Luminescence of Fe3+ in single crystals of LiAl5O8

We have measured the luminescent properties of single crystals of LiAl₅O₈:Fe³⁺. In addition to a zero-phonon line due to Fe³⁺ in A-sites, we have observed another sharp fluorescent line at 699.2 nm which we assign to Fe³⁺ occupying B-sites. The excitation spectrum of the B-site Fe³⁺ shows characteristics similar to those of the A-site Fe³⁺ but are also shifted towards longer wavelengths. The spectra of the single crystals are compared with those of ordered and disordered powder samples.     

Microstructure characterization and magnetic behavior of NiAlxFe2−xO4 and Ni1−yMnyAl0.2Fe1.8O4 ferrites

NiAl_xFe_2−xO₄ and Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites were prepared by the conventional ceramic method and were characterized by X-ray diffraction, scanning electron microscopy, and magnetic measurements. The single spinel phase was confirmed for all prepared samples. A proper explanation of data is possible if the Al³⁺ ions are assumed to replace Fe³⁺ ions in the A and B sites simultaneously for NiAl_xFe_2−xO₄ ferrites, and if the Mn²⁺ ions are assumed to replace Ni²⁺ ions in the B sites for Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites. Microstructural factors play an important role in the magnetic behavior of Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites with large Mn²⁺ content.     

Al掺杂的尖晶石型LiMn2O4的结构和电子性质

采用基于密度泛函理论的第一性原理方法, 在广义梯度近似(GGA)和GGA+U方法下对尖晶石型LiMn₂O₄及其Al掺杂 的尖晶石型LiAl_0.125Mn_1.875O₄晶体的结构和电子性质进行了计算. 结果表明: 采用GGA方法得到尖晶石型LiMn₂O₄是立方晶系结构, 其中的Mn离子为+3.5价, 无法解释它的Jahn-Teller 畸变. 给出的LiMn₂O₄能带结构特征也与实验结果不符. 而采用GGA+U方法得到在低温下的LiMn₂O₄和其掺杂 体系LiAl_0.125Mn_1.875O₄的晶体都是正交结构, 与实验一致. 也能明确地确定Mn的两种价态Mn³⁺/Mn⁴⁺的分布并且能够说明Mn³⁺O₆的z方向有明显的Jahn-Teller 畸变, 而Mn⁴⁺O₆则没有畸变. LiMn₂O₄的能带结构与实验比较也能够符合. 采用GGA+U方法对Al掺杂体系的LiAl_0.125Mn_1.875O₄的研究表明, 用Al替换一个Mn不会明显地改变晶体的电子性质, 但可以有效地消除Al³⁺O₆ 八面体的Jahn-Teller畸变, 从而改善正极材料LiMn₂O₄的性能, 这与电化学实验的观察结果相一致.     

Nature of unusual spontaneous and field-induced phase transitions in multiferroics RMn2O5

Complex magnetic, magnetoelectric and magnetoelastic studies of spontaneous and field-induced phase transitions in TmMn₂O₅ were carried out. In the vicinity of spontaneous phase transition temperatures (35 and 25 K) the magnetoelectric and magnetoelastic dependences demonstrated the jumps of polarization and magnetostriction induced by the field ∼150 kOe. These anomalies can be attributed to the influence of magnetic field on the conditions of incommensurate-commensurate phase transition at 35 K and the reverse one at 25 K. In b-axis dependences the magnetic field-induced spin-reorientation phase transition was also observed below 20 K. Finally the magnetoelectric anomaly associated with metamagnetic transition is observed below the temperature of rare-earth subsystem ordering at relatively small critical fields of 5 kOe. This variety of spontaneous and induced phase transitions in RMn₂O₅ stems from the interplay of three magnetic subsystems: Mn³⁺, Mn⁴⁺, R³⁺. The comparison with YMn₂O₅ highlights the role of rare earth in low-temperature region (metamagnetic and spin-reorientation phase transitions), while the phase transition at higher temperatures between incommensurate and commensurate phases should be ascribed to the different temperature dependences of Mn³⁺ and Mn⁴⁺ ions. The strong correlation of magnetoelastic and magnetoelectric properties observed in the whole class of RMn₂O₅ highlights their multiferroic nature.     

Luminescence of Mn ions in Tb3Al5O12 garnet

The paper is dedicated to investigation of the Mn²⁺ luminescence in Tb₃Al₅O₁₂ (TbAG) garnet, as well as the processes of excitation energy transfer between host cations (Tb³⁺ ions) and activators (Mn²⁺ and Mn²⁺-Ce³⁺ pair ions) in single crystalline films of TbAG:Mn and TbAG:Mn,Ce garnets which can be considered as promising luminescent materials for conversion of LED's radiation. Due to the effective energy transfer between TbAG host and activator, Mn²⁺ ions in TbAG possess the bright orange luminescence in the bands peaked at 595 nm with a lifetime of 0.64 ms which are caused by the ⁴T₁→⁶A₁ radiative transitions. The simultaneous process of energy transfer is realized in TbAG:Mn,Ce: (i) from Tb³⁺ to Mn²⁺ ions; (ii) from Tb³⁺ cations to Ce³⁺ ions and then partly to Mn²⁺ ions through Tb³⁺ ion sublattice and Ce-Mn dipole-dipole interaction.     

EPR, luminescence and IR studies of Mn activated ZnGa2O4 phosphor

Electron paramagnetic resonance (EPR), luminescence and infrared spectra of Mn²⁺ ions doped in zinc gallate (ZnGa₂O₄) powder phosphor have been studied. The EPR spectra have been recorded for zinc gallate phosphor doped with different concentrations of Mn²⁺ ions. The EPR spectra exhibit characteristic spectrum of Mn²⁺ ions (S=I=5/2) with a sextet hyperfine pattern, centered at g_eff=2.00. At higher concentrations of Mn²⁺ ions, the intensity of the resonance signals decreases. The number of spins participating in the resonance has been measured as a function of temperature and the activation energy (E_a) is calculated. The EPR spectra of ZnGa₂O₄: Mn²⁺ have been recorded at various temperatures. From the EPR data, the paramagnetic susceptibility (χ) at various temperatures, the Curie constant (C) and the Curie temperature (θ) have been evaluated. The emission spectrum of ZnGa₂O₄: Mn²⁺ (0.08 mol%) exhibits two bands centered at 468 and 502 nm. The band observed at 502 nm is attributed to ⁴T₁→⁶A₁ transition of Mn²⁺ ions. The band observed at 468 nm is attributed to the trap-state transitions. The excitation spectrum exhibits two bands centered at 228 and 280 nm. The strong band at 228 nm is attributed to host-lattice absorption and the weak band at 280 nm is attributed to the charge-transfer absorption or d⁵→d⁴s transition band. The observed bands in the FT-IR spectrum are assigned to the stretching vibrations of M-O groups at octahedral and tetrahedral sites.     

Synthesis and luminous characteristics of Ba2MgSi2−xAlxO7: 0.1Eu, 0.1Mn phosphor for WLED

The shift of the emission band to longer wavelength (yellow-orange) of the Ba₂MgSi_2−xAl_xO₇: 0.1Eu²⁺ phosphor under the 350-450 nm excitation range has been achieved by adding the codoping element (Mn²⁺) in the host. The single-host silicate phosphor for WLED, Ba₂MgSi_2−xAl_xO₇: 0.1Eu²⁺, 0.1Mn²⁺ was prepared by high-temperature solid-state reaction. It was found experimentally that, its three-color emission peaks are situated at 623, 501 and 438 nm, respectively, under excitation of 350-450 nm irradiation. The emission peaks at 438 and 501 nm originate from the transition 5d to 4f of Eu²⁺ ions that occupy the two Ba²⁺ sites in the crystal of Ba₂MgSi_2−x Al_xO₇, while the 623 nm emission is attributed to the energy transfer from Eu²⁺ ions to Mn²⁺ ions. The white light can be obtained by mixing the three emission colors of blue (438 nm), green (501 nm) and red (623 nm) in the single host. When the concentrations of the Al³⁺, Eu²⁺ and Mn²⁺ ions were 0.4, 0.1 and 0.1 mol, respectively, the sample presented intense white emission. The addition of Al ion to the host leads to a substantial change of intensity ratio between blue and green emissions. White light could be obtained by combining this phosphor with 405 nm light-emitting diodes. The near-ultraviolet GaN-based Ba₂MgSi_1.7 Al_0.3O₇: 0.1Eu²⁺, 0.1Mn²⁺ LED achieves good color rendering of over 85.     

Sm共掺对Sr4Al14O25:M (M=Mn4+, Cr3+）荧光粉发光性能的影响

用固相反应法合成了Sr₄Al₁₄O₂₅:M和Sr₄Al₁₄O₂₅:(M+Sm³⁺)(M=Mn⁴⁺, Cr³⁺)荧光粉, 研究了其发光性能．Sm的共掺并没有改变Sr₄Al₁₄O₂₅:Cr³⁺激发带和发射带的位置, 但是显著提高了材料的发光性能;Sm共掺Sr₄Al₁₄O₂₅:Mn⁴⁺反而降低了发光强度． 对于Cr³⁺, Sm³⁺共掺的Sr₄Al₁₄O₂₅荧光粉, 呈现了从Sm³⁺到Cr³⁺ 的辐射形式的能量传递过程,说明了Sm的共掺对于Sr₄Al₁₄O₂₅:Cr³⁺荧光粉的发光强度提高的原因．     

Green emitting long lasting phosphorescence (LLP) properties of Mg2SnO4:Mn phosphor

A novel long-lasting phosphorescence phosphor, Mn²⁺-activated Mg₂SnO₄, has been synthesized and its optical properties have been investigated. The Mg₂SnO₄:Mn²⁺ emits green light with high luminance, upon UV irradiation, centered at 499 nm from the spin forbidden transitions of the d-electrons in Mn²⁺ ions. The CIE chromaticity coordinates of the Mg₂SnO₄:Mn²⁺ phosphor are x=0.0875 and y=0.6083 under 254 nm UV excitation. The phosphorescence can be observed by the naked eyes (0.32 mcd/m²) in the dark clearly for over 5 h after the 5 min UV irradiation. Thermoluminescence has been studied and the mechanism of the long-lasting phosphorescence has been discussed.     

Electron spin resonance of diluted solid solutions of MnO2 in Y2O3

Electron spin resonance spectra of Mn²⁺ in diluted solid solutions of MnO₂ in Y₂O₃ have been studied at room temperature for Mn concentrations between 0.20 and 2.00 mol%. Isolated Mn²⁺ ions in sites with two different symmetries were observed, as well as Mn²⁺ ions coupled by the exchange interaction. The relative concentration of isolated to coupled Mn²⁺ ions decreases with increasing manganese concentration. The results are consistent with the assumption that the manganese ions occupy preferentially the C₂ symmetry sites. A theoretical calculation based on this model yields an effective range of the exchange interaction between Mn²⁺ ions of 0.53 nm, of the same order as that of Mn²⁺ ions in CaO.     

Energy transfer and excitation wavelength dependent long-lasting phosphorescence in Pr activated Y3Al5O12

Long-lasting phosphorescence (LLP) was observed in Pr³⁺-doped Y₃Al₅O₁₂ (YAG:Pr) after it was excited by 240 or 290 nm light. The photoluminescence (PL) and LLP properties were studied. It is interesting that the PL and LLP spectra were different. In the PL emission spectra both the emissions of d-f and f-f transitions of Pr³⁺ ions were observed. However, in the LLP spectra of YAG:Pr the emissions of d-f transition were absent. It is deduced that the differences were due to the energy transfer process between traps and emission centers. On the other hand, significant differences were observed between the two LLP spectra after the sample was excited by 240 and 290 nm lights, respectively. The thermoluminescence (TL) properties were also studied. It is suggested that these studies will be significant for understanding the mechanism of LLP phenomenon.     

The structure and luminescence properties of a novel orange emitting phosphor Y3MnxAl5−2xSixO12

A series of phosphors with the composition Y₃Mn_xAl_5−2xSi_xO₁₂ (x=0, 0.05, 0.1, 0.15, 0.2, 0.3, 0.4, 0.5, 0.6) was prepared through solid state reactions. X-ray powder diffraction analysis of samples shows that when co-doping content does not exceed 16% of Al³⁺, equimolar co-doping of Mn²⁺ and Si⁴⁺ does not change the garnet structure of phosphors, but makes the interplanar distance to decrease a certain extent. However, if the co-doping content exceeds 16%, new phases will form in the samples. The excitation and emission spectra of samples show that Mn²⁺ in Y₃Mn_xAl_5−2xSi_xO₁₂ emits broadband orange light (peak wavelength varies from 586 to 593 nm). With an increment in co-doping content, the emission intensity of the phosphors increases when the value of x is lower than 0.1 while it decreases when it is higher than 0.1 and the emission peak moves to a longer wavelength.     

A comparative study of the optical properties of Fe3+ in ordered LiGa5O8 and LiAl5O8

Measurements are reported on the fluorescence and excitation spectra of Fe³⁺-doped LiGa₅O₈ in the ordered phase. Spectral determinations were made with powder samples containing 0.01 to 1% atomic weight of Fe³⁺, within the temperature range 300 K to 25 K. A comparison is presented between the optical properties of trivalent iron in lithium gallate and in lithium aluminate, LiAl₅O₈, both in their ordered phases. The best fit with crystal field parameters B, C, and Dq, yields the following values for these parameters: Dq = 906 cm^-1, B = 594 cm^-1, and C = 3 737 cm^-1. As is the case with LiAl₅O₈:Fe³⁺, the Stokes shift in LiGa₅O₈:Fe³⁺ is very large, 3 624 cm^-1, although somewhat smaller than the 4 300 cm^-1 seen in LiAl₅O₈:Fe³⁺.     

Mn activated MgSrAl10O17 green-emitting phosphor—A luminescence and EPR study

This paper reports on the luminescence and electron paramagnetic resonance (EPR) investigations on MgSrAl₁₀O₁₇:Mn²⁺ green-emitting phosphor. Single-phase MgSrAl₁₀O₁₇ was successfully synthesized by the one-step solution combustion route without the need for post-annealing at a higher temperature. Crystallization of the powder was confirmed by X-ray diffraction. The luminescence of Mn²⁺- activated MgSrAl₁₀O₁₇ shows a strong green-emission peak around 515 nm due to the ⁴T₁→⁶A₁ transition of Mn²⁺ ions under the excitation (453 nm). The EPR spectra of Mn²⁺ ions exhibit a sextet hyperfine structure centered at g ≈1.995. The Mn²⁺ ion occupies Mg sites which are in tetrahedral symmetry. The magnitude of the hyperfine splitting (A) indicates that Mn²⁺ is in a moderately ionic environment. The number of spins participating in resonance (N), the paramagnetic susceptibility (χ) and the zero-field splitting parameter (D) have been evaluated and discussed.     

Photoluminescence properties of Eu and Mn-activated BaMgP2O7 as a potential red phosphor for white-emission

A phosphate compound, BaMgP₂O₇ was co-doped with Eu²⁺ and Mn²⁺ for making a red-emitting phosphor. The phosphor was prepared by a solid-state reaction at high temperature. The photoluminescence properties were investigated under ultraviolet (UV) ray excitation. From a powder X-ray diffraction (XRD) analysis, the formation of single-phased BaMgP₂O₇ with a monoclinic structure was confirmed. In the photoluminescence spectra, the BaMgP₂O₇:Eu,Mn phosphor emits two distinctive colors: a blue band centered at 409 nm originating from Eu²⁺ and a red band at 615 nm caused by Mn²⁺. Also, efficient energy transfer from Eu²⁺ to Mn²⁺ in the BaMgP₂O₇:Eu,Mn system was verified by observing that the excitation spectra of BaMgP₂O₇:Eu,Mn emitted at 409 and 615 nm by Eu²⁺ emission and Mn²⁺ emission, respectively, are almost the same as that of BaMgP₂O₇:Eu monitored at 409 nm. The optimum concentration of Eu²⁺ ions in BaMgP₂O₇:0.015Eu excited at 309 nm wavelength is 1.5 mol%. With an increase of Mn²⁺ content up to 17.5 mol%, a systematic decline in the intensity of the excitation spectrum by Eu²⁺ and a gradual growth in the intensity of emission band by Mn²⁺ were observed. Accordingly, the optimum concentration of Mn²⁺ in BaMgP₂O₇:0.015Eu,Mn is 17.5 mol%. The maximum spectral overlap between emission of Eu²⁺ and excitation of Mn²⁺ is achieved in a composition of BaMgP₂O₇:0.015Eu,0.175Mn, resulting in considerable red-emission at 615 nm.     

EPR and photoluminescence properties of green light emitting LaAl11O18:Mn phosphors

The LaAl₁₁O₁₈:Mn²⁺ powder phosphor has been prepared using a self-propagating synthesis. Formation and homogeneity of the LaAl₁₁O₁₈:Mn²⁺ phosphor has been verified by X-ray diffraction and energy dispersive X-ray analysis respectively. The EPR spectra of Mn²⁺ ions exhibit resonance signals with effective g values at g≈4.8 and g≈1.978. The signal at g≈1.978 exhibits six-line hyperfine structure and is due to Mn²⁺ ions in an environment close to tetrahedral symmetry, whereas the resonance at g≈4.8 is attributed to the rhombic surroundings of the Mn²⁺ ions. It is observed that the number of spins participating in resonance for g≈1.978 increases with decreasing temperature obeying the Boltzmann law. Upon 451 nm excitation, the photoluminescence spectrum exhibits a green emission peak at 514 nm due to ⁴T₁ (G)→⁶A₁ (S) transition of Mn²⁺ ions. The crystal field parameter Dq and Racah inter-electronic repulsion parameters B and C have been evaluated from the excitation spectrum.     

Phase coexistence in annealed CaMn7O12

The structural phase transition in annealed CaMn₇O₁₂ has been investigated by using high resolution synchrotron radiation powder diffraction. There is a phase coexistence phenomenon: two different crystallographic phases coexist in the material between 410 and 458 K. The first one is trigonal and it has a charge ordering (CO) of the Mn³⁺ and Mn⁴⁺ ions, while the second one is cubic and charge delocalized (CD). The volume fraction of the CD phase increases with temperature from 22% at 418 K up to 100% at 468 K. Both phases have domains of at least 150 nm at each temperature. The annealing of CaMn₇O₁₂ relaxed a part of the strains in the lattice, but did not influence the phase coexistence phenomenon.     

Synthesis and characterization of Sr3Al2O6：Eu2＋, Dy3＋ phosphors prepared by sol-gel-combustion processing

A type of red luminescent Sr3Al2O6:Eu2+, Dy3+ phosphor powder is synthesised by sol-gel-combustion processing, with metal nitrates used as the source of metal ions and citric acid as a chelating agent of metal ions. By tracing the formation process of the sol-gel, it is found that it is necessary to reduce the amount of NO3- by dropping ethanol into the solution for forming a stable and homogeneous sol-gel. Thermogravimetric and Differential Scanning Calorimeter Analysis, x-ray diffractionmeter, scanning electron microscopy and photoluminescence spectroscopy are used to investigate the luminescent properties of the as-synthesised Sr3Al2O6:Eu2+, Dy3+. The results reveal that the Sr3Al2O6 crystallises completely when the combustion ash is sintered at 1250 C. The excitation and the emission spectra indicate that the excitation broadband lies mainly in a visible range and the phosphors emit a strong light at 618 nm under the excitation of 472 nm. The afterglow of (Sr0.94Eu0.03Dy0.03)3Al2O6 phosphors sintered at 1250 ℃ lasts for over 1000 s when the excited source is cut off.     

EPR observation of phase transitions in calcium cadmium acetate hexahydrate: Using Mn2+ and Cu2+ ions as probe

Results of temperature dependence of EPR spectra of Mn²⁺ and Cu²⁺ ions doped calcium cadmium acetate hexahydrate (CaCd(CH₃COO)₄·6H₂O) have been reported. The investigation has been carried out in the temperature range between room temperature (～ 300 K) and liquid nitrogen temperature. A I-order phase transition at 146 ± 0.5 K has been confirmed. In addition a new II-order phase transition at 128 ± 1 K has been detected for the first time. There is evidence of large amplitude hindered rotations of CH₃ groups which become frozen at ～ 128 K. The incorporation of Cu²⁺ and Mn²⁺ probes at Ca²⁺ and Cd²⁺ sites respectively provide evidence that the phase transitions are caused by the molecular rearrangements of the common coordinating acetate groups between Ca²⁺ and Cd²⁺ sites. In contradiction to the previous reports of a change of symmetry from tetragonal to orthorhombic below 140 K, the symmetry of the host is concluded to remain tetragonal in all the three observed phases between room temperature and liquid nitrogen temperature.     

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