Eu掺杂KNN陶瓷的制备及可调性发光研究

稀土离子掺杂铁电陶瓷是一类新型光致变色材料, 在光开关、光信息存储等领域具有潜在应用价值。本研究采用水热法制备了(K_0.5 Na_0.5)_1-xEu_xNbO₃(KNN:xEu)前驱体粉体, 随后利用高温烧结得到对应陶瓷样品。在465 nm激发下, 观察到615 nm处有强的红色发光, 对应于Eu ³⁺的 ⁵D₀→ ⁷F₂跃迁。通过紫外光照射, KNN:Eu陶瓷从乳白色变为深灰色。随后经过200 ℃加热10 min, 着色陶瓷又变回到初始颜色, 显示出良好的光致变色行为。紫外照射和反复加热循环可以有效调控该陶瓷的发光强度。且经过多次循环之后, 发光强度没有明显衰减。在紫外光照射下, KNN:0.06Eu陶瓷发光强度的可调比(ΔR_t)高达83.9%, 说明发光具有良好的可调性。进而结合发光中心和色心之间的能量转移, 对KNN:Eu陶瓷的光致变色和发光机理进行了解释。     

自蔓延低温合成SrAl2O4∶Eu2+,Dy3+及其粒径控制与发光性能

本文采用自蔓延低温(600℃)方法合成了铝酸盐长余辉材料SrAl2O4∶Eu2+,Dy3+;通过添加聚乙二醇(PEG)有效控制材料的粒径,并采用XRD,SEM,PL等测试方法对粒径、形貌、发光性能等进行了研究。随着PEG量的增加,材料粒径呈减小趋势;未添加PEG时,材料粒径范围在0.2～1.2μm;当PEG的量为0.4%时,材料初始亮度最高,为19110mcd/m2,余辉衰减最慢,材料粒径分布在0.1～0.8μm;当PEG量为0.6%时,粒径最小,粒径范围在0.1～0.5μm。添加PEG后材料的发光亮度有所提高,而余辉衰减变化不明显。实验结果表明:自蔓延低温合成SrAl2O4∶Eu2+,Dy3+时,通过添加PEG能有效控制合成材料的粒径,借助于PL测试手段以及余辉衰减实验,激发、发射光谱测定所得的检测波长分别为516nm、363nm,合成了粒径细小且发光性能优良的发光材料。     

Silica shell-assisted synthetic route for mono-disperse persistent nanophosphors with enhanced in vivo recharged near-infrared persistent luminescence

Near-infrared (NIR) persistent-luminescence nanoparticles have emerged as a new class of background-free contrast agents that are promising for in vivo imaging.The next key roadblock is to establish a robust and controllable method for synthesizing monodisperse nanoparticles with high luminescence brightness and long persistent duration.Herein,we report a synthesis strategy involving the coating/etching of the SiO2 shell to obtain a new class of small NIR highly persistent luminescent ZnGa2O4∶Cr3+,Sn4+ (ZGOCS) nanoparticles.The optimized ZGOCS nanoparticles have an excellent size distribution of ～15 nm without any agglomeration and an NIR persistent luminescence that is enhanced by a factor of 13.5,owing to the key role of the SiO2 shell in preventing nanoparticle agglomeration after annealing.The ZGOCS nanoparticles have a signal-to-noise ratio ～3 times higher than that of previously reported ZnGa2O4∶Cr3+ (ZGC-1) nanoparticles as an NIR persistent-luminescence probe for in vivo bioimaging.Moreover,the persistent-luminescence signal from the ZGOCS nanoparticles can be repeatedly re-charged in situ with external excitation by a white lightemitting diode;thus,the nanoparticles are suitable for long-term in vivo imaging applications.Our study suggests an improved strategy for fabricating novel high-performance optical nanoparticles with good biocompatibility.     

Recent Progress in GaN‐Based Light‐Emitting Diodes

In the last few years the GaN‐based white light‐emitting diode (LED) has been remarkable as a commercially available solid‐state light source. To increase the luminescence power, we studied GaN LED epitaxial materials. First, a special maskless V‐grooved c‐plane sapphire was fabricated, a GaN lateral epitaxial overgrowth method on this substrate was developed, and consequently GaN films are obtained with low dislocation densities and an increased light‐emitting efficiency (because of the enhanced reflection from the V‐grooved plane). Furthermore, anomalous tunneling‐assisted carrier transfer in an asymmetrically coupled InGaN/GaN quantum well structure was studied. A new quantum well structure using this effect is designed to enhance the luminescent efficiency of the LED to ～72%. Finally, a single‐chip phosphor‐free white LED is fabricated, a stable white light is emitted for currents from 20 to 60 mA, which makes the LED chip suitable for lighting applications.     

Reproducible on-off switching of solid-state luminescence by controlling molecular packing through heat-mode interconversion

Organic luminescent solids are attracting increasing interest in various fields of application. Modification or alteration of the chemical structures of their component molecules is the most common approach for tuning their luminescence properties. However, for dynamic tuning or switching of solid-state luminescence with high efficiency and reproducibility successful examples are limited as chemical reactions in the solid state frequently encounter insufficient conversion, one-way reactions or loss of their luminescence properties. One promising approach is to control the luminescence properties by altering the mode of solid-state molecular packing without chemical reactions. Here, we show that 2,2':6',2'-terpyridine, practically non-luminescent in the form of amorphous solid or needle crystal, shows strong blue luminescence upon formation of a plate crystal. Efficient and reproducible on-off switching of solid-state luminescence is demonstrated by heat-mode interconversion between the plate and needle crystals. Because alteration of the mode of molecular packing does not require chemical reactions, the present findings would open the way for the development of novel organic luminescent solids that can be switched on and off by external thermal stimuli.     

长余辉蓄光玻璃的制备及其性能研究

利用传统陶瓷制备方法合成了SrAl2O4:Eu,Dy长余辉发光粉体,该磷光体主发射波长位于520nm,余辉时间长达8h以上。并以硼硅酸盐低熔点玻璃为底材,掺杂该发光粉体,在一定温度下烧成,结果制得长余辉蓄光玻璃。研究还表明,烧成温度对该玻璃的发光性能影响较大,随着温度的升高,发光强度及余辉时间明显下降。     

多色长余辉材料的发光性质及动态防伪应用

发光防伪具有可视性强、设计简便的特点, 是众多防伪技术中常用的方法。传统防伪材料存在发光颜色单一、防伪图案和颜色静态的缺点, 易于模仿, 亟需开发可实现动态、可靠防伪性能的发光材料。本工作采用水热法制备了铬掺杂镓锗酸锌多色长余辉材料, 并对其余辉性能和动态防伪应用进行研究。实验结果表明: 通过改变镓锗比, 可以调节蓝绿光和红光区的发射强度, 实现发光颜色的可调。该系列样品在波长为254和365 nm的紫外光激发下分别呈现白色和红色, 发光颜色具有多模态发光特征。此外该系列样品具有多色的余辉发光, 不同颜色的衰减速率不同, 可以实现余辉颜色随时间发生动态变化的效果。据此设计成的防伪图案, 发光颜色在时间维度上具有动态变化特性, 可显著提高防伪安全性, 表明所制备的铬掺杂镓锗酸锌多色长余辉材料在动态防伪领域有重要的应用前景。     

Electroluminescence microspectroscopy of silicon nanocrystals obtained by Si(+) ion implantation in SiO(2)

Room-temperature electroluminescence (EL) has been measured at both macroscopic and microscopic levels from metal-oxide-semiconductor devices containing silicon nanocrystals (Si-nc) embedded in silicon dioxide (SiO(2)) obtained by high-temperature annealing (1050 and 1100?°C) after Si(+) ion implantation. It is found that spatially integrated (macroscopic) EL is dominated by a near-infrared band centered where the photoluminescence (PL) band of Si-nc (from 700 to 1000?nm) is located. However, on a microscopic scale, EL emission is inhomogeneous, the sample surface exhibiting many visible spots of micron-order diameter. EL spectra from a microscopic surface of ～1?μm(2)(μEL) on visible spots have revealed dominant contributions between ～550 and ～650?nm, attributed to oxide defects. These spectral features rapidly decrease with distance from a bright spot, while lower-intensity near-infrared contributions (750-950?nm) remain unaffected up to relatively large distances before eventually becoming extinct. The macroscopic EL measurements can be explained as a superposition of the μEL and PL spectra. A luminescent mechanism is proposed in which charge carriers mostly tunnel through high-defect-density channels in the oxide, yielding bright visible spots, while Si-nc in these channels and their surroundings contribute to the luminescence by hosting electron-hole recombinations (EL) and/or exhibiting PL due to optical excitation from the nearby visible EL spot.     

Ce-YAG微晶玻璃的制备及其发光性能

采用高温固相熔融法在弱还原气氛下制备了Ce3+离子掺杂的Y2O3-A12O3-SiO2(SAY)系基础玻璃,并在1250℃~1300℃热处理一定时间制备了晶相为YAG的黄色微晶玻璃。通过XRD、SEM研究了微晶玻璃的结构及相组成;激发和发射光谱分析了Ce3+离子在玻璃及微晶玻璃不同基质中的发光特性,以及Al2O3/Y2O3摩尔比对微晶玻璃样品发光性能的影响。结果表明:基础玻璃经热处理能得到Ce-YAG微晶玻璃,晶粒大小在80~120nm范围内,晶粒发育良好。该微晶玻璃样品能被450nm有效激发,并在530nm处有宽带发射峰,归属于Ce3+的5d-4f(2F2/7)。该微晶玻璃在LED照明领域中有很大的应用开发价值。Al2O3和Y2O3的摩尔含量变化对微晶玻璃发光性能有较大影响,在Al2O3/Y2O3的摩尔比为1.5时,样品的发光性能最佳。     

发光波长可调的聚吡咯甲烷的制备及光学特性

聚合物发光材料因其拥有诸多优点,在有机发光二极管器件方面的应用前景广阔.然而,对于蓝光聚合物发光材料,由于其发光性能、使用寿命等方面仍然存在不足,难以满足全色显示的需要.以吡咯类单体和4-乙基苯甲醛单体为原料,采用溶液缩聚法制备了3种聚吡咯甲烷(聚{吡咯-[2,5-二(4-乙基苯甲烷)]}(PPE)、聚{N-甲基吡咯-...     

Specific Recognition of Breast Cancer Cells In Vitro Using Near Infrared-Emitting Long-Persistence Luminescent Zn3Ga2Ge2O10:Cr3+ Nanoprobes

Nano-Micro Letters - In this paper, near-infrared emitting long-persistence luminescent Zn3Ga2Ge2O10:Cr3+ (ZGG) nanoparticles with diameters of 30–100 nm and bright luminescence were...     

Luminescence characteristics of dental ceramics for retrospective dosimetry: a preliminary study

Ceramic materials that are widely employed in dental prosthetics and repairs exhibit luminescent properties. Because of their use in the body, these materials are potentially of interest in situations where retrospective dosimetry for individuals is required but where monitoring was not planned. The luminescent properties of dental ceramics obtained from Germany, Spain and the UK were examined. Linear dose-response characteristics were obtained in the range < 100 mGy to 10 Gy using thermoluminescence (TL), optically stimulated luminescence (OSL) and infrared-stimulated luminescence (IRSL) measurement techniques. Measurements of time-resolved luminescence were also performed to examine the nature of the luminescence recombination under visible (470 nm) and IR (855 nm) stimulation. The results obtained by TL and optically stimulated techniques suggest that there may be deeper traps than previously observed in certain types of dental ceramic. Such traps may be less susceptible to optical and athermal fading than was reported in earlier studies.     

稀土掺杂上转换发光玻璃陶瓷的制备及性能

实验制备了一类含有SrF2∶Yb3+,Tm3+及SrF2∶Yb3+,Er3+的透明发光玻璃和玻璃陶瓷,对比研究了热处理工艺对玻璃陶瓷相组成、微观结构和光谱性能的影响规律。研究表明,玻璃陶瓷具有立方SrF2纳米晶相均匀分布于玻璃基体的复相结构,利用HRTEM可观测到SrF2纳米晶相的(111)晶面,其晶粒尺度在10~30nm之间,且该析晶相中富集有Yb3+/Tm3+和Yb3+/Er3+。基于此,玻璃陶瓷在980nm LD激光激发下的上转换发光强度较玻璃样品有较大提高。其上转换发光机制分别主要为Yb3+-Yb3+之间的合作上转换,Yb3+-Tm3+和Tm3+-Tm3+之间的交叉弛豫能量传递过程,以及Yb3+-Er3+之间的能量传递上转换。     

Mechanism of energy transfer in Sr2CeO4:Eu3+ phosphor

Blue–white phosphor Sr₂CeO₄ belongs to a particular class of optical materials whose luminescence is governed by optical transitions associated with the electron charge transfer. The originality of its crystallographic structure, a chain-like sequence of luminescent centers, permits an effective transfer of the electronic excitation energy from the host to doped centers. Sr₂CeO₄, рure and doped with Eu³⁺-ions of different concentrations, was synthesized by the Pechini citrate-gel method. The luminescence spectra and luminescence decay curves of Sr₂CeO₄ and Sr₂CeO₄:Eu³⁺ at 300 and 80 K were investigated. The performed experiments revealed the Förster nonradiative energy transfer under the energy migration condition from the crystal host to the doped europium ions.     

Mechanism of energy transfer in Sr2CeO4:Eu phosphor

Blue–white phosphor Sr₂CeO₄ belongs to a particular class of optical materials whose luminescence is governed by optical transitions associated with the electron charge transfer. The originality of its crystallographic structure, a chain-like sequence of luminescent centers, permits an effective transfer of the electronic excitation energy from the host to doped centers. Sr₂CeO₄, рure and doped with Eu³⁺-ions of different concentrations, was synthesized by the Pechini citrate-gel method. The luminescence spectra and luminescence decay curves of Sr₂CeO₄ and Sr₂CeO₄:Eu³⁺ at 300 and 80 K were investigated. The performed experiments revealed the Förster nonradiative energy transfer under the energy migration condition from the crystal host to the doped europium ions.     

Using gold nanoclusters as selective luminescent probes for phosphate-containing metabolites

Glutathione-bound gold nanoclusters (AuNCs@GSH) can emit reddish photoluminescence under illumination of ultraviolet light. The luminescence of the AuNCs@GSH is quenched when chelating with iron ions (AuNCs@GSH-Fe(3+)), presumably resulting from the effective electron transfer between the nanoclusters and iron ions. Nevertheless, we found that the luminescence of the gold nanoclusters can be restored in the presence of phosphate-containing molecules, which suggested the possibility of using AuNCs@GSH-Fe(3+) complexes as the selective luminescent switches for phosphate-containing metabolites. Phosphate-containing metabolites such as adenosine-5'-triphosphate (ATP) and pyrophosphate play an important role in biological systems. In this study, we demonstrated that the luminescence of the AuNCs@GSH-Fe(3+) is switched-on when mixing with ATP and pyrophosphate, which can readily be observed by the naked eye. It results from the high formation constants between phosphates and iron ions. When employing fluorescence spectroscopy as the detection tool, quantitative analysis for phosphate-containing metabolites such as ATP and pyrophosphate can be conducted. The linear range for ATP and pyrophosphate is 50 μM to sub-millimolar, while the limit of detection for ATP and pyrophosphate are ～43 and ～28 μM, respectively. Additionally, we demonstrated that the luminescence of the AuNCs@GSH-Fe(3+) can also be turned on in the presence of phosphate-containing metabolites from cell lysates and blood plasma.     

Synthesis and spectral properties of Ce[Ag(CN)2]3

Cerium ion luminescence in crystalline hosts forms the basis of many blue phosphor and scintillator technologies. We report the synthesis of luminescent single crystals of cerium dicyanoargentate. The luminescence properties are characterized using both steady-state and time-resolved spectroscopy. The broad, overlapping dicyanoargentate and Ce³⁺ emissions are decomposed into three Gaussians, revealing the characteristic dicyanoargentate emission at 350 nm while the Ce³⁺ 5d–4f transitions are observed at 359 nm and 391 nm. Excitation measurements show that the 4f–5d Ce³⁺ absorption overlaps the 320 nm emission of the dicyanoargentate ions, leading to a strong coupling between the dicyanoargentate energy donors and Ce³⁺ acceptors. We conclude that the cerium is excited through an energy transfer process from the dicyanoargentate species, resulting in strong room temperature luminescence.     

Bioconjugated superstructures of CdTe nanowires and nanoparticles: multistep cascade Förster resonance energy transfer and energy channeling

Nanoparticle/nanowire assemblies with a degree of radial organization were prepared around luminescent semiconducting CdTe nanowires using bioconjugation with streptavidin and D-biotin linkers. Red-emitting nanowires (6.62 +/- 1.55 nm diameter, 512 +/- 119 nm length) and green-emitting nanoparticles (3.2 +/- 0.7 nm diameter) were surface-modified with biotin, while orange-emitting nanoparticles (4.1 +/- 1.2 nm diameter) were decorated with streptavidin. CdTe nanocrystals produced two fuzzy layers around the nanowires in which the diameter of CdTe nanoparticles decreased with the distance from the nanowire axis. F?rster resonance energy transfer (FRET) from the outside layer of nanoparticles to the central nanowire was observed for nanowires conjugated with 4.1 nm CdTe. Addition of 3.2 nm CdTe resulted in a red-orange-green optical progression with band gaps of CdTe decreasing toward the axis of the superstructure. In this case, 4-fold luminescence enhancement of the nanowire luminescence was observed and was attributed to multistep FRET. This observation indicated the accumulation of photogenerated excitons in the cascade terminal. A simple model of multiconjugated superstructure with cascade energy transfer is developed and used to describe and understand the experimental data. The experimental data and theoretical model suggest the possibility of utilization of the prepared superstructures with radial symmetry in several classes of optoelectronic devices including nanomaterials for energy collection. They can also be a convenient model object for the investigation of methods of energy funneling in nanoscale assemblies.     

烧成条件对长余辉蓄光玻璃光学性能的影响

以ＳｒＡｌ_２Ｏ_４：Ｅｕ,Ｄｙ长余辉发光粉体和低熔点硼硅酸盐玻璃为原料,在一定条件下合成了长余辉蓄光玻璃．研究结果表明,烧成温度和保温时间对该玻璃的发光效果影响较大．温度越高,保温时间越长,由于空气的氧化作用,蓄光玻璃的发光效果越差,本试验控制烧成温度在７５０～８００℃间,保温时间在 １０ｍｉｎ以内,能合成性能较好的蓄光玻璃．余辉衰减曲线表明蓄光玻璃的发光性能较之原始发光粉体有所下降．ＳＥＭ分析表明,低温合成的蓄光玻璃中,所含能继续保持发光性质的粉体料,明显比高温合成样要多．     

Sm3+/Ce3+/Tb3+共掺CaO-B2O3-SiO2发光玻璃的制备及发光性能研究

采用高温熔融法制备了Sm3+/Ce3+/Tb3+共掺杂的CaO-B2O3-SiO2发光玻璃材料,并用荧光分光光度计和CIE色度坐标对其发光性能进行了研究。发射光谱表明,在374nm激发下,Sm3+/Ce3+/Tb3+共掺杂CaO-B2O3-SiO2发光玻璃的发射光谱中同时观测到了红橙光、蓝光和绿光的发射带,这些发射带的混合实现了白光发射。此外,在Sm2O3和Tb4O7含量不变的情况下,随着CeO2含量的减小,Sm3+/Ce3+/Tb3+共掺杂发光玻璃的发光颜色在白光区逐渐由蓝光区附近过渡到黄光区附近。