Inter- and intraconfigurational luminescence of Er 3+ ions in BaY 2 F 8 under VUV excitation

Using energy- and time-resolved spectroscopy the luminescence properties of Er 3+ doped BaY 2 F 8 crystals were investigated at 10 v K under VUV synchrotron radiation excitation. Radiative intraconfigurational f - f and interconfigurational d - f transitions in Er 3+ ions were observed under f - d excitation. Whereas the onset of 4 S 3/2 population via f - d excitation starts at 59 900 v cm m 1 , efficient excitation of emissions arising from the 2 P 3/2 state begins only above 67 000 v cm m 1 in VUV region. Such behaviour can be explained by a cross-relaxation process of the type ( 2 F(2) 5/2 , 4 I 15/2 ) M ( 2 P 3/2 , 2 P 3/2 ) taking place within f -states of Er 3+ ions finally populating the emitting 2 P 3/2 state.     

近紫外荧光粉SrAl_2Si_2O_8∶Ce~(3+)的光致发光特性

采用高温固相反应法制备了xCe~(3+)(x=0.01%,0.05%,0.10%和0.30%)激活的Sr_(1-x)Al_2Si_2O_8近紫外荧光粉,利用X射线衍射(XRD)和扫描电镜(SEM)检测出荧光粉的物相结构,通过光致发光谱(PL)和激发光谱(PLE)表征了荧光粉的发光性质。结果显示,在中波紫外光激发下,发射峰位于长波紫外区,归属于Ce~(3+)的5d→2 F5/2和5d→2 F7/2跃迁。激发波长308nm时,观察到近紫外SrAl_2Si_2O_8荧光粉的发光强度随Ce~(3+)掺杂量增加而先增大后减小,同时发射峰位置红移。280和325nm波长选择性激发条件下的差异性发射行为表明SrAl_2Si_2O_8∶Ce~(3+)具有两种性质不同的发光中心,该结论由监测320和390nm发射时获得的形状具有明显区别的激发光谱亦可得以验证。离子半径的匹配性支持Ce~(3+)优先取代Sr~(2+),同时Van Uitert的经验公式估算结果推断出低浓度的Ce~(3+)生成九配位的Ce(Ⅰ)发光中心,高浓度掺杂情况下部分相互近邻的Ce~(3+)有效配位数减小,形成八配位的Ce(Ⅱ)发光中心。紫外280nm激发下峰位348nm的发射谱带源于Ce(Ⅰ)和Ce(Ⅱ)发光中心共同贡献,紫外325nm激发下发射峰位于378nm的发射带则主要对应于Ce(Ⅱ)发光中心。紫外光激发下Ce~(3+)发射出较强的近紫外光,表明SrAl_2Si_2O_8∶Ce~(3+)是一种适用于研发紫外荧光光源的荧光粉体材料。     

Na2SrMg(PO4)2: Ce3+, Mn2+荧光粉的发光性质及其能量传递机理

采用高温固相法制备了Na₂SrMg(PO₄)₂: Ce³⁺, Mn²⁺ (NSMP: Ce³⁺, Mn²⁺) 荧光粉, 并对其发光性质及Ce³⁺ 对Mn²⁺ 的能量传递机理进行了研究. Ce³⁺ 和Mn²⁺ 在334 nm 和617 nm 的发射峰分别为Ce³⁺ 的5d→4f 跃迁和Mn²⁺ 的⁴T₁(⁴G)→⁶A₁(⁶S) 跃迁产生. Ce³⁺ 对Mn²⁺ 的发光有较强的敏化作用, 根据Dexter能量传递效率公式判断Na₂SrMg(PO₄)₂ 中Ce³⁺ 对Mn²⁺ 的能量传递属于电偶极-电四极相互作用引起的共振能量传递.     

Optical spectroscopy of Mn2+ ions in CaCl2 single crystals

Abstract

In the present investigation the excitation and fluorescence spectra and lifetimes of Mn²⁺ ions in calcium chloride, for various manganese concentrations and sample temperatures have been studied for the first time. The fluorescence spectrum consists of an asymmetric broad band, which upon lowering the sample temperature, shifts its maximum from 580 nm at 300 K to 596 nm at 11 K. This luminescence band was associated with the ⁴T_lg(⁴G)→⁶A_lg(⁶S) spin-forbidden transition in the manganese ions occupying Ca-sites in the lattice of CaCl₂. The excitation spectrum of the Mn²⁺ fluorescence revealed the features of manganese ions in octahedral coordination and consisted of nine excitation peaks which were associated with Mn²⁺-crystal-field-sensitive transitions. A crystal field analysis of the wavelength positions of these transitions by means of the model developed by Curie et al. allowed us to determine the magnitude of the cubic field splitting 10Dq, the reduced Racah parameter B', the Koide-Pryce covalency parameter ε and the spin transfer coefficients f _[sgrave] and f _σ. From the measurement of the temperature dependence of the Mn²⁺ fluorescence lifetime, we have also obtained information about the different mechanisms which are involved in the relaxation of excited Mn²⁺ ions in this host crystal in the temperature range (11–300 K).     

Optical Spectroscopic Study of Al 2 O 3 : Ti 3+ Under Hydrostatic Pressure

This work investigates the effect of hydrostatic pressure on the excitation, emission and lifetime of Ti 3+ - doped Al 2 O 3 in the 0-110 kbar range. The application of pressure induces band shifts that are correlated with the corresponding local structural changes undergone by the TiO 6 complex. The increase of the Stokes-shift and the reduction of the Jahn-Teller (JT) splittings under pressure are analysed in terms of a simple model based on linear electron-phonon couplings to the a_{1_{\rm g}} and the JT e g vibrational modes.     

Ce3+/Eu2+共掺Ca3Si2O4N2荧光粉的光学特性

采用高温固相法制备了一种新型的白光LED用Ca3Si2O4N2∶Eu2+,Ce3+,K+荧光粉。利用X射线衍射仪对样品的物相结构进行了分析,结果表明:Ce3+和K+离子的掺杂没有改变Ca3Si2O4N2∶Eu2+荧光粉的主晶相。利用荧光光谱仪对样品的发光性能进行了测试,发现样品在355 nm激发下得到的发射光谱为峰值位于505 nm的单峰,是Eu2+离子5d-4f电子跃迁引起的。Ca3Si2O4N2∶Eu2+荧光粉通过Ce3+和K+离子的掺杂,发光明显增强。当Ce3+的摩尔分数为1%时,荧光粉的发光强度达到最大值,是单掺Eu2+离子荧光粉发光强度的168%。通过光谱重叠的方法计算Ce3+→Eu2+能量传递临界的距离为2.535 nm。     

Spectroscopic and laser properties of Er3+-doped monoclinic BaY2F8 single crystals

The luminescence and absorption properties of Ba(Y_1−x Er _x )₂F₈ (x=0.001, 0.01, 0.05, 0.1, 0.2 and 0.3) and the Er³⁺-ion decay kinetics of luminescent transitions from three initial laser states, the⁴S_3/2,⁴F._9/2 and⁴I_11/2 manifolds, were measured. The crystal-field splitting schemes for allJ-manifolds which are involved in (J →J′)-luminescence transitions and stimulated emission parameters of Er³⁺ -ions in BaY₂F₈ were determined. A comparison of laser powers and efficiencies of BaY₂F₈ and Y₃Al₅O₁₂, Lu₃Al₅O₁₂ and LiYF₄ single crystals doped with Er³⁺-ions shows the similar performance of these materials.

     

Thermally stimulated luminescence properties of BaY 2 F 8 :Ce Crystals

Wavelength resolved thermally stimulated luminescence (TSL) measurements were performed on BaY 2 F 8 :1.8 v mol% Ce crystals after X-ray irradiation at 10 v K and at 300 v K, in order to obtain preliminary information about both trap levels and recombination centres. After irradiation at 10 v K, the TSL glow curve shows the presence of a strong peak at 50 v K, together with additional structures at approximately 20 and 170 v K. The TSL spectrum is dominated by the characteristic doublet emission due to transitions from the lowest energy level of the 5d configuration to the spin-orbit split 2 F ground state of Ce 3+ . Above RT, the glow curve exhibits a peak at 60 v C, whose spectrum is again dominated by Ce 3+ emission. The TSL emission is in accordance with radio-luminescence (RL) spectra performed in the 10-300 v K region. Moreover, RL spectra at temperatures lower than 200 v K display an additional weak high energy band at around 4.5 v eV assigned to host lattice transitions.     

Optical spectroscopy of Cr3+ ions in LiF single crystals

This paper reports on the luminescence spectrum, its excitation-wavelength dependence and decaytime of Cr³⁺:LiF crystals. In contrast to Al₂O₃ and MgO, where the Cr³⁺ luminescence at low temperature is due to the R-line and its vibronic sideband, luminescence from Cr³⁺:LiF is assigned to the broad-band ⁴ T ₂⁴ A ₂ transition. A periodic structure in the vibronic sidebands of this transition occurs with energy separations of ca. 60 meV. The linear polarisation of the vibronic sidebands shows that their radiative transition takes place from the lowest excited level of the ⁴ T ₂ state, i.e. ⁴ B ₁, into the ⁴ A ₂ ground state of Cr³⁺ ions in orthorhombic symmetry sites. The crystal-field parameters calculated from the experimental data, and luminescence decay-time of the two polarized configurations of the ⁴ B ₁(⁴ T ₂)⁴ A ₂ transition are also reported.     

KAlF_4∶ Ce,Tb磷光体的发光特性及Ce~(3+)对Tb~(3+)的敏化作用

采用溶液反应法和高温固相反应法合成了ＫＡ１Ｆ４基质化合物及ＫＡ１Ｆ４∶Ｃｅ，Ｔｂ磷光体，测定了磷光体的激发光谱和发射光谱，研究了在碱金属氟铝酸盐基质中Ｃｅ３＋对Ｔｂ３＋的能量传递，根据Ｃｅ３＋、Ｔｂ３＋在ＫＡｌＦ４中的能级关系，分析了其发光特性和Ｃｅ３＋对Ｔｂ３＋能量传递过程     

Vibronic Transitions of Trivalent Er and Ce in BaY2F8 Single Crystals

High resolution (0.02 cm^?1) Fourier transform spectroscopy was applied in the 9–300 K and 100–24,000cm^?1 ranges, respectively, to detect in Er^3? and Ce^3? doped BaY₂F₈ single crystals (1) the narrow line spectra due to the intraconfigurational 4f→4f transitions of the rare earths (RE) and (2) the possible vibronic tails accompanying the zero-phonon lines. The ²F_5/2→²F_7/2 transition was monitored for the Ce^3?-doping and the crystal field splitting of the initial and final manifold was determined. Weak vibronic spectra accompanying six among the nine investigated 4f→4f transitions of Er^3? and the ²F_5/2→²F_7/2 transition of Ce^3? were detected. The vibronic spectra amplitude was found to scale with the RE contents. On the basis of the IR- and Raman-active vibrational modes, either measured or quoted in the literature, most of the vibronic lines could be successfully assigned to the lattice modes. Violations of the selection rules were envisaged and discussed.     

Recombination processes in lanthanum beryllate single crystals doped with Ce3+ and Pr3+ ions

The paper presents experimental results on recombination processes in lanthanum beryllate (BLO) single crystals (undoped BLO, and doped with 0.5 at % by Ce³⁺ and Pr³⁺ ions) obtained using XRL-spectroscopy at T = 8, 80 and 290 K and thermoluminescence technique in the temperature range of 8–650 K. The paper discusses spectra of the steady-state XRL-luminescence recorded in the energy range from 1.5 to 6.2 eV at different temperatures between 8 and 290 K; temperature dependences of XRL intensity recorded in the temperature range from 8 to 650 K; thermoluminescence glow curves recorded in spectral-integrated regime after X-ray exposure at T₀ = 8 or 290 K.     

Luminescent properties of Ce in MSO4 (M: Ca, Sr and Ba) and the effect of Na co-doping

The optical properties of Ce³⁺ in CaSO₄, SrSO₄ and BaSO₄ are reported. The Ce³⁺ ion shows 4f⁰5d¹→²F_5/2,²F_7/2 luminescence in all three sulphates. Co-doping with Na⁺ does not change the local surrounding of the Ce³⁺ ion, but enhances the amount of Ce³⁺ ions built in. Under optical excitation, besides the typical Ce³⁺ doublet emission in the ultraviolet spectral region, band emission around 445 nm was observed. This band emission was not assigned to emission from a Ce³⁺ centre, but to emission from an impurity-trapped exciton. Under X-ray excitation, both Ce³⁺ emission and an emission band around 380 nm was observed. This band was assigned to emission from a self-trapped exciton.     

Absorption of Dy3+ and Nd3+ ions in BaR 2F8 single crystals

The Dy³⁺ absorption and excitation spectra of BaY₂F₈ and BaYb₂F₈ single crystals are investigated in the ultraviolet, vacuum ultraviolet, and visible ranges at a temperature of 300 K. These crystals exhibit intense broad absorption bands due to the spin-allowed 4f-5d transitions in the range (56–78) × 10^?3 cm^?1 and less intense absorption bands that correspond to the spin-forbidden transitions in the range (50–56) × 10^?3 cm^?1. The Nd³⁺ absorption spectra of BaY₂F₈ single crystals are studied in the range (34–82) × 10^?3 cm^?1 at 300 K for different crystal orientations.     

Optical spectroscopy of heavily Ho-doped BaY2F8 crystals

The ultraviolet, visible, and near IR (0.8-2.4 μm) luminescence spectra of BaY₂F₈ single crystals heavily doped with Ho³⁺ ions (10 and 30 mol%) have been investigated at room temperature and 12 K, together with the luminescence decay curves (up to 300 μs) of the visible emission. Excitation in the visible region gives rise to very strong emission bands originating from the first ⁵I₇ level and located around 2070 nm. However the ⁵I₇ emission is not observed upon excitation at wavelengths shorter than 300 nm. The inter-ionic processes are found to shorten the decay times of the levels emitting in the visible region with respect to the corresponding radiative lifetimes.     

Thermodynamics stability,electronic structures and spectroscopic properties of defects and Ce3+ ions in Y2O3

Thermodynamic properties, electronic structures and spectroscopic properties of defects and Ce³⁺ in Y₂O₃ are studied by using the hybrid density functional theory associated with multi-reference configuration interaction ab-initio calculations. Thermodynamic transition energy levels of the easily generated oxygen vacancies in the host are analyzed according to HSE06-calculated formation energies, which may be conducive to interpretations of the persistent luminescence (PersL) of Y₂O₃-based phosphors. Besides, the locations of impurity states (caused by V_O and Ce³⁺) in energy bands are obtained from derived density of states. Moreover, energies and oscillator strengths of 4f₁ → 5d₁₋₅ transitions of Ce³⁺ ions (at Y1 and Y2 sites) calculated from the CASSCF/CASPT2/RASSI−SO method agree reasonably well with experimental excitation spectra of Y₂O₃: Ce³⁺ phosphors, achieving the assignment of excitation spectra. The presented calculations can be applied to identify luminescent centers in Ce³⁺-doped phosphors and reveals possible native defects and their roles in the PersL of phosphors.     

12CaO·7Al_2O_3∶Ce~(3+)透明陶瓷的制备及其闪烁特性研究

采用高温固相法制备了不同Ce3+掺杂浓度的12Ca O·7Al2O3(C12A7∶x%Ce3+)陶瓷样品。在350 nm紫外光激发下,样品的发射光谱呈现为主峰位于440 nm的宽带,来源于Ce3+的5d1→2F5/2和2F7/2的辐射跃迁。随着Ce3+掺杂浓度的增加,发射强度增大;当Ce3+摩尔分数超过0.7%时,有杂质相出现。为了进一步提高光致发光强度,采用自蔓延燃烧法合成了C12A7∶0.5%Ce3+陶瓷样品。在H2气氛下热处理,通过改变笼中阴离子基团的种类和数目提高了陶瓷闪烁特性(发光强度和衰减时间)。结果表明,C12A7∶Ce3+陶瓷是可应用于闪烁体的潜在材料。     

含Ce3+,Tb3+简单氟化物磷光体的荧光特性

采用溶液反应和固相反应合成了ＣａＦ２：Ｃｅ,Ｔｂ和ＡｌＦ３：Ｃｅ,Ｔｂ磷光体,研究了它们的光谱特性,结果发现,在ＣａＦ：Ｃｅ,Ｔｂ和ＡｌＦ３：Ｃｅ,Ｔｂ中Ｃｅ＾３＋对Ｔｂ＾３＋的能量传递不能有效进行,有时Ｔｂ＾３＋甚至对Ｃｅ＾３＋起猝灭作用。     

真空紫外光激发下Ce3+、Tb3+激活的BaCa2(BO3)2的发光性质

利用XRD、VUV及UV光谱等方法对Ce³⁺、Tb³⁺离子掺杂以及Ce³⁺、Tb³⁺离子共掺的3种BaCa₂(BO₃)₂荧光粉的相纯度、发光性质、浓度猝灭现象进行研究。结果表明:3种荧光粉在VUV波段有较好的吸收,基质吸收带位于140～190 nm范围。Ce³⁺在BaCa₂(BO₃)₂的最低4f5d跃迁带位置在360 nm附近,其5d→²F_J(J=5/2, 7/2)发射峰分别位于393,424 nm。Tb³⁺掺杂的样品在172 nm激发下的发射光谱由4个窄带组成,分别对应⁵D₄→⁷F_J(J=3,4,5,6)的跃迁,其中占主导位置的是⁵D₄→⁷F₅的跃迁,大约位于543 nm处,主要为绿光发射。在Ce³⁺,Tb³⁺离子共掺杂的BaCa₂(BO₃)₂光谱中,观察到Ce³⁺-Tb³⁺离子间有能量传递。