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.     

Luminescent and scintillation properties of the Pr3+ doped single crystalline films of Lu3Al5−xGaxO12 garnet

The Pr³⁺ d–f luminescence was investigated in the single crystalline films (SCF) of Lu₃Al_5−xGa_xO₁₂:Pr garnet solid solution at x = 1–3, grown by the liquid phase epitaxy (LPE) method from the melt-solution based on the PbO–B₂O₃ flux. The shape of CL spectra and decay kinetics of Pr³⁺ ions in Lu₃Al_5−xGa_xO₁₂ SCFs strongly depend on the total gallium concentration x and distribution of Ga³⁺ ions between the tetrahedral and octahedral position of the garnet host. The best scintillation properties of Lu₃Al_5−xGa_xO₁₂:Pr SCF are achieved at the nominal Ga content in melt-solution in the x = 2–2.5 range.     

Site selective 4f5d spectroscopy of CaF2 : Pr

Spectroscopic investigations were performed on a single crystal of CaF₂ doped with 0.05% Pr³⁺. Three different Pr³⁺ sites with different luminescent properties were identified. The 4f² →4f¹5d¹ excitation spectrum of the first site has a sharp maximum at 221.3 nm. Excitation in the 4f5d bands of this site yields strong 4f5d emissions in the UV/VIS part of the spectrum and also weaker intraconfigurational 4f² emissions. By comparing the intraconfigurational 4f emissions and their decay times with data from the literature, these 4f5d bands are assigned to transitions on Pr³⁺ ions on a site with C_4V symmetry. The fd excitation spectrum of the second site has a zero phonon line at 223.3 nm. Upon selective excitation in this band, only 4f5d emission is observed. Probably, these 4f5d bands correspond to Pr³⁺ ions on a O_h site. The third set of 4f5d bands has a 4f5d onset at 208 nm. By comparison of the luminescence spectra of the intraconfigurational 4f² transitions with literature data, these transitions are assigned to Pr³⁺ on an L site. Excitation in these 4f5d band yields ¹S₀ emission followed by emission from the ³P₀ state. The present results clarify some contradictions reported in the literature.     

Crystal structure and luminescence properties of Lu3+ and Mg2+ incorporated silicate garnet [Ca3−(x+0.06)LuxCe0.06](Sc2−yMgy)Si3O12

The yellow-emitting phosphor [Ca_3?(x+0.06)Lu_xCe_0.06](Sc_2?yMg_y)Si₃O₁₂ obtained from Lu³⁺ and Mg²⁺ co-modified green-emitting silicate garnet Ca₃Sc₂Si₃O₁₂:Ce³⁺ (CSS:Ce³⁺) exhibits promising applications for white LEDs. In this paper, we discuss the effect of charge balance on the garnet structure formation. The changes of bond length and covalence caused by the replacement of Lu³⁺ and Mg²⁺ for Ca²⁺ and Sc³⁺ are analyzed. The shift of the Ce³⁺ emission and excitation can be attributed to the combined results from crystal field splitting effect and centroid shift of Ce³⁺ 5d levels. Thermal stability is analyzed according to configurational coordinate diagram.     

Growth and the luminescence properties of a lutetium gadolinium garnet doped with Ce3+ and Pr3+ ions

Crystals of lutetium gadolinium garnet solid solutions (Lu_{1 − x} Gd _x )Al₅O₁₂ (0 ≤ x ≤ 0.6) doped with Ce³⁺ and Pr³⁺ ions have been prepared by the horizontal directional crystallization method, and their optical and luminescence properties have been investigated. It has been established that the introduction of gadolinium into the lutetium garnet lattice leads to a decrease in the antisite luminescence (Lu_Al centers) in the UV spectral range and to sensitization of the Ce³⁺ ion luminescence. By contrast, the presence of gadolinium results in the quenching of the Pr³⁺ luminescence due to the nonradiative excitation transfer from Pr³⁺ ions to Gd³⁺ ions.     

VUV spectroscopic properties of Ce and Pr-doped AREP2O7-type alkali rare earth diphosphates (A=Na, K, Rb, Cs; RE=Y, Lu)

Spectroscopic properties of Ce³⁺ and Pr³⁺-doped AREP₂O₇-type alkali rare earth diphosphates (A=Na, K, Rb, Cs; RE=Y, Lu) have been investigated using VUV spectroscopy technique. Ce³⁺-doped samples show typical Ce³⁺ emission in the range of 325-450 nm. The strong host absorption band starting at around 160 nm indicates that the optical band gap of AREP₂O₇ hosts is at least 7.7 eV, and the host→Ce³⁺ energy transfer process is rather efficient. However, AREP₂O₇:Pr³⁺ samples show less efficient host→Pr³⁺ energy transfer. The direct Pr³⁺ 4f²→4f¹5d¹ excitation, which are 12160±640 cm⁻¹ higher respect to that of Ce³⁺, leads to strong 4f¹5d¹→4f² emission bands in the range of 230-325 nm but no obvious 4f²→4f² emission lines.     

The study of two-color excitation upconversion of Pr(0.5)Yb(3):ZBLAN

The excited state absorption upconversion of Pr(0.5)Yb(3):ZBLAN glass material, under two-color excitation of the 960 nm semiconductor laser and the Xe lamp light simultaneously, is reported in this article. It was found that the upconversion emission spectra of 480.1, 519.0, 601.9 and 631.8 nm coincide with the common emission spectra. Meanwhile, the upconversion-excitation spectrum has three obvious peaks under two-color excitation, and they respectively correspond to the 856.0 nm upconversion excitation transition [¹G₄(Pr³⁺)→¹I₆(Pr³⁺) and ¹G₄(Pr³⁺)→³P₁(Pr³⁺)], the 789.0 nm upconversion excitation transition ¹G₄(Pr³⁺)→³P₂(Pr³⁺), and the 803.7 nm upconversion excitation transition ³H₆(Pr³⁺)→¹D₂(Pr³⁺). The upconversion excitation transition ¹G₄(Pr³⁺)→¹I₆(Pr³⁺) is strong because its oscillator strength f = 23.040×10⁻⁶ is large, which results in a large peak appearing in the upconversion excitation spectrum. That is just the new interesting two-color excitation upconversion luminescence phenomenon of Pr(0.5)Yb(3):ZBLAN induced by one laser and one continuous normal light simultaneously.     

Spectral-kinetic characteristics of Pr luminescence in LiLuF4 host upon excitation in the UV-VUV range

Spectral-kinetic study of Pr³⁺ luminescence has been performed for LiLuF₄:Pr(0.1 mol%) single crystal upon the excitation within 5-12 eV range at T=8 K. The fine-structure of Pr³⁺ 4f ²→4f 5d excitation spectra is shown for LiLuF₄:Pr(0.1 mol%) to be affected by the efficient absorption transitions of Pr³⁺ ions into 4f 5d involving 4f ¹ core in the ground state. Favourable conditions have been revealed in LiLuF₄:Pr(0.1 mol%) for the transformation of UV-VUV excitation quanta into the visible range. Lightly doped LiLuF₄:Pr crystals are considered as the promising luminescent materials possessing the efficient Pr³⁺³P₀ visible emission upon UV-VUV excitation. The mechanism of energy transfer between Lu³⁺ host ion and Pr³⁺ impurity is discussed.     

The influence of Pr co-doping on the luminescent properties of Lu2O3:5 mol% Eu films

Uniform and crack free polycrystalline lutetium oxide (Lu₂O₃:(Eu,Pr)) films were fabricated by Pechini sol-gel method combined with the spin-coating technique. X-ray diffraction (XRD) and atomic force microscope (AFM) characterizations indicated that the obtained film was composed of polycrystalline cubic Lu₂O₃ phase with an average grain size around 30 nm. The photoluminescence(PL) spectra and decay performances of the Lu₂O₃:5 mol% Eu films co-doped by 0-0.5 mol% Pr³⁺ with different concentrations were characterized. It was found that the afterglow was reduced obviously due to the introduction of 0-0.5 mol% Pr³⁺ in the Lu₂O₃:5 mol% Eu films coupled by decrease in the emission intensity at 612 nm. The mechanism of afterglow diminishing was discussed based on the thermoluminescence measurements.     

Laser performance of holmium-doped Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> and (Lu,Y)<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> crystals pumped by Tm:fiber laser

Optical properties of Ho³⁺-doped Lu₃Al₅O₁₂ and (Lu,Y)₃Al₅O₁₂ crystals were investigated and compared. Substitution of Y for Lu in the host garnet Lu₃Al₅O₁₂ results in broad absorption and emission spectra, and improvements in the laser behavior of Ho³⁺. Pumped by Tm:fiber laser, a maximum output power of 5.02 and 5.73 W of Ho-doped Lu₃Al₅O₁₂ and (Lu,Y)₃Al₅O₁₂ have been obtained, respectively. The center lasing wavelength are 2124.5 and 2123.0 nm for Lu₃Al₅O₁₂ and (Lu,Y)₃Al₅O₁₂, respectively.     

Influence of lead-related centers on luminescence of Ce3+ and Pr3+ centers in single crystalline films of aluminium perovskites and garnets

Luminescence characteristics of Ce³⁺- and Pr³⁺-doped aluminium perovskite (LuAlO₃, YAlO₃) and garnet (Lu₃Al₅O₁₂, Y₃Al₅O₁₂) single crystalline films, prepared by the liquid phase epitaxy method with the use of the PbO-based flux, were investigated by the time-resolved spectroscopy methods in the 80–300 K temperature range. The influence of various lead-related centers on the characteristics of the Ce³⁺- and Pr³⁺-related luminescence centers was studied. It was found that the presence of lead-related centers in the single crystalline films results in a decrease of the quantum efficiency and appearance of undesirable slow components in the luminescence decay kinetics. The possibilities of improving the scintillation characteristics of the single crystalline films were considered.     

A spectroscopic investigation of Y 3 Al 5 O 12 :Pr 3 + in translucent ceramic form: Crystal field analysis assisted by configuration-interaction

This paper presents an investigation of Pr³⁺ doped in the D₂ site of Y₃Al₅O₁₂ (YAG), for the first time on a translucent ceramic sample free of spurious phases, impurity or pair sites. The optical study is carried out by optical absorption, excitation, and emission by selective excitation into ¹D₂ and ³P₀, at different temperatures between 20 K and 60 K, in the 4 300-23 000 cm^-1 range. A detailed account of the line assignments is given. 67 over 91 levels of the 4f² configuration are determined. Several crystal field calculations within the ground configuration 4f² and the larger matrix 4f^2+4f6p are carried out. The energy level fit is slightly improved by configuration interaction. The ³P₂ and ¹I₆ levels are strongly mixed together by the large 6th order crystal field parameters. In sintered samples with different Pr³⁺ concentrations, satellite lines with intensities increasing quadratically with the concentration are observed. A few weak lines forbidden in D₂ site symmetry are observed. Received 9 November 2001 and Received in final form 8 February 2002     

Luminescent properties of trivalent praseodymium-doped lanthanum aluminum germanate LaAlGe2O7

The luminescent characteristics of Pr³⁺-activated LaAlGe₂O₇ were investigated. In response to excitement using 448 nm blue light, the emission spectra involved most of the ³P₀→³H_J transitions. The dominant emission came from the ³P₀→³H₄ transition at 487 nm. ¹D₂ fluorescence quenching was observed in highly doped samples and is related to the cross-relaxation processes among neighboring Pr³⁺ ions. In contrast with conventional Pr³⁺-activated phosphors, the extraordinary excitation spectra showed only intense f-f transition of Pr³⁺ ions, while the 4f-5d transition was eliminated. This is ascribed to photoionization. By analyzing absorption and excitation spectra, it is recognized that no efficient energy transfer occurs between Pr³⁺ and the host lattice in LaAlGe₂O₇.     

超声喷雾共沉淀法制备的Lu3Al5O12∶Eu3+ 纳米粉体发光特性

采用新型超声喷雾共沉淀法技术,以Lu₂O₃、Eu₂O₃、Al(NO₃)₃·9H₂O为原料,制备了不同浓度Eu³⁺离子掺杂的Lu₃Al₅O₁₂纳米粉体.用X射线粉末衍射表征了获得纳米粉体的相,用扫描电镜观察了纳米粒子的形貌.测定了粉体的激发光谱、⁷F₀-⁵D₂声子边带谱与发射光谱.研究了不同高温烧结温度与Eu³⁺掺杂浓度对纳米粒子的发光强度与粒子形貌的影响规律.研究表明,当烧结温度高于900 ℃时,粉体发光强度明显增强,并且随着煅烧温度的增加,发光强度有所增强.Eu³⁺离子的最佳掺杂浓度为5~7 mol%.根据稀土离子Eu³⁺光学跃起矩阵元的特点,从发射光谱获得Eu³⁺光学跃起的J-O参量Ω₂与Ω₄.在Eu³⁺掺杂浓度均为5 mol%时,其强度参量达最小,电-声子耦合最强.然后随着掺杂浓度的进一步提高,强度参量略有增加,电-声子耦合减弱.说明Eu-O键强增加,共价性增强,Eu³⁺的局域环境对称性降低.Ω₂值低于Eu³⁺在玻璃与晶体基质中的情况,这是由于纳米粒子中存在着大量的缺陷以及晶体的结构畸变导致纳米粒子的对称性下降所致.     

PHASE DEPENDENCE OF LUMINESCENT EMISSION OF Eu2+ DOPED SrAl2O4

In this work, we made five samples of SrAl₂O₄: Eu²⁺, Dy³⁺, the α phase and β phase SrAl₂O₄:Eu²⁺,Dy³⁺ powder and pellet samples, and α phase single crystal. We have measured the emission spectra of all the samples. All the emission peaks are around 520 nm, which correspond to the transition from 4f⁶5d¹(²E_g) to 4f⁷(⁸S_7/2) of Eu²⁺ in SrAl₂O₄ host. The intensity of emission of the β phase is stronger than that of the α phase. We believe that it is because the Eu²⁺ ions have occupied the two types of sites in the α phase SrAl₂O₄ host and the lifetime of the transition of Eu²⁺ in the A site is longer than that in the B site. This result also proves that the β phase of the material is brighter than the α phase. In addition, the β phase can be achieved by quenching technique.     

Inter- and intraconfigurational optical transitions of the Pr ion for application in lighting and scintillator technologies

In this paper, a review of the application of the Pr³⁺ inter- and intraconfigurational optical transitions in lighting and scintillator technologies is presented. The possibility of generating more than one visible photon for each incident ultraviolet photon can be realized with the Pr³⁺ intraconfigurational emission emanating from the Pr³⁺¹S₀ state. The development of such materials can significantly improve the overall energy conversion of fluorescent lamps. Scintillators based on the intraconfigurational optical transitions emanating from the Pr³⁺³P₀ state has lead to the development and commercialization of the Gd₂O₂S:Pr³⁺ scintillator for application in computed tomography (CT). The development of fast scintillators for positron emission tomography (PET) and security applications can be realized with the efficient Pr³⁺ interconfigurational transitions (4f¹5d¹→4f²) in a solid.     

Luminescence from the Pr 4f5d and S0 states in LiLaP4O12

The photoluminescence and excitation spectra of Pr³⁺ activated LiLaP₄O₁₂ has been investigated in the 10-300 K temperature region. At all temperatures, the luminescence consists of optical transitions emanating from both the Pr³⁺ 4f¹5d¹ and the ¹S₀ states. However, at low temperatures the emission spectrum is dominated by the intraconfiguration emission transitions emanating from the Pr³⁺¹S₀ state. With increasing temperature, there is an exchange of intensity between the two emitting states; emission transitions from the ¹S₀ state exhibit strong intensity quenching while the 4f¹5d¹→4f² emission transitions reveal intensity gain. These results are explained on the basis of thermal population of the 4f¹5d¹ state by the ¹S₀ state. The energy barrier of 0.05 eV (403 cm⁻¹) for the nonradiative process is determined from the temperature dependence of the ¹S₀ lifetime.     

Investigation of structural features of the Y3Al5O12: Ce3+/Lu2O3 crystal phosphors formed by the colloidal chemical method

The specific features of the crystal structure of crystal phosphors Y₃Al₅O₁₂: Ce³⁺/Lu₂O₃ (Lu₂O₃: Ce) synthesized by the colloidal chemical method have been investigated by neutron diffraction at room temperature. The influence of the method used for introducing Lu₂O₃ into the system on the structure and luminescence properties of the samples has been analyzed. The investigation has revealed that the spectra of the samples prepared under the most nonequilibrium conditions are characterized by the Stokes shift and high photoluminescence intensity. This has been explained by the disorder of their crystal structure due to the formation of stable associates of defects.     

The energy transfer processes in LaMgB5O10:Pr, Mn

Pr³⁺, Mn²⁺ singly doped and co-doped LaMgB₅O₁₀ samples were prepared by solid-state reaction and their spectroscopic properties were investigated by synchrotron radiation VUV light. Significant spectra overlap between the Mn²⁺⁶A_1g→(⁴E_g, ⁴A_1g) excitation (centered at 412 nm) and the Pr³⁺¹S₀→(¹I₆, ³P_J) emission (410 nm) provided the possibility of energy transfer from Pr³⁺ to Mn²⁺. In the LaMgB₅O₁₀:Pr³⁺, Mn²⁺ samples investigated, the expected energy transfer process was observed as comparing the emission spectra of LaMgB₅O₁₀:Pr³⁺, Mn²⁺ samples with that of the LaMgB₅O₁₀:Mn²⁺. The shorter decay time of the ¹S₀→(¹I₆, ³P_J) transition in the co-doped samples was also an evidence of energy transfer from Pr³⁺ to Mn²⁺. By analyzing the energy transfer process, it was found that the energy transfer process in LaMgB₅O₁₀:Pr³⁺, Mn²⁺ was likely of resonant energy transfer and the re-absorption process can be excluded. The critical distances of energy transfer based on the electric dipole-dipole interaction and electric dipole-quadrupole interaction were calculated to be 4.78 and 9.46 Å in LaMgB₅O₁₀:Pr³⁺, Mn²⁺, respectively, which are smaller than the mean distance of Pr³⁺ and Mn²⁺ (17 Å) in the highest concentration-doped sample. The near neighboring PrMn clusters formed in the LaMgB₅O₁₀ host is responsible for the energy transfer process.     

Photo- and radio-excited luminescence properties of Eu-doped La2O3–Al2O3 based eutectics

Eutectic crystal of 0.5% Eu-doped 30LaAlO₃–70Al₂O₃ (vol %) was prepared by micro-pulling down (μ-PD) technique under nitrogen atmosphere. Being excited at a wavelength of 320 nm, the crystal exhibited intense emission band with a maximum at 450 nm which is corresponding to 4f⁶5d-4f⁷(⁸S_7/2) transitions of Eu²⁺. The decay time and fluorescence quantum efficiency (QE) were determined to be about 475 ns and 60%, respectively. When alpha-ray excited the crystal, both Eu²⁺ 4f⁶5d-4f⁷(⁸S_7/2) and Eu³⁺ 4f⁶-4f⁶ (⁵D₀-⁷F_1,2) emission peaks were observed at 435 nm and 600 nm. By the pulse height spectra, the relative scintillation light yield of the crystal was about 4% compared with that of BGO commercial scintillator.