is preferable to the PTM in the calculations of SH parameters are discussed. The angular distortions of Mo ³⁺ centers in both garnet crystals are predicted.     

Infrared spectroscopy and lattice dynamical calculations of Gd3Al5O12, Tb3Al5O12 and Lu3Al5O12 single crystals

The infrared (IR) reflectance spectra of Gd₃Al₅O₁₂, Tb₃Al₅O₁₂ and Lu₃Al₅O₁₂ single crystals are studied for the first time. At room temperature, 15 infrared active modes for Lu₃Al₅O₁₂ and 14 for Gd₃Al₅O₁₂, Tb₃Al₅O₁₂, out of the 17 theoretically predicted, have been experimentally recorded. The complex dielectric function the refractive index, the absorption coefficient as well as the longitudinal (ω_LO) and transverse (ω_TO) frequencies of the long-wavelength T_1u modes are determined by the Kramers-Kronig transformation of the reflectance spectra. The experimental data are compared and discussed with the theoretical results obtained by the rigid ion model. Our theoretical analysis reveals that the bonds in the tetrahedra exhibit a covalent character while those in the dodecahedra almost ionic character, which is in accordance with the results for other materials of this crystal family.     

Aerosol Synthesis of Highly Dispersed Y3Al5O12:Ce3+ Phosphor with Intense Photoluminescence

Physics of the Solid State - A simple method of pyrolysis of an aerosol solution of yttrium, aluminum, and cerium nitrates with the addition of urea or citric acid, followed by brief annealing, is...     

Infrared emission and defect centres in Er and Yb codoped Y3Al5O12 phosphors

YAG phosphor powders doped/codoped with Er³⁺/(Er³⁺ + Yb³⁺) have been synthesised by using the solution combustion method. The effect of direct pumping into the ⁴I_11/2 level under 980 nm excitation of doped/codoped Er³⁺/Yb³⁺−Er³⁺ in Y₃Al₅O₁₂ (YAG) phosphor responsible for an infrared (IR) emission peaking at ∼1.53 μm corresponding to the ⁴I_13/2→⁴I_15/2 transition has been studied. YAG exhibits three thermally-stimulated luminescence (TSL) peaks at around 140°C, 210°C and 445°C. Electron spin resonance (ESR) studies were carried out to identify the centres responsible for the TSL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0176 is identified as O⁻ ion, while centre II with an isotropic g-factor 2.0020 is assigned to an F⁺ centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal-annealing experiments and this centre (assigned to F⁺ centre) seems to originate from an F-centre (oxygen vacancy with two electrons) and these two centres appear to correlate with the observed high-temperature TSL peak in YAG phosphor.     

Luminescence and scintillation properties of advanced Lu3Al5O12:Pr3+ single crystal scintillators

In this paper we present the luminescence and scintillation properties of Lu₃Al₅O₁₂:Pr (LuAG:Pr) single crystals with Pr³⁺ concentration of 0.13 wt %, grown by the Czochralski method. The light yield and energy resolution were measured under 662 keV γ-ray excitation. The dominant emission band peaking at 310 nm with a shoulder at 370 nm was observed in the photoluminescence spectrum. High light yield of 24,500 ph/MeV and an energy resolution of 5.3 % were obtained for a 6 × 6 × 2 mm³ LuAG:Pr sample. Light yield dependence on sample height and shaping time was measured. The estimated photofraction in pulse height spectrum and total mass attenuation coefficient at 662 keV γ-rays were also determined and compared with the theoretical ones calculated using the WinXCom program.     

Co-doped Y2O3:Tb3+/Tm3+ multicolor emitting phosphors for thermometry

In this study, the new temperature-dependent phosphor, Y2O3:Tb3+/Tm3+, was investigated for high-temperature thermometry. The photoluminescence intensity at 456?nm emitted from Tm3+ was strong at temperatures higher than 1100?K, whereas the peak intensities emitted from Tb3+ decreased due to the thermal quenching effect. Thus, the intensity ratio between those emissions showed an appropriate variation for thermometry over a wide temperature range. In addition, the phosphors showed a distinct change of visible emission colors from green to blue with increasing temperature. These findings suggest the applicability of these phosphors in visual thermo-sensors.     

Dielectric relaxations in undoped,Ce-doped and Ce,Zr-codoped Lu3Al5O12 single crystals

Dielectric spectroscopy was performed on single crystals of pure, Ce-doped or Ce,Zr-codoped Lu₃Al₅O₁₂, before and after UV- or X-irradaiation, at various frequencies within the range 100 Hz–1 MHz as the temperature was scanned from 110 to 353 K. All samples previously subjected to ionising radiations gave spectra showing loss peaks with Arrhenius characteristics of permanent dipoles relaxation. We attribute the dipoles to defect-stabilised pairs of anion–anion vacancies (oxygen ions and oxygen vacancies) that have captured holes and photo-electrons separately, thus forming O^?- and F⁺-like centers. The dielectric relaxation peaks disappeared in undoped or doped samples annealed at 573 K, suggesting that charge carrier traps are relatively deep. UV–visible absorption spectra have also been measured, which tend to support our proposed interpretation. Further evidence for deep traps has come from thermally stimulated luminescence experiments.