用于包装防伪的稀土上转换发光材料

目的 从增强稀土离子发光的角度考察上转换发光调控及性能,综述稀土发光材料在光学防伪领域的应用,以期为上转换材料与包装材料的功能化研究提供参考。方法 检索近几年文献,介绍上转换发光纳米材料的发光机理、发光性能及调控、光学材料打印技术的研究进展。结果 稀土掺杂的上转换发光纳米材料表现出优异的发光性能,但随着粒径减小,纳米颗粒出现发光效率、量子产量低的问题。利用纳米颗粒表面钝化、表面等离子体耦合、与有机配体结合和外场调节等手段,可以使发光材料的发光效能显著增强。利用喷墨打印、丝网印刷、纳米压印光刻和气溶胶喷印等技术,可以使稀土掺杂的上转换发光纳米材料被打印成多样的防伪图案,在光学防伪、信息存储与标记等领域具有重大应用潜力,有望成为新型功能包装材料。结论 在光学材料合成技术、光学调控和打印技术的共同推动下,稀土掺杂上转换发光纳米材料因其特殊的光学特性,有望为功能化包装防伪技术作出贡献。     

Excited State Modulation for Organic Afterglow: Materials and Applications

Organic afterglow materials, developed recently by breaking through the difficulties in modulating ultrafast‐decayed excited states, exhibit ultralong‐lived emission for persistent luminescence with lifetimes of several orders of magnitude longer than traditional fluorescent and phosphorescent emissions at room temperature. Their exceptional properties, namely ultralong luminescent lifetime, large Stokes shifts, facile excited state transformation, and environmentally sensitive emission, have led to a diverse range of advanced optoelectronic applications. Here, the organic afterglow is reviewed from the perspective of fundamental concepts on both phenomenon and mechanism, examining the technical challenges in relation to excited state tuning and lifetime elongation. In particular, the advances in material design strategies that afford a large variety of organic afterglow materials for a broad utility in optoelectronics including lighting and displays, anti‐counterfeiting, optical recording, chemical sensors and bio‐imaging are highlighted.     

Triply Hiding Optical Information via Excitation-Dependent Allochroic Photoluminescence Based on Cellulose Derivates

Optical encryption technologies are widely used in information security, whereas the technology with one single optical secret key can be easily cracked. Here, a triple encryption is reported, which hides patterned information in excitation-dependent allochroic materials with long afterglow, enhancing the security level. The allochroic materials are based on a uniaxial co-assembly structure of cellulose nanocrystals (CNCs) and silica. The assembled CNCs present blue emission with quantum yield of 19.8% under 367 nm UV radiation. The blue emission is maintained in the inverse structure when CNCs are calcinated and converted to carbon dots (CDs). The inverse uniaxial-assembly structure improves the CD emission by 6.7 times. The assembly structure can even improve the phosphorescence of CDs, leading to excellent excitation-dependent allochroic properties. Specifically, the materials maintain a cyan long afterglow luminescence at 480 nm after removing 365 nm UV light, whose lifetime is 0.492 s. Changing the excitation wavelength to 254 nm, a UV emission at 343 nm can be obtained, alongside a blue long afterglow luminescence of 420 nm, whose lifetime is 1.574 s. Combining with blue afterglow materials, optical encryption labels are prepared, which hide different patterned information in three scenarios: natural light, UV light, and afterglow luminescence.     

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365nm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。     

长余辉发光材料的研究进展

铝酸盐长余辉发光材料因为其优异的性能,是一类新型储能和环保材料.本文主要综述了90年代发展起来的铝酸盐体系长余辉发光材料的研究进展.总结了铝酸盐长余辉材料的发光特征和长余辉特性,指出了制备技术上的最新方法,概括了长余辉发光模型,并提出了今后研究和应用的发展方向.     

长余辉发光材料的研究进展

长余辉发光材料因其具有特殊的储能发光性能,是一类绿色环保型材料.综述了主要体系长余辉发光材料的研究历程,总结了长余辉材料的制备方法和余辉效应,概括了长余辉发光研究上存在的问题,提出了今后研究和应用的发展方向.     

天然多糖基室温磷光油墨的制备及防伪应用

目的 为解决常规发光防伪油墨环境不友好，防伪性能单一等问题，以生物基材料为刚性主体结构，芳香磺酸类化合物为客体分子制备水性生物基室温磷光油墨，探索其性能调控因素及包装防伪应用性能。方法 将生物基材料与芳香磺酸类化合物溶于水中获得室温磷光油墨，调控油墨组分、含量等因素，研究其对油墨黏度、油墨层磷光性能的作用机理，并套印不同发光颜色、余辉时长的防伪油墨，获得多色、动态发光的防伪图案，挖掘其包装防伪应用潜力。结果 实验表明，在水性油墨中，生物基材料添加的质量分数为8%，芳香磺酸类化合物添加量为0.16%时，油墨干燥后获得最佳的长余辉发光效果；使用模板刮涂方式印刷防伪图案，模板厚度为0.5mm时，防伪图案综合效果最佳。结论 具有丰富氨基、羟基等基团的生物基材料（如羧甲基壳聚糖、海藻酸钠），能形成具有强氢键作用的刚性结构，有效抑制芳香磺酸类化合物的非辐射跃迁，提升了所制备油墨的发光寿命和效率，有效提升了包装防伪油墨的环境友好度及防伪性能。     

Multiple Stimuli-Response Polychromatic Carbon Dots for Advanced Information Encryption and Safety

Optical information encryption and safety have aroused great attention since they are closely correlated to data protection and information safety. The development of multiple stimuli-response optical materials for constructing large-capacity information encryption and safety is very important for practical applications. Carbon dots (CDs) have many gratifying merits, such as polychromatic emission, diverse luminous categories, and stable physicochemical properties, and are considered as one of the most ideal candidates for information protection. Herein, carbon core, functional groups, solvents, and other crucial factors are reviewed for outputting polychromatic emission of multiple luminous categories. In particular, substrate engineering strategies have been emphasized for their critical role in yielding excellent optical features of multiple luminous categories. High-capacity information encryption and safety strategies are reviewed by relying on the rich optical properties of CDs, such as polychromatic emission, multiple luminous categories of fluorescence, afterglow, and upconversion, as well as external-stimuli-assisted optical changes. Some perspectives for preparing excellent CDs and further developing information security strategies are proposed. This review provides a good reference for the manipulation of polychromatic CDs and the development of next-generation information encryption and safety.     

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。     

Cr<Superscript>3+</Superscript> activated Zn<Subscript>3</Subscript>Al<Subscript>2</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript>: a novel near-infrared long persistent phosphor

The near-infrared (NIR) long persistent phosphors have gained considerable attention owing to the potential applications in in vivo imaging. A novel NIR long-persistent phosphors Zn₃Al₂Ge₃O₁₂:Cr³⁺ was successfully synthesized by a high temperature solid-state reaction. The luminescent properties and the afterglow behaviors of the Zn₃Al₂Ge₃O₁₂:Cr³⁺ were investigated in detail. On the basis of thermoluminescence analyses, the mechanism of the persistent afterglow of the phosphors was also discussed briefly. The afterglow duration of this phosphor can last more than 12 h with the 650–750 nm emission range after stoppage of 254 nm ultraviolet light irradiation. Specifically, the persistent luminescence intensity and duration were regulated by changing Cr³⁺ doping concentration. All the results indicate that the Cr³⁺ activated Zn₃Al₂Ge₃O₁₂ has promising potential of practical applications.     

硅酸盐长余辉发光材料的最新研究进展

系统地分析和概括了稀土离子激活硅酸盐体系长余辉发光材料的种类、特性、组成、结构、发光机理和制备技术。并根据长余辉发光材料研究现状，探讨了硅酸盐长余辉发光材料的研究方向与发展前景。     

Carbon Dots‐in‐Matrix Boosting Intriguing Luminescence Properties and Applications

As a new class of luminescent nanomaterials, carbon dots (CDs) have aroused significant interest because of their fascinating photoluminescence properties and potential applications in biological, optoelectronic, and energy‐related fields. Strikingly, embedding CDs in host matrices endow them with intriguing luminescent properties, in particular, room temperature phosphorescence and thermally activated delayed fluorescence, due to the confinement effect of the host matrix and the H‐bonding interactions between CDs and the matrix. Here, the state‐of‐the‐art strategies for introducing CDs in various host matrices are summarized, such as nanoporous materials, polyvinyl alcohol, polyurethane, potash alum, layered double hydroxides, amorphous silica, etc. The resultant luminescent properties of the composites and their emission mechanisms are discussed. Their applications in bioimaging, drug delivery/release, sensing, and anticounterfeiting are also presented. Finally, current problems and challenges of CDs‐based composites are noted for future development of such luminescent materials.     

发光稀土高分子研究进展及应用

目的 探究稀土高分子光学性能的研究情况,开发其应用潜力,从发光机理、制备、应用3个方面综述稀土高分子的研究进展,给后续的研究提供参考。方法 经过大量文献的搜集、翻阅,对发光稀土高分子的研究进展进行整理及总结。结果 稀土高分子的发光机理以中心稀土离子发光、天线效应和共荧光效应为主,按成键与否将其分为掺杂型稀土高分子和键合型稀土高分子,主要应用于农用塑料薄膜、防伪油墨、夜光纤维、荧光探针、太阳能电池等领域。结论 稀土高分子具有良好的综合性能,目前已应用于多个领域,深入研究稀土高分子的光学性能具有必要的科研意义和价值。     

Recent progress on the spectroscopy of rare earth ions in core-shells, nanowires, nanotubes, and other novel nanostructures

Research and development of nanoscale luminescent and laser materials are part of the rapidly advancing nanoscience and nanotechnology. Because of unique spectroscopic properties and luminescent dynamics of f-electron states, doping luminescent rare earth ions into nano-hosts has been demonstrated as an optimistic approach to developing highly efficient and stable nanophosphors for various applications. In this article, we review the most recent progress in spectroscopic measurements of rare earth ion-activated low-dimensional nanostructures including nanolayers, core-shells, nanowires, nanotubes, and nanodisks. Among a large volume of work reported in the literature on many members of the rare earth series including Ce3+, Pr3+, Nd3+, Eu3+, and Er3+, we focus on recent findings in the spectroscopic and luminescence properties of Eu3+ doped nanolayers, core-shells, and nanotubes, because Eu3+ ions have been extensively studied and widely used as an ideal probe for fundamental understanding of nano-phenomena. Specifically, the dependence of the optical properties of rare earth ions on nanostructures is discussed in detail.     

长余辉(寿命)发光材料研究的最新进展

综述了近几年来长余辉发光材料研究的最新进展,包括三方面:新材料研制,新应用领域的开拓和发光机理研究的模型.材料方面,主要介绍了红光、蓝光研究的进展与获得长余辉发光的关键因素-结构缺陷形成的陷阱态,以及稀土掺杂的作用.为促进新材料的研究着重概述了对长余辉发光机理研究的新进展,除了载流子传输与隧穿效应外,还介绍了两种最新观点;双光子吸收与V_K中心模型,并对其存在的问题作了评述.应用方面,除了已有的弱光照明与显示领域外,还在向光电信息功能,特别是二维图像存储,高能粒子射线探测方面发展.     

In Situ Confining Citric Acid-Derived Carbon Dots for Full-Color Room-Temperature Phosphorescence

Room-temperature phosphorescence has received much attention owing to its potential applications in information encryption and bioelectronics. However, the preparation of full-color single-component-derived phosphorescent materials remains a challenge. Herein, a facile in situ confining strategy is proposed to achieve full-color phosphorescent carbon dots (CDs) through rapid microwave-assisted carbonization of citric acid in NaOH. By tuning the mass ratio of citric acid and NaOH, the obtained CDs exhibit tunable phosphorescence wavelengths ranging from 483 to 635 nm and alterable lifetimes from 58 to 389 ms with a synthesis yield of up to 83.7% (>30 g per synthesis). Theoretical calculations and experimental results confirm that the formation of high-density ionic bonds between cations and CDs leads to efficient afterglow emission via the dissociation of CD arrangement, and the evolution of the aggregation state of CDs results in redshifted phosphorescence. These findings provide a strategy for the synthesis of new insights into achieving and manipulating room-temperature phosphorescent CDs, and prospect their applications in labeling and information encryption.     

White Light Afterglow in Carbon Dots Achieved via Synergy between the Room-Temperature Phosphorescence and the Delayed Fluorescence

Carbon dot (CD) based long-lived afterglow emission materials have attracted attention in recent years, but demonstration of white-light room-temperature afterglow remains challenging, due to the difficulty of simultaneous generation of multiple long-lived excited states with distinct chromatic emission. In this work, a white-light room-temperature long-lived afterglow emission from a CD powder with a high efficiency of 5.8% and Commission International de l'Eclairage (CIE) coordinates of (0.396, 0.409) is realized. The afterglow of the CDs originates from a synergy between the phosphorescence of the carbon core and the delayed fluorescence associated with the surface C?N moieties, which is accomplished by matching the singlet state of the surface groups of the CDs with the long-lived triplet state of the carbon core, resulting in an efficient energy transfer. It is demonstrated how the long-lived afterglow emission of CDs can be utilized for fabrication of white light emitting devices and in anticounterfeiting applications.     

热释发光-正电子湮灭法研究SrAl2O4基磷光体长余辉发光机制

利用传统陶瓷制备方法合成了长余辉SrAl2O4：Eu，Dy发光粉材料，并利用热释发光—正电子湮灭法对该材料的发光性能及机理进行了研究。研究结果表明，掺杂的Eu在基质材料中主要充当发光中心，而Dy离子主要充当陷阱能级。正电子湮灭试验结果表明，Sr0.94Al2O4：Eu0.02和Sr0.94Al2O4：Eu0.02，Dy0.04存在带负电中心的缺陷，共掺杂的Dy^3 进到Sr^2 位，同时产生一定量的Sr空位，热释发光谱结果表明，单掺杂Eu离子的磷光体中缺陷陷阱深度较深，约为0．95eV，随着Dy的共掺杂，热释发光强度相应增加，陷阱深度降为0．51eV，对于长余辉发光机制，认为陷阱能级捕获的空穴与介稳态(Eu^1 )^*的复合，导致了长余辉现象的发生，并且由于陷阱深度的变化，导致余辉性能出现较大的差异。     

Excitation-dependent carbon dots powders based on dehydration condensation by microwave–hydrothermal method

A green and economical microwave–hydrothermal method is employed to prepare carbon dots (CDs) that low-cost dl-malic acid serves as the carbon source and the formamide serves simultaneously as the pyrolysis solvent and carbon source. In the reaction process, neither assistant catalytic treatment nor further surface modification is necessary. We obtain better disperse CDs powders whose quantum yield reaches 25% as well as explain the dehydration condensation reaction mechanism based on the analysis by XPS and FTIR data. The luminescent properties are investigated in detail, and the results reveal that the excitation-dependent feature of as-prepared CDs has the potential for anti-counterfeiting mark and luminescence picture field.     

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．