Resonant inelastic x‐ray scattering from highly correlated dysprosium compounds

Dy₂O₃ and Dy metal's resonant inelastic x‐ray scattering (RIXS) spectra were measured in the Beijing Synchrotron Radiation Facility. As a bulk sensitive probe and two‐photon process, RIXS provides more information on the electronic structure of matter. In this full RIXS experiment, the 2p⁶4fⁿ→ 2p⁵4fⁿ5d¹ (2p⁵4f^{n + 1}5d⁰) → 2p⁶3d⁹4fⁿ5d¹ (2p⁶3d⁹4f^{n + 1}5d⁰) channel of two samples (Dy₂O₃ and Dy metal) was studied. Further comparison shows that there are many differences in the RIXS spectra. Dy metal has only a single resonance and its 5d band is broader than that of Dy₂O₃. In the resonant regime, it has a lower final state energy, whereas in the non‐resonant regime it exceeds Dy₂O₃. This causes a broader bandwidth of the main final state B and a narrower bandwidth in the resonant and non‐resonant regime. The pre‐edge structure in Dy L₃ absorption spectra was also resolved using RIXS, which cannot be seen in conventional XAS owing to 2p core hole lifetime broadening. Copyright © 2005 John Wiley & Sons, Ltd.     

X-ray M4,5 resonant Raman scattering from Gd with final 4p hole: calculations with 4p–4d–4f configuration interaction in the final state and comparison with the experiment

We present calculations of resonant Raman scattering (RRS) at the M_4,5 thresholds of Gd in the scattering channel 3d¹⁰4f⁷→3d⁹4f⁸→[4p⁵4f⁸↔4d⁸4f⁹]. We have included in the final state the interaction between the two configurations within the brackets, having one 4p and two 4d holes, respectively. The influence of the configuration interaction on the scattering spectra is shown to be important. The calculations are made within a purely ionic model including only the spectral features dispersing with the incident photon energy and do not account for the M₄ to M₅ Coster-Kronig conversion. The calculations are compared with recent experimental results on Gd metal. The agreement is excellent when choosing the excitation energy in the M₅ region. In the M₄ region the calculations agree with the measurements by assuming that the Coster-Kronig contribution is approximated in shape by the RRS spectrum measured with direct M₅ excitation. The implications of the results are discussed.     

Chemical analysis of semiconducting and metallic SmS thin films by X-ray photoelectron spectroscopy

We studied the chemical state of semiconducting and metallic SmS thin films by X-ray photoelectron spectroscopy (XPS), which were fabricated using dual-target magnetron sputtering by controlling the power applied to both metal and chalcogenide targets. On the basis of the valence band spectra obtained, it was suggested that semiconducting SmS has the final state corresponding to the Sm²⁺(4f⁶) configuration below the Fermi level, and metallic SmS has mainly the Sm³⁺(4f⁵) final state and a virtual band state in the Sm 5d band, contributing to the delocalization of 4f electrons and the emergence of metallic conductivity (4f⁶d⁰-4f⁵d¹). Thus, the spectra of our fabricated SmS thin films correspond to the band structure obtained from the dielectric property. This is the first work performed on the intrinsically prepared metallic SmS while the former works done for the sample transformed from semiconductor to metal phase by hard polishing.     

An efficient blue-emitting phosphor LiCaPO4:Eu2+ for white LEDs

A new blue-emitting phosphor LiCaPO₄: Eu²⁺ was synthesized by solid state reaction at a relatively low temperature of 900 °C. It gives a single intense emission band centering at 470 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. The dependence of luminescence intensities on Eu²⁺ concentration was investigated. The phosphor, with a single excitation band extending from 250 to 400 nm, could be efficiently excited by near-ultraviolet light-emitting diodes and is believed to be a promising blue-emitting phosphor for white light-emitting diodes.     

Nonradiative decay from 5d states of rare earths in crystals

Nonradiative decay from 4f^n?1 5d states was investigated for trivalent rare earths in Y₃Al₅O₁₂. The rates of both 5d→4f and 5d→5d transitions were determined from measurements of the lifetimes and intensities of 5d fluorescence from Ce³⁺ and Pr³⁺. Because of the stronger ion-lattice coupling, nonradiative decay rates for transitions involving 5d states are much faster than those between 4f states. Decay rates are dependent upon the temperature and the energy gap to the next-lower level. The temperature dependences of the 5d fluorescence lifetimes from 77 to 700°K are reported.     

The 4d auger,coster-kronig,and recombination spectra of the lanthanides

A complete set of electron-excited 4d-basedAuger spectra of the lanthanide metals from lanthanum to lutetium (except the unstable promethium) is presented, in both differential and integral forms. It is believed that the set is more representative of clean surfaces of the lanthanides than any published hitherto. With the help of binding energy and electron loss measurements made in this laboratory and elsewhere, values of the various possible Auger, Coster—Kronig, and direct recombination transition energies are calculated, and for each transition a “centre of gravity” is derived based on relative intensities of final state multiplets, electron occupation of core levels, etc. By using arguments based on trends in the spectra across the series, on theoretically and experimentally derived values of U_eff for the difference 4fⁿ⁺¹→4f^n?1, and on plausibility, values of U_eff for 4fⁿ→ 4f^n?2 as well as for the other final state hole pair configurations are allocated. The relaxed transition energies so calculated are then compared with the experimental energies, from which it is possible in most cases to make assignment of the spectral features to the various transitions. As a result it is found that there are some significant disagreements with the theoretical rates of McGuire for lanthanide free atoms. The reasons for these disagreements are discussed, and an empirical model based on effective 4f and 5d populations and on the restrictions imposed by spin alignment is used to resolve the differences qualitatively.     

Luminescent properties of Eu2+and Dy3+ ions in Ba4Al2O7 phosphor for solid state lighting

In this paper we report the combustion synthesis of rare earth (RE=Eu, Dy) doped Ba₄Al₂O₇ phosphors. Prepared phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), CIE color co-ordinates and their photoluminescence (PL) properties were also investigated. In case of Ba₄Al₂O₇: Eu²⁺, the emission spectra show unique band centered at 495 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺, and PL emission spectra of Dy³⁺ ion under 348 nm excitation give two bands centered at 478 nm (blue) and 575 nm (yellow), which originate from the transitions of ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 of Dy³⁺, respectively. The results indicate that the Eu²⁺ and Dy³⁺ activated Ba₄Al₂O₇ phosphor could find application in solid state lighting.     

Intra- and inter-configurational luminescence spectroscopy of Pr3+ -doped YPO4 nanophosphors

Nanopowders of YPO₄ phosphors with different Pr³⁺doping were successfully prepared by a sol gel method under different synthesis conditions. The crystallite size and strain show a strong dependence on the Pr³⁺ doping concentration and on the annealing temperature. By annealing at 300 °C one can obtain the xenotime structure of the pure YPO₄. The crystallite size can be controlled by controlling the annealing temperature and it increases with increasing the annealing temperature. The room temperature inter-configurational 4f² ↔ 4f5d and intra-configurational 4f²↔ 4f² emission-excitation transitions spectra are measured and investigated. Upon 4f² → 4f5d excitation transition, all the samples present broad intense emission bands attributed to 4f5d → 4f² emission transitions and peaks in red region assigned to ¹D₂→³H₄ transition as photon cascade emission phenomena (PCE). The presence of only ¹D₂→³H₄ transition is discussed. In addition, the ¹D₂ energy level lifetimes as well as the refractive indexes were determined and discussed.     

Review of Ni-like ion X-ray laser research at Lawrence Livermore National Laboratory

We have demonstrated saturated output on several nickel-like ion X-ray lasers ranging from niobium to silver by using a psec, high-power, chirped-pulse-amplification, tabletop laser. These results have been achieved at wavelengths from 20.3 to 13.9 nm on the Ni-like 3d⁹4d¹S₀→3d⁹4p¹P₁ laser line using a total of 5 to 7 J of energy in a traveling wave excitation scheme. Strong amplification is also observed for Ni-like Sn at 11.9 nm. Gain of 41 cm⁻¹, gain-length product of 18, and output energy of 12 μJ are measured for the Ni-like Pd line at 14.7 nm. For Ni-like Mo, experiments are done using multilayer mirrors to obtain two-dimensional images of the output aperture of the laser and to measure the total laser energy as a function of various parameters such as the delay between the short and long pulses and the energy of the two pulses. For Mo we measure an output energy of 2 μJ and a gain-length product of 16.6. To model the Mo experiments, the LASNEX code is used to calculate the hydrodynamic evolution of the plasma and provide the temperatures and densities to the XRASER code, which then does the kinetics calculations to determine the gain. The temporal and spatial evolution of the plasma is studied both with and without radiation transport included for the 4f and 4p→3d Ni-like Mo resonance lines. High gains are predicted and observed for both the 3d⁹4d¹S₀→3d⁹4p¹P₁ laser line at 18.9 nm and the 3d⁹4f¹P₁→3d⁹4d¹P₁ photopumped line at 22.6 nm.     

Synthesis and luminescence properties of Na2Ba2Si2O7:Eu2+ phosphor

Green-emitting phosphor Na₂Ba₂Si₂O₇:Eu²⁺ has been synthesized by a conventional high-temperature solid-state reaction. The phase structure and luminescence properties are characterized by the X-ray powder diffraction, diffuse reflectance spectra, photoluminescence excitation and emission spectra, temperature-dependent emission spectra, respectively. It can be efficiently excited in the wavelength range of 325–400 nm and consists of a strong broad green band centered at about 501 nm, which is ascribed to 4f⁶6s⁰5d¹ → 4f⁷6s²5d⁰ transition of Eu²⁺. The critical quenching concentration of Eu²⁺ in the Na₂Ba₂Si₂O₇ host is about 0.8 mol % and corresponding quenching behavior is ascribed to be electric dipole–dipole interaction. Furthermore, the phosphor has good thermal stability property, and the activation energy for thermal quenching is calculated as 0.34 eV.     

Vacuum ultraviolet 5d14f9-4f10 emission of Ho3+ ions in alkaline-earth fluorides

Time-resolved emission and excitation spectra as well as emission decay kinetics of CaF₂, SrF₂, BaF₂ doped with HoF₃ were investigated. Intensive emission bands near 168 nm, having long decay time, are caused by the spin-forbidden transitions from the 5d¹4f⁹ high-spin states to the ground ⁵I₈ states of Ho³⁺ ions. Weak spin allowed 5d¹4f⁹(low-spin)-4f¹⁰ emission band at 158 nm was observed only in CaF₂–Ho crystals. Spin allowed and spin-forbidden excitation bands were observed near 166 and 155 nm, respectively, in all studied crystals. Fast component of spin-forbidden emissions due to multiphonon relaxation to low-lying 4f¹⁰ Ho³⁺ level also was observed for all crystals.     

Giant enhancement of the valence band photoemission intensity in γ-Ce

We have observed a giant enhancement of the Ce valence band emission above the 4d absorption threshold. It is interpreted as being due to autoionization decay following 4d¹⁰4f¹ → 4d⁹4f² transitions. By taking advantage of this effect we have been able to make a determination of the location of the 4f levels in γ-Ce.     

Emission-tunable phosphors Ca9MgM′ (PO4)7: Eu2+,Mn2+ (M′=Li,Na, K) for white light-emitting diodes

A series of single-composition phosphors Ca₉MgM′(PO₄)₇:xEu²⁺, yMn²⁺ (CMM′ P:Eu²⁺, Mn²⁺; M′=Li, Na, K; 0.003≤x≤0.03; 0 ≤y≤0.1) were synthesized by solid state reactions. Upon excitation at 337 nm, phosphors Ca₉MgM′ (PO₄)₇: Eu²⁺ exhibit strong blue emissions centered at 417 (Ca₉MgLi(PO₄)₇:Eu²⁺), 457 (Ca₉MgNa(PO₄)₇:Eu²⁺), and 453 (Ca₉MgK(PO₄)₇:Eu²⁺) nm respectively, which correspond to the 4f⁶5d¹→4f⁷ transitions of Eu²⁺ ions, Through an effective resonance-type energy transfer, CMM′P:Eu²⁺,Mn²⁺ phosphors exhibit a series of colors by adjusting the concentration of Mn²⁺. The result indicates that CMM′P:Eu²⁺,Mn²⁺ can be potentially used as a UV excited phosphor for white light-emitting diodes (LEDs).     

Energy resolved imaging with a stratified phosphor detector

Polycrystalline solid state solutions of Ba_ySr_1 − yCl₂ have been produced; these adopt the cubic fluorite phase for y ≤ 0.30. The cubic structure minimizes optical scattering from grain boundaries, and so for y ≤ 0.30 the materials are transparent, a key advantage for ceramic scintillators and phosphors. The substitution of Sr²⁺ ions with Ba²⁺ ions has the advantage that it substantially increases the x-ray absorption coefficient with respect to pure SrCl₂. Additional doping with rare earth ions such as Sm²⁺ and Eu²⁺ gives bright x-ray phosphor materials. The Sm or Eu-doped materials show a broad 4f⁵5 d¹ → 4f⁶ emission peaked at 685 nm or a broad 4f⁶5 d¹ → 4f⁷ emission peaked at 406 nm respectively. These materials have been tested as x-ray phosphors and the spatial resolution was determined to be at least 6 LP/mm, whilst the x-ray radioluminescence intensity is around 40% that of the commercial x-ray phosphor Gd₂O₂S:Tb. A stratified phoswich structure, comprising Eu and Sm-doped layers of Ba_ySr_1 − yCl₂ was produced in which the relative intensities of the two emissions varies with x-ray beam energy; this can be used for energy discrimination in imaging by way of emission spectra as opposed to the more commonly used pulse shape discrimination. A dual energy imaging technique based on these bi-layered structures and utilizing a semi-professional grade digital SLR camera is described and composition-sensitive imaging has been demonstrated.     

High-temperature VUV spectroscopy of KYF4 crystals doped with Nd3+, Er3+ and Tm3+ ions

Thermal quenching of 5d-4f luminescence from Nd³⁺, Er³⁺ and Tm³⁺ ions doped into KYF₄ crystals has been investigated in the temperature range up to ∼750 K where this luminescence is completely quenched. The obtained temperatures of thermal quenching (T_q) are ∼270, 495, 450 K for Nd³⁺, Er³⁺, Tm³⁺, respectively. At high temperatures, thermal quenching of 5d-4f luminescence from Nd³⁺ and Er³⁺ is accompanied by the appearance of 4f-4f luminescence from the lower-energy 4f levels. It has been shown that the dominating mechanism of thermal quenching for Nd³⁺ and Er³⁺ ions is thermally stimulated non-radiative transitions (intersystem crossing) from the 5d states to lower-energy 4f levels, namely ²G(2)_9/2 and ²F(2)_7/2, respectively, whereas for the Tm³⁺ ion, thermally stimulated ionization of 5d electrons to the conduction band states is responsible for thermal quenching of 5d-4f luminescence. The energy gap between the lowest Tm³⁺ 5d level and the bottom of the KYF₄ conduction band has been estimated to be 0.66 eV.     

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.     

Observation of interband transitions in polarized electron energy loss spectra of Gd(0001)

We have detected the 4f ⁷(5d6s)³→4f ⁸(5d6s)² interband transition in an angular-resolved, inelastic scattering experiment with spin-polarized, low-energy electrons from ferromagnetic Gd(0001). The spectrum of the inelastic scattering asymmetry clearly reveals the dominant spin-dependent energy loss mechanism involved. Furthermore its comparison with elastic scattering data allows a characterization of the combined role of diffraction and energy loss processes in inelastic electron scattering.     

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.     

Luminescence of La3F3[Si3O9]:Ce

The luminescence properties of Ce³⁺ in La₃F₃[Si₃O₉] are reported. Excitation and emission bands corresponding to 4f¹→5d¹ transitions of Ce³⁺ were identified. The center of gravity of the 5d states lies at remarkable high energy (43.2×10³ cm⁻¹) for Ce³⁺ in a silicate compound. This high value is attributed to the combined oxygen/fluoride coordination of the Ce³⁺ ion. Emission from the lowest 4f5d level to the ²F_5/2 and ²F_7/2 levels was found at 32.4×10³ and 30.4×10³ cm⁻¹. These results are compared with literature data on silicates and fluorides. From the values found for Ce³⁺, predictions are made for the positions of the 4f5d bands of Pr³⁺ and Er³⁺ in La₃F₃[Si₃O₉]. For both ions, it is concluded that in this host lattice emission is expected from high lying 4fⁿ energy levels.     

SrB4 O7 : Eu磷光粉的制备及其发光性能

采用高温固相法合成了SrB₄O₇ : Eu荧光粉,并研究了不同原料、掺杂浓度、煅烧温度等因素对其发光性能的影响。发射光谱测试结果表明:SrB₄O₇ : Eu荧光粉的最佳Eu掺杂浓度为2%左右,进一步增大掺杂浓度会导致浓度猝灭。煅烧温度对基质组成影响较大,随着温度的升高,基质中BO₄四面体所占比例增大,有利于Eu³⁺离子的还原。以水合硼酸锶为原料制得样品的发光强度高于以SrCO₃和H₃BO₃为原料制得样品的发光强度。