Nanosized strontium aluminate phosphors prepared via a reverse microemulsion route

Nanosized strontium aluminate phosphors co-activated by Eu²⁺ and Dy³⁺ were prepared via a novel reverse microemulsion process. This new synthesis technique lowered the synthesis temperature of SrAl₂O₄: Eu²⁺, Dy³⁺ phosphors to as low as 900 °C, and also reduced the particle size to the nanometer scale (around 40 nm). In the microemulsion process, the constituent cations were trapped by numerous nano-scaled micelles, leading to a shortening of the inter-diffusion length and enhancement of the precursor reactivity. The excitation intensity and emission peaks of nanosized SrAl₂O₄: Eu²⁺, Dy³⁺ phosphors significantly increased with increasing heating temperatures.     

Eu2+和Dy3+掺杂浓度对Sr2MgSi2O7材料的荧光和长余辉性能的影响

采用高温固相法制备得到Sr₂MgSi₂O₇: Eu²⁺和Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺发光粉, 并详细研究了Eu²⁺和Dy³⁺的掺杂浓度对Sr₂MgSi₂O₇材料的荧光和长余辉性能的影响。所有样品都在470 nm附近呈现较宽的发光峰, 这可归因于Eu²⁺离子的4f⁶5d→4f⁷电子能级跃迁。当Eu²⁺掺杂浓度超过淬灭浓度, 其浓度淬灭效应导致发光粉的荧光强度下降和余辉时间减短。同时, 发射峰的峰位随Eu²⁺浓度的增加而发生红移, 这主要由于晶体场分裂能和斯托克斯位移变化造成的, 而电子云扩大效应变化所产生的影响相对较弱。Dy³⁺离子会抑制荧光, 但有助于延长余辉时间。当其掺杂浓度超过10mol%时, Eu²⁺\Dy³⁺离子通过隧道复合机制发生浓度淬灭, 从而使材料的长余辉寿命减少。     

Preparation, patterning and luminescent properties of nanocrystalline Gd2O3:A (A=Eu, Dy, Sm, Er) phosphor films via Pechini sol–gel soft lithography

Nanocrystalline Gd₂O₃:A (A=Eu³⁺, Dy³⁺, Sm³⁺, Er³⁺) phosphor films and their patterning were fabricated by a Pechini sol–gel process combined with a soft lithography. X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and optical microscopy, UV/vis transmission and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 500 °C and that the crystallinity increased with the elevation of annealing temperatures. Uniform and crack free non-patterned phosphor films were obtained by optimizing the composition of the coating sol, which mainly consisted of grains with an average size of 70 nm and a thickness of 550 nm. Using micro-molding in capillaries technique, we obtained homogeneous and defects-free patterned gel and crystalline phosphor films with different stripe widths (5, 10, 20 and 50 μm). Significant shrinkage (50%) was observed in the patterned films during the heat treatment process. The doped rare earth ions (A) showed their characteristic emission in crystalline Gd₂O₃ phosphor films due to an efficient energy transfer from Gd₂O₃ host to them. Both the lifetimes and PL intensity of the rare earth ions increased with increasing the annealing temperature from 500 to 900 °C, and the optimum concentrations for Eu³⁺, Dy³⁺, Sm³⁺, Er³⁺ were determined to be 5, 0.25, 1 and 1.5 mol% of Gd³⁺ in Gd₂O₃ films, respectively.     

Sr2Si5N8:Eu2+荧光粉的制备及其发光性能研究

以Sr₂CO₃、Si₃N₄和Eu₂O₃为原料, 以C为主要还原剂, 采用碳热还原氮化工艺合成Sr₂Si₅N₈:Eu²⁺荧光粉, 着重研究了C、Sr₂CO₃添加量及Eu²⁺浓度对产物物相及发光性能的影响。研究结果表明: 当C与Si₃N₄的摩尔比 n_c/=9/5时,合成出Sr₂Si₅N₈:Eu²⁺单相荧光粉, 添加适当过量的Sr₂CO₃可提高合成产物的N含量, 且荧光粉的发光强度与其N含量呈现正相关关系。在450 nm蓝光激发下, 受Eu²⁺的4f⁶5d¹ → 4f⁷跃迁作用, Sr₂Si₅N₈:Eu²⁺荧光粉在550~700 nm波段范围产生非对称宽带发射。随着Eu²⁺掺杂浓度由1.5mol%增加到20mol%, 荧光粉的发光强度先增强后减弱, 达到2mol%时发生浓度淬灭现象; 发射主峰由608 nm逐步红移至641 nm; CIE色坐标从(0.606, 0.393)位移至(0.656, 0.343), 是一种可用于白光LED的优质红色荧光粉。     

紫外激发蓝色荧光粉Sr2-x-yB5O9Cl:xEu2+,yTb3+的合成和发光性能

采用高温固相反应法合成Sr_2-x-yB₅O₉Cl:xEu²⁺,yTb³⁺蓝色荧光粉。用X射线衍射表征材料的晶体结构、用荧光光谱仪测定Eu²⁺和Tb³⁺的掺杂浓度,研究了助溶剂H₃BO₃过量浓度和反应温度对荧光粉发光性质的影响。结果表明,单掺杂Eu²⁺时,其浓度猝灭机理为电偶极-电偶极交互作用机制,浓度猝灭临界距离为R_C=1.71 nm。在紫外（230-410 nm）波段有强而宽的吸收带,表明此粉是一种近紫外白光LED用的蓝色荧光粉。     

Valency states of Yb, Eu, Dy and Ti ions in Li2B4O7 glasses

Absorption and emission spectra of Eu and Dy, Yb and Ti ions in Li₂B₄O₇ glasses grown in oxygen and hydrogen gas atmospheres were measured for valency states and lattice-sites analysis. For the Li₂B₄O₇ glass doped with Eu²⁺, Eu³⁺ and Dy³⁺ ions which were grown in oxidizing and reducing atmospheres, absorption and emission bands due to these ions were investigated before and after γ-irradiation. For the Yb³⁺-doped Li₂B₄O₇ glass, a weak, broad band was observed near the sharp 976.3 nm absorption band. The origin of this band is discussed in comparison with other glasses. Moreover, irradiation experiments using γ-rays were also performed in order to investigate the possibility of valency change of Yb ions. It was found that Ti⁴⁺ ions, which are produced under oxidizing atmosphere, change to Ti³⁺ ions after γ-irradiation with a dose of 10⁵ Gy. An additional absorption band observed at about 500 nm is due to the Ti³⁺ ions accompanied by charge-compensating vacancy and does not give any emission.     

无机盐溶胶-凝胶工艺制备长余辉发光粉体的研究

以无机盐为原料,成功地制备了均一、稳定、透明的SrAl2O4溶胶.系统地研究了无机盐溶胶一凝胶工艺制备SrAl₂O₄:Eu²⁺,Dy³⁺长余辉发光粉体的工艺条件及其影响因素,并通过透射电镜和荧光光谱分析对粉体的微结构、表面形态及发光性能进行了表征.实验结果表明,在适宜的工艺条件下,可制备颗粒均匀的针状纳米发光粉体,其发光特性与传统的高温固相烧结法相似,但烧结温度可降低300℃左右.     

Eu3+、Dy3+和Er3+对制备堇青石晶相转变的对比表征

以菱镁矿风化石、工业Al₂O₃和SiO₂微粉为原料, 固相反应烧结合成制备堇青石。通过在反应物中分别加入不同含量的Eu₂O₃、Dy₂O₃和Er₂O₃, 研究分析和对比了Eu³⁺、Dy³⁺和Er³⁺对堇青石晶相组成、晶粒大小、晶胞常数、结晶度及显微结构的影响。采用XRD和SEM表征试样中的晶相和显微结构, 利用X'Pert Plus软件对结晶相的晶胞参数和结晶度进行分析, 采用半定量法对试样晶相组成进行计算, 利用Scherrer公式计算堇青石的晶粒大小。结果表明: 由于Eu₂O₃、Dy₂O₃和Er₂O₃的加入, 通过固相反应烧结所得堇青石试样中出现了莫来石相, Eu³⁺、Dy³⁺和Er³⁺对Mg²⁺的置换作用改变了堇青石相晶格常数和晶胞体积。随着添加剂含量的增加, 堇青石结构中液相量增加, 相对结晶度降低, 常温致密度提高, 堇青石晶粒粒径减小。综合对比分析, Eu₂O₃对堇青石晶相转变的影响程度最弱, Er₂O₃对堇青石晶相转变的影响程度最强, 对提高合成堇青石的烧结性和热震稳定性效果最好。     

YVO4∶Eu3+,Bi3+红色荧光粉的水热合成及其荧光性能

以Y₂O₃、Eu₂O₃、Bi(NO₃)₃·H₂O、浓HNO₃、偏钒酸铵、氨水、无水乙醇和一缩二乙二醇为原料,采用聚乙烯吡咯烷酮(PVP)辅助水热法合成YVO₄: Eu³⁺, Bi³⁺纳米颗粒。使用X射线衍射(XRD)、扫描电镜(SEM)、红外光谱(IR)和荧光光谱(FL)等手段对产品进行了表征和分析。结果表明：合成的样品为YVO₄: Eu³⁺, Bi³⁺纳米颗粒,均具有四方晶相结构,其微结构随反应溶液的的pH值变化。YVO₄: Eu³⁺, Bi³⁺纳米颗粒在619 nm处有较强的红光发射(电偶极跃迁⁵D₀→⁷F₂),在594 nm有较弱的橙光发射(磁偶极跃迁⁵D₀→⁷F₁)。随着Eu/Bi比值的增大材料的荧光先增强后减弱,在Eu/Bi比值为5时样品的红光发射最强。溶液的pH值影响YVO₄: Eu³⁺, Bi³⁺纳米晶的发光强度,其中pH值为10时的样品其红光发射最强。并探讨了YVO₄: Eu³⁺, Bi³⁺纳米晶的发光机理。     

Effect of heat treatment on photoluminescence behavior of BaMgAl10O17:Eu phosphors

The blue phosphor of BaMgAl₁₀O₁₇:Eu²⁺ (BAM) powders were prepared by solid-state reaction. The thermal degradation of BAM phosphor significantly reduces the intensity of the blue emission. BAM is reduced by an amount of 50% after heating at around 800 °C for 1 h. Photoluminescence (PL) excitation and emission spectra showed that the blue emission of 450 nm peak decreased with increasing annealing temperature. The ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transition of Eu³⁺ were observed at 590 and 615 nm emission lines over 1100 °C. Electron paramagnetic resonance (EPR) spectrum also detected two signals of Eu²⁺, corresponding to g=3.7156(9) for 88 mT, and g=2.9507(9) for 133 mT. X-ray absorption near edge structure (XANES) spectrum decreased the intensity of Eu²⁺ for 6977 eV with increasing annealing temperature, while high-energy peak of Eu³⁺ for 6984 eV was increased. The combined use of X-ray and neutron data by the Rietveld refinement appears to support that the secondary phase of EuMgAl₁₁O₁₉ magnetoplumbite structure in BAM may be formed by heat treatment.     

Characterization of intermetallic phases and oxides formed in annealed Ni/Al multilayer structures

Two different multilayer structures composed of ten alternating Ni and Al thin films were sputter deposited on Si (111) substrates. These multilayers with individual Ni and Al thin film thicknesses of about 25 nm and 38 nm and of 25 nm and 13 nm, respectively, have the average compositions of Ni_0.50Al_0.50 and Ni_0.75Al_0.25. The samples were heat treated in a differential scanning calorimeter instrument with a constant heating rate of 40 °C min ⁻¹ in Ar from room temperature to 550 °C. The compositions of as-deposited and heat-treated samples were studied with high-resolution Auger electron spectroscopy (AES) rotational depth profiling. X-ray photoelectron spectroscopy (XPS) analyses show an excess of Ni in both annealed samples. X-ray diffraction measurements of annealed multilayers show the formation of Ni₂Al₃ and NiAl₃ phases in the Ni_0.50Al_0.50 sample and the presence of Ni₃Al and Ni A1₃ phases with some excess of Ni in the Ni_0.75Al_0.75 sample. AES and XPS investigations of the reacted layers after 15 min annealing in air at 500 °C disclose considerably different surface oxide thin films: on the Ni_0.50Al_0.50 layer the oxide thin film consists of Al₂O₃ with a small amount of NiO, whereas that on the top of the Ni_0.75Al_0.25 layer is thicker and consists of NiO on top and some Al₂O₃ below.     

Evaluation of the capabilities of several ions to sensitize Nd in the laser material LNA (La0.9Nd0.1MgAl11O19)

In the hexaaluminate laser material La_0.9Nd_0.1MgAl₁₁O₁₉ also known as LMA:Nd the Nd³⁺ fluorescence can be enhanced by codoping the matrix with rare-earth (REⁿ⁺) or transition metal (TM^m+) ions. A large number of potential donor ions D (D = Mn²⁺, Dy³⁺, Tb³⁺, Eu²⁺, Eu³⁺ and Ti³⁺) are studied in the hexaaluminate host. The D→Nd³⁺ energy transfer, t he, luminescent efficiency as well as the back-transfer strongly depend on the overlap of the D emission and Nd³⁺ absorption, the concentration of the two ions and their localization in the crystal host. In this paper the optical properties — absorption and emission — of the D and Nd³⁺ ions as well as the D→Nd³⁺ interactions are considered using a Forster-Dexter's approach, to compare the capabilities of the different donors in the Nd³⁺-doped hexaaluminate host. The C_DNd and R₀ parameters are estimated in each case, and the results discussed in terms of the localization of the donor ions, their absorption and emission as well as their lifetime properties.     

Preparation and photoluminescence properties of Eu-doped Ga2O3 nanorods

GaOOH:Eu³⁺ nanorods with different aspect ratios were prepared by hydrothermal method at 140 °C. - and β-Ga₂O₃:Eu³⁺ were converted from as-prepared GaOOH:Eu³⁺ particles by calcination at 500 and 850 °C, respectively. The products were characterized with X-ray diffraction (XRD), transmission electron microscope (TEM) and photoluminescence (PL). Results show that solution pH values play a key role in the formation of the GaOOH:Eu³⁺ powders with different morphologies and - and β-Ga₂:Eu³⁺ inherit the morphology of GaOOH:Eu³⁺ exactly. The photoluminescence characteristics of β-Ga₂O₃:Eu³⁺ were also investigated. Experimental results reveal that the color purity of β-Ga₂O₃:Eu³⁺ nanorods with high aspect ratio is enhanced in comparison with β-Ga₂O₃:Eu³⁺ nanorods with low aspect ratio.     

Sol–gel synthesis and luminescence of unexpected microrod crystalline Ca5La5(SiO4)3(PO4)3O2:Dy phosphors employing different silicate sources

Ca₅La₅(SiO₄)₃(PO₄)₃O₂ doped with Dy³⁺ were synthesized by sol–gel technology with hybrid precursor employed four different silicate sources, 3-aminopropyl-trimethoxysilane (APMS), 3-aminopropyl-triethoxysilane (APES), 3-aminopropyl-methyl-diethoxysilane (APMES) and tetraethoxysilane (TEOS), respectively. The SEM diagraphs show that there exist some novel unexpected morphological structures of microrod owing to the crosslinking reagents than TEOS as silicate source for their amphipathy template effect. X-ray pictures confirm that Ca₅La₅(SiO₄)₃(PO₄)₃O₂:Dy³⁺ compound is formed by a pure apatitic phase. The Dy³⁺ ions could emit white light in Ca₅La₅(SiO₄)₃(PO₄)₃O₂ compound, and the ratio of Y/B is 1.1, when the Dy³⁺ doped concentration is 1.0 mol%.     

Cathodoluminescence of rare-earth-doped zinc aluminate films

Eu-, Tb-, and Tm-doped zinc aluminate (ZnAl₂O₄) thin film phosphors were prepared by the spray pyrolysis technique at an ambient pressure. The effects of preparation conditions on the cathodoluminescence properties of the films were studied. Films containing Tb³⁺ and Tm³⁺ ions exhibited green and blue cathodoluminescence, respectively. For films doped with europium, both red emission lines from Eu³⁺ and a broad blue–green emission band from Eu²⁺ were observed. The CIE (Commission Internationale de L'Eclairage) chromatic coordinates, dominant wavelength, and color purity were determined for each phosphor. The luminance and efficiency of these phosphors at a current density of 57 μA/cm² are found to be linearly dependent on the excitation voltage.     

Eu2+/Tb3+掺杂的Sr2Si5N8基荧光粉的制备与发光性能

采用碳热还原氮化法合成了Eu²⁺/Tb³⁺掺杂的Sr₂Si₅N₈基荧光粉, 并重点研究了Tb³⁺-Eu²⁺共掺时Sr₂Si₅N₈基荧光粉的发光性能。研究结果表明: 由于Tb³⁺的f → d间的跃迁是自旋允许的, Sr₂Si₅N₈:Tb³⁺在330 nm激发光下, 在490、543、585和623 nm四处各有一发射峰, 它们分别来源于Tb³⁺的⁵D₄ → ⁷F_j (j = 6、5、4、3)能级跃迁; 掺入Tb³⁺对Sr_1.96Si₅N₈:0.04Eu²⁺的激发谱和发射谱的形状及峰位无明显影响, 当共掺离子Tb³⁺浓度为x = 0.01时, 样品发射强度比未共掺的Sr_1.96Si₅N₈:0.04Eu²⁺提高了约20%, Tb³⁺主要通过电多极能量传递的方式转向Eu²⁺。     

——————————CaSi2O2N2:Eu2+中空荧光纤维的制备及其发光性能研究

采用静电纺丝与气相还原氮化相结合的方式制备了用于白光LED的CaSi₂O₂N₂:Eu²⁺荧光纤维。通过调节纺丝溶液溶剂的配比, 得到了空心结构的Ca-Si-O-Eu纳米纤维和CaSi₂O₂N₂:Eu²⁺荧光纳米纤维。样品在微观上保持中空纤维结构, 宏观上也保持薄膜的状态。利用X射线衍射对样品物相结构进行分析, Ca-Si-O-Eu中空纤维在1300℃保温5 h后得到层状结构的CaSi₂O₂N₂, Eu²⁺离子的掺入没有改变CaSi₂O₂N₂的主晶相。在400 nm激发光照射下CaSi₂O₂N₂:Eu²⁺荧光纤维在550 nm附近具有一个宽发射峰, 对应着Eu²⁺离子4f⁶5d→4f⁷跃迁。与CaSi₂O₂N₂:Eu²⁺荧光粉或普通荧光纤维膜比较, 制备的中空荧光纤维膜有更高的发射光强度。     

Electrical characterization of Ta2O5 films deposited by laser reactive ablation of metallic Ta

Tantalum oxide films have been deposited by 355 nm pulsed laser ablation of metallic Ta target in O₃/O₂ ambient. The structure and the composition of as-deposited and annealed films were examined by X-ray diffraction and Fourier transform infrared spectroscopy. The measurements of the current–voltage and capacitance–voltage characteristics of the Al/Ta₂O₅/Si capacitors were performed to reveal the electrical properties of the Ta₂O₅ films. The effects of annealing temperature on the characteristics of thin films have been studied. The results suggest that the films annealed above 700°C have the structure of orthorhombic β-Ta₂O₅, thc annealing treatment at high temperature decreases the bulk trap charge, the border trap, and the interface trap densities of as-deposited films, and improves significantly the dielectric and electrical properties of Ta₂O₅ film.     

实验优化设计中频反应溅射Al2O3:Ce薄膜发光性质研究

为了得到最优发光的薄膜材料成分参数,采用均匀设计和二次通用旋转组合设计相结合的方法建立发光强度与薄膜中氧含量和Ce³⁺ 离子掺杂浓度的回归方程,并用遗传算法求其取最大值时的解。用中频反应磁控溅射技术制备了相应成分的Al₂O₃:Ce非晶薄膜。在320nm光激发下,获得了较理想的发射光谱,对薄膜发光机理分析表明:薄膜的光致发光来自于Ce³⁺ 离子的5d1激发态向基态4f1的两个劈裂能级的跃迁。发光强度强烈的依赖于薄膜的掺杂浓度和氧元素含量。XPS检测表明,Al₂O₃:Ce薄膜中存在Ce³⁺ 。Ce³⁺ 含量和薄膜的化学成分是通过X射线散射能谱(EDS)测量的。薄膜试样的晶体结构应用X射线衍射分析。     

Si3N4掺杂氮化对Sr3SiO5:Eu2+荧光粉发光性能的影响

采用高温固相法制备Si₃N₄掺杂氮化Sr_2.99SiO_5-6xN_4x:0.01Eu²⁺荧光粉。采用XRD、EDS和SEM测试结果表明: N^3-进入Sr₃SiO₅基质晶格中取代部分O^2-离子, 形成了单一相Sr_2.99SiO_5-6xN_4x:0.01Eu²⁺固溶体。PL&PLE荧光光谱测试结果显示, Sr_2.99SiO_5-6xN_4x:0.01Eu²⁺荧光粉在344nm紫外光的激发下发射出红橙光, 属于Eu²⁺离子典型的 4f⁶5d¹→4f⁷电子跃迁。随着N浓度的增加, Sr_2.99SiO_5-6xN_4x:0.01Eu²⁺荧光粉发射光谱和激发光谱的强度明显增强。热稳定性测试结果表明, Si₃N₄掺杂氮化能够显著提高Sr₃SiO₅:Eu²⁺荧光粉的热稳定性。通过Arrhennius模型拟合结果表明横向穿越过程(crossover)引起的Sr₃SiO₅:Eu²⁺荧光粉氮化前后的温度猝灭。