半导体纳米晶体的光致发光特性及在生物材料荧光标记中的应用

介绍了半导体纳米晶体（亦称量子点）的结构特征和光致发光特点，并与有机荧光染料分子的光致发光性质作了对比。结合本实验室所做的工作，对半导体纳米晶体用于生物材料的连接、标记和检测作了综述。     

无机半导体纳米晶光学性质的设计、调控及其生物医学应用

半导体纳米晶由于其丰富的能带结构和光学性质,在光电器件和生物医学应用等领域展现出了广阔的应用前景,且在过去的几十年中得到了广泛关注.因此,对其光学性质进行理性设计和精确调控具有重要的研究意义.本文简要综述了本研究组近年来在不同能带隙的无机半导体纳米晶的可控制备技术以及利用DNA纳米技术和蛋白质自组装手段构建具有特异光学性质的纳米结构等方面的相关研究工作,最后对这些纳米晶和纳米结构的独特光学性质及其在生物医学领域的应用研究进行了总结.     

半导体CdTe纳米晶的合成及其光学性能

半导体CdTe纳米晶的合成及其光学性能;CdTe;纳米晶;光学性能     

Ⅰ-Ⅲ-Ⅵ族半导体纳米晶

半导体纳米晶是近年来发展起来的一类新型功能材料,因其独特的量子限域效应和光电性质,在太阳电池、发光二极管、光电探测器、生物标记、非线性光学等领域中具有潜在的应用。与目前研究比较多的Ⅱ-Ⅵ和Ⅳ-Ⅵ族纳米晶相比,Ⅰ-Ⅲ-Ⅵ族半导体纳米晶,不含镉和铅等重金属元素,具有毒性小、带隙窄、光吸收系数大、Stokes位移大、自吸收小以及发光波长在近红外区等特点,有望成为新一代低成本太阳电池和低毒荧光量子点生物标记材料, 还可用于发光二极管和光电探测等领域。因此,Ⅰ-Ⅲ-Ⅵ族半导体纳米晶的合成、性质及应用研究成为近期纳米晶研究领域的热点之一。本文将综述Ⅰ-Ⅲ-Ⅵ族半导体纳米晶的研究进展,着重介绍其制备方法、光学性质及其在生物标记、太阳电池等领域的应用。     

Mn:ZnSe/ZnS核-壳结构纳米晶的无膦法制备和光学性质

以溶于十八烯的Se作为Se前驱体,在无膦条件下制备得到了具有较高量子产率的Mn:ZnSe纳米晶.为了进一步提高纳米晶的稳定性和发光强度,运用外延生长的方法进行ZnS壳层包覆并得到了具有核-壳结构的Mn:ZnSe/ZnS纳米晶.X射线衍射、透射电子显微镜及吸收和荧光光谱测试结果表明,该方法合成的Mn:ZnSe纳米晶以及核-壳结构Mn:ZnSe/ZnS纳米晶均为闪锌矿结构,具有良好的单分散性,包覆ZnS外壳层后量子产率可达到60%以上.此外,对ZnS壳层厚度和Mn2+的掺杂量对Mn:ZnSe/ZnS纳米晶发光强度的影响及发光机制也进行了初步讨论.     

无机纳米晶-生物界面作用的分子机制

无机纳米晶材料以其独特的光、电、磁、力学性质,成为疾病诊断与治疗功能的关键材料.本文总结了无机纳米晶的表面化学活性、离子释放性、晶相结构、晶格缺陷、表面吸附和表面修饰等与尺寸相关的理化性质与生物效应之间的关系.综述了无机纳米晶与蛋白质、磷脂生物膜间的界面相互作用,探讨了纳米晶-生物界面作用的分子机理.这有助于理解无机纳米晶的生物行为和毒理性质,指导设计安全、高效的纳米晶生物医学材料.     

Ag∶InP/ZnSe纳米晶的合成与生物成像

采用高温热注入法, 以P[N(CH3)2]3为磷源合成了具有近红外荧光的Ag∶InP/ZnSe纳米晶. 采用紫外|可见|近红外吸收光谱(UV|Vis|NIR)、 荧光光谱、 透射电子显微镜(TEM)、 X 射线衍射(XRD)等对产物的结构和光学性质进行了表征, 并分析了Ag掺杂浓度和温度对InP纳米晶荧光性能的影响. 通过调节Ag掺杂浓度和反应温度, 发现当Ag掺杂量为6%, 反应温度为200 ℃时, Ag∶InP纳米晶的发光效率最高. 将制备的Ag∶InP的表面包覆ZnSe, 粒子的荧光效率从原来的20%提高到45%. 将具有近红外荧光的Ag∶InP/ZnSe纳米晶应用于细胞成像, 结果表明制备的荧光纳米晶在细胞成像中清晰可见且毒性较低.     

纳米粒子的分类合成及其在生物领域的应用

纳米粒子是当今最受关注也是最常报道的一类纳米材料,尺寸处于纳米级别是纳米粒子的突出特点,这赋予其在化学、光学、电学和磁学等方面优于传统块体材料的独特性能,因而纳米粒子越来越受到人们的重视,并广泛应用于很多领域,尤其是生物医药领域。本文围绕可生物应用的纳米粒子,从组成以及结构的角度着手,将纳米粒子分为有机纳米粒子、无机纳米粒子以及有机/无机杂化纳米粒子。同时结合近三年国内外关于各类纳米粒子新颖的合成报道,分别阐述了上述不同种类纳米粒子所具有的适合生物应用的物理和化学方面的特征,并针对不同类别的新型纳米粒子,着重描述了其具体合成方法和潜在的生物应用。最后,简单介绍了纳米粒子在生命科学这一领域的具体应用实例,如刺激响应感应器、生物特异性标记及基因药物载体等,并展望了纳米粒子在该领域的长远发展。     

碲化镉纳米晶的制备及应用

基于自身的量子限域效应、尺寸效应、介电限域效应、宏观量子隧道效应和表面效应,碲化镉(CdTe)纳米晶独特的性质在非线性光学、磁介质、催化、医药及功能材料等方面得到了广泛的应用,并且展现出极为广阔的应用前景,同时对生命科学和信息技术的持续发展以及物质领域的基础研究也产生了深刻的影响。本文以 CdTe 纳米晶为对象,详细介绍了其5种典型的制备方法和应用的最新进展。在制备方面,5种典型的制备方法各有利弊,如何在温和的条件下制备出形貌和尺寸可控的 CdTe 纳米晶仍是一个值得追求的目标。通过自组装技术可以制备形貌独特,性能优异的 CdTe 纳米材料,进而实现 CdTe 半导体纳米器件的研制,具有重要的科学意义,是今后研究的热门方向。在应用方面,CdTe纳米晶不但实现了其在光电器件、生物学等领域的应用,而且将会在这些领域继续深化和延伸,开发出新的应用领域。本文同时对 CdTe 纳米晶的发展趋势也进行了展望。     

硅纳米晶的制备及其在太阳电池中的应用研究

硅纳米晶由于量子限域效应的作用而产生了多种不同于体硅材料的新特性,如荧光效应显著、光学带隙可调等,因而在微电子、光伏、生物医学等领域受到极大的重视。本文介绍了分立的硅纳米晶颗粒和硅纳米晶薄膜的制备方法,并对比了不同方法制备硅纳米晶体的优缺点。着重介绍了硅纳米晶体在太阳电池中应用的几种方式,包括利用纯硅纳米晶薄膜制备太阳电池、硅纳米晶体与有机薄膜基质结合形成复合结构太阳电池、含有硅纳米晶颗粒的硅墨水在太阳电池中的应用等。     

Organic Semiconductor Micro/Nanocrystals for Laser Applications

Organic semiconductor micro/nanocrystals (OSMCs) have attracted great attention due to their numerous advantages such us free grain boundaries, minimal defects and traps, molecular diversity, low cost, flexibility and solution processability. Due to all these characteristics, they are strong candidates for the next generation of electronic and optoelectronic devices. In this review, we present a comprehensive overview of these OSMCs, discussing molecular packing, the methods to control crystallization and their applications to the area of organic solid-state lasers. Special emphasis is given to OSMC lasers which self-assemble into geometrically defined optical resonators owing to their attractive prospects for tuning/control of light emission properties through geometrical resonator design. The most recent developments together with novel strategies for light emission tuning and effective light extraction are presented.     

Shape Control of Colloidal Semiconductor Nanocrystals

Shape control of inorganic nanocrystals is important for understanding basic size- and shape-dependent scaling laws, and may be useful in a wide range of applications. Methods for controlling the shapes of inorganic nanocrystals are evolving rapidly. This paper will focus on how we currently control the shape of semiconductor nanocrystals using CdSe as example.     

II-VI族半导体荧光纳米微粒及复合荧光微球的制备及应用

本文简单介绍了半导体荧光纳米微粒（又称量子点）的基本概念和荧光性质，评述了II－VI族半导体荧光纳米微粒（NCs）的制备和性质研究进展，尤其对基于荧光纳米微粒的复合荧光微球的制备、性质及改进方法进行了详细的讨论，指出目前存在问题和发展方向。     

Block Copolymer-Templated Synthesis and Organization of Semiconductor Nanocrystals

Summary: Templates formed by the self-assembly of amphiphilic block copolymers in selective solvents have been found to be instrumental in controlling critical parameters in semiconductor nanomaterials fabrication, including particle size, shape, and composition. These tunable nanoreactors exhibit rich polymorphism and have enabled the synthesis of a variety of nanostructures such as dots, wires, tubes, hollow spheres, and 2-D structures by growth-under-confinement at room temperature. The encapsulated particles have optical and electronic properties that are dependent upon physical dimensions and morphology, and exhibit inherent stability and functionalization flexibility, thus opening up promising prospects through their integration into functional optoelectronic and biological systems.     

Organic Nanocrystals with Bright Red Persistent Room‐Temperature Phosphorescence for Biological Applications

Persistent room‐temperature phosphorescence (RTP) in pure organic materials has attracted great attention because of their unique optical properties. The design of organic materials with bright red persistent RTP remains challenging. Herein, we report a new design strategy for realizing high brightness and long lifetime of red‐emissive RTP molecules, which is based on introducing an alkoxy spacer between the hybrid units in the molecule. The spacer offers easy Br−H bond formation during crystallization, which also facilitates intermolecular electron coupling to favor persistent RTP. As the majority of RTP compounds have to be confined in a rigid environment to quench nonradiative relaxation pathways for bright phosphorescence emission, nanocrystallization is used to not only rigidify the molecules but also offer the desirable size and water‐dispersity for biomedical applications.     

Shape-Controlled Nanocrystals for Catalytic Applications

The activity, selectivity, and long-term stability of catalyst nanoparticles can be enhanced by shape modulation. Such shaped catalytic nanocrystals have well-defined surface crystalline structures on which the cleavage and recombination of chemical bonds can be rationally controlled. Metal and metal oxide nanocrystals have been synthesized in various shapes using wet chemistry techniques such as reducing metal precursors in the presence of the surface-capping agents. The surface-capping agents should be removed prior to the catalytic chemical reaction, which necessitates clean catalytically active surface. The removal process should be performed very carefully because this removal often causes shape deformation. A few examples in which the surface-capping agents contribute positively to the chemical reactions have been reported. The examples described in this review include shaped metal, metal composite, and metal oxide nanocrystals that show enhanced catalytic activity, selectivity, and long-term stability for various gas-phase, liquid-phase, or electrocatalytic reactions. Although most of the studies using these shaped nanocrystals for catalytic applications have focused on low-index surfaces, nanocrystals with high-index facets and their catalytic applications have recently been reported. By bridging surface studies with nanoparticle catalysts using shape modulation, catalysts with improved properties can be rationally designed.