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1.
Powders of calcium yttrium silicate, Ca3Y2(Si3O9)2, containing 0.1-3% Tb3+ were prepared using a sol-gel method and characterized with XRD, IR, UV-vis and UV-VUV spectroscopies at room temperature and 10 K. Structural analysis revealed pure monoclinic phase of Ca3Y2(Si3O9)2 after heat-treatment at 1000 °C. Infrared spectroscopy showed that between 800 and 900 °C a short-range structural organization of the components proceeded, yet without crystallization. A strong emission of Tb3+ had been observed both in the green part of the spectrum due to the 5D47FJ transitions and in the blue-violet region owing to the 5D37FJ radiative relaxation. The color of the light could be tuned from yellowish-green to bluish-white both by means of the dopant content and the temperature of synthesis. Efficient luminescence of Tb3+-doped Ca3Y2(Si3O9)2 phosphors could also be obtained upon stimulation with vacuum ultraviolet synchrotron radiation demonstrating that an energy transfer from the host to the Tb3+ ions takes place.  相似文献   

2.
Luminescence emission and uv-excitation properties of LaOBr: Tb3+, LaOBr: Ce3+, and LaOBr: Tb3+, Ce3+ phosphors were studied. The visible emission spectra of La0.995Tb0.005OBr consists of5D3,47F3–6 transitions in the wavelength range of 410–630 nm. The excitation of the Tb3+ ion gives a broad 4f → 5d transition band at 254 nm and weaker4f → 4f transition lines above 300 nm. The uv-excitation and emission of La0.995Ce0.005OBr at 290, 315, 355 (excitation), and 440 nm (emission) originate from transitions between the 4f-ground state and the four crystal field components of the5d2D excited state. The sensitization of Tb3+ luminescence in LaOBr with Ce3+ at varying concentrations is described and discussed. With increasing Ce3+ concentration the 5D37F transitions of Tb3+ quench totally and the5D47F transitions begin to quench gradually. The excitation spectrum of the5D47F5 transition of Tb3+ consists of four bands due to Tb3+ and Ce3+, of which the three Ce3+ bands increase in intensity and the Tb3+ band decreases as the Ce3+ concentration is increased.  相似文献   

3.
Three new compounds, Cs2Bi2ZnS5, Cs2Bi2CdS5, and Cs2Bi2MnS5, have been synthesized from the respective elements and a reactive flux Cs2S3 at 973 K. The compounds are isostructural and crystallize in a new structure type in space group Pnma of the orthorhombic system with four formula units in cells of dimensions at 153 K of a=15.763(3), b=4.0965(9), c=18.197(4) Å, V=1175.0(4) Å3 for Cs2Bi2ZnS5; a=15.817(2), b=4.1782(6), c=18.473(3)  Å, V=1220.8(3)  Å3 for Cs2Bi2CdS5; and a=15.830(2), b=4.1515(5), c=18.372(2) Å, V=1207.4(2) Å3 for Cs2Bi2MnS5. The structure is composed of two-dimensional 2[Bi2MS52−] (M=Zn, Cd, Mn) layers that stack perpendicular to the [100] axis and are separated by Cs+ cations. The layers consist of edge-sharing 1[Bi2S66−] and 1[MS34−] chains built from BiS6 octahedral and MS4 tetrahedral units. Two crystallographically unique Cs atoms are coordinated to S atoms in octahedral and monocapped trigonal prismatic environments. The structure of Cs2Bi2MS5, is related to that of Na2ZrCu2S4 and those of the AMMQ3 materials (A=alkali metal, M=rare-earth or Group 4 element, M′= Group 11 or 12 element, Q=chalcogen). First-principles theoretical calculations indicate that Cs2Bi2ZnS5 and Cs2Bi2CdS5 are semiconductors with indirect band gaps of 1.85 and 1.75 eV, respectively. The experimental band gap for Cs2Bi2CdS5 is ≈1.7 eV, as derived from its optical absorption spectrum.  相似文献   

4.
The magnetic circular dichroism (MCD) for the three low-energy absorption bands of the Eu(C2H5SO4)3·9H2O crystal has been measured at room temperature. It may be well understood from the MCD as well as from other experimental results that two of these bands, 7F15D0 and 7F05D1, are of magnetic dipole origin. However, the MCD of another band at about 18650 cm?1, 7F15D1, cannot be interpreted as being only one electric dipole in origin, which has been pointed out by several investigations. The present MCD analysis indicates that although this broad band consists of one electric- and two magnetic-dipole transitions, each of which has a sizeable absorption strength, the MCD spectrum originates exclusively from the two magnetic dipole transitions  相似文献   

5.
Ce3+ and/or Tb3+ doped LaPO4 nanofibers and microbelts have been prepared by a combination method of sol-gel process and electrospinning. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL), low voltage cathodoluminescence (CL) and time-resolved emission spectra as well as kinetic decays were used to characterize the resulting samples. SEM and TEM results indicate the as-formed precursor fibers and belts are smooth, and the as-prepared nanofibers and microbelts consist of nanoparticles. The doped rare-earth ions show their characteristic emission under ultraviolet excitation, i.e. Ce3+ 5d-4f and Tb3+5D4-7FJ (J=6-3) transitions, respectively. The energy transfer process from Ce3+ to Tb3+ in LaPO4:Ce3+, Tb3+ nanofibers was further studied by the time-resolved emission spectra. Under low-voltage electron beam excitation, LaPO4:Ce3+, Tb3+ microbelt phosphors have a higher intensity than that of nanofiber phosphors.  相似文献   

6.
Optical absorption and emission spectra are reported for single crystals of the cubic elpasolite Cs2NaSmCl6. The variable temperature spectra obtained at high resolution are assigned using energies and relative intensities. Transitions from the ground level, 6H52 to cystal fi levels of 6H72-152, 6F12-112, 4G52-92, 4F32,52, 4I92, and 6P32, 52 are located and characterized. Intensity calculations are reported for magnetic dipole allowed transitions. The dominance of vibronic intensity in 6H526F 12-92 and 6P32, 52 transitions is accounted for qualitatively through the ligand polarization model involving quadrupole metal (Sm3+)-ligand (Cl?) interaction mechanisms. The Eu″(6H52)→E′(6H12) Eu′(6F12) no-phonon transition is postulated to be pure electric quadrupole allowed. The ground state magnetic moment is determined to be very small from magnetic circular dichroism (MCD) spectra.This study has led to the assignment of nearly all of the crystal field levels in the visible and IR region for Cs2NaSmCl6. A total of 27 such levels were identified, 17 from no-phonon transitions and the rest from vibronic transitions. The magnetic dipole intensity calculated using intermediate coupling Oh wavefunctions along with a crystal field analysis of the splitting pattern was used in the assignment of the levels. Vibronic bands were observed for all transitions and their vibrational symmetries were tentatively assigned. MCD data were used to determine the magnet moment of the ground state.  相似文献   

7.
The magnetic ordering of the Fe2P-type Tb6FeTe2, Tb6CoTe2 Tb6NiTe2 and Er6FeTe2 phases (space group P6¯2m) has been investigated through magnetization measurement and neutron powder diffraction. Tb6FeTe2, Tb6CoTe2 and Tb6NiTe2 demonstrate high-temperature ferromagnetic and low-temperature spin reorientation transitions, whereas Er6FeTe2 shows antiferromagnetic transition, only.The Tb6FeTe2 and Tb6NiTe2 phases show same high-temperature collinear ferromagnetic structure, whereas Tb6FeTe2 is the commensurate non-collinear ferromagnet and Tb6NiTe2 is the canted ferromagnetic cone with K1=[0, 0, ±3/10] and K2=[±2/9, ±2/9, 0] wave vectors at 2 K. The magnetic structure of Er6FeTe2 is a flat spiral with K1=[0, 0, ±1/10] at 2 K. The magnetic entropy change for Tb6NiTe2 is ΔSm=−4.86 J/kg K at 229 K for the field change Δμ0H=0-5 T.In addition, novel Fe2P-type Gd6FeTe2, Zr6FeTe2, Hf6FeTe2, Dy6NiTe2, Zr6NiTe2 and Hf6NiTe2 phases have been obtained.  相似文献   

8.
Solid solution investigations in the CsHSO4–CsH2PO4system, carried out as part of an ongoing effort to elucidate the relationship between proton conduction, hydrogen bonding, and phase transitions, yielded the new compound Cs5(HSO4)3(H2PO4)2. Single-crystal X-ray diffraction methods revealed that Cs5(HSO4)3(H2PO4)2crystallizes in space groupC2/c(or possiblyCc), has lattice parametersa=34.066(19) Å,b=7.661(4) Å,c=9.158(6) Å, andβ=90.44(6)°, a unit cell volume of 2389.9(24) Å3, a density of 3.198 Mg m−3, and four formula units in the unit cell. Sixteen non-hydrogen atoms and five hydrogen sites were located in the asymmetric unit, the latter on the basis of geometric considerations rather than from Fourier difference maps. Refinement using anisotropic temperature factors for all non-hydrogen atoms and fixed isotropic temperature factors for all hydrogen atoms yielded residuals based onF2(weighted) andFvalues, respectively, of 0.0767 and 0.0340 for observed reflections [F2>2σ(F2)]. The structure contains layers of (CsH2XO4)2that alternate with layers of (CsHXO4)3, whereXis P or S. The arrangement of Cs, H, andXO4groups within the two types of layers is almost identical to that in the end-member compounds, CsH2PO4and CsHSO4-II, respectively. Although P and S each reside on two of the threeXatom sites in Cs5(HSO4)3(H2PO4)2, the number of protons in the structure appears fixed. In addition, the correlation of S–O and S–OH bond distances with O···O distances, where the latter represents the distance between two hydrogen-bonded oxygen atoms, was determined from a review of literature data.  相似文献   

9.
采用高温固相法合成了NaBaPOM4:Tb3+绿色荧光粉, 并研究了材料的发光性质. NaBaPOM4:Tb3+材料呈多峰发射, 发射峰位于437、490、543、587和624 nm, 分别对应Tb3+5D37F45D47FJ=6, 5, 4, 3跃迁发射, 主峰为543 nm; 监测543 nm发射峰, 所得激发光谱由4f75d1宽带吸收(200-330 nm)和4f-4f 电子吸收(330-400 nm)组成, 主峰为380 nm. 研究了Tb3+掺杂浓度, 电荷补偿剂Li+、Na+、K+和Cl-, 及敏化剂Ce3+对NaBaPOM4:Tb3+材料发射强度的影响. 结果显示: 调节激活剂浓度、添加电荷补偿剂或敏化剂均可以在很大程度上提高材料的发射强度.  相似文献   

10.
采用优化的高温固相方法制备了稀土离子Eu3+和Tb3+掺杂的La7O6(BO3)(PO42系荧光材料,并对其物相行为、晶体结构、光致发光性能和热稳定性进行了详细研究。结果表明,La7O6(BO3)(PO42:Eu3+材料在紫外光激发下能够发射出红光,发射光谱中最强发射峰位于616 nm处,为5D07F2特征能级跃迁,Eu3+的最优掺杂浓度为0.08,对应的CIE坐标为(0.610 2,0.382 3);La7O6(BO3)(PO42:Tb3+材料在紫外光激发下能够发射出绿光,发射光谱中最强发射峰位于544 nm处,对应Tb3+5D47F5能级跃迁,Tb3+离子的最优掺杂浓度为0.15,对应的CIE坐标为(0.317 7,0.535 2)。此外,对2种材料的变温光谱分析发现Eu3+和Tb3+掺杂的La7O6(BO3)(PO42荧光材料均具有良好的热稳定性。  相似文献   

11.
The crystal and electronic structures, and luminescence properties of Eu2+, Ce3+ and Tb3+ activated LiSi2N3 are reported. LiSi2N3 is an insulator with an indirect band gap of about 5.0 eV (experimental value ∼6.4 eV) and the Li 2s, 2p states are positioned on the top of the valence band close to the Fermi level and the bottom of the conduction band. The solubility of Eu2+ is significantly higher than Ce3+ and Tb3+ in LiSi2N3 which may be strongly related to the valence difference between Li+ and rare-earth ions. LiSi2N3:Eu2+ shows yellow emission at about 580 nm due to the 4f65d1→4f7 transition of Eu2+. Double substitution is found to be the effective ways to improve the luminescence efficiency of LiSi2N3:Eu2+, especially for the partial replacement of (LiSi)5+ with (CaAl)5+, which gives red emission at 620 nm, showing highly promising applications in white LEDs. LiSi2N3:Ce3+ emits blue light at about 450 nm arising from the 5d1→4f15d0 transition of Ce3+ upon excitation at 320 nm. LiSi2N3:Tb3+ gives strong green line emission with a maximum peak at about 542 nm attributed to the 5D47FJ (J=3-6) transition of Tb3+, which is caused by highly efficient energy transfer from the LiSi2N3 host to the Tb3+ ions.  相似文献   

12.
The synthesis and the crystal structure of Cs2Nb6Br5F12 containing octahedral niobium clusters are presented in this work. This bromofluoride is based on a Nb6Li12Fa6 (L=Br and F) unit and crystallizes in the orthorhombic system (space group, Cccm; Z=4; a=9.2446(2) Å, b=13.6256(3) Å, and c=17.1665(4) Å; R=0.0241). Fluorine and bromine are randomly distributed on the inner ligand positions, Li, that edge-bridge the Nb6 cluster whereas fluorine fully occupies the apical positions (La). The units are linked to each other by apical ligands leading to an original one-dimensional unit connection. The cesium atoms are statistically distributed on several sites that describe parallel channels along the [1 0 0] direction. The influence of fluorine ligands upon the stabilization of this structure type as well as the structural relationships with Ba2Zr6Cl17(B), Nb6F15, and NaMo6Cl13 will be evidenced and discussed.  相似文献   

13.
The luminescence properties of Cs3Bi2Cl9, α-Cs3Sb2Cl9, and β-Cs3Sb2Cl9 are reported and compared with those of Cs3Bi2Br9. The first two compounds have comparable luminescence properties which can be described in terms of a band model. Deep center emission is observed for both compounds, whereas edge emission is observed only for Cs3Bi2Cl9. The optical transitions of β-Cs3Sb2Cl9 are localized on the Sb3+ ion. The orientation of the lone-pair orbitals of the ns2 ions seems to play an important role in the formation of the cationic valence band. The α-β transformation must therefore have a considerable influence on the spectral properties of Cs3Sb2Cl9.  相似文献   

14.
The solid state synthesis of Cs4Nb6Fi8.5Ii3.5Ia6 starting from Nb6F15 binary fluoride, as well as its crystal structure determined by X-ray single crystal diffraction, are presented in this work. This novel cluster compound is based on a Nb6Ii3Fi6Li3Ia6 (L=F, I) discrete unit and crystallizes in the monoclinic system (space group C2/m; Z=4 ; a=10.4363(4) Å, b=18.1227(7) Å, c=19.5102(9) Å β=101.223(1)°, V=3619.5(3) Å3, R1=0.057; wR2=0.159). This halide is the first octahedral niobium cluster compound containing unshared terminal Ia ligands together with ordered μ2-Ii and μ2-Fi ligands on nine inner positions whilst the three last ones (Li) are slightly affected by a I/F random occupancy. The structural findings are discussed and compared with those of Nb6F15, Nb6I11, CsNb6I11 and the fluorochlorides and fluorobromides recently reported.  相似文献   

15.
The Ba2GdNbO6: Eu3+/Dy3+ and Li+-doped Ba2GdNbO6: Eu3+/Dy3+ phosphors were prepared by solid-state reaction process. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and photoluminescence (PL) as well as lifetimes, was utilized to characterize the resulting phosphors. Under the excitation of ultraviolet light, the Ba2GdNbO6: Eu3+/Dy3+ and Li+-doped Ba2GdNbO6: Eu3+/Dy3+ show the characteristic emissions of Eu3+ (5D0-7F1,2,3 transitions dominated by 5D0-7F1 at 593 nm) and Dy3+ (4F9/2-6H15/2,13/2 transitions dominated by 4F9/2-6H15/2 at 494 nm), respectively. The incorporation of Li+ ions into the Ba2GdNbO6: Eu3+/Dy3+ phosphors has enhanced the PL intensities depending on the doping concentration of Li+, and the highest emission was obtained in Ba2Gd0.9NbO6: 0.10Eu3+, 0.01Li+ and Ba2Gd0.95NbO6: 0.05Dy3+, 0.07Li+, respectively. An energy level diagram was proposed to explain the luminescence process in the phosphors.  相似文献   

16.
The core-shell structured YNbO4:Eu3+/Tb3+@SiO2 particles were realized by coating the YNbO4:Eu3+/Tb3+ phosphors onto the surface of spherical silica via a sol-gel process. The obtained materials were characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform IR spectroscopy (FT-IR), photoluminescence (PL) spectra, and cathodoluminescence (CL) spectra. The results indicate that 600 °C annealed samples consist of amorphous silica core and crystalline YNbO4:Re shell, having perfect spherical morphology with uniform size distribution. Upon excitation by UV or electron beam, these phosphors show the characteristic 5D0-7F1-4 emission lines of Eu3+ and the characteristic 5D4-7F3-6 emission lines of Tb3+. The PL intensities of Eu3+ can be tuned by altering the annealing temperature and the coating number of YNbO4:Eu3+ layers.  相似文献   

17.
Using the method of laser fluorescence, inelastic collisions with rare gas atoms of electronically excited 7Li2 molecules in the υ = 2 and 4 levels were studied. Vibrational transitions ranging from Δ = +2 to ?4 were observed. The simultaneous rotational transitions were completely resolved, and detailed rate constants kΔυ, ΔJ for specific collision- induced quantum jumps Δυ, ΔJ were determined. The effect of secondary rotational relaxation was eliminated by an extrapolation to zero pressure. By integration over ΔJ, rate constants kΔυ, were found. They are, within the error limits, independent of the collision partner and on the initial υ (2 or 4) and depend rather weakly on Δυ. These findings are compared with theoretical results from various methods, generally based on a collinear collision model. The apparent disagreement in all respects suggests strongly the importance of rotational degrees of freedom in the collision. Experimental evidence for this is the large amount of V — R transfer observed, which about equals the V — T transfer. The mean cross sections σ(Δυ) for specific vibrational transitions Δυ range between 6 and 15 A2, among the largest ever observed.  相似文献   

18.
The kinetics of the oxidation of cysteine and captopril via octacyanomolybdate(V) and octacyanotungstate(V) in a buffered acidic media (pH range 2.20–4.80) have been studied spectrophotometrically. The rate law for the oxidation is: Rate = k [RSH] [Ox] [H+]−1, where RSH is cysteine or captopril and Ox is Cs3[Mo(CN)8] or Cs3[W(CN)8]. The activation parameters (Ea, ΔH#, ΔG#, ΔS#) for the oxidation of cysteine and captopril via Cs3[Mo(CN)8] or Cs3[W(CN)8] have been determined. The results indicate that Cs3[Mo(CN)8] is more reactive than Cs3[W(CN)8] as an oxidizing agent. Effects of pH, ionic strength, temperature, dielectric constant of the reaction medium and copper(II) ions on the oxidation rate have been studied. Mechanisms for the oxidation of cysteine to cystine and captopril to the corresponding disulfide have been proposed.  相似文献   

19.
采用优化的高温固相方法制备了稀土离子Eu~(3+)和Tb~(3+)掺杂的La_7O_6(BO_3)(PO_4)_2系荧光材料,并对其物相行为、晶体结构、光致发光性能和热稳定性进行了详细研究。结果表明,La_7O_6(BO_3)(PO_4)_2∶Eu~(3+)材料在紫外光激发下能够发射出红光,发射光谱中最强发射峰位于616 nm处,为5D0→7F2特征能级跃迁,Eu~(3+)的最优掺杂浓度为0.08,对应的CIE坐标为(0.610 2,0.382 3);La_7O_6(BO_3)(PO_4)_2∶Tb~(3+)材料在紫外光激发下能够发射出绿光,发射光谱中最强发射峰位于544 nm处,对应Tb~(3+)的5D4→7F5能级跃迁,Tb~(3+)离子的最优掺杂浓度为0.15,对应的CIE坐标为(0.317 7,0.535 2)。此外,对2种材料的变温光谱分析发现Eu~(3+)和Tb~(3+)掺杂的La_7O_6(BO_3)(PO_4)_2荧光材料均具有良好的热稳定性。  相似文献   

20.
CaIn2O4:Dy3+/Pr3+/Tb3+ blue-white/green/green phosphors were prepared by the Pechini sol-gel process. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), diffuse reflectance, photoluminescence (PL) and cathodoluminescence (CL) spectra as well as lifetimes were utilized to characterize the samples. The XRD results reveal that the samples begin to crystallize at 800 °C and pure CaIn2O4 phase can be obtained after annealing at 900 °C. The FE-SEM images indicate that the CaIn2O4:Dy3+, CaIn2O4:Pr3+ and CaIn2O4:Tb3+ samples consist of spherical grains with size around 200-400 nm. Under the excitation of ultraviolet light and low-voltage electron beams (1-5 kV), the CaIn2O4:Dy3+, CaIn2O4:Pr3+ and CaIn2O4:Tb3+ phosphors show the characteristic emissions of Dy3+ (4F9/2-6H15/2 and 4F9/2-6H13/2 transitions, blue-white), Pr3+ (3P0-3H4, 1D2-3H4 and 3P1-3H5 transitions, green) and Tb3+ (5D4-7F6,5,4,3 transitions, green), respectively. All the luminescence is resulted from an efficient energy transfer from the CaIn2O4 host lattice to the doped Dy3+, Pr3+ and Tb3+ ions, and the corresponding luminescence mechanisms have been proposed.  相似文献   

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