硫化锰电子结构的软X射线共振非弹性散射研究

利用软X射线共振非弹性散射谱(resonant inelastic soft X-ray scattering, RIXS)对3d过渡金属硫化物中的硫化锰(MnS)电子结构进行了研究.通过分析Mn²⁺的2p⁶3d⁵→2p⁵3d⁶→2p⁶3d⁵二次光子过程，得到了共振非弹性散射谱中的两类非弹性峰，d-d电子跃迁和电荷转移(charge-transfer)跃迁.这两部分跃迁分别共振增强于L边附近及伴随峰附近.基于Hartree-Fock方法的多重态计算分别模拟了原子近似下和立方体O_h对称群下共振非弹性散射谱及吸收谱.计算得MnS实际晶体场10Dq值介于0.80eV—0.85eV之间.对MnS和MnO CT跃迁差异的讨论表明MnS较强的CT跃迁来源于其较窄的能隙宽度. 关键词： 软X射线共振非弹性散射 软X射线吸收谱 d-d跃迁 电荷转移     

Dy含量对红色长余辉发光材料Sr3Al2Ｏ6:Eu2＋,Dy3＋性能的影响

采用溶胶凝胶法制备了Sr₃Al₂Ｏ₆:Eu^2＋,Dy^3＋红色长余辉发光材料,利用X射线衍射仪对材料的物相进行了分析,结果表明,1200℃下制备的样品的物相为Sr₃Al₂Ｏ₆,少量的Eu和Dy掺杂没有影响样品的相组成.采用荧光分光光度计、照度计测定了样品的发光特性.结果表明Sr₃Al₂Ｏ关键词： 红色长余辉 3Al₂Ｏ₆')" href="#">Sr₃Al₂Ｏ₆ 溶胶凝胶法     

Phosphorescent and thermoluminescent properties of SrAl2O4:Eu,Dy phosphors prepared by solid state reaction method

Long persistent SrAl₂O₄:Eu²⁺ phosphors co-doped with Dy³⁺ were prepared by the solid state reaction method. The main diffraction peaks of the monoclinic structure of SrAl₂O₄ were observed in all the samples. The broad band emission spectra at 497 nm for SrAl₂O₄:Eu²⁺, Dy³⁺ were observed and the emission is attributed to the 4f⁶5d¹ to 4f⁷ transition of Eu²⁺ ions. The samples annealed at 1100–1200 °C showed similar broad TL glow curves centered at 120 °C. The similar TL glow curves suggest that the traps responsible for them are similar. The long afterglow displayed by the phosphors annealed at different temperatures, may be attributed to the Dy³⁺ ions acting as the hole trap levels, which play an important role in prolonging the duration of luminescence.     

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.     

Photoluminescence and phosphorescence properties of MAl2O4:Eu, Dy (M=Ca, Ba, Sr) phosphors prepared at an initiating combustion temperature of 500 °C

Eu²⁺ and Dy³⁺ co-doped calcium aluminate, barium aluminate and strontium aluminate phosphors were synthesized at an initiating combustion temperature of 500 °C using urea as an organic fuel. The crystallinity of the phosphors was investigated by using X-ray diffraction (XRD) and the morphology was determined by a scanning electron microscope (SEM). The low temperature monoclinic structure for both CaAl₂O₄ and SrAl₂O₄ and the hexagonal structure of BaAl₂O₄ were observed. The effect of the host materials on the photoluminescence (PL) and phosphorescence properties were investigated by using a He-Cd Laser and a Cary Eclipse fluorescence spectrophotometer, respectively. The broad band emission spectra observed at 449 nm for CaAl₂O₄:Eu²⁺, Dy³⁺, 450 nm (with a shoulder-peak at 500 nm) for BaAl₂O₄:Eu²⁺, Dy³⁺ and 528 nm for SrAl₂O₄:Eu²⁺, Dy³⁺ are attributed to the 4f⁶5d¹ to 4f⁷ transition in the Eu²⁺ ion in the different hosts.     

Dy3+ emission in M5(PO4)3F (M = Ca, Ba) phosphor

Ultrafine M₅(PO₄)₃F:Dy³⁺ (M = Ca, Ba) phosphors were prepared via combustion process using metal nitrates as precursors. The formation of crystalline phosphate was confirmed by X-ray diffraction pattern. The PL excitation spectra show the excitation peaks observed at 250 to 400 nm due to f → f transition of Dy³⁺ ion, which are useful for solid-state lighting purpose (mercury free excitation). The PL emission of Dy³⁺ ion by 348 nm excitation gave an emission at 489 nm (blue), 582 nm (yellow) and 675 nm (red). All the characteristics of BYR emissions like BGR indicate that Dy doped Ca₅(PO₄)₃F and Ba₅(PO₄)₃F phosphors are good candidates that can be applied in solid-state lighting phosphor (mercury free excited lamp phosphor) and white light LED.      

Spectator and participator processes in the resonant photon-in and photon-out spectra at the Ce L3 edge of CeO2

We study both theoretically and experimentally the photon-in and photon-out spectra of CeO₂, which are caused by the Ce 2p to Ce 5d excitation followed by the three different de-excitation channels: (i) Ce 3d to Ce 2p (denoted by 3d-RXES), (ii) O 2p to Ce 2p (v-RXES), and (iii) Ce 5d to Ce 2p (RIXS). In 3d- and v-RXES, the 5d electron plays a role of a spectator, but in RIXS it is a participator. By extending our single impurity Anderson model (SIAM), which was used recently for our calculations of v- and 3d-RXES spectra of CeO₂, we study the polarization dependence in the spectator and participator spectra, and we perform more detailed calculations for 3d- and v-RXES spectral features, as well as new calculations for the RIXS spectrum with charge transfer excitations. The polarization dependence is different for the spectator and participator spectra; we have no polarization correlation between the incident and emitted photons for the spectator spectra but a strong polarization correlation for the participator spectrum. The theoretical calculations predict that the charge transfer excitations in RIXS occur in the transfer-energy range overlapped with v-RXES, but the RIXS and v-RXES spectra can be discriminated by taking advantage of the different polarization dependence. The overlapped RIXS and v-RXES spectra are observed successfully by our experiments and well reproduced by our SIAM calculations.     

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.     

Analysis of the spectra of In XII–XIV and Sn XIII–XV in the far-VUV region

The 4p ⁶4d?(4p ⁶5p + 4p ⁶4f + 4p ⁵4d ²) transitions in the spectra of In XIII-Sn XIV and the 4p ⁶4d ²?(4p ⁶4d5p + 4p ⁶4d4f + 4p ⁵4d ³) transitions in the spectra of In XII-Sn XIII are investigated. About 150 spectral lines in the wavelength range 120–160 Å, which is important for projection vacuum UV lithography, have been classified for the first time. The fine structure intervals of the ground state 4p ⁶4d ² D and the energies of eight levels of the 4p ⁶5p, 4p ⁶4f, and 4p ⁵4d ² configurations are measured in each spectrum of In XIII and Sn XIV. The energies of all levels of the ground configuration 4p ⁶4d ² and the energies of 35 levels of the interacting configurations (4p ⁶5p + 4p ⁶4f + 4p ⁵4d ³) are determined in the spectra of In XII and Sn XIII. The resonant transitions 4p ^{6 1} S ₀?4p ⁵4d ¹ P ₁ in the spectra of In XIV and Sn XV are also identified. The semiempirical parameters of the configurations under study determined by mean-square fitting of measured level energies are in agreement along both isoelectronic and isonuclear sequences of the spectra.     

Momentum‐resolved resonant inelastic X‐ray scattering on a single crystal under high pressure

A single‐crystal momentum‐resolved resonant inelastic X‐ray scattering (RIXS) experiment under high pressure using an originally designed diamond anvil cell (DAC) is reported. The diamond‐in/diamond‐out geometry was adopted with both the incident and scattered beams passing through a 1 mm‐thick diamond. This enabled us to cover wide momentum space keeping the scattering angle condition near 90°. Elastic and inelastic scattering from the diamond was drastically reduced using a pinhole placed after the DAC. Measurement of the momentum‐resolved RIXS spectra of Sr_2.5Ca_11.5Cu₂₄O₄₁ at the Cu K‐edge was thus successful. Though the inelastic intensity becomes weaker by two orders than the ambient pressure, RIXS spectra both at the center and the edge of the Brillouin zone were obtained at 3 GPa and low‐energy electronic excitations of the cuprate were found to change with pressure.     

Microscopic magnetic property of perpendicular magnetic films of DyxCo100−x measured using soft X-ray magnetic circular dichroism

We have carried out X-ray absorption measurements with its magnetic circular dichroism (MCD) of perpendicular magnetic films of Dy_xCo_100−x (15?x?33) at Dy M_4,5 and Co L_2,3 absorption edges to investigate electronic and spin states of the Dy 4f and Co 3d states, respectively. The replacement of major spin between Dy 4f and Co3d is clearly observed in the spectra between 20?x?25. The expected values of the orbital angular moment ∣〈L_z〉∣ of Dy 4f were estimated to be 1.4-0.8 μ_B while that of Co 3d was estimated to be around 0.2 μ_B.     

Thermoluminescence studies of LiBa2B5O10:RE (RE=Dy, Tb and Tm)

LiBa₂B₅O₁₀:RE³⁺ (RE=Dy, Tb and Tm) was synthesized by the method of high-temperature solid-state reaction and the thermoluminescence (TL) properties of the samples under the irradiation of the γ-ray were studied. The result showed that Dy³⁺ ion was the most efficient activator. When the concentration of Dy³⁺ was 2 mol%, LiBa₂B₅O₁₀:Dy³⁺ exhibited a maximum TL output. The kinetic parameter of LiBa₂B₅O₁₀:0.02Dy was estimated by the peak shape method, for which the average activation energy was 0.757 eV and the frequency factor was 1.50×10⁷ s⁻¹. By the three-dimensional (3D) TL spectrum, the TL of the sample was contributed to the characteristic f-f transition of Dy³⁺. The dose-response of LiBa₂B₅O₁₀:0.02Dy to γ-ray was linear in the range from 1 to 1000 mGy. In addition, the decay of the TL intensity of LiBa₂B₅O₁₀:0.02Dy was also investigated.     

Formation of a stable bivalent state of Yb ions in Na4Y6F22:Ce3+, Yb3+ crystal under intense UV irradiation

The evolution dynamics of absorption spectra induced in samples of Na₄Y₆F₂₂:Ce³⁺, Yb³⁺ crystal by radiation resonant with 4f-5d transitions of Ce³⁺ ions was studied and analyzed. It was found that at least two types of color centers with different life times are induced in the studied crystal. It is established that the group of absorption bands in the UV spectral range that demonstrate long-term stability after excitation is caused by the 4f ¹³–4f ¹²5d transitions of bivalent ytterbium ions. The sequence of processes that lead to the reduction of ytterbium ions from the trivalent to the bivalent state is proposed.     

Luminescence in LaBaB9O16 prepared by combustion synthesis

LaBaB₉O₁₆ phosphors activated by various ions belonging to ns², 3dⁿ and 4fⁿ configurations were prepared by combustion synthesis. Phosphors’ synthesis and luminescence spectra are reported. Most of the activators displayed intense characteristic emission. Pr³⁺→Gd³⁺, Ce³⁺→Tb³⁺, Ce³⁺→Dy³⁺, Ce³⁺→Mn²⁺ and Bi³⁺→Mn²⁺ energy transfers were also observed. In particular, Ce³⁺→Tb³⁺ energy transfer leads to an efficient green emitting phosphor.     

Effects of dopant concentrations on phosphorescence properties of Eu/Dy-doped Sr3MgSi2O8

Long afterglow Sr₃MgSi₂O₈: Eu, Dy phosphor with high brightness was prepared by sintering at high temperature and weak reductive atmosphere. The luminescent properties of this photoluminescent pigment were studied systematically by investigating concentration effects. The analytical results indicated that the main emission peaks appear at 482 nm. The excitation and emission spectra of this phosphor show that both of them are broadband. This is ascribed to the 4f⁷→4f⁶5d¹ transition of Eu²⁺ in the pigment matrix, which is in good agreement with the calculated value of 470 nm, and implies that luminescent centers Eu²⁺ occupy the deca-coordinated Sr²⁺ sites with the host of Sr₃MgSi₂O₈.     

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.     

Magnetic and transport properties of Dy substituted layered perovskite La1.3Sr1.7Mn2O7

The effect of Dy substitution for La site in layered manganese oxides La1.3-x Dyx Sr1.7 Mn2O7 on the magnetic and electrical properties has been investigated.With the La 3+ substituting by Dy3+,the long range three-dimensional ferromagnetism transition and the insulator-metal transition disappear.These effects are attributed to the lattice distortion due to the substitution of the smaller Dy3+.Addtionally,the small Dy3+ is inclined to occupy the R site which is in the rock-salt layer,then the distribution of La,Sr,Dy ions in Dy-doped sample should be more orderly than that in La1.3 Sr1.7 Mn2O7,so there is only one insulator-metal transition in the ρ-T curve of the sample with x = 0.05 and x = 0.1.     

Wn(n=3—27)原子团簇结构的第一性原理计算

使用密度泛函理论下的第一性原理方法,对W_n原子团簇(n=3—27)的结构特性进行了理论计算. 得到了W_n团簇(n=3—7)的最低能量结构和(n=8—27)的局域能量极小的典型结构. 使用凝胶模型,提出的电子组态1s²1p⁶1d¹⁰2s²1f¹⁴2p⁶3s ^{关键词： W团簇 结构性质 稳定性 从头计算}     

Magnetic circular polarization of luminescence of dysprosium-yttrium aluminum garnet Dy0.2Y2.8Al5O12

Magnetic circular polarization of the luminescence of the radiative 4f-4f transitions ⁶ H _15/2→⁶ F _9/2 in dysprosium-yttrium aluminum garnet Dy_0.2Y_2.8Al₅O₁₃ was studied at T=85 K. The revealed features of the spectral dependences of the magnetically polarized luminescence of Dy³⁺ ions are attributed to the quasi-Ising behavior of rare-earth ions in the garnet structure. The symmetry of the wave functions for a number of Stark sublevels of the multiplets of the ground configuration 4f(n) that combine in observed radiative transitions is determined.