Y2O2S:Eu3+,Zn2+,Ti4+荧光体的缺陷及红色长余辉发光性质

采用高温固相法合成了红色长余辉材料Y2O2S:Eu3+,Zn2+,Ti4+,实现了余辉发光中心和缺陷中心之间的能量传递。通过XRD、荧光发射和激发光谱、余辉发射光谱与衰减曲线、色坐标和热释光谱测试手段对Y2O2S:Eu3+,Zn2+、Y2O2S:Eu3+,Ti4+、Y2O2S:Eu3+,Zn2+,Ti4+和Y2O2S:Eu3+,Mg2+,Ti4+进行了结构与性能的表征,发现其荧光发射与余辉发射基本一致,红色余辉发光主峰位于625 nm附近,来源于Eu3+的5D0→7F2跃迁发射。相比而言,Y2O2S:Eu3+,Zn2+,Ti4+余辉发光性能最好,可持续1.5 h左右。     

Structural investigation and luminescent properties of BaZr(BO<Subscript>3</Subscript>)2:Eu<Superscript>3+</Superscript> phosphors containing Si

Si⁴⁺-doped BaZr(BO₃)₂:Eu³⁺ phosphors are prepared by a conventional solid-state reaction. The influence of Si⁴⁺ addition on the charge transfer state of Eu³⁺-O^2– and photoluminescence (PL) properties of BaZr(BO₃)₂:Eu³⁺ are discussed. Room temperature PL spectra indicated that efficient emission is obtained by Si doping. Increased values for the peak-peak ratio (PPR) of BaZr(BO₃)₂:Eu³⁺ at higher Si doping concentrations implied that the Eu³⁺ ion is located in a more asymmetric environment in BaZr_0.8Si_0.2(BO₃)₂:Eu³⁺ than in the undoped samples. The Judd-Ofelt parameters Ω_λ (λ=2,4) were calculated from the PL data, giving results that were consistent with those from the PPR. The maximum radiative quantum efficiency was achieved at a Si doping concentration of 20 mol%.     

Novel trichromatic phosphor Co-doped with Eu, Tb in SiO2 gel matrix

The Eu, Tb co-doped SiO2 matrix tricolor fluorescence system was prepared by sol-gel technique. Red emission at 618 nm, green emission at 543 nm and blue emission at 350-500 nm were observed in the PL spectra of the sample, indicating that Eu^3＋, Eu^2＋ and Tb^3＋ ions coexisted in the matrix. In the co-doped sample, the blue emission of Eu^2＋ was much stronger than that of the sample single doped with Eu, which implied that the electron transfer between Eu^3＋ and Tb^3＋ maybe happened in the SiO2 matrix. The influences of the annealing temperature and Tb concentration on the PL spectra of the samples were investigated. The optimal doped concentration of Tb was determined to be 0.2% and the optimal annealing temperature 850℃. Annealed at 600℃, Tb^3＋ had a sensitizing effect on Eu^3＋ in the SiO2 matrix, and the emission intensity of Eu^3＋ in the Eu, Tb co-doped sample was more than four times that of the single doped sample, which could be attributed to the energy transfer from Tb^3＋ to Eu^3＋.     

Synthesis and luminescence properties of Eu3+, Sm3+ doped (YxGd1-x)2O3:Si4+, Mg2+ long-lasting phosphor

A novel red long-lasting phosphor, (Y_1−x Gd _x )₂O₃:Eu³⁺, Sm³⁺, Si⁴⁺, Mg²⁺, was synthesized by the co-precipitation method using oxalate precipitation as the precursor. X-ray diffraction (XRD), scanning electronic microscopy (SEM), integrated thermal analyzer (TG), and photoluminescence spectra (PL) as well as the ST-900PM weak light photometer were used to study the synthesis conditions, morphology, luminescence properties, and the decay time of the phosphor. The XRD results show that the products synthesized at 1400°C for 4 h have good crystallization without any detectable impurity phases. Based on the PL spectra, the optimal conditions are as the following. The molar ratios of Y³⁺ to Gd³⁺ and Eu³⁺ to Sm³⁺ are 2:8 and 3:1, respectively, and the contents of Mg²⁺ and SiO₂ are 5mol% and 3mol%, respectively. The decay time monitored by the ST-900PM weak light photometer is 7200 s, increasing 44% and 100%, respectively, compared with the Eu³⁺ and Sm³⁺ single-doped phosphors. The results indicate that the energy transfer is from Sm³⁺ to Eu³⁺ ion, and Sm³⁺ is a good sensitizer to Eu³⁺.     

Photoluminescence and cathodoluminescence properties of CaLaGa<Subscript>3</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>3+</Superscript> phosphors

The CaLaGa₃O₇:Eu³⁺ phosphor was prepared by a chemical co-precipitation method. Field emission scanning electron microscopy (FE-SEM), laser particle size analysis, X-ray diffraction (XRD), photoluminescence (PL), and cathodoluminescence (CL) spectra were utilized to characterize the synthesized phosphor. The results revealed that the phosphor was composed of microspheres with a slight agglomerate phenomenon and was spherically shaped. The average grain size was about 1.0 μm. Eu³⁺ ions, as luminescent centers, substituted La³⁺ ions into the single crystal lattice of CaLaGa₃O₇ with the sites of C_s. Although the CL spectrum was greatly different from the PL spectrum, it had the strongest red emission corresponding to the ⁵D₀ →⁷F₂ transition of Eu³⁺. Under the excitation of UV light (287 nm) and electron beams (1.0–7.0 kV), the chromaticity coordinates of the phosphor were found to be in the nearly red and orange light regions, respectively.     

Thermal degradation of BaAl2Si2O8：Eu2＋ phosphor excited by near ultraviolet light

Eu2+ doped BaAl2Si2O8 phosphor was synthesized by one-step calcination of precursors that were prepared by chemical co-precipitation.The thermal degradation properties of BaAl2Si2O8:Eu2+ were investigated by photoluminescence,lifetime and chromaticity coordinate measurements.BaAl2Si2O8:Eu2+ is efficiently excited by incident light of 250-400 nm,which matches the emission of near ultraviolet LED chips well.BaAl2Si2O8:Eu2+ exhibits broad blue emission at 470 nm because of the 4f65d1-4f7(8S7/2) transition of Eu2+ ions,and the emission band shows an unusual blue shift with bandwidth broadening and emission intensity decreasing as the annealing temperature is increased.The luminescence decay and CIE chromaticity coordinates of BaAl2Si2O8:Eu2+ were determined to investigate its application in white LEDs.     

基于掺铕钨酸盐荧光强度比的非接触温度传感

为了突破传统测温技术应用的局限性,利用NaY （WO₄）₂：Eu³⁺玻璃陶瓷（glass ceramics,GC）实现了具有非接触、实时响应、自校准等优势的双模荧光强度比（luminescence intensity ratio,LIR）测温。采用高温熔融淬灭法制备出含NaY （WO₄）₂：Eu³⁺纳米晶的透明GC样品,并进行系列光谱测量和热敏性能分析。结果表明,样品中Eu³⁺的激发态能级⁵D₁和⁵D₀和基态能级⁷F₂和⁷F₀为两对独立的热耦合能级,可分别基于这两对热耦合能级实现性能优异的双模LIR温度传感。该双模LIR测温技术数据可靠、测温范围广、灵敏度高,再结合GC材料优势,是可用于光纤温度传感器的核心技术材料。     

Potential red-emitting phosphor GdNbO4:Eu3+,Bi3+ for near-UV white light emitting diodes

A red-emitting phosphor GdNbO₄:Eu³⁺,Bi³⁺ was prepared by a high temperature solid-state reaction technique. The phosphor was characterized by X-ray diffraction (XRD), particle size analyzer and fluorescence spectrometer. The single phase of GdNbO₄:Eu³⁺,Bi³⁺ was obtained at 1150°C and the average particle diameter was about 2.30 ??m. Excitation and emission spectra reveal that the phosphor can be efficiently excited by ultraviolet (UV) light (394 nm) and emit the strong red light of 612 nm due to the Eu³⁺ transition of ⁵D₀??⁷F₂. The optimum content of Eu³⁺ doped in the phosphor GdNbO₄:Eu³⁺ is 20mol%. The phosphor Gd_0.80NbO₄:0.20Eu³⁺,0.03Bi³⁺ shows much stronger photoluminescence intensity and better chromaticity coordinates (x=0.642, 0.352) than GdNbO₄:Eu³⁺. It is confirmed that Gd_0.80NbO₄:0.20Eu³⁺,0.03Bi³⁺ is a potential candidate for near-UV chip-based white light emitting diodes.     

Preparation of Gd2O3:Eu3+ downconversion luminescent material and its application in dye-sensitized solar cells

Gd₂O₃:Eu³⁺ downconversion luminescent powder was prepared using the homogeneous precipitation method. Its optical properties were analyzed and it was introduced into a dye-sensitized solar cell (DSSC). As a luminescence medium, Gd₂O₃:Eu³⁺ improved light harvesting via conversion luminescence and increased the photocurrent of the DSSC. As a p-type dopant insulating rare earth oxides form an energy barrier, and the Gd₂O₃:Eu³⁺ elevated the energy level of the oxide film and increased the photovoltage. The photoelectric conversion efficiency for a DSSC with Gd₂O₃:Eu³⁺ doping (6:100) reached 7.01%, which was 17.4% higher than the photoelectrical conversion efficiency of a DSSC without Gd₂O₃:Eu³⁺ doping.     

Luminescent Cu doped CdTe nanocrystals via cation exchange of Cu7Te5 nanocubes: From undoped to doped emission

In II-VI group, the doping in CdTe nanocrystals (NCs) is more difficult than other chalcogenides. In this communication, CdTe nanocrystals containing Cu impurities were carefully synthesized based on controlled reverse cation exchange process between as-prepared Cu₇Te₅ nanocubes and Cd²⁺ ions. By well-defined Cu₇Te₅ nanocubes, the obtained CdTe NCs kept the original morphology. The concentration of Cu impurities in CdTe NCs was controlled by the regulation such reverse cation exchange. Additionally, the regulation from band gap (BG) photoluminescence (PL) to the coexistence of the bandgap emission, dopant emission, and surface-state emission was realized. This tailoring from undoped to doped emission in the case of Cu impurities is helpful to study the Cu related doping in telluride NCs.     

Preparation and luminescence characteristics of Sr3SiO5：Eu^2＋ phosphor for white LED

The Sr3SiO5：Eu^2＋ phosphor was synthesized by high temperature solid-state reaction. The emission spectrum of Sr3SiO5：Eu^2＋ shows two bands centered at 487 and 575 nm, which well agree with the theoretic values of emission spectrum. The excitation spectrum for 575 nm emission center has several excitation bands at 365, 418, 458 and 473 nm. And the results show that the emission spectrum of Sr3SiO5：Eu^2＋ is influenced by the Eu^2＋ concentration. The relative emission spectra of the white-emitting InGaN-based YAG：Ce^3＋ LED and Sr3SiO5：Eu^2＋ LED were investigated. The results show that the color development of InGaN-based Sr3SiO5：Eu^2＋ is better than that of InGaN-based YAG：Ce^3＋, and the CIE chromaticity of InGaN-based Sr3SiO5：Eu^2＋ is （x=0.348, y=0.326）.     

Hydrothermal synthesis of ultrathin Bi2MO6 (M=W,Mo) nanoplates as new host substances for red-emitting europium ion

Ultrathin Bi2MO6 (M?W, Mo) nanoplates were synthesized by a simple hydrothermal method. SEM, EDS and XRD were used to investigate the morphologies and compositions of the samples from BiONO3 nanoplates along with some nanoparticles, to precursory Bi2WO6 nanoplates and Bi2MoO6 nanoparticles, and to final Bi2MO6 nanoplates. The possible formation mechanism of products was proposed. The experimental results exhibited that Bi2MO6 nanoplates had stronger light adsorption in ultraviolet–visible range. Bi2MO6 nanoplates were useful host for rare earth ions, Eu3twas successfully doped in Bi2MO6 nanoplates and an energy efficiently transferred from Bi3t to Eu3t, displaying intense red color under ultraviolet (UV) light excitation. The morphologies of products kept constant after doping. It is suggested that Bi2MO6:Eu nanoplates have promising application in fluorescent mark.     

Microstructure investigation and multicolor upconversion in Yb~(3+)/Ln~(3+)(Ln=Er/Tm/Ho) ions doped α-Sialon

Yb~(3+)/Ln~(3+)(Ln=Er/Tm/Ho)-α-sialon ceramics were fabricated by hot press sintering technique.Their microstructure and luminescent properties were studied by XRD,EDS,HRTEM and photoluminescence measurements.The results showed that the sintered ceramics consisted ofα-Sialon with a trace amount ofβ-Sialon phase.The frequency upconversion and downconversion properties of Yb~(3+)/Ln~(3+)(Ln=Er/Tm/Ho)-α-Sialon ceramics were investigated under 980 nm low-power excitation.The different concentrations of Yb~(3+)/Ln~(3+)(Ln=Er/Tm/Ho)produced multicolor emissions characteristics of each Ln~(3+)ion as a result of the energy transfer from Yb~(3+)to Er~(3+),Tm~(3+)and Ho~(3+)ions.The EDS spectra measurements and mappings showed that the Ln~(3+)ions were well incorporated in theα-Sialon matrix.Temporal evolution of the emission decay behavior has been investigated to understand the energy transfer mechanism.     

Internal energy transfer phenomenon and light-emission properties of γ-LiAlO2 phosphor doped with Mn2+

γ-LiAlO₂:Mn²⁺ phosphor was synthesized using the cellulose-citric acid sol-gel method, and its light emission and energy transfer properties were investigated. Excitation and emission spectrum analysis revealed a decrease in intensity of the spectrum as the amount of Mn²⁺ doping increased. Blasse’s equation determined the maximum distance for energy transfer between Mn²⁺ ions as 4.3142 nm. Dexter’s theory verifies that the mechanism of energy transfer between Mn²⁺ ions conforms to an electric dipole and electric quadrupole interaction.     

近红外发射荧光材料的研究

近红外发射材料在便携式近红外光谱仪、太阳能电池、光学通信、环境监测等领域有着潜在应用价值.其主要包含掺杂过渡金属离子(如Cr~(3+))、掺杂稀土离子(如Yb~(3+),Eu~(2+))的荧光粉以及半导体量子点(如Ag_2S,PbS).结合以上分类,介绍了近年来近红外发射材料的研究进展.     

Investigation of the electronic structure and photoluminescence properties of Eu3＋ in Sr2Mgl_xZnxSi207 （0 〈x 〈 1）

Undoped and Eu 3+-doped Sr 2 Mg 1-x Zn x Si 2 O 7 (0≤x≤1) powder crystals were obtained by conventional solid-state reaction.X-ray diffraction,inductively coupled plasma analysis,and Fourier transform infrared spectroscopy results implied that a complete solid-solution formed between Sr 2 MgSi 2 O 7 and Sr 2 ZnSi 2 O 7 as well as local structural adjustment.Excitation spectra exhibited O 2-Eu 3+ charge transfer (CT) bands centered at 250 nm for Sr 2 MgSi 2 O 7:Eu 3+ and 258 nm for Sr 2 ZnSi 2 O 7:Eu 3+.Emission spectra exhibited a major band around 616 nm,which showed the environment around Eu 3+ was non-centrosymmetric in both Sr 2 MgSi 2 O 7:Eu 3+ and Sr 2 ZnSi 2 O 7:Eu 3+.In addition,first principles calculations within the local density approximation (LDA) of density functional theory (DFT) were used to calculate the electronic structure of Sr 2 MgSi 2 O 7 and Sr 2 ZnSi 2 O 7.Calculated results were correlated with experimental UV-vis reflection spectra and the observed shift of the O 2-Eu 3+ CT band.     

立方相Lu2O3:Eu3+纳米晶的可控合成和发光性质

采用水热方法, 通过调节前驱体的pH值, 得到不同形貌的立方相Lu₂O₃:Eu³⁺纳米棒、纳米片和纳米颗粒。利用粉末X射线衍射(XRD)、扫描电镜(SEM)、傅里叶变换红外(FTIR)光谱、光致发光(PL)谱和荧光寿命(FL)等技术对所制备的纳米晶进行了系列表征。随着纳米晶尺寸的减少, 样品的荧光强度明显减弱, 这是由于吸附在纳米晶表面的OH^-含量逐渐增加, 加速了非辐射弛豫从而降低了发光效率。此外, 也观测到源于纳米晶表面Eu³⁺离子的逐渐加强的624 nm发射以及在长波侧不断延伸的电荷迁移带长激发尾。     

Effect of Tm-Er concentration ratio on the photoluminescence of Er-Tm:Al2O3 thin films fabricated by pulsed laser deposition

Er-Tm codoped amorphous aluminum oxide （a-Al2O3） thin films have been prepared by an alternative pulsed laser deposition. The phase structure and the surface of the deposited thin films were characterized by the X-ray diffraction （XRD） and scanning electron microscopy （SEM）, respectively. Effective photoluminescence （PL） in the region of 350-900 nm was observed when pumped at 325 nm, and the PL performance has been improved by modifying the Tm^3＋ concentration. With the increasing of [Tm]/[Er] concentration ratio, the intensity of emission of 382 nm and 500 nm bands was improved effectively while that of 765 nm band increased smoothly. Our results suggest that the resonant energy transfer and cross relaxation between Tm^3＋ and Er^3＋ play an important role in the evolution of the luminescent response.     

Effect of Tm-Er concentration ratio on the photoluminescence of Er-Tm:Al2O3 thin films fabricated by pulsed laser deposition

Er-Tm codoped amorphous aluminum oxide (a-Al2O3) thin films have been prepared by alternative pulsed laser deposition. The phase structure and surface of the deposited thin films were characterized by the X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Effective photoluminescence (PL) in the region of 350-900 nm was observed when pumped at 325 nm, and the PL performance has been improved by modifying the Tm³⁺ concentration. With the increasing of [Tm]/[Er] concentration ratio, the intensity of emission of 382 nm and 500 nm bands was improved effectively while that of 765 nm band increased smoothly. Our results suggest that the resonant energy transfer and cross relaxation between Tm³⁺ and Er³⁺ play an important role in the evolution of the luminescent response.     

白光LED用橙色发射荧光粉Y_3Mg_2AlSi_2O_(12)∶Ce~(3+)的制备研究

采用X射线衍射(XRD)、扫描电子显微镜(SEM)、激发-发射光谱及反射光谱等手段,研究了以尿素为燃料的溶胶-凝胶燃烧法,制备白光LED用Y_3Mg_2AlSi_2O_(12)∶Ce~(3+)荧光粉过程中的还原温度、Ce~(3+)浓度等因素,对荧光粉结构、形貌和发光性能的影响.比较了溶胶-凝胶燃烧法和高温固相反应法制备的Y_3Mg_2AlSi_2O_(12)∶Ce~(3+)荧光粉的结晶度、形貌和发光性能,并从反应过程对造成两者差异的原因进行了讨论.