New observations on the pressure dependence of luminescence from Eu2+-doped MF2 (M = Ca, Sr, Ba) fluorides

The luminescence from Eu2+ ions in MF2 (M = Ca, Sr, Ba) fluorides has been investigated under the pressure range of 0-8 GPa. The emission band originating from the 4f(6)5d(1) -> 4f(7) transition of Eu2+ ions in CaF2 and SrF2 shows the red-shift as increasing pressure with pressure coefficients of -17 meV/GPa for CaF2 and -18 meV/GPa for SrF2. At atmospheric pressure, the emission spectrum of BaF2:Eu2+ comprises two peaks at 2.20 and 2.75 eV from the impurity trapped exciton (ITE) and the self-trapped exciton (STE), respectively. As the pressure is increased, both emission peaks shift to higher energies, and the shifting rate is slowed by the phase transition from the cubic to orthorhombic phase at 4 GPa. Due to the phase transition at 4-5 GPa pressure, the ITE emission disappears gradually, and the STE emission is gradually replaced by the 4f(6)5d(1) -> 4f(7) transition of Eu2+. Above 5 GPa, the pressure behavior of the 4f(6)5d(1) -> 4f(7) transition of EU2+ in BaF2: EU2+ is the same as the normal emission of Eu2+ in CaF2 and SrF2 phosphors.

Synthesis and optical properties of europium-doped ZnS: Long-lasting phosphorescence from aligned nanowires

Quasi-aligned Eu2+-doped wurtzite ZnS nanowires on Au-coated Si wafers have been successfully synthesized by a vapor deposition method under a weakly reducing atmosphere. Compared with the undoped counterpart, incorporation of the dopant gives a modulated composition and crystal structure, which leads to a preferred growth of the nanowires along the [0110] direction and a high density of defects in the nanowire hosts. The ion doping causes intense fluorescence and persistent phosphorescence in ZnS nanowires. The dopant Eu2+ ions form an isoelectronic acceptor level and yield a high density of bound excitions, which contribute to the appearance of the radiative recombination emission of the bound excitons and resonant Raman scattering at higher pumping intensity. Co-dopant Cl- ions can serve not only as donors, producing a donor-acceptor pair transition with the Eu2+ acceptor level, but can also form trap levels together with other defects, capture the photoionization electrons of Eu2+, and yield long-lasting (about 4 min), green phosphorescence. With decreasing synthesis time, the existence of more surface states in the nanowires forms a higher density of trap centers and changes the crystal-field strength around Eu2+. As a result, not only have an enhanced Eu2+ -4f(6)5d(1)-4f(7) intra-ion transition and a prolonged afterglow time been more effectively observed (by decreasing the nanowires' diameters), but also the Eu2+ related emissions are shifted to shorter wavelengths.

Photoluminescence of doped ZnS nanoparticles under hydrostatic pressure

The pressure dependence of the photoluminescence from ZnS : Mn2+, ZnS : Cu2+, and ZnS : Eu2+ nanoparticles were investigated under hydrostatic pressure up to 6 GPa at room temperature. Both the orange emission from the T-4(1) - (6)A(1) transition of Mn2+ ions and the blue emission from the DA pair transition in the ZnS host were observed in the Mn-doped samples. The measured pressure coefficients are -34.3(8) meV/GPa for the Mn-related emission and -3(3) meV/GPa for the DA band, respectively. The emission corresponding to the 4f(6)5d(1) - 4f(7) transition of Eu2+ ions and the emission related to the transition from the conduction band of ZnS to the t(2) level of Cu2+ ions were observed in the Eu- and Cu-doped samples, respectively. The pressure coefficient of the Eu-related emission was found to be 24.1(5) meV/GPa, while that of the Cu-related emission is 63.2(9) meV/GPa. The size dependence of the pressure coefficients for the Mn-related emission was also investigated. The Mn emission shifts to lower energies with increasing pressure and the shift rate (the absolute value of the pressure coefficient) is larger in the ZnS : Mn2+ nanoparticles than in bulk. Moreover, the absolute pressure coefficient increases with the decrease of the particle size. The pressure coefficients calculated based on the crystal field theory are in agreement with the experimental results. (C) 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduction of Eu3+ to Eu2+ in MAl2Si2O8 (M = Ca, Sr, Ba) in air condition

In general, the reduction of Eu3+ to Eu2+ in solids needs an annealing Process in a reducing atmosphere. in this paper, it is of great interest and importance to find that the reduction of Eu3+ to Eu2+ can be realized in a series of alkaline-earth metal aluminum silicates MAl2Si2O8 (M = Ca, Sr, Ba) just in air condition. The Eu2+-doped MAl2Si2O8 (M = Ca, Sr, Ba) powder samples were prepared in air atmosphere by Pechini-type sol-gel process. It was found that the strong hand emissions of 4f(6)5d(1)-4f(7) from Eu2+ were observed at 417, 404 and 373 nm in air-annealed CaAl2Si2O8, SrAl2Si2O8 and BaAl2Si2O8, respectively, under ultraviolet excitation although the Eu3+ precursors were employed. In addition, under low-voltage electron beam excitation, Eu2+-doped MAl2Si2O8 also shows strong blue or ultraviolet emission corresponding to 4f(6)5d(1)-4f(7) transition.

Study on stimulated emission of Eu2+ in crystal KMgF3 : Eu2+

The line emission peak of Eu2+ ion in crystal KMgF3 is at 360 nm. The probability of stimulated emission on 4f(7) (P-6(7/2))-> 4f(7)(S-8(7/2)) transition was predicted with a four-level decay model of Eu2+6P7/2 excited states proposed by the authors. Optic gain and net gain coefficient (g = 11.4 +/- 3.2)cm(-1) of 360 nm emission in crystal KMgF3 : Eu2+ were measured by ASE method, and the predication was proved by experiment. The net gain coefficient can be increased by annealing or doping crystal KMgF3 : Eu2+ with Gd3+ or Ce3+.

Growth and vibrational spectra of doped KMgF3 single crystal

The different ions doped KMgF3 single crystals are prepared by the vertical Bridgman method. The near-infrared absorption spectra for different parts of all as-growth crystals indicate that there is the best transparency in middle part. The correlation between the vibronic frequencies of Eu2+ and the site displacement of Cu+ co-doped ions is firstly studied, which indicates that Cu+ ions replace the site of the Mg2+ ions. The co-doped Eu2+ counteracts the charge misfit causing by the replacement of Mg2+ with Cu+. The overlapping of the emission spectra of the Eu2+ and the excitation spectra of the Cu+ results in the energy transfer from Eu2+ to Cu+.

XAFS at Eu-L-3 edge and UV-VUV excited luminescence of europium doped strontium borophosphate prepared in air

The local structure and the valences of europium in SrBPO5:Eu prepared in air were checked by means of XAFS at Eu-L-3 edge. From the EXAFS results, it was discovered that the doped europium atoms were nine-coordinated by oxygen atoms and the distances of bond Eu-O were 2.42 Angstrom in the host. From the XANES data, it was found that the divalent and trivalent europium coexisted in the matrix. The emission spectra excited by VUV or UV exhibited a prominent broad band due to the 4f(6)5d-4f(7) transition of Eu2+ ions, which indicated that the trivalent europium ions were reduced in air in the matrix at high temperature by the defects [V-Sr]" formed by aliovalent substitution between Sr2+ and Eu3+ ions. The VUV excitation spectra in 100-200 nm range showed that the matrix had absorption bands with the maxima at about 130 and 150 nm, respectively.

VUV excited luminescence of europium activated calcium borophosphate prepared in air

XAFS (EXAFS and XANES) at Eu-L-3 edge were used to determine the local structure and the valences of europium in CaBPO5:Eu prepared in air. The results of EXAFS showed that the doped europium atoms were nine-coordinated by oxygen atoms and the distances of bond Eu-O were 2.39 Angstrom in the host lattice. XANES at Eu-L-3 edge exhibited that Eu2+ and Eu3+ coexisted in the matrix. The luminescent spectrum of the material excited by VUV at 147 nm presented a similar spectrum with that excited by f-f transition of Eu2+ at 396 nm and f-d transition of Eu2+ at 312 nm. The broad emission band due to both 4f(6)5d - 4f(7) transition of EU2+ and f - f transition of Eu3+ could be observed in emission spectra, which indicated that the trivalent europium ions were reduced in air in the matrix at high temperature by the defects [V-Cn]" formed by aliovalent substitution between Ca2+ and Eu3+ ions. The UV excitation spectrum showed the typical f-f transition of Eu3+ and f-d transition of Eu2+. The bands with the maxima at about 113 and 158 nm in VUV excitation spectrum were assigned to originate from the absorption of the host lattice.

COMPARATIVE-STUDY OF CA4Y6(SIO4)(6)O-A PHOSPHORS PREPARED BY SOL-GEL AND DRY METHODS (A=PB2+,EU3+, TB3+,DY3+)

Ca4Y6(SiO4)(6)O:A (A = Pb2+, Eu3+, Tb3+, Dy3+) phosphors have been prepared by two methods: the sol-gel method and the conventional dry method. The crystallization processes and the luminescence characteristics of the phosphors were studied, The sol-gel method features low-temperature formation of the phosphor, leading to successful preparation of Pb2+-activated phosphors which could not be prepared by the dry method at high temperature. The (4f)(8-)(4f)(7)(5d)(1) absorption band of Tb3+ and the charge-transfer (CT) band of Eu3+ have higher energies and narrower half-widths in the sol-gel-derived phosphors than in the phosphors prepared by the dry method, respectively. The Tb3+ and Dy3+ ions show stronger emission in the former than in the latter. Both the yellow-to-blue intensity ratio (Y:B) of Dy3+ and the red-to-orange intensity ratio (R:O) of Eu3+ in the sol-gel-derived phosphors are smaller than those for the phosphors derived by the dry method.

KZnF_3:Eu~(2+)晶体生长及其光谱特性

随着固体激光晶体材料的迅速发展,紫外和短波激光材料越来越引起人们的极大兴趣,使得围绕低价稀土离子的研究工作异常活跃。En~(2+)4f~7组态内f→f跃迁发射有可能实现激光振荡,Eu~(2+)激活并可产生锐峰发射的若干晶体,储能高,阈值低,是有前景的短波固体激光材料。为了探索新的紫外固体激光材料,本文采用坩埚下降法生长了KZnF_3:Eu~(2+)晶体,

Eu~(2+)激活的Al_2O_3及BeAl_2O_4体系的光谱结构

Eu~(2+)4f~7组态内f→f跃迁发射有可能实现激光振荡,Eu~(2+)激活并可产生锐峰发射的若干晶体,储能高、阈值低,是有前景的短波可见固体激光材料的后备物。 Eu~(2+)实现f→f跃迁发射的条件是4f~65d吸收下限位于~6P_l能级之上。符合这一条件的基质化合物必须满足若干结晶学和光谱学条件。为此,许多作者从不同角度建立了相关的判

CRITERION ON F-]F TRANSITION EMISSION OF EUROPIUM(II) AND ITS APPLICATION IN COMPLEX FLUORIDES

The criterion on 4f~7(~6P_J)→4f~7 (~8S_(7/2))(i. e. f→f)transition emission of Eu~(2+) ions was established based on chemical band properties and crystal field effects. By means of the criterion, we have predioted, designed and synthesized 40 Eu~(2+)-doped complex fluorides. The sharp emissions of f→f transition of Eu~(2+) ions were observed in these doped compounds. The condition for applying this criterion is briefly discussed.

Tb~(3+)离子4f~75d组态能级的电子云扩大效应

研究了电子云扩大效应对Tb3+离子5d能级的影响.利用光谱理论,将电子云扩大效应比率β同Tb3+离子4f75d组态的自旋允许和禁阻跃迁能级的能级差联系起来,通过复杂晶体化学键理论确定了化学键的共价性、相应键体积极化率以及配体离子的有效电荷与β的线性关系,同时得到了对β有影响并与Tb3+离子自身相关的因子.

Study of energy transfer in KMgF3 : Eu-X (X = Gd, Cr, Ce) by the decay model of P-6(7/2) exited state of Eu2+

Energy transfer processes between Eu2+ and Gd3+, Cr3+, Ce3+ ions in KMgF3, which are difficult to study spectroscopically, have been investigated by using the proposed four-level decay model of the P-6(7/2) excited state of the Eu2+ ion. Gd3+ and Ce3+ transfer its energy to the vibronic transition of the P-6(7/2) --> S-8(7/2) transition of Eu2+, whereas Cr3+ receive energy from Eu2+ via the d-d interaction. The energy transfer from the Eu2+ 4f(6)5d level to the Ce3+ 4f5d state is observed spectroscopically, and the energy transfer mechanism is discussed. (C) 2001 Elsevier Science B.V. All rights reserved.

双色三光子共振电离测量钐原子高激发态4f~6s7S新能级

本文报道用双色三光子共振电离法测量钐原子高激发态78个新能级。这些新测定的偶宇称能级属于4f~66s7S电子构型,位于33477～37758cm~(-1)能量范围。