Eu2+掺杂MgY2Al3Si2O11N青光荧光粉的制备和发光性能

采用高温固相法合成了一系列Eu²⁺掺杂的MgY²Al³Si²O¹¹N(MYASON)青光荧光粉。详细探讨了不同制备方法对荧光粉的物相结构和发光强度的影响,利用X射线衍射精修和X射线光电子能谱实验证明Si⁴⁺-N^3-离子对成功掺入石榴石晶格中。通过荧光光谱、寿命衰减曲线和变温光谱研究了发光性能,研究结果表明,用365 nm紫外光激发MYASON∶Eu²⁺荧光粉时,在青光区域呈现不对称宽带发射,峰值为490 nm,可以为紫外芯片激发的白光发光二极管有效提供青光成分。     

全光谱白光发光二极管用Eu3+掺杂Ca2KZn2(VO4)3黄色荧光粉的制备及光学性能

基于蓝光芯片激发黄色荧光粉或近紫外芯片激发三基色荧光粉构建的白光发光二极管(WLED)在青光区域呈现明显的凹口,导致白光的色彩性能不够理想。为了弥补这一缺陷,实现全光谱白光,我们设计了Eu³⁺掺杂Ca₂KZn₂(VO₄)₃黄色荧光粉,其发射波长范围为400~750 nm。在387 nm激发下,在所制荧光粉中可同时获得来自VO₄^3-基团和Eu³⁺的发射光。Eu³⁺在Ca₂KZn₂(VO₄)₃基质中的最佳掺杂浓度(物质的量分数)为0.05,且VO₄^3-基团向Eu³⁺的能量传递效率达到64.9%。基于变温的发射光谱,揭示了所制荧光粉的热稳定性并发现VO₄^3-基团和Eu³⁺的激活能分别为0.538和0.510 eV。此外,将所制黄色荧光粉与商用蓝色荧光粉和近紫外芯片进行封装整合,得到可发射暖白光的WLED器件,其色温和显色指数分别为3843 K和85.8。     

Li+,Eu3+共掺杂La2MoO6红色荧光粉的Pechini法合成及近紫外/蓝光激发下的发光特征

采用Pechini法合成了白光LED用红色荧光粉La_1.9-xMoO₆:0.10Eu³⁺,xLi⁺(x=0,0.10,0.20,0.25),并对样品分别进行了X射线衍射(XRD)、扫描电子显微镜(SEM)、电子能谱(EDX)以及荧光光谱(PL)等技术手段分析。 PL光谱显示该荧光粉可被近紫外光(395 nm)和蓝光(466 nm)有效激发,产生616和623 nm强的红光发射,归属于Eu³⁺的⁵D₀→⁷F₂电偶极跃迁。该荧光粉与近紫外LED芯片(370~410 nm)和蓝光LED芯片(450~470 nm)均匹配良好,具有潜在的商业应用价值。 共掺Li⁺离子作为敏化剂能显著提高荧光粉的发光强度,且最优掺杂量为x=0.20。     

Eu2+掺杂KCaCl3晶体的生长及发光性能

通过坩埚下降法生长出不同物质的量分数Eu²⁺掺杂的KCa_1-xEu_xCl₃(x=0.005、0.01、0.02、0.03、0.05)单晶,并对晶体进行了X射线粉末衍射、热重、透过率、光致发光光谱、衰减时间、X射线激发发射光谱等测定。通过相图及结构分析,判断出该晶体为一致熔融化合物,并得出其为正交结构,晶胞参数为a=0.75604 nm,b=1.04823 nm,c=0.72657 nm,空间群为Pnma(62)。在紫外光的激发下,晶体在434 nm左右有一个宽的发射峰,对应于Eu²⁺的4f⁶5d¹→4f⁷跃迁;光致衰减时间1.473μs,晶体在X射线激发下的发光强度随Eu²⁺离子浓度增加而增强。     

Gd2ZnTiO6∶Dy3+, Eu3+单基质白光荧光粉的制备与发光性能

采用溶胶-凝胶法制备出Dy³⁺, Eu³⁺共掺杂Gd₂ZnTiO₆白光荧光粉. 通过X射线衍射(XRD)、 扫描电子显微镜(SEM)、 光致发光(PL)光谱对荧光粉的物相、 形貌及荧光性质进行了表征. 结果表明, 所制备的样品均为双钙钛矿结构, 属于单斜晶系(空间群: P2₁/n), 形貌为2~5 μm无规则形状的颗粒. 在392 nm近紫外光的激发下, Gd₂ZnTiO₆∶Dy³⁺,Eu³⁺荧光粉展现出Dy³⁺的蓝光、 黄光发射以及Eu³⁺的特征红光发射. 此外, 通过调节Dy³⁺和Eu³⁺的掺杂浓度, 可实现低色温的暖白光发射. 基于样品优异的荧光性能, 该荧光粉在近紫外激发白光LED中具有一定的开发潜力.     

一种新型的红色荧光粉——Ca4GdO(BO3)3:Eu3+

采用高温固相法制备了一种新型的红色荧光粉——Ca₄GdO(BO₃)₃:Eu³⁺.研究了它在X射线、真空紫外和紫外激发下的发光性能,研究表明,样品无论是在X射线、真空紫外还是在紫外的激发条件下,样品都能发出很强的红光.它的主发射峰在610 nm,而且其它位置的发射峰都很弱;它很容易被254nm、172 nm和X射线所激发而发出很强的红光,因此是一种具有潜在应用价值的红色荧光粉.研究表明Gd³⁺离子与激活剂(Eu³⁺)存在着一种能量传递的过程,而这种能量的传递过程可能跟二次吸收有关.     

荧光粉Ba5-3x/2B4O11∶xEu3+的制备及发光性能

采用高温固相烧结法成功制备了Ba_5-3x/2B₄O₁₁∶xEu³⁺(x=0.02~0.22)荧光粉,利用XRD和SEM等对荧光粉进行了结构和形貌表征。 在激发波长为393 nm的条件下,发射峰(596、621、657和706 nm)与Eu³⁺的⁵D₀-⁷F_J(J=1,2,3,4)电子跃迁相对应,其中621 nm最强发射峰由Eu³⁺离子⁵D₀→⁷F₂电偶极跃迁造成。 文章还研究了Eu³⁺掺杂浓度对Ba_5-3x/2B₄O₁₁∶xEu³⁺发光性能的影响,结果表明,荧光粉的发光强度随着Eu³⁺掺杂量的增加呈现先增大后减小的趋势,Eu³⁺最佳掺杂量为0.16。     

Cs2ZnCl4∶Ce3+,Mn2+的合成及其多模发光性能

近年来,低维无铅金属卤化物由于其独特的光学性质、低毒性和优异的环境稳定性等优点受到了广泛关注。采用水热法成功制备Cs₂ZnCl₄∶Ce³⁺、Cs₂ZnCl₄∶Mn²⁺以及Cs₂ZnCl₄∶Ce³⁺,Mn²⁺等微米晶,并利用X射线衍射仪、荧光光谱仪等表征手段对其物相和发光特性进行了系统性研究。研究结果表明,Cs₂ZnCl₄微米晶为正交相零维结构,其发射光谱依赖于掺杂离子的激发波长,例如,Ce³⁺离子掺杂的Cs₂ZnCl₄微米晶在254nm的激发条件下,其发射光谱峰位位于350nm,对应于Ce³⁺离子4f-5d的跃迁;Mn²⁺离子掺杂的Cs₂ZnCl₄微米晶在361nm的激发条件...     

LiBa0.95-yBO3∶0.05Tb3+,yBi3+荧光粉的制备及荧光性质

以硼酸和碳酸盐为原料,用高温固相法制备了可被(近)紫外光(369、254 nm)有效激发的Tb³⁺单掺杂Li Ba1-xBO3∶xTb³⁺(物质的量分数x=0.02、0.03、0.04、0.05、0.06、0.07)及Bi³⁺和Tb³⁺共掺杂LiBa_0.95-yBO₃∶0.05Tb³⁺,y Bi³⁺(物质的量分数y=0.02、0.03、0.04、0.05、0.06、0.07)的2个系列荧光粉,产物的结构和形貌分别用粉末X射线衍射(PXRD)和扫描电子显微镜进行表征。PXRD测定结果表明2个系列的产物均为纯相LiBaBO3。通过对第一系列产物荧光光谱的测定,筛选出发光强度最好的产物,据此确定铽离子的最佳掺杂量;在此基础上制备出铋离子掺杂量不同的第二系列荧光粉。荧光光谱测定的实验结果表明,Tb³⁺/Bi³⁺共掺杂的荧光粉的发光强度好于Tb³⁺单掺杂的荧光粉,这说明Bi³⁺对Tb³⁺有敏化作用;而且随着Bi³⁺掺杂量的增加,产物的荧光强度表现出先增加后减小的趋势,当Bi³⁺的掺杂量y=0.03时,产物的荧光强度达到最大。Bi³⁺和Tb³⁺之间存在偶极-四极相互作用而进行能量传递。系列荧光粉的CIE坐标显示其发光颜色在一定程度上呈现出由绿色光到白光的渐变趋势。     

在发光二极管背光源上极具应用前景的Beta-sialon (Si6-zAlzOzN8-z):Eu2+窄带绿色荧光粉

基于氮化镓的白光发光二极管(LED)是目前一项崭新的背光源技术,广泛应用于宽色域、高光效的液晶显示屏。 在此项技术中,作为关键材料的荧光粉决定着背光单元的色域范围、发光效率和可靠性,因而要求它应具合适的发射波长和窄带发射。 β-sialon:Eu²⁺(sialon:silicon aluminum oxynitride(赛龙))就是一款非常适合背光应用的绿色荧光粉,这得益于其位于525~545 nm发射峰和只有55 nm狭窄的峰宽。 此文回顾和综述了β-sialon:Eu²⁺的合成方法、光谱特性、电子结构、晶体结构、可靠性和它的具体应用。 计算模拟和实验测试结果表明,Eu²⁺位于沿c轴方向的大孔道之中,并与6个最紧邻的(O,N)原子等距离配位。 因而,Eu²⁺的狭窄发射峰源自于Eu²⁺局域结构的高度对称性。 β-sialon:Eu²⁺的发射波长和带宽都能通过组成裁剪,即z值,进行调控;低z值组成能够实现更短波长发射和更窄带宽。 与传统的基于钇铝石榴石(YAG)荧光粉的背光源相比,β-sialon:Eu²⁺再搭配红色荧光粉制备的背光源具有更宽的色域,色域范围可提高15%以上。 其优异的发光性能和高可靠性使得β-sialon:Eu²⁺成为应用于先进显示屏的极其重要的绿色发光材料。     

KCl-KBO2-K2CO3, K2MoO4-KBO2-K2CO3, and K2WO4-KBO2-K2CO3 ternary systems

phase diagrams of KCl-KBO₂-K₂CO₃, K₂MoO₄-KBO₂-K₂CO₃, and K₂WO₄-KBO₂-K₂CO₃ ternary systems were studied by a calculation-experimental method and differential thermal analysis (DTA). The coordinates of ternary eutectics were determined to be E ₁: 622°C, 8.5 mol % KBO₂, 56.5 mol % KCl, and 35 mol % K₂CO₃; E ₂: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂MoO₄; E ₃: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂WO₄. The specific heats of melting of the eutectics were determined.     

Solubility in the Na2Cr2O7-(NH4)2Cr2O7-K2Cr2O7-H2O system

Solubility in the Na₂Cr₂O₇-(NH₄)₂Cr₂O₇-K₂Cr₂O₇-H₂O four-component water-salt system at 25, 50, and 75°C was studied for the first time. Phase field boundaries for individual salts and potassium and ammonium dichromate solid solutions, monovariant lines, and invariant points were determined. Experimental data were used to optimize the looped isohydric process of potassium dichromate preparation involving additional salts.     

Li2O-TiO2-SiO2-P2O5和Li2O-TiO2-Al2O3-P2O5体系锂离子固体电解质的制备及性能研究

一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…     

The preparation of NbH5(Me2PCH2CH2Me2)2 and NbHL2(Me2PCH2CH2PMe2)2 (L = CO or C2H4)

MMe₅(dmpe) (M = Nb or Ta, dmpe = Me₂PCH₂CH₂PMe₂) reacts with H₂ (500 atm) and dmpe in THF at 60°C to give MH₅(dmpe)_2? NbH₅(dmpe)₂ readily reacts with two mol of CO or ethylene (L) to give NbHL₂(dmpe)₂. The exchange of the hydride ligand with the ethylene protons in NbH(C₂H₄)₂(dmpe)₂ is not rapid on the ¹H NMR time scale (60 MHz) at 95°C.     

Li2SO4-Na2SO4-H2O和Li2SO4- K2SO4-H2O溶液的体积性质

本文用高精度数字式振荡管密度计测定了288K至318K温度范围内Li₂SO₄ + Na₂SO₄ + H₂O和 Li₂SO₄ + K₂SO₄ + H₂O三元体系的密度。混合溶液的离子强度范围从0.1到4.5 mol.kg_–1,混合溶液中Na₂SO₄和K₂SO₄的离子强度分数为0.2,0.4,0.6和0.8。用密度实验值拟合得到了不同温度下Pitzer离子相互作用模型混合参数θ_V和 ψ_V,模型的计算值与实验值的偏差在±0.002 g.cm_–3以内。用Pitzer模型计算了不同离子强度下三元体系的混合体积。     

(H2NC4H8NCH2CH2NH2)(HNCH2CH2NH2)3Zn2Ge2Se8: A new,templated one-dimensional ternary semiconductor stabilized by mixed organic cations

The novel, 1D semiconductor (H₂NC₄H₈NCH₂CH₂NH₂)(HNCH₂CH₂NH₂)₃Zn₂Ge₂Se₈ has been synthesized under solvothermal conditions using N-(2-aminoethyl)piperazine as solvent and templating agent at 200 °C. The material was characterized by single crystal and powder X-ray diffraction, IR and Raman spectroscopy and thermogravimetric analysis. The compound consists of 1D anionic [Zn₂Ge₂Se₈]⁴⁻ chains made of alternating edge-shared [ZnSe₄] and [GeSe₄] tetrahedra that charged balanced by one N-(2-aminoethyl)piperazinium and three piperazinium cations. The optical properties were investigated with solid state UV–Vis/near IR spectroscopy and the results show that the solid is a medium gap semiconductor with an absorption edge at 1.8 eV.     

NaBO2-NaCl-Na2CO3, NaBO2- Na2CO3-NaMoO4, NaBO2- Na2CO3-NaWO4, and NaBO2-NaCl-Na2WO4 ternary systems

The phase diagrams of the NaBO₂-NaCl-Na₂CO₃, NaBO₂-Na₂CO₃-Na₂MoO₄, NaBO₂- Na₂CO₃-Na₂WO₄, and NaBO₂-NaCl-Na₂WO₄ ternary systems were studied by a calculation-experimental method and differential thermal analysis. The coordinates of ternary eutectics were determined: E ₁: 612°C, 16 mol % NaBO₂, 42 mol % NaCl, and 42 mol % Na₂CO₃; E ₂: 568°C, 12 mol % NaBO₂, 28 mol % Na₂CO₃, and 60 mol % Na₂MoO₄; E ₃: 575°C, 12 mol % NaBO₂, 32 mol % Na₂CO₃, and 56 mol % Na₂WO₄; E ₄: 628°C, 8 mol % NaBO₂, 20 mol % NaCl, and 72 mol % Na₂WO₄; and E ₅: 655°C, 9 mol % NaBO₂, 53 mol % NaCl, and 38 mol % Na₂WO₄.     

Synthesis and characterization of inorganic solid electrolytes of Li2O-SiO2-P2O5 and Li2O-TiO2-SiO2-P2O5 systems

The lithium-ion-conducting inorganic solid electrolytes in the oxide systems Li₂O-SiO₂-P₂O₅ and Li₂O-TiO₂-SiO₂-P₂O₅ were prepared by the solid-state reaction, and the electrolyte pellet made by cold-pressing method had diameter of 13 mm and was about 1 mm thick. Phase identification and surface morphology of the products were carried out by X-ray diffraction and scanning electron microscopy. Ionic conductivity of the pellets was investigated through ac impedance. The results show that the adding of other cations can improve the ionic conductivity of the solid electrolyte, and the sintering temperature and duration can influence the ionic conductivity. The maximum ionic conductivity in the samples is 9.9 × 10⁻⁴ S/cm in the Li₂O-TiO₂-SiO₂-P₂O₅ system. Original Russian Text ? W. Li, M. Wang, Z.H. Li, X.F. Shang, H. Wang, Y.W. Wang, Y.B. Xu, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 11, pp. 1341–1345.     

Polymorphism in the Sc2Si2O7-Y2Si2O7 system

This paper examines the structural changes with temperature and composition in the Sc₂Si₂O₇-Y₂Si₂O₇ system; members of this system are expected to form in the intergranular region of Si₃N₄ and SiC structural ceramics when sintered with the aid of Y₂O₃ and Sc₂O₃ mixtures. A set of different compositions have been synthesized using the sol-gel method to obtain a xerogel, which has been calcined at temperatures between 1300 and 1750 °C during different times. The temperature-composition diagram of the system, obtained from powder XRD data, is dominated by the β-RE₂Si₂O₇ polymorph, with γ-RE₂Si₂O₇ and δ-RE₂Si₂O₇ showing very reduced stability fields. Isotherms at 1300 and 1600 °C have been analysed in detail to evaluate the solid solubility of the components. Although, the XRD data show a complete solid solubility of β-Sc₂Si₂O₇ in β-Y₂Si₂O₇ at 1300 °C, the ²⁹Si MAS-NMR spectra indicate a local structural change at x ca. 1.15 (Sc_2−xY_xSi₂O₇) related to the configuration of the Si tetrahedron, which does not affect the long-range order of the β-RE₂Si₂O₇ structure. Finally, it is interesting to note that, although Sc₂Si₂O₇ shows a unique stable polymorph (β), Sc³⁺ is able to replace Y³⁺ in γ-Y₂Si₂O₇ in the compositional range 1.86?x?2 (where x is Sc_2−xY_xSi₂O₇) as well as in δ-Y₂Si₂O₇ for compositions much closer to the pure Y₂Si₂O₇.     

Formation of [Cp2TiSbMe2]2, [Cp2TiSb(SiMe3)2]2 and [Cp2TiCl]2·2Mes4Sb2

Reactions of [Cp₂Ti(btmsa)] (btmsa = bis(trimethylsilyl)acetylene) with R₄Sb₂ (R = Me, Me₃Si) give [Cp₂TiSbMe₂]₂ (1) or [Cp₂TiSb(SiMe₃)₂]₂ (2) respectively. [Cp₂TiCl]₂·2Mes₄Sb₂ (3) is serendipitously formed from [Cp₂Ti(btmsa)] and Mes₂SbH containing NH₄Cl traces.