Eu2+, Cr3+共掺杂的MAl12O19 (M=Ca, Sr, Ba) 的发光性质及能量传递

三基色荧光粉中, 红色荧光粉性能较差, 为获得性能优良的红色荧光粉, 本文采用高温固相法合成了Eu²⁺, Cr³⁺单掺杂及共掺杂的碱土金属多铝酸盐MAl₁₂O₁₉ (M =Ca, Sr, Ba) 发光体. 实验表明, 在以上三种基质中均存在Eu²⁺→Cr³⁺的能量传递, 利用能量传递可以有效将Eu²⁺的蓝光或绿光转换为红光. 三种碱土金属多铝酸盐基质的晶体结构相似,但Eu²⁺, Cr³⁺发光受晶体场影响,导致在不同的基质中Eu²⁺, Cr³⁺间能量传递效率不同.通过光谱分析及能量传递效率计算发现, 相同掺杂浓度下,CaAl₁₂O₁₉中Eu²⁺→Cr³⁺的能量传递效率最高,SrAl₁₂O₁₉次之, BaAl₁₂O₁₉最低.红光转换率在CaAl₁₂O₁₉中最高.     

Low thermal quenching and high-efficiency Ce, Tb-co-doped Ca3Sc2Si3O12 green phosphor for white light-emitting diodes

Low thermal quenching and high-efficiency Ca₃Sc₂Si₃O₁₂:Ce³⁺ (CSSO:Ce³⁺) phosphors with co-doping Tb³⁺ ion were prepared by a solid state method and the properties of these phosphors were investigated. The results showed that co-doping of Tb³⁺ not only enhances the photoluminescence remarkably and decreases the thermal quenching of the phosphor, but also heightens the performances of the LEDs fabricated with the phosphor. A high-efficiency and low color temperature white LED was fabricated with the prepared CSSO:1%Ce³⁺, 0.5%Tb³⁺ and a red phosphor, indicating that CSSO:1%Ce³⁺,0.5%Tb³⁺ phosphor is a suitable green phosphor for the fabrication of high-efficiency white LEDs.     

Synthesis and characterization of monodisperse spherical core-shell structured SiO2@Y3Al5O12:Ce3+/Tb3+ phosphors for field emission displays

Nanocrystalline Y₃Al₅O₁₂: Ce³⁺/Tb³⁺ (average crystalline size 30 nm) phosphor layers were coated on non-aggregated, monodisperse and spherical SiO₂ particles by the sol-gel method, resulting in the formation of core-shell structured SiO₂@Y₃Al₅O₁₂:Ce³⁺/Tb³⁺ particles. X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, photoluminescence, cathodoluminescence spectra, as well as lifetimes were utilized to characterize the core-shell structured SiO₂@Y₃Al₅O₁₂:Ce³⁺/Tb³⁺ phosphor particles. The obtained core-shell structured phosphors consist of well-dispersed submicron spherical particles with a narrow size distribution. The thickness of the Y₃Al₅O₁₂:Ce³⁺/Tb³⁺ shells on the SiO₂ cores (average size about 500 nm, crystalline size about 30 nm) could be easily tailored by varying the number of deposition cycles (100 nm for four deposition cycles). Under the excitation of ultraviolet and low-voltage electron beams (1–3 kV), the core-shell SiO₂@Y₃Al₅O₁₂:Ce³⁺/Tb³⁺ particles show strong yellow-green and green emission corresponding to the 5d–4f emission of Ce³⁺ and ⁵D₄–⁷F _J (J = 6, 5, 4, 3) emission of Tb³⁺, respectively. These phosphors may have potential application in field emission displays.     

硼酸对亚微米级Ca3Sc2Si3O12:Ce绿色荧光粉的制备及发光性能的影响

采用凝胶-燃烧法合成了Ca₃Sc₂Si₃O₁₂ ∶Ce绿色LED用荧光粉,用X射线粉末衍射(XRD)、扫描电镜(SEM)、荧光光谱仪等对合成产物进行了分析和表征.结果表明:通过添加H₃BO₃做助熔剂,制得的荧光粉晶相纯正,颗粒形貌均呈现为较规则的类球形,而且所得荧光粉的粒径均小于1 μm.发射光谱呈现为一宽带,发射主峰位于505 nm,该宽峰对应于Ce³⁺关键词： 白光LED 荧光粉 3Sc₂Si₃O₁₂ ∶Ce')" href="#">Ca₃Sc₂Si₃O₁₂ ∶Ce 发光     

Effective energy transfer between Ceand Eu in CaAl2Si2O8 host under vacuum ultraviolet illumination

We presented the energy transfer from Ce³⁺ to Eu²⁺ in CaAl₂Si₂O₈ host. The Ce³⁺-doped CaAl₂Si₂O₈ phosphor had a strong emission band at 378 nm under the vacuum ultraviolet (VUV) light. This emission spectrum of Ce³⁺ well overlapped with the excitation spectrum of Eu²⁺ under the UV illumination. As a result, the energy transfer from Ce³⁺ to Eu²⁺ in CaAl₂Si₂O₈ matrix was observed under VUV excitation, which resulted in a significant enhancement of the emission peak intensity at 446 nm. More details about the luminescent properties were presented.     

Ba3Tb(BO3)3 ∶Ce3+:一种白光LED用绿色荧光粉

采用高温固相法合成了Ba₃Tb(BO₃)₃和Ba₃Tb(BO₃)₃ ∶Ce³⁺两种绿色荧光粉,并研究了材料的发光性质.Ba₃Tb(BO₃)₃材料呈多峰发射,发射峰位于439,493,547,589和629 nm,分别对应Tb³⁺的⁵D关键词： 白光LED 3Tb(BO₃)₃')" href="#">Ba₃Tb(BO₃)₃ 3+')" href="#">Ce³⁺ 发光特性     

Luminescence and energy transfer of white-light emitting CaAl2SiO6:Ce3+, Tb3+ phosphors

A novel white-light emitting CaAl₂SiO₆: Ce³⁺, Tb³⁺ phosphor has been prepared by a sol–gel method. X-ray diffractometry and spectrofluorometry were used to characterize structural and optical properties of the samples. The results indicate that the crystal structure of the phosphor is a single phase of CaAl₂SiO₆. The excitation band of the phosphor covers a wide region from 240 nm to 380 nm. CaAl₂SiO₆: Ce³⁺, Tb³⁺ phosphors show four emission bands: one at 400 nm for Ce³⁺ and three at 487 nm, 543 nm and 585 nm for Tb³⁺. With appropriate tuning of Tb³⁺ content, white light with different hues can be achieved under UV radiation. The energy transfer mechanism from Ce³⁺ to Tb³⁺ in CaAl₂SiO₆ host was demonstrated to be dipole–dipole interaction.     

Luminescence properties of cerium-doped di-strontium magnesium di-silicate phosphor by the solid-state reaction method

A series of Sr₂MgSi₂O₇:xCe³⁺ (x?=?1.0%, 2.0%, 3.0%, 4.0% and 5.0%) phosphors were synthesized by the solid-state reaction method. The phosphor with optimum thermoluminescence, photoluminescence and mechanoluminescence (ML) intensity was characterized by X-ray diffraction, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and Fourier transform infrared techniques. The trapping parameters (i.e. activation energy, frequency factor and order of the kinetics) of each synthesized phosphor have been calculated using the peak shape method and the results have been discussed. Under ultraviolet excitation (325?nm), Sr₂MgSi₂O₇:xCe³⁺ phosphors were composed of a broad band peaking at 385?nm, belonging to the broad emission band which emits violet-blue color. Commission International de I’Eclairage coordinates have been calculated for each sample and their overall emission is near violet-blue light. In order to investigate the suitability of the samples for industrial uses, color purity and color rendering index were calculated. An ML intensity of optimum [Sr₂MgSi₂O₇:Ce³⁺ (3.0%)] phosphor increases linearly with increasing impact velocity of the moving piston which suggests that these phosphors can be used as fracto-ML-based devices. The time of the peak ML intensity and the decay rate did not change significantly with respect to increasing impact velocity of the moving piston.     

Luminescent properties of a new green emitting Eu doped CaZrSi2O7 phosphor for WLED applications

CaZrSi₂O₇ (CZS), a modification of the thortveitite family, was prepared as a polycrystalline powder material by the conventional solid-state reaction method. Structural, thermal and photoluminescence (PL) properties of the prepared material were investigated in order to evaluate its potentiality. XRD patterns confirm the monoclinic phase of CaZrSi₂O₇: Eu²⁺ phosphors.. Emissions arising from transitions between the 5d and 4f orbital gaps of Eu²⁺ are manifested in the broadband excitation and emission spectra with major peaks at 363 and 512 nm, respectively. The excitation wavelength matches well with that of the emission of the ultraviolet-light emitting diode (UV-LED). Concentration quenching occurs when the Eu²⁺ concentration is beyond 0.05 and the dipole-dipole interaction was the reason for the corresponding quenching mechanism. The temperature dependence of emission intensity of CZS: Eu²⁺ phosphor was investigated and it showed better thermal stability than the standard YAG: Ce³⁺ phosphor.     

Ce$lt;sup$gt;3+$lt;/sup$gt;在LiBaBO$lt;sub$gt;3$lt;/sub$gt;中的发光特性及晶体学格位

采用固相法制备了LiBaBO₃：Ce³⁺发光材料.测得LiBaBO₃：Ce³⁺材料的发射光谱为一不对称的单峰宽谱,主峰位于440 nm;监测440 nm发射峰,可得其激发光谱为一主峰位于370 nm的宽谱.利用van Uitert公式计算了Ce³⁺取代LiBaBO₃中Ba²⁺时所占晶体学格位,得出438 nm发射带归属于九配位的Ce³⁺发射,而469 nm发射带起源于八配位的Ce³⁺发射.研究了Ce³⁺浓度对LiBaBO₃：Ce³⁺材料发光强度的影响,结果显示,随Ce³⁺浓度的增大,发光强度呈现先增大后减小的趋势,Ce³⁺浓度为3mol%时强度最大,造成其浓度猝灭的原因为电偶极-偶极相互作用.引入Li⁺,Na⁺或K⁺可增强LiBaBO₃：Ce³⁺材料的发射强度.利用InGaN管芯（370 nm）激发LiBaBO₃：Ce³⁺材料,获得了很好的蓝白光发射,色坐标为（x=0.291,y=0.297）. 关键词： 白光发光二极管 3：Ce³⁺')" href="#">LiBaBO₃：Ce³⁺ 晶体学格位 发光特性     

Thermoluminescence characteristics of rare-earth-doped LiCaBO3 phosphor

LiCaBO₃ was synthesized by high-temperature solid-state reaction. The influence of different rare earth dopants, i.e. Dy³⁺, Tb³⁺, Tm³⁺ and Ce³⁺, on thermoluminescence (TL) of LiCaBO₃ phosphor was discussed. We studied the TL properties and some dosimetric characteristics of Ce³⁺-activated LiCaBO₃ phosphor in detail. The effect of the concentration of Ce³⁺ on TL was investigated, the result of which showed that the optimum Ce³⁺ concentration was 1 mol%. The TL kinetic parameters of LiCaBO₃:0.01Ce³⁺ were studied by computer glow curve deconvolution (CGCD) method. The three-dimensional (3D) TL emission spectra were also studied, peaking at 431 and 474 nm due to the characteristic transition of Ce³⁺. We also studied the linearity, annealing condition, reproducibility, fading and different heating rate of the LiCaBO₃:0.01Ce³⁺ phosphor.     

Luminescence in trivalent rare earth activated Sr4Al2O7 phosphor

In this paper we report the combustion synthesis of trivalent rare-earth (RE³⁺ = Dy, Eu and Ce) activated Sr₄Al₂O₇ phosphor. The prepared phosphors were characterized by the X-ray powder diffraction (XRD) and photoluminescence (PL) techniques. Photoluminescence emission peaks of Sr₄Al₂O₇:Dy³⁺ phosphor at 474 nm and 578 nm in the blue and yellow region of the spectrum. The prepared Eu³⁺ doped phosphors were excited by 395 nm then we found that the characteristics emission of europium ions at 615 nm (⁵D₀?⁷F₂) and 592 nm (⁵D₀?⁷F₁). Photoluminescence (PL) peaks situated at wavelengths of 363 and 378 nm in the UV region under excitation at around 326 nm in the Sr₄Al₂O₇:Ce³⁺ phosphor.     

Observation of green emission from Ce-doped gadolinium oxide nanoparticles

Green emission at around 500 nm is observed in Gd₂O₃:Ce³⁺ nanoparticles and the intensity is highly dependent on the concentration of Ce³⁺ in the nanoparticles. The luminescence of this emission displays both picosecond (ps) and millisecond (ms) lifetimes. The ms lifetime is over four orders of magnitude longer than typical luminescence lifetimes (10-40 ns) of Ce³⁺ in traditional Ce³⁺ doped phosphors and therefore likely originates from defect states. The picosecond lifetime is shorter than the typical Ce³⁺ value and is also likely due to defect or surface states. When the samples are annealed at 700 °C, this emission disappears possibly due to changes in the defect moieties or concentration. In addition, a blue emission at around 430 nm is observed in freshly prepared Gd₂O₃ undoped nanoparticles, which is attributed to the stabilizer, polyethylene glycol biscarboxymethyl ether. On aging, the undoped particles show similar emission to the doped particles with similar luminescence lifetimes. When Eu³⁺ ions are co-doped in Gd₂O₃:Ce nanoparticles, both the green emission and the emission at 612 nm from Eu³⁺ are observed.     

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.     

Luminescence studies on the blue-green emitting Sr4Al14O25:Ce phosphor synthesized through solution combustion route

New blue-green emitting Sr₄Al₁₄O₂₅:Ce³⁺ phosphor is reported in this paper. The polycrystalline samples of phosphor were prepared by the conventional solution combustion method and checked for crystallization and phase by X-ray diffraction. Photoluminescence studies reveal the emission at 472 and 511 nm that correspond to the transition between lowest T_2g level of the 5d state to the ²F_5/2 and ²F_7/2 ground state levels of the Ce³⁺. The excitation at 275 nm corresponds to O²⁻→Ce⁴⁺ charge transfer processes to lowest 5d state of Ce ion (T_2g). Phosphorescence decay procedures reveal the existence of slow, medium, and fast component involved in the process. Varying the γ-dose (1-6 Gy), thermoluminescence (TL) measurements were made and glow curve maximum is obtained at 383 K. The phosphor seems to follow a first-order kinetics due to non-shifting T_m property. The T_m-T_stop method followed by the repeated initial rise method is applied to determine the distribution of activation energies and corresponding maximum positions. Chi-square minimization procedures provide the appropriate peak positions and other trapping parameters. From deconvolution results, the activation energies are found to be 0.84 and 1.06 eV, while the frequency factor is of the order of 10¹⁰ and 10¹¹ s⁻¹, respectively.     

Morphology and photoluminescence of BaAl12O19:Mn2+ green phosphor prepared by flux method

This paper reports that the green phosphor BaAl11.9O19:0.1Mn2+ is prepared by a flux assisted solid state reaction method.The effect of flux systems on the crystal structure,morphology and luminescent properties of the phosphor are studied in detail.The samples are characterized by the application of x-ray diffraction patterns,scanning electron microscopy patterns,luminescent spectra and decay curves.The results show that a pure phase BaAl12O19 can be achieved at the firing temperature above 1300℃ by adding the proper flux system,the firing temperature is reduced at least 200℃ in comparison with the conventional solid state reaction method.Maximum photoluminescence emission intensity is observed at 517 nm for(AlF3+Li2CO3) flux system under vacuum ultraviolet region(147 nm) excitation.The photoluminescence emission intensity and the decay time of these phosphor is found to be more superior to that of the corresponding sample prepared by the conventional solid state reaction method implying the suitability of this route for the preparation of display device worthy phosphor materials.     

Luminescent properties of green- or red-emitting Eu-doped Sr3Al2O6 for LED

Eu²⁺-doped Sr₃Al₂O₆ (Sr_3−xEu_xAl₂O₆) was synthesized by a solid-state reaction under either H₂ and N₂ atmosphere or CO atmosphere. When H₂ was used as the reducing agent, the phosphor exhibited green emission under near UV excitation, while CO was used as the reducing agent, the phosphor mainly showed red emission under blue light excitation. Both emissions belong to the d-f transition of Eu²⁺ ion. The relationship between the emission wavelengths and the occupation of Eu²⁺ at different crystallographic sites was studied. The preferential substitution of Eu²⁺ into different Sr²⁺ cites at different reaction periods and the substitution rates under different atmospheres were discussed. Finally, green-emitting and red-emitting LEDs were fabricated by coating the phosphor onto near UV- or blue-emitting InGaN chips.     

Eu3+掺杂的Sr2CeO4发光材料的光致发光研究

利用高温固相反应法制备了Eu³⁺掺杂的Sr₂CeO₄样品,并对其吸附水前后的光谱特性进行了研究.结果发现,对于刚制备的Sr_2-xEu_xCeO_4+x/2样品, 在Ce⁴⁺—O^2-的电荷迁移激发中,只有强激发带(～35700cm^-1)与Eu³⁺离子间存在能量传递,而弱激发带 (～29400cm^-1)只是引起Ce⁴⁺—O^2-的电荷迁移发射;在Sr_2-xEu_xCeO_4+x/2样品吸附水后,Eu³⁺的线状吸收跃迁强度显著增加, Ce⁴⁺—O^2-两个激发带均向Eu³⁺离子传递能量. Ce⁴⁺—O^2-强激发带通过交换作用向Eu³⁺离子传递能量,而弱激发带与Eu³⁺离子间的能量传递机理是非辐射多极子近场力的相互作用. 关键词： 2-xEu_xCeO_4+x/2')" href="#">Sr_2-xEu_xCeO_4+x/2 发光性质 能量传递 吸附水     

Luminescence of Ce and Pr doped Sr2Mg(BO3)2 under VUV-UV and X-ray excitation

This report presents the luminescence properties of Ce³⁺ and Pr³⁺ activated Sr₂Mg(BO₃)₂ under VUV-UV and X-ray excitation. The five excitation bands of crystal field split 5d states are observed at about 46 729, 44 643, 41 667, 38 314 and 29 762 cm⁻¹ (i.e. 214, 224, 240, 261 and 336 nm) for Ce³⁺ in the host lattice. The doublet Ce³⁺ 5d→4f emission bands were found at about 25 840 and 24 096 cm⁻¹ (387 and 415 nm). The influence of doping concentration and temperature on the emission characteristics and the decay time of Ce³⁺ in Sr₂Mg(BO₃)₂ were investigated. For Pr³⁺ doped samples, the lowest 5d excitation band was observed at about 42017 cm⁻¹ (238 nm), a dominant band at around 35714 cm⁻¹ (280 nm) and two shoulder bands were seen in the emission spectra. The excitation and emission spectra of Ce³⁺ and Pr³⁺ were compared and discussed. The X-ray excited luminescence studies show that the light yields are ∼3200±230 and ∼1400±100 photons/MeV of absorbed X-ray energy for the samples Sr_1.86Ce_0.07Na_0.07Mg(BO₃)₂ and Sr_1.82Pr_0.09Na_0.09Mg(BO₃)₂ at RT, respectively.     

NIR to visible upconversion in Er/Yb co-doped CaYAl3O7 phosphor obtained by solution combustion process

Using the combustion synthesis, CaYAl₃O₇:Er³⁺ phosphor powders co-doped with Yb³⁺ have been prepared at low temperatures (550 °C) in a few minutes. Formation of the compound was confirmed by X-ray powder diffraction. Near-infrared to visible upconversion fluorescence emission in the Er³⁺ doped CaYAl₃O₇ phosphor powder has been observed. The effect of co-doping with triply ionized ytterbium in the CaYAl₃O₇:Er³⁺ phosphor has been studied and the process involved is discussed.