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.     

Luminescence of Pr-doped LiCaAlF6 and LiSrAlF6 crystals

The spectral and kinetic parameters of LiCaAlF₆:Pr and LiSrAlF₆:Pr single crystals are studied at LHeT and room temperature (RT). Photon cascade emission (PCE), i.e., ¹S₀→¹I₆ and ³P₀→³H_j, ³F_j transitions after Pr³⁺ excitation via 4f²→4f 5d absorption results in the conversion of the vacuum ultraviolet photon to two visible photons. The excitation and photoemission spectra as well as decay times have been measured and compared with those for CaF₂:Pr and SrF₂:Pr crystals. X-ray luminescence was measured to study the emission origin from both ¹S₀ and ³P₀ states of Pr³⁺. An intense phosphorescence of LiSrAlF₆:Pr was observed in the visible range after X-irradiation at RT, contrary to LiCaAlF₆:Pr.     

R2Fe14B(R=Ce,Pr,Gd)磁晶各向异性常数K1,K2随温度的变化

本文在1.5—300K温度范围内测量了R₂Fe₁₄B(R=Ce,Pr,Gd)各向异性常数K₁,K₂和各向异性场H_A随温度的变化。同时用单离子模型计算了Pr³⁺离子对Pr₂Fe₁₄B磁晶各向异性的贡献,得到与实验值半定量符合的结果。 关键词：     

Effects of Zn impurities on the electronic properties of Pr doped CaTiO3

Microcosmic investigations of weak red-emitting materials are crucial for their further development and application. In this work, we have focused on the band structures and electronic properties of Pr mono- and (Zn, Pr) co-doped CaTiO₃ using density functional theory. Zn substitution for Ca or Ti tends to form clusters energetically with Pr substituting for Ca in CaTiO₃. In Pr mono-doped CaTiO₃, the O_2p→Ti_3d transition in CaTiO₃ host corresponds to the centered 330 nm excitation spectra. The gap states above the valence band of ∼1.30 eV and ∼2.06 eV are hybridized by Pr_4f, O_2p and Ti_3d orbitals. They are mainly due to Pr_4f orbitals in CaTiO₃:Pr. The former gap level is related to red emission at 614 nm due to ¹D₂→³H₄ transition of Pr³⁺ activator. The latter is related to the excitation spectra centered at 380 nm due to the low-lying Pr-to-mental intervalence charge transfer transitions (Pr³⁺-O²⁻-Ti⁴⁺?Pr⁴⁺-O²⁻-Ti³⁺). The band structures of (Zn, Pr) co-doped CaTiO₃ keep the similar gap levels to those in Pr mono-doped CaTiO₃. The incorporation of Zn brings out the two stronger localized gap states, which are hybridized by Pr_4f, O_2p and Ti_3d orbitals, in comparison with those in Pr mono-doped CaTiO₃. Therefore, when Zn impurities are added into Pr doped CaTiO₃, the present calculations visualize the two enhanced levels and the distorted structures around Pr.     

Enhanced hydrogen production by doping Pr into Ce0.9Hf0.1O2 for thermochemical two-step water-splitting cycle

We synthesized (Ce_0.9Hf_0.1)_1−xPr_xO_2−δ (x=0, 0.05 and 0.1) using the polymerized complex method. The synthesized samples, as well as the samples after thermochemical two-step water-splitting cycles have a fluorite structure and Pr exists in the solid solutions with both trivalent and tetravalent states, as suggested by powder X-ray Diffraction (XRD) Patterns. The reduction fraction of Ce⁴⁺ in redox cycles (oxidation step in air) and two-step water-splitting cycles (oxidation step in steam) indicates that the addition of Pr into Ce–Hf oxide solid solution cannot improve the reduction fraction of Ce⁴⁺ during the redox cycles but both the reduction fraction of Ce⁴⁺ and H₂ yield are significantly enhanced during two-step water-splitting cycles. The chemical composition of 10 mol% Pr doped Ce_0.9Hf_0.1O₂ exhibits the highest reactivity for hydrogen production in H₂-generation step by yielding an average amount of 5.72 ml g⁻¹ hydrogen gas, which is much higher than that evolved by Ce_0.9Hf_0.1O₂ (4.50 ml g⁻¹). The enhancement effect of doping Pr on the performance during two-step water-splitting cycles is because of the multivalent properties of Pr, which can: (1) reduce the amount of Ce³⁺ oxidized by contamination air (contamination air eliminated by partial oxidation of Pr³⁺ to Pr⁴⁺) in H₂-generation step; (2) enhance the reaction rate in H₂-generation step by improving the ionic conductivity (extrinsic oxygen vacancies created by the substitution of Ce⁴⁺ by Pr³⁺).     

Effects of compositional phase transitions on luminescence of Sr1−xCaxTiO3:Pr

The mixed-compound of Sr_1−xCa_xTiO₃ has shown several compositional phase transformations. Photoluminescence and excitation spectra of the samples with different x and doped with 0.2% Pr³⁺ were investigated. Changes in the emission spectra were observed in different phases. The blue emission at 491 nm from ³P₀ state was found quite strong in the tetragonal phase, and was thermally quenched in the orthorhombic phases. The intensity of the red luminescence from ¹D₂ increases with increasing content of calcium. The strongest red emission is obtained from CaTiO₃:Pr³⁺. The results are discussed based on the configuration coordinate model and interaction of Pr with the charge transfer exciton state of the Ti complex.     

Potential PDP phosphors with strong absorption around 172 nm: Rare earth doped NaLaP2O7 and NaGdP2O7

NaLaP₂O₇ and NaGdP₂O₇ powder samples are prepared by solid-state reactions at 750 and 600 °C, respectively, and the VUV-excited luminescence properties of Ln³⁺ (Ln=Ce, Pr, Tb, Tm, Eu) in both diphosphates are studied. Ln³⁺ ions in both hosts show analogous luminescence. For Ce³⁺-doped samples, the five Ce³⁺ 5d levels can be clearly identified. As for Pr³⁺ and Tb³⁺-doped samples, strong 4f-5d absorption band around 172 nm is observed, which matches well with Xe-He excimer in plasma display panel (PDP) devices. As a result, Pr³⁺ can be utilized as sensitizer to absorb 172 nm VUV photon and transfer energy to appropriate activators, and Tb³⁺-doped NaREP₂O₇(RE=La, Gd) are potential 172 nm excited green PDP phosphors. For Tm³⁺ and Eu³⁺-doped samples, the Tm³⁺-O²⁻ charge transfer band (CTB) is observed to be at 177 nm, but the CTB of Eu³⁺ is observed at abnormally low energy position, which might originate from multi-position of Eu³⁺ ions. The similarity in luminescence properties of Ln³⁺ in both hosts indicates certain structural resemblance of coordination environment of Ln³⁺ in the two sodium rare earth diphosphates.     

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.     

Laser induced emission spectra of Pr3+ in CaF2 at low temperatures

The luminescence spectra of Pr³⁺ in CaF₂, excited with the 4765.05 Å line of the argon ion laser at low temperatures, consist of many more emission lines than the maximum allowed via the ³P₀→³H_4,5,6; ³F_2,3,4 transitions of a single Pr³⁺-site. Based upon their intensity, appropriate splittings and concentration dependence, these emission lines are divided into three groups, attributed to different sites of Pr³⁺ in CaF₂. The existence of Pr³⁺ ions in defect sites of different symmetries is supported by theoretical calculations. The laser emission spectra of Pr³⁺ at low temperatures are compared with room temperature emission spectra obtained with excitation of the ³P₀ state alone, and with low temperature spectra of Pr³⁺ in different hosts, reported in the literature.     

Spectroscopic properties of Pr:KY(MoO4)2 crystal as a visible laser gain medium

A Pr³⁺-doped KY(MoO₄)₂ single crystal was grown by the Czochralski method. The polarized absorption and fluorescence spectra of the Pr³⁺:KY(MoO₄)₂ crystal were measured at room temperature. The stimulated emission cross-sections for the transitions from the ³P₀ multiplet were estimated from the fluorescence spectra. The fluorescence lifetime of the ³P₀ multiplet was estimated from the fluorescence decay curve at room temperature. The analysis of spectral properties shows that the Pr³⁺:KY(MoO₄)₂ crystal is a promising gain medium for visible lasers.     

Y1-xPrxBa2Cu3O7+δ的红外反射谱

测量了温度范围为4.2—300K的Y_1-xPr_xBa₂Cu₃O_7+δ(x=0,0.1,0.2,0.4,0.5,0.61.0)的红外反射谱,发现在低温下Ba模有双模行为,随着x值增大双模强度反转,在YBa₂Cu₃O_7+δ中已被判定为Y模的位于194cm^-1的反射峰的位置与Pr的含量无关,即用Pr部份或全部替代Y时此峰不发生频移。建议Pr在Y_1-xPr_xBa₂Cu₃O_7+δ,中是正4价,Pr的替代使原来可移动的空穴被定域在Pr的周围,使超导电性受到压制。 关键词：     

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.     

Doping effects of Nb5+ on red long afterglow phosphor CaTiO3:Pr3+

A series of Nb5+ codoped red long afterglow phosphors CaTi1 xNbxO3:Pr03.+002 (0 ≤ x ≤ 0.05) is prepared by a solid state reaction method. Their photoluminescence, phosphorescence and thermoluminescence are investigated. The results indicate that codoping Nb5+ can improve the photoluminescence and phosphorescence property of CaTiO3:Pr3+ significantly. When 3-mol% Nb5+ is codoped, the emission intensity of CaTiO3:Pr3+ is enhanced twice, while the afterglow time is extended from 10 min to about 40 min. Thermoluminescence results reveal that the trapping level of CaTiO3:Pr3+ is reduced from 0.82 eV to 0.62 eV by codoping Nb5+. The effect of Nb5+ doping on enhancing the photoluminescence intensity and afterglow time of CaTiO3:Pr3+ is discussed.     

YAG:Pr3+的真空紫外光谱分析及其4f5d能级的研究

用共沉淀法制备出不同掺杂浓度的钇铝石榴石(Y₃Al₅O_{12，YAG)：Pr³⁺粉末.在不同温度下用同步辐射的真空紫外光(VUV)作为激发光 源测量了其发射和激发光谱.对YAG：Pr³⁺被VUV激发后的发光过程进行了分析， 并估算了YAG：Pr³⁺的声子能量、黄昆因子S及Stokes位移.当用170nm光激发样 品时，可能存在自陷激子和通过自陷激子能量传递引发的³P0发射 ，这种跃迁途径不同于用240nm和289nm两个波长激发后的跃迁途径；对Pr³⁺在Y AG中的4f5d能级进行了研究，从而对其4f5d组态有了一个较清晰的认识. 关键词： 3+')" href="#">YAG：Pr³⁺ 同步辐射 4f5d能级 VUV}     

Enhancement of red spectral emission intensity of Y3Al5O12:Ce phosphor via Pr co-doping and Tb substitution for the application to white LEDs

We have enhanced color-rendering property of a blue light emitting diode (LED) pumped white LED with yellow emitting Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) phosphor using addition of Pr and Tb as a co-activator and host lattice element, respectively. Pr³⁺ addition to YAG:Ce phosphor resulted in sharp emission peak at about 610 nm through ¹D₂→³H₄ transition. And when Tb³⁺ substituted Y³⁺ sites, Ce³⁺ emission band shifted to a longer wavelength due to larger crystal field splitting. Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and (Y_1−xTb_x)₃Al₅O₁₂:Ce³⁺ phosphors were coated on blue LEDs to fabricate white LEDs, respectively, and their color-rendering indices (CRIs, R_a) were measured. As a consequence of the addition of Pr³⁺ or Tb³⁺, CRI of the white LEDs improved to be R_a=83 and 80, respectively. Especially, blue LED pumped (Y_0.2Tb_0.8)₃Al₅O₁₂:Ce³⁺ white LED showed both strong luminescence and high color-rendering property.     

Luminescence of Ca(NbO3)2:Pr at ambient and high hydrostatic pressure

In this contribution, photoluminescence and time-resolved photoluminescence spectra of Ca(NbO₃)₂ doped with Pr³⁺ obtained at high hydrostatic pressure up to 72 kbar applied in a diamond anvil cell are presented. At ambient conditions, the emission spectrum obtained in the time interval 0-1 μs is dominated by spin-allowed transitions from the ³P₀ state. On the other hand, transitions from ¹D₂, characterized by a decay time equal to 30 μs dominate the steady-state luminescence.At pressures lower than 60 kbar, the continuous wave emission spectrum consists of sharp lines peaking between 600 and 625 nm, related to the ¹D₂→³H₄ transition and three lines at 500, 550 and 650 nm related to emission transitions originating from the ³P₀ level of Pr³⁺. The emission from the ¹D₂ excited state depends weakly on the pressure. Its decay time decreases from 33 μs at ambient pressure to less than 22 μs at 68 kbar. On the other hand, the ³P₀ emission is strongly pressure dependent. At pressures of 60 kbar and higher, the Pr³⁺ emission intensity from the ³P₀ state decreases. This is accompanied by a strong shortening of the luminescence decay time.The observed pressure quenching of the f-f emission transitions and the concomitant lifetime shortening have been attributed to increasing crossover from the ³P₀ state of Pr³⁺ to a Pr³⁺-trapped exciton state.     

Effect of Ce co-doping on KY3F10:Pr crystals

A spectroscopic investigation on the effect of Ce³⁺ co-doping in fluoride KY₃F₁₀:Pr³⁺ crystals is presented. In particular spectroscopic measurements of three different samples of KY₃F₁₀ crystal doped with 0.3at% Pr³⁺ and co-doped with 0at%, 0.17at% and 0.3at% Ce³⁺ are discussed. Details on the growth of the crystals are also reported. Measurements were performed in the temperature range 10-300 K. Fluorescence and lifetime measurements have shown a cross relaxation between ³P₀-¹D₂ levels of Pr³⁺ and ²F_7/2-²F_5/2 of Ce³⁺. Data exhibit that this effect is strictly related to the Cerium concentration.     

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.     

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.