新型红色荧光粉KMgLa(PO4)2∶Eu3+的发光特性

采用高温固相法制备了Eu3+掺杂的KMgLa(PO4)2荧光粉.采用X射线衍射技术及光谱技术研究了材料的晶相及发光特性.研究结果显示,少量的Eu3+并未影响KMgLa(PO4)2的晶相;以260 nm紫外光或394 nm近紫外光作为激发源时,KMgLa(PO4)2∶Eu3+都发射红色光,主发射峰位于595 nm,对应Eu3+的5 D0→7F2跃迁发射;随着Eu3+掺杂量的逐渐增大,对应KMgLa(PO4)2∶ Eu3+材料的发射强度随之增大,当掺杂量为0.06Eu3+时,发射强度最大,且存在浓度猝灭现象,对应的临界距离为1.696 nm;材料的CIE参数显示,材料位于红色区域.     

CaF2：xYb3+, yEr3+纳米颗粒的合成及其上转换发光性质

采用水热合成法制备了CaF₂：xYb³⁺,yEr³⁺（x=0.1~0.8,y=0.01~0.08）纳米颗粒,利用X射线粉末衍射仪、透射电子显微镜和F-4600荧光分光光度计表征了样品的物相和形貌尺寸,并探究了Yb³⁺和Er³⁺掺杂浓度对样品的上转换发光性质的影响。结果表明,所合成的样品为立方相,球形颗粒,平均直径为 12 nm,敏化剂Yb³⁺的最佳掺杂摩尔分数为20%,而激活剂Er³⁺的最佳掺杂摩尔分数为6%。此时,绿光与红光的强度之比最大。     

A red oxide phosphor,SreScAlO5：Eu^2＋ with perovskite-type structure,for white light-emitting diodes

Sr2ScAlO5：Eu^2＋, a red oxide phosphor with a perovskite-type structure, has been synthesized through a solid-state reaction and its luminescence properties have been investigated. An absorption band centering at 450 nm is observed from the diffuse reflection spectra and the excitation spectra, indicating that the phosphor can match perfectly with the blue light of InGaN light-emitting diodes. A broad red emission band at 620 nm is found from the emission spectra, originating from the 4f^65d-4f^7 transition of the Eu^2＋ ions. The best doping content of Eu in this material is about 5%. S Sr2ScAlO5：Eu^2＋ is a highly promising red phosphor for use in white light-emitting diodes.     

Optical properties and photonic density of states in one-dimensional and three-dimensional liquid-crystalline photonic crystals

ABSTRACT

Complex optical investigations were performed in one-dimensional (cholesteric) and three-dimensional (Blue Phase II) liquid-crystalline photonic crystals. Spectra of optical transmission and luminescence in the range of the photonic stop band contain information about the local anisotropy, characteristics of the photonic stop band, photonic density of states. We determine the photonic density of states in one-dimensional and three-dimensional liquid-crystalline photonic crystals employing measurements of polarised luminescence. The width of the photonic band gap, density of states and the optical characteristics related to the density of states essentially change with temperature in one-dimensional cholesteric photonic crystal. Drastic transformation of the density of states was found at the transition from one-dimensional to three-dimensional (Blue Phase II) photonic crystal. The results of our investigations demonstrate the possibility to employ the applied method for various types of photonic structures.     

焦硅酸镥(Lu2Si2O7:Ce)闪烁晶体的生长与发光性能研究

铈掺杂的焦硅酸镥晶体(简写为LPS:Ce)是新近发现的一种具有潜在应用价值的无机闪烁晶体.本文用提拉法成功地生长出尺寸为φ15mm×40mm的LPS:Ce晶体.XRD结构测试表明,该晶体属于单斜晶系,C2/m空间群,晶体中分布有少量的LPS和石英颗粒包裹体.对从毛坯中切割出的无色透明晶体样品在室温下分别进行了透射光谱、紫外激发、X射线激发发射光谱和衰减时间测试.结果表明,铈(Ce3+)离子掺杂使LPS晶体的紫外吸收边从175nm红移到350nm,紫外和X射线激发的荧光光谱中都可以分解出384nm和412nm两个发射峰,它们分别对应于电子从铈(Ce3+)离子的5d轨道向4f轨道的两个能级(2F5/2和2F7/2)的辐射跃迁,从衰减曲线中可以拟合出一个38.75ns的时间常数.这些发光特征与该晶体独特的晶体结构密切相关.     

A Cd(II) Luminescent Coordination Grid as a Multiresponsive Fluorescence Sensor for Cr(VI) Oxyanions and Cr(III), Fe(III), and Al(III) in Aqueous Medium

Hydro(solvo)thermal reactions of Cd(NO₃)₂, N-(pyridin-3-ylmethyl)-4-(pyridin-4-yl)-1,8-naphthalimide (NI-mbpy-34), and 5-bromobenzene-1,3-dicarboxylic acid (Br-1,3-H₂bdc) afforded a luminescent coordination polymer, {[Cd(Br-1,3-bdc)(NI-mbpy-34)(H₂O)]∙2H₂O}_n (1). Single-crystal X-ray diffraction analysis showed that 1 features a two-dimensional (2-D) gridlike sql layer with the point symbol of (4⁴·6²), where the Cd(II) center adopts a {CdO₅N₂} pentagonal bipyramidal geometry. Thermogravimetric (TG) analysis confirmed the thermal stability of 1 up to about 340 °C, whereas XRPD patterns proved the maintenance of crystallinity and framework integrity of 1 in CH₂Cl₂, H₂O, CH₃OH, and toluene. Photoluminescence studies indicated that 1 displayed intense blue fluorescence emissions in both solid-state and H₂O suspension-phase. Owing to the good fluorescent properties, 1 could serve as an excellent turn-off fluorescence sensor for selective and sensitive Cr(VI) detection in water, with LOD = 15.15 μM for CrO₄²⁻ and 14.91 μM for Cr₂O₇²⁻, through energy competition absorption mechanism. In addition, 1 could also sensitively detect Cr³⁺, Fe³⁺, and Al³⁺ ions in aqueous medium via fluorescence-enhancement responses, with LOD = 2.81 μM for Cr³⁺, 3.82 μM for Fe³⁺, and 3.37 μM for Al³⁺, mainly through an absorbance-caused enhancement (ACE) mechanism.     

Controlling Cr3+/Cr4+ concentration in single-phase host toward tailored super-broad near-infrared luminescence for multifunctional applications

Full control on the valence of the active ions in solids to improve properties is the central topic of chemistry and materials. Cr³⁺ and Cr⁴⁺ ions generally emit wavelength-different near-infrared (NIR) light. Here, we have developed a chromium valence-controllable single-phase phosphor, Mg₂GeO₄:Cr³⁺,Cr⁴⁺ to achieve super-broad NIR luminescence. High Li ⁺ content charge compensators can stabilize Cr³⁺, whereas high-temperature sintering tends to facilitate the formation of Cr⁴⁺. Through fine adjusting the synthesis conditions, pure Cr³⁺ or Cr⁴⁺ luminescence can be obtained with peak emission locating at 935 nm and 1190 nm, respectively. Super broad band dual emission spanning from 650 nm to 1600 nm is realized via fully controlling the concentration ratio of Cr³⁺ to Cr⁴⁺ in a single host. By measuring the transmission spectra of several foodstuff illuminated by our phosphors, non-destructive analysis in food safety areas can be realized. This study provides a new strategy for exploiting super broad band NIR luminescent materials.     

Circularly Polarized Luminescence of a Stereogenic Curved Paraphenylene Anchoring a Chiral Binaphthyl in Solution and Solid State

A curved stereogenic [6]paraphenylene ([6]PP), anchoring a chiral binaphthyl scaffold at 7,7’-positions, was prepared and investigated for its properties as a solid-state circularly polarized luminescence (CPL) dye. X-ray analysis revealed a helically twisted structure of PP units induced by axial chirality of binaphthyl framework. The curved [6]PP exhibits fluorescence in powder and polymethyl methacrylate (PMMA) film as well as solution. A significant increase in quantum yield was observed for a non-fluid PMMA film owing the suppression of the molecular motion. The g_CPL values of the dye in solution and as PMMA film were almost the same (4.3–4.4×10⁻³) and lager than that in powder. TD-DFT calculations in the excited state suggest that the exciton can be delocalized into a twisted PP unit to produce a larger magnetic transition dipole moment.     

Preparation of a Lanthanide–Titanium Oxo Cluster–Polymer Composite by CuI-Catalyzed Click Chemistry

Incorporating metal clusters within the skeleton of the organic polymers through a click reaction cannot only effectively prepare cluster–polymer composites, but also effectively avoid the cluster aggregation. Herein, an azide-containing lanthanide–titanium oxo cluster of Eu₈Ti₁₀-N₃ ( Eu₈Ti₁₀-N₃ =[Eu₈Ti₁₀(μ₃-O)₁₄(H₂O)₄(OAc)₂(tbba)₃₀(paza)₄(THF)₂] ⋅ 4 THF ⋅ 8 H₂O ( 1 ), Htbba=4-tert-butylbenzoic acid, Hpaza=4-azidobenzoate, HOAc=acetic acid, THF=tetrahydrofuran) through an in situ solvothermal reaction of 4-azidobenzoic acid and 4-tert-butylbenzoic acid. Reaction of 1 with PEG ( PEG =methoxypoly(ethyleneglycol)alkyne, 2000 g mol⁻¹) through Cu^I-catalyzed click chemistry generates a lanthanide–polymer composite of Eu₈Ti₁₀-N₃@PEG ( 2 ). Investigation with IR, ¹H NMR and ICP-OES of 2 indicates that the structural integrity of 1 is maintained in 2 . Study of the luminescent properties of 1 and 2 reveals that the quantum yield of 1 itself basically remains unchanged in 2 . Significantly, the formation of 2 cannot only effectively prevent the cluster 1 from aggregation, but also greatly enhance its solubility and adhesion to the substrate. Owing to the solubility and adhesion of luminescent materials being the key to their practical application, present work is thus of great significance for the development of metal cluster–polymer composite luminescent materials.