Emission analysis of Tb:MgAl2O4 powder phosphor

This paper reports the emission analysis of green-emitting Tb³⁺-doped MgAl₂O₄ phosphors. Uniformity of the phase of the Tb³⁺-doped MgAl₂O₄ phosphor has been checked by X-ray diffraction (XRD) technique and show common bands existing in the results of Fourier transform infrared (FT-IR). This phosphor exhibits weak blue, orange emissions and a strong emission at λ_exci=350 nm. The blue and green-orange emissions are ascribed to ⁵D₃→⁷F_J and ⁵D₄→⁷F_J (where J=3-6) transitions of Tb³⁺ ions, respectively. These phosphors have shown a strong, more prominent green emission from ⁵D₄→⁷F₅ at 543 nm. The results have indicated that MgAl₂O₄:Tb³⁺ could be a potential candidate as agreen-emitting powder phosphor.     

Mn, Cr-co-doped MgAl2O4 phosphors for white LEDs

The Mn-, Cr-doped and Mn, Cr-co-doped MgAl₂O₄ powders have been synthesized via a gel-solid reaction method. Energy transfer from Mn²⁺ to Cr³⁺ has been observed for the first time in the co-doped MgAl₂O₄ phosphors. When excited with blue light with a wavelength of 450 nm at room temperature, both green emission from Mn²⁺ around 520 nm and red emission from Cr³⁺ around 675and 693 nm were generated. Moreover, the color of the emission can be modified by controlling the doping concentrations of Mn²⁺ and Cr³⁺. Therefore, MgAl₂O₄: Mn²⁺, Cr³⁺ could be used as a single-phased phosphor for white LED with a blue LED chip. The energy transfer in terms of Mn²⁺ to Cr³⁺ is determined by means of radiation and reabsorption.     

Role of Ti in the luminescence process of Al2O3:Si,Ti

Al₂O₃:Si,Ti, prepared under oxidizing condition at high temperature, gives PL emission around 430 nm when excited with 240 nm. The Al₂O₃:C, TL/OSL phosphor, also shows emission around 430 nm, which corresponds to characteristic emission of F-center. Thus, to identify the exact nature of luminescent center in Al₂O₃:Si,Ti, fluorescence lifetime measurement studies were carried out along with the PL,TL and OSL studies. The PL and TL in Al₂O₃:Si,Ti show emission around 430 nm and the time-resolved fluorescence studies show lifetime of about 43 μs for the 430 nm emission, which is much smaller than the reported lifetime of ∼35 ms for the 430 nm emission (F-center emission) in Al₂O₃:C phosphor. Therefore, the emission observed in Al₂O₃:Si,Ti phosphor was assigned to Ti⁴⁺ charge transfer transition. Fluorescence studies of Al₂O₃:Si,Ti do not show any traces of F and F⁺ centers. Also, Ti⁴⁺ does not show any change in the charge state after gamma-irradiation. On the basis of the above studies, a mechanism for TSL/OSL process in Al₂O₃:Si,Ti is proposed.     

Photoluminescence in MgxSr1−xAl2O4:Eu, Ndand electron-vibrational interaction in the Eu 5d states

Green phosphor compositions Mg_xSr_1−xAl₂O₄:Eu, Nd (with x=0.05-0.25) were prepared by solid state reaction method. The effect of Mg substitution on photoluminescence characteristics was investigated. The photoluminescence show intense green emission for MgSrAl₂O₄:Eu²⁺, Nd³⁺ with long persistence. This green emission corresponds to transitions from 4f⁶5d¹ to 4f⁷ of Eu²⁺ ion. Comparative analysis of the excitation and emission spectra were used to evaluate the crystal field splitting of the 5d states of Eu²⁺ and the parameters of electron-vibrational interaction, such as Huang-Rhys factor, effective phonon energy, and zero-phonon line position.     

Investigation of defect centres responsible for TL/OSL in MgAl2O4:Tb

Magnesium aluminate doped with Tb³⁺ (MgAl₂O₄:Tb³⁺) was prepared by combustion synthesis. Three thermoluminsence (TL) peaks at 120, 220 and 340 °C were observed. PL and TL emission spectrum shows that Tb³⁺ acts as the luminescent centre. Optically stimulated luminescence (OSL) was observed when stimulated by 470 nm blue light.Electron spin resonance (ESR) studies were carried out to identify the defect centres responsible for the TL and OSL processes in MgAl₂O₄:Tb³⁺. Two defect centres were identified in irradiated MgAl₂O₄:Tb³⁺ phosphor by ESR measurements which was carried out at room temperature and these were assigned to V and F⁺ centres. V centre (hole centre) is correlated to 120 and 220 °C TL peaks and F⁺ centre (electron centre), which acts as a recombination centre is correlated to 120, 220 and 340 °C.     

Eu red long afterglow in Y2O2S:Ti, Eu phosphor through afterglow energy transfer

Eu,Ti co-doped Y₂O₂S:0.03Ti,0.03Eu phosphors and single Eu or Ti doped Y₂O₂S phosphors were prepared and their luminescent properties were investigated in detail by photoluminescence (PL) spectra, long afterglow spectra and thermoluminescence spectra measurements. The results showed that Y₂O₂S:Ti,Eu phosphors possess orange-red afterglow color with afterglow time above 5 h. The reddish afterglow color, which corresponds to a set of linear Eu³⁺ emissions at low-energy range (540-630 nm), was demonstrated to come from the energy transfer process from yellow Ti afterglow emissions, the proposed energy transfer mechanism may well explain the Eu³⁺ afterglow emission.     

First principles study of the electron structures of CaCu3Mn4O12 and CaCu3Ti4O12

The electronic structures of CaCu₃Mn₄O₁₂ and CaCu₃Ti₄O₁₂ are investigated from HF SCF LCAO calculation. In CaCu₃Mn₄O_12, the band and the density of states show a spin asymmetric ferrimagnetic character with a small energy gap. The Mn spin is anti-aligned with the Cu spin, and the total spin moment is 9 μ_B. Our calculation correctly reproduces the observed antiferromagnetic insulating character of CaCu₃Ti₄O₁₂. The gap in the band structure, which is 2.15 eV, reasonably agrees with the experimental value 1.5 eV. The electron density populations at different planes show clearly that the electron density has symmetric character. A tilted Mn(Ti) orbital implies a typical tilted three-dimensional network of MnO₆ (TiO₆) octahedra due to doping of the Jahn–Teller ion Cu. There is no covalency between Ca, Cu and Mn(Ti) atoms. In contrast, there are stronger bonds and somewhat likely covalency between Cu and O atoms, and also between Mn(Ti) and O atoms.     

White-light long-lasting phosphorescence from Tb-activated Y2O2S phosphor

The white-light long-lasting phosphors Y₂O₂S:Tb³⁺, Sr²⁺ or/and Zr⁴⁺ were prepared and studied. The white-light afterglow emission after the irradiation with 254 nm UV are composed of the blue light emission and the yellowish-green light emission, originating from the transitions of ⁵D₃→⁷F₅, ⁵D₄→⁷F₅ in Tb³⁺ when the Tb³⁺ concentration is not higher than 0.3 at%. The codoped Sr²⁺ and Zr⁴⁺ ions act as trap-creating ions. The afterglow can last over 21 min in the dark for Y₂O₂S:Tb³⁺0.3%, Sr²⁺4%, Zr⁴⁺4% after irradiation by 254 nm ultraviolet light. Y₂O₂S:Tb³⁺ may be a promising material for the development of white-light long-lasting phosphor since the Tb³⁺ has a high luminescent efficiency and the dominant excitation band of 4f →5d is located at 220-300 nm.     

Novel ultraviolet photoluminescence of ZnO/ZnGa2O4 composite layers

ZnO/ZnGa₂O₄ composite layers were synthesized by simple thermal oxidation of ZnS substrates with gallium in the air. The continuous-wave and time-resolved photoluminescence measurements for the composites were performed at room temperature. It is found that the visible deep level emission from ZnO in ZnO/ZnGa₂O₄ composite layer was almost suppressed. In addition, the UV emission with long lifetime was also observed in comparison with that of pure ZnO layer without ZnGa₂O₄.     

Multiferroic properties of Bi0.8La0.2FeO3/CoFe2O4 multilayer thin films

Bi_0.8La_0.2FeO₃/CoFe₂O₄ (BLFO/CFO) multilayer thin films (totally 20 layers BLFO and 19 layers CFO) were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition. X-ray diffraction and transmission electron microscope measurements show that the films are polycrystalline and consisted of multilayered structure. Ferroelectric hysteresis loops with remnant polarization and saturated polarization of 4.2 and 13.3 μC/cm², respectively, were observed. On the other hand, the films show well-shaped magnetization hysteresis loops with saturated and remnant magnetization of 34.7 and 11.4 emu/cm³, respectively, which are significantly larger than pure BLFO thin films deposited under the same conditions. These results indicate that constructing epitaxial superlattice might be a promising way to fabricate multiferroics with improved properties.     

Photoluminescence properties of Eu3+-doped Gd2MoB2O9 phosphors for LED-based solid-state-lighting

Investigation was performed on luminescent properties of novel Gd_2−x Eu _x MoB₂O₉ (0.02≤x≤2.0) phosphors. The excitation spectra consist of broad band and intense narrow lines. The 4f-4f transitions are situated in a favorable position for excitation by GaN chip emission. The emission spectra consist of transitions from the ⁵D₀ level to the lower ⁷F manifold, and the emission shows no concentration quenching at higher doping level. The decay time spectra of the ⁵D₀ → ⁷F₂ emission are recorded. Under 395 nm excitation, the intensity of ⁵D₀ → ⁷F₂ transition of GdEuMoB₂O₉ is 1.2 times stronger than that of commercial Eu³⁺:Y₂O₂S phosphor. Gd₂MoB₂O₉:Eu³⁺ phosphors are promising candidates for near-UV-based solid-state-lighting (SSL).     

Afterglow phenomenon in Erbium and Titanium codoped GD2O2S phosphors

A series of new long-lasting phosphor Gd₂O₂S:xEr,Ti are prepared by the conventional high-temperature solid-state method and their luminescent properties are systematically investigated in this paper. The characteristic afterglow emission of Er, which is due to the transition of ⁴F_9/2→⁴I_15/2 and ⁴S_3/2→⁴I_15/2, is reported for the first time. XRD, photoluminescence, long-lasting phosphorescence and decay curves are used to characterize the synthesized phosphors. The possible energy transfer mechanism of Gd₂O₂S:xEr,Ti is also investigated.     

Opto-electronic response of spinels MgAl2O4 and MgGa2O4 through modified Becke-Johnson exchange potential

A first-principles technique capable of describing the state accurately near to excited states of semiconductors and insulators, namely the modified Becke-Johnson (mBJ) exchange potential approximation is used to investigate the opto-electronic response of magnesium spinel oxides: MgAl₂O₄ and MgGa₂O₄. The predicted bandgaps using the mBJ exchange approximation show a significant improvement over previous theoretical work using the common LDA and GGA, and are very closer to the experimental results. Band gap dependent optical parameters, like dielectric constant, index of refraction, reflectivity and optical conductivity are calculated and analyzed.     

Optical characterization of fourfold (Td)- and sixfold (Oh)-transition-metal species in MgAl2O4:Co by time-resolved spectroscopy

This work investigates the origin of novel visible photoluminescence (PL) bands observed in the spinel MgAl₂O₄:Co²⁺. Besides the well-known fourfold-coordinated Co²⁺(T_d) PL at 670 nm [N.V. Kuleshov, V.P. Mikhailov, V.G. Scherbitsky, P.V. Prokoshin and K.V. Yumashev, J. Lumin. 55 (1993) 265.], a rich structured PL band at 686 nm was also observed that we associate with uncontrolled impurities of sixfold coordinated Cr³⁺(O_h) by time-resolved spectroscopy and lifetime measurements and their variation with temperature. We also show that the lifetime of the Co²⁺(T_d) emission at 670 nm varies from τ=6.7 μs to 780 ns on passing from T=10 to 290 K. This unexpected behaviour for T_d systems is related to the excited-state crossover (⁴T₁↔²E), making the emission band to transform from a narrow-like emission from ²E at low temperature to a broad structureless band from ⁴T₁ at room temperature.     

Resonance paramagnetique electronique du manganese divalent dans ZnAl2O4

The electron paramagnetic resonance spectrum of a single crystal of ZnAl₂O₄ (spinel structure) doped with manganese displays a fine structure characteristic of a purely cubic crystal field. Contrary to MgAl₂O₄: Mn²⁺, where the degree of inversion is sizable, ZnAl₂O₄ therefore is a normal spinel.     

Enhanced luminescence of Ca3B2O6:Dy phosphors by Na-codoping for LED applications

The Ca_2.95−yDy_0.05B₂O₆:yNa⁺ (0≤y≤0.20) phosphors were synthesized at 1100 °C in air by the solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), photoluminescence excitation (PLE), photoluminescence (PL) spectra and thermoluminescence (TL) spectra. The PLE spectra show the excitation peaks from 300 to 400 nm due to the 4f-4f transitions of Dy³⁺. This mercury-free excitation is useful for solid-state lighting and light-emitting diodes (LEDs). The emission of Dy³⁺ ions on 350 nm excitation was observed at 480 nm (blue) due to the ⁴F_9/2→⁶H_15/2 transitions, 575 nm (yellow) due to ⁴F_9/2→⁶H_13/2 transitions and 660 nm (red) due to weak ⁴F_9/2→⁶H_11/2 emissions. The PL results from the investigated Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors show that Dy³⁺ emissions increase with the increase of the Na⁺ codoping ions. The integral intensity of yellow to blue (Y/B) can be tuned by controlling Na⁺ content. By the simulation of white light, the optimal CIE value (0.328, 0.334) can be achieved when the content of Na⁺-codoping ions is y=0.2. The results imply that the Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors could be potentially used as white LEDs.     

A revisit of photoluminescence property for vanadate oxides AVO3 (A:K, Rb and Cs) and M3V2O8 (M:Mg and Zn)

We revisited the vanadium oxide phosphors, AVO₃ (A:K, Rb, and Cs) and M₃V₂O₈ (A:Mg and Zn) for a revaluation of possibility of these compounds for lighting applications, and the internal quantum efficiency (η) and luminescent colour properties for AVO₃ (A:K, Rb, and Cs) and M₃V₂O₈ (A:Mg, and Zn) have been presented. The AVO₃ showed the broadband emission from 380 to 800 nm, and the η for the KVO₃, RbVO₃ and CsVO₃ were 4%, 79% and 87%, respectively. The CIE colour coordinates are located at white region on the chromaticity diagram. The M₃V₂O₈ (A:Mg and Zn) also exhibited a quite broadband emission between 410 and 900 nm, indicating yellow luminescent colour. The Zn₃V₂O₈ showed high η value, 52%, compared to that of the Mg₃V₂O₈ (η=6%). This enhancement of η in the Zn₃V₂O₈ could be due to the increasing exciton diffusion assisted by the hybridizations of Zn 3d and O 2p orbitals for the valence band, and Zn 4s and Ti 3d orbitals for the conduction band.     

Synthesis and luminescent properties of Y6W2O15:Eu phosphors

In this paper, a novel phosphor, Y₆W₂O₁₅:Eu³⁺ was synthesized by thermal decomposition and phase transition of its decatungstate gel precursor. With stepwise increase of temperature to 750 °C, a crystalline phase of Y₆W₂O₁₅:Eu³⁺forms that gives intense red emission when excited at 466 nm, the emission is attributed to the Eu³⁺ ions transitions from ⁵D₀ excited states to ⁷F_J (J=0-4) ground states. The long excitation wavelength proves the Eu³⁺ transition follows the photoexcitation of the oxygen-metal (O→W lmct) charge transfer bands in yttrium tungstate. Some structural information regarding Y₆W₂O₁₅ provided by luminescence is in accord with that characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The long-wavelength excitation properties of this material may find application in the production of red phosphors for white light-emitting diodes (LEDs).     

Comparative structural and photoluminescent study of Eu-doped La2O3 and La(OH)3 nanocrystalline powders

Eu³⁺-doped La₂O₃ nanocrystalline powder was prepared by polymer complex solution method and further used for preparation of Eu³⁺-doped La(OH)₃. Structural and optical characterization was carried out by powder X-ray diffraction and photoluminescent spectroscopy. XRD measurements confirmed the formation of hexagonal La₂O₃ and its recrystallization into La(OH)₃ in a humid atmosphere. Excitation spectra show redshift of host lattice and charge transfer emission bands in La(OH)₃ while bands that correspond to Eu³⁺f–f transitions are placed at same wavelengths in both samples. Photoluminescence spectra recorded over the temperature range from 10 K to 300 K show that intensities of emission lines in Eu³⁺-doped La₂O₃ do not depend on temperature as much as in La(OH)₃ sample. Observed dominant ⁵D₀→⁷F₂ and markedly visible ⁵D₀→⁷F₀ emissions in doped La₂O₃ indicate that Eu³⁺ ion is located in a structural site without an inversion center. On the other hand, in Eu³⁺-doped La(OH)₃⁵D₀→⁷F₀ transition is barely visible while ⁵D₀→⁷F₂ is not prominent, and with temperature drop three ⁵D₀→⁷F_J (J=1, 2, 4) transitions become almost of the same intensity. In both La₂O₃ and La(OH)₃ structures Eu³⁺ ion replaces La³⁺ in non-centrosymmetric C_3v and C_3h crystallographic sites, respectively, and difference in symmetry of the crystal field around europium ion is explained by comparing shape and volume of these sites. Decay times of the ⁵D₀- level recorded over the temperature range 10−300 K revealed that emission lifetime values in La₂O₃ (~0.7 ms) are almost two times higher than in La(OH)₃ (~0.4 ms), and unlike in La₂O₃, lifetime in La(OH)₃ is temperature dependent.     

LD抽运Er3+，Yb3+共掺磷酸盐玻璃被动调Q激光器的理论分析和数值计算

研究了以Co²⁺:MgAl₂O₄晶体为饱和吸收体的LD抽运Er³⁺,Yb³⁺共掺磷酸盐玻璃激光器.针对双掺离子之间的能量传递和Er³⁺的多种跃迁过程，结合Co²⁺:MgAl₂O₄晶体中Co²⁺离子的饱和吸收特性，给出了详尽的速率方程，在其基础上进行了数值分析，分析了输出镜透过率、激光介质长度、谐振腔长度、腔内往返损耗、饱和吸收体长度对激光阈值、峰值功率、单脉冲能量以及脉冲宽度的影响.