电子俘获材料的研究现状及在红外检测方面的应用

电子俘获材料在辐射剂量测定、光信息处理、光存储、红外光检测等许多技术领域具有广泛的应用。本文详细介绍了电子俘获材料的发光原理、材料种类、制备方法以及研究现状,并针对该材料在红外光检测方面的应用,提出了在室温下该材料存在红外光检测上限的观点。针对电子俘获材料存在性质不稳定及在制备过程中需用到硫化类材料易造成污染等问题,建议进一步改进材料制备方法。最后,文中指出玻璃陶瓷类电子俘获材料会有很好的发展前景,并对该种材料未来的发展前景进行了展望。     

ZnS中电子陷阱能级对光生电子弛豫过程的影响

采用微波吸收法,测量了在不同助熔剂条件及不同气氛下烧制的ZnS材料受到超短激光脉冲激发后的光电子衰减过程,并且测量了材料的热释光曲线。样品A采用过量的SrCl作为助熔剂,在1150℃下灼烧制备而成;其热释光曲线显示材料中有浅电子陷阱,电子陷阱密度小,光生电子衰减过程为双指数衰减过程,快过程寿命为45ns,慢过程寿命为312ns。样品B中加入了少量的NaCl作为助熔剂;热释光曲线显示有浅电子陷阱和深电子陷阱,且都有较高的密度,其光电子寿命为1615ns。在NH₄Br气氛中烧制样品C,热释光谱显示只有浅电子陷阱形成,光电子寿命为1413ns。结果表明材料的光电子寿命和浅电子陷阱密切相关,浅电子陷阱密度越大,光生电子寿命越长,深电子陷阱对光生电子瞬态过程影响很小。     

双脉冲注入式LD模块的红外能级寿命可见区测试系统

Er3+的4I_13/2能级寿命的长短对评估Er3+掺杂材料在光通讯波段的应用十分重要。基于980 nm双脉冲注入式LD激发下的Er3+激发态吸收上转换发光,测量在不同双脉冲时间间隔下的上转换红光发光强度,再根据上转换红光的发光强度随双脉冲时间间隔的变化关系,推导出了Er3+红外4I_13/2能级寿命的拟合公式,实现了红外能级寿命的可见区测量。因此,结合兼具时间间隔可调和同步脉冲取样的双脉冲注入式LD模块和光电倍增管(R2658),就可以实现所有Er3+红外能级寿命的测量,这是一种十分经济的微秒量级荧光寿命测试系统。     

电子俘获材料SrS:Eu,Sm,Er的光谱特性和光存储特性

提出一种Er3+改进的电子俘获光存储材料SrS∶Eu0.002,Sm0.002,Erx,其中,0≤x≤0.006。通过水热反应,研究了不同退火温度对荧光粉晶相形成的影响,以及不同含量的Er3+对荧光粉的发光性质以及光存储特性的影响。结果表明,Er3+的引入导致荧光增强及光存储特性提高。当Er3+的摩尔分数x=0.003时,荧光强度、光激励发光强度及光存储量出现最大值,分别为不含Er3+时的1.9倍、2倍和3.5倍。同时,Er3+的掺入不改变样品的晶体结构和衰减特性。     

磷光寿命法研究无保护流体室温磷光的重原子效应和发光动力学参数

以两种卤代萘为模型化合物，基于磷光寿命的定义τ＝τ^-，τ0＝1／kp和其与各速率常数的关系，导出了一种类似于Stern-Volmer方程的线性方程：τ0／τ＝（kp_kic)/kp=1 kic/kp=1 Ksv.c。通过测定不同重原子微扰剂浓度时的磷光寿命，探讨了从两种途径计算流体室温磷光发射相关动力学参数的可行性和方法，通过这些参数对比讨论了KI和TINO3两种重原子微扰剂对这两种卤代萘无保护流体室温磷光发射的重原子效应的差异。     

电致发光衰减测量系统的搭建及应用

发光衰减是发光的重要过程,测量发光寿命对研究发光机理十分重要,但传统研究在概念和方法上存在两个差错：(1)概念上认为衰减等同于激发态数目的减少,而忽视了衰减是发光强度的下降,两者是不同的概念;(2)方法上基于激发态规律推导,假设的边界条件不符合实际,没有实验的支持。同时,传统方法对设备的要求很高,且只限于光致发光。为了纠正差错,降低成本,搭建了一套全新的电致发光衰减测量系统,可用于所有可以周期激发的发光类型。从能量转换原理出发,采用周期激发,用脉冲间隔时间作为时间尺度来度量发光衰减持续的时间,通过脉冲间隔时间与发光寿命的对比,相应地发光强度有不同的变化,根据该现象简便地测量出发光寿命。基于该原理搭建的发光衰减测量系统,实验结果表明了发光强度随着激发频率,先保持不变然后逐渐下降,通过测量下折点即能够推算出发光衰减寿命,而且还发现发光衰减寿命与初始发光强度呈正相关的关系。认为发光寿命是发光强度的变化,是区别于传统研究以激发态数目为研究对象的一大创新,同时通过实验证明了发光寿命与初始亮度相关,也拓展了对发光寿命的新认识。     

Photochemistry at high temperatures – potential of ZnO as a high temperature photocatalyst

Direct conversion of solar radiation into useful, storable and transportable chemical products is the primary goal of solar chemistry. In this paper we discuss some fundamental aspects of photochemistry at elevated temperatures. We show that luminescence can serve as an indicator of the potential use of a system as a photoconverter. As an example we present experimental data on the chemical potential and on the lifetime of the excited states of ZnO. The low luminescence quantum yield together with a lifetime of about 200 ps indicate that an efficient photochemical conversion on ZnO is highly improbable. We believe this to be a general feature of chemical systems based on a semiconductor photocatalyst, in particular of photoreactions at a solid/gas interface. Received: 18 June 1996 / Accepted: 20 September 1996     

ZnqCl2及其衍生物的电子光谱性质的含时密度泛函理论研究

采用从头算法(abinitio)和密度泛函理论(DFTB3LYP)方法,对二氯取代的八羟基喹啉锌(ZnqCl2)及其2种衍生物的基态结构进行优化,同时用abinitioHF单激发组态相互作用(CIS)法在6-31G(d)基组上优化其最低激发单重态几何结构,用含时密度泛函理论(TD-DFT/B3LYP)及6-31G(d)基组计算吸收和发射光谱。计算表明,该类物质电子在基态与激发态间的跃迁,主要是在配体8-羟基喹啉(q)环内的电荷转移,电子从含O的苯酚环转移至含N的吡啶环上,发射光谱的计算值与实验值基本符合。该类化合物的电子亲和能较大,都是优良的电子传输材料,改变中心金属原子对配合物光谱性质影响不大。     

Muon and positron induced luminescence in KBr and CuCl

The exciton luminescence induced by muon implantation in two selected halides is compared with that induced by positron irradiation. The data include wavelength and lifetime spectra for potassium bromide and lifetime spectra for cuprous chloride, recorded at the ISIS Pulsed Muon Facility. For each material, the spectra for positron-induced and muon-induced luminescence are indistinguishable; that is, no influence of muonium formation on the self-trapped exciton state can be discerned.     

发光寿命在发光特性表征中的重要影响

吸收是发光的前提条件,吸收变了,发光的其他特性也就随之而变.但是发光寿命的长短又会反过来影响吸收的多少,这不仅存在于光致发光中,而且是一个普遍规律.从电场引起的场致发光中发现,在同一种材料中掺入两种发光寿命长短相差悬殊的发光中心Cu和Mn,利用激发电源频率的变化,明确地显示出发光寿命短的Cu的发光与发光寿命长的Mn的发光强度之比随频率的增加而增大,而且也显示了Cu的两种发光也有这种规律.实验结果说明,这种规律只取决于发光中心的寿命长短,而与激发方式及猝灭原因无关.     

Spectral information from minerals relevant for luminescence dating

The paper reviews basic spectral features of luminescence from minerals used in dating and allied research. Luminescence production is a result of multiple interactions within the imperfect crystal lattice and spectral information is not limited to the emission of light. Results of spectral investigations of luminescence emission during thermal stimulation (TL) or optical stimulation (OSL) form the main part of the paper. However, information on luminescence excitation and light absorption spectroscopy is also presented and possible links between luminescence production in minerals and particular lattice defects are considered. Quartz and feldspars, the most commonly used minerals, receive special attention, but the review includes other materials such as polymineral fine-grained fractions from sediments, zircon, calcite and other salts (halite, sulfate), meteorites, flint, volcanic materials (obsidian, tephra), ceramics and metallurgical slags. Although a wide range of different luminescence emission wavebands occur, it can be shown that certain emissions dominate in particular materials. Basic dosimetric properties are often known just for single emission wavebands of a particular mineral, and are listed in this case. The paper also aims to provide a starting point and inspiration for the study of other TL and OSL emissions, with particular regard to their potential and suitability for dating and related dosimetry tasks. These investigations, involving palaeodose determination based on an emission waveband with known characteristics, need careful separation of the particular emission peak, which may be influenced by its behaviour during the dating procedure (sample preparation, irradiation, preheat treatments, luminescence measurements, etc.). Spectral information available in this context and some technical remarks on the experimental conditions will be given to pave the way for conventional TL or OSL measurements in luminescence dating and dosimetry using natural or semi-natural materials.     

微波吸收法研究Mn,Cu掺杂对ZnS:Mn,Cu光生载流子复合过程的影响

采用微波吸收法，测量了ZnS:Mn,Cu粉末材料受到超短脉冲激光激发后，其光生电子和浅束缚态电子的衰减过程.发现Mn,Cu的浓度对导带电子的寿命有明显的影响，提高掺杂浓度会使光生电子的寿命大大缩短，还研究了掺杂浓度对光致发光强度的影响. 关键词： 发光材料 硫化锌 光电子 微波吸收技术     

兼具三线态-三线态湮灭上转换与单光子吸收上转换特性的氮杂蒽衍生物发光性能研究

弱光上转换是将低能量光子转换为高能量光子的过程,在三维荧光显微成像、太阳能电池、光催化等领域具有广泛的潜在应用,因而成为有机荧光材料领域的热点课题。目前基于三线态-三线态湮灭机制有机弱光上转换材料（TTA-UC）的研究已较为深入,有关发光机理及应用研究均有较多报道;然而针对另一种有机弱光上转换机理——基于单光子热带吸收的弱光上转换（OPA-UC）的研究目前还较为少见。氮杂蒽衍生物由于具有良好的结构刚性和平面性,高的荧光量子产率,是研究TTA-UC和OPA-UC两种有机上转换发光的理想模型分子结构。通过研究比较三种氮杂蒽衍生物：酚藏花红（PSF）、藏红T（SFT）、亚甲基紫（MTV）各自TTA-UC和OPA-UC的发光性能差异,分析探讨了分子结构对OPA-UC发光性能及TTA-UC敏化效率的构效关系。实验发现酚藏花红和藏红T由于具有较高的荧光量子产率,同时辐射衰减常数较大,其主要衰减过程为辐射衰减;而亚甲基紫具有较高的分子内电荷转移能力(ICT),因而非辐射衰减部分更多。研究三种分子的TTA-UC性能,发现亚甲基紫的三线态能级过低无法进行三线态-三线态能量转移过程,而藏红T由于拥有更高的三线态寿命而具有更高的上转换发光效率(9.69%),是酚藏花红体系(3.16%)的3倍。进一步研究酚藏花红和亚甲基紫的OPA-UC性能差异,发现相同浓度条件(10-3 mol·L-1)下亚甲基紫(0.12%)的OPA-UC发光效率相较于酚藏花红(0.059%)更高,且随着浓度的升高,亚甲基紫的OPA-UC发光增强效应更大。进一步研究表明,在TTA-UC发光过程中,敏化剂的敏化效率主要受分子三线态寿命以及系间窜跃能力影响,寿命越长,系间窜跃能力越强,敏化效率越高;而在OPA-UC发光过程中,湮灭剂分子的发光学率主要受ICT影响,ICT能力越大,分子发光效率越高。使用氮杂蒽分子廉价易得,对未来高性能TTA-UC和OPA-UC发光分子的设计具有一定的实际意义。     

双波长Pr3+掺杂12CaO·7Al2O3的光存储特性

采用化学共沉淀法制备了Pr3+掺杂的12CaO·7Al2O3(C12A7:Pr3+)材料.通过X射线衍射(XRD)、发射光谱、激发光谱、余辉衰减曲线、热释发光及光激励发光等测试手段系统研究了C12A7:Pr3+材料的微观结构和光学性质.结果表明,C12A7是一种理想的适合Pr3+掺杂的基质材料,C12A7:Pr3+具有...     

Positronium formation and thermostimulated luminescence: A common nature and combined application to studies of organic systems

Polymeric membrane materials with highly developed intrinsic microporosity for gas separation are studied. The porosity can be essentially improved by filling the polymer with nonorganic components (zeolites). This porosity, herein referred to as artificially induced, turned out, in some cases, to be higher than that of the constituent components. The reasons for this effect are not always clear. To gain additional insights into the nature of this effect, an experimental study is suggested with the use of a combination of two methods related by being based on track processes: positron annihilation lifetime spectroscopy PALS and thermostimulated luminescence (TSL). The present paper summarizes and discusses both recently published results and completely new data.     

粉末DCEL发光区的随机性

粉末DCEL屏(夹心式)的发光区是在紧靠阳极的一个很薄(大约1μm)的区域内,这是至今所有研究者一致的结论。本文作者在实验中证实,粉末DCEL屏的发光区位置具有随机性,通常它可出现在任何难以预料的位置上,比如在靠近阴极或者在发光粉层中间以及靠近阳极,甚至同时在所有上述位置上出现,也有时发光区占据整个的发光粉层。实验还证实,发光区的位置与形成方式,电极材料,电压极性,发光材料和屏的结构等因素有关,发光区出现在紧靠阳极的区域只是一种特定条件下的结果。文章讨论了发光区形成的原因及其规律性,认为发光区的位置取决于发光粉层内电位分布不均匀性的具体情况。     

Realization of receptive fields with excitatory and inhibitory responses on equilibrium-state luminescence of electron trapping material

Our theoretical modelings and experimental observations illustrate that the equilibrium-state luminescence of electron-trapping materials (ETMs) can be controlled to produce either excitatory or inhibitory responses to the same optical stimulus. Because of this property, ETMs have a unique potential in optical realization of neurobiologically based parallel computations. As a classic example, we have controlled the equilibrium-state luminescence of a thin film of this stimulable storage phosphor to make it behave similarly to the receptive fields of sensory neurons in the mammalian visual system, which are responsible for early visual processing.     

Blue LED Excitable Temperature Sensors Based on a New Europium(III) Chelate

A new europium(III) chelate is synthesized and characterized. The wavelength of sensitization of Eu³⁺ luminescence is shifted further into visible so that efficient excitation with 425, 435 and 450-nm LEDs becomes possible. Photophysical properties and temperature dependence of luminescence are investigated in toluene solution and various polymer matrixes. The sensor materials are also characterized in terms of cross-sensitivity to oxygen and photostability. The sensor material based on the europium complex immobilized into poly(vinylidene chloride-co-acrylonitrile) shows negligible cross-sensitivity to oxygen and is particularly attractive for applications at physiological conditions. Other materials can be applied for sensing and imaging purposes at room temperatures. The new materials can also be used for compensating optical (oxygen, CO₂ etc.) sensors for temperature effects.     

介质中含孤立发光中心的纳米粒子的辐射寿命概率分布

含发光中心的纳米粒子在介质中随机分布,造成局域介质相对折射率的随机分布,导致了纳米粒子辐射寿命的涨落.分析纳米粒子数量在线度为发射光波长量级的体积内的概率密度,由此得出局域介质相对折射率的概率密度.通过纳米粒子辐射寿命对折射率的依赖关系,得到纳米粒子辐射寿命概率密度的解析表达.在此基础上,分析了Meltzer等人的实验中,含Eu³⁺离子的Y₂O₃粒子在甲醇溶液中辐射寿命的相对偏移量的涨落,并得出辐射寿命的不确定度(均方差)与纳米粒子体积、体积密度等物理量的关系.     

Enhanced Lanthanide Luminescence Using Silver Nanostructures: Opportunities for a New Class of Probes with Exceptional Spectral Characteristics

The photophysical effects of europium tetracycline immobilized in thin polyvinyl alcohol films coated onto silver nanostructures have been investigated. Complimentary to recent reports from our laboratories that the close proximity of luorophores to silver nanostructures can enhance their intrinsic radiative decay rate, we show that up to a 16-fold enhancement in lanthanide luminescence is possible, accompanied by a notable reduction in luminescence lifetime. These results suggest the potential future development of a new class of significantly brighter lanthanide based probes with exceptional spectral properties, which can probably undergo significantly more excitation–emission event cycles due to the reduced lifetime, substantially increasing detectability.