可溶液加工的有机-无机杂化钙钛矿:超越光伏应用的“梦幻”材料

有机-无机杂化钙钛矿材料是可通过溶液工艺低温制备得到的直接带隙半导体晶体薄膜.在众多可溶液加工的半导体材料中,有机-无机杂化钙钛矿薄膜是为数不多的低缺陷密度、双极子传输性能优异的晶体薄膜,同时兼具宽光谱吸收和长载流子扩散距离等特性,是平面异质结太阳能电池的理想选择.另外,作为低缺陷密度的直接带隙半导体晶体材料,杂化钙钛矿薄膜具有优异的发光特性.其发光波长可通过能带工程(在分子水平上改变其组分)进行调节,因此有望在发光二极管和激光等光电器件中得到新应用.总结了钙钛矿材料的优异特性和目前应用研究的进展,并对其未来发展做了展望.     

《化学通报》网络版(Chemistry Online)2005年第11期论文摘要

[w123]具有纳米结构的有机发光材料研究进展**Progress in Research on Organic Nanomaterials for Luminescence赵雷黄维*(复旦大学先进材料研究院上海200433)对有机纳米发光材料制备方法以及材料的性能作了较为全面的综述。有机纳米发光材料由于存在分子间作用力(范德华力)或氢键以及具有小的Frenkel激子半径,与无机半导体纳米微粒以及纳米金属有着很大的区别,具有自己独特的光电性能,同时又兼具了有机发光材料响应速度快、可进行分子设计和纳米材料的尺寸效应等优点,在新型光电器件方面具有潜在应用前景。综合研究现状,本文也提出了该…     

PAMAM树形分子模板法原位合成发紫光CdS量子点的研究

半导体纳米粒子由于具有明显的量子尺寸效应,被形象地称为量子点(quantum dots)。量子点的发射波长可以通过改变粒子尺寸进行调节,并且由于是多电子体系发光,其荧光寿命较长,量子产率和光学稳定性能均优于荧光染料,可望成为新一代的发光材料和荧光探针[1,2]。为此,制备尺寸可控、荧光量子产率高、水溶性的半导体量子点成为很多科研人员的研究目标。树形分子科学的发展,为纳米材料的合成开辟了一条崭新的道路。人们利用树形分子独特的结构特征,将其作为纳米反应器和纳米容器,合成了尺寸均匀、分散性好的Ag、Cu、Pt、Pd等纳米簇[3￣7]。1998…     

含三苯胺的二苯乙烯化合物的合成及其电致发光性能

电致发光器件在光通讯、光信息处理、视频器件、测控仪器等光电子领域有着广泛而重要的应用价值.无机半导体二极管、半导体粉末、半导体薄膜等电致发光器件尽管已取得了令人注目的成就,但由于其复杂的器件制备工艺,高驱动电压、低发光效率,不能大面积平板显示,能耗较高以及难以解决短波长(如蓝光)等问题,使得无机电致发光材料的进一步发展受到一定的影响.相比之下,有机化合物可通过分子设计的方法合成数量巨大、种类繁多的有机化合物发光材料,使得有机材料构成的电致发光器件有着众多的优势,并成为目前电致发光领域的前沿研究课题之一.有关材料的制备^[1~3],发光机理^[4,5],电致发光器件的制备和性能^[6,7]的研究工作取得了相当大的进展.得到了各种发光颜色的器件,器件的发光亮度也较高.但由于电/光转换效率(量子效率)较低(小于10%),而且稳定性差,目前还只能制备出一些原型器件.     

Dip-pen刻蚀技术直接制造蛋白质纳米阵列

美国西北大学 Mirkin等 [1～ 3] 发明的 Dip- pen( DPN,译为蘸水笔技术 )纳米刻蚀技术是以 SPM的针尖为笔 ,通过超分子相互作用使被书写的分子或纳米材料粘在针尖上 ,以某种材料为基底 ,通过合理的超分子相互作用的设计将针尖上的分子或纳米材料书写到基底上 ,从而实现纳米刻蚀和纳米制造的目的 .很显然 ,这种技术对纳米器件、纳米传感器、高密度存储以及生物芯片的制造具有重要意义[4～ 7] .近年来 ,Mirkin研究组和其他几个研究集体利用这种技术成功地制造了有机分子纳米图形与阵列 [8] ;无机氧化物 [9]、金属纳米粒子 [10 ,11]、高分…     

有机低分子凝胶因子

糖苷、甾核、氨基酸等类型结构化合物是近年来有机低分子凝胶因子的研究重点,联（并）苯、有机金属化合物以及二元凝胶体系等方面有了新的拓展。本文综述了2000年以来有机低分子凝胶因子主要结构类型、表征方法和应用的研究进展,分析了凝胶因子在敏感性材料、无机纳米材料、固体燃料、固体电解质、药物控释等方面的应用,展望了其在分子识别、光电材料、半导体材料、生物催化等方面的潜在应用。     

聚集诱导发光有机小分子无机纳米复合材料的研究进展

有机-无机复合荧光纳米材料制备简便,生物相容性好,成像性能优异,在化学和生物传感、生物成像、催化及能源材料等领域受到很多关注.传统的荧光有机小分子与无机材料复合时,常发生荧光猝灭,而聚集诱导发光(Aggregation-InducedEmission,AIE)有机小分子在聚集态具有高发光量子产率,为有机-无机复合荧光纳米材料的研究提供了机遇.由于AIE有机小分子功能化的无机纳米材料独特的优点,人们对其设计、合成及应用进行了较多研究.综述了AIE有机小分子和多种类型的无机纳米结构(金属纳米颗粒、钙钛矿材料、层状材料、氧化物、硫化物等)复合材料的制备和应用的新进展,特别是在化学和生物传感、生物成像、药物输运、光热治疗、催化以及能源等领域的应用,并对其发展前景进行了展望.     

基于过渡金属配合物的阻变存储材料

阻变型电存储依靠外加电场作用下存储介质的导电性高低差异,即电学双稳态或多稳态来实现数据存取,并具有高容量、高柔韧性、低成本、低能耗、可规模化等优点,为下一代高密度存储技术提供新前景. 除了无机氧化物、碳纳米材料、有机小分子和有机聚合物半导体材料之外,近年来,过渡金属配合物在阻变型电存储方面的应用也引起广泛关注. 本文对迄今为止报道的大部分基于过渡金属配合物的阻变存储材料进行了总结和讨论,主要包括第VⅢ族金属[包括Fe（Ⅱ）、Ru（Ⅱ）、Co（Ⅲ）、Rh（Ⅲ）、Ir（Ⅲ）、Pt（Ⅱ）等配合物]、第IB族和ⅡB族金属[Cu（Ⅱ）、Au（Ⅲ）、Zn（Ⅱ）等配合物]和镧系过渡金属配合物[Eu（Ⅲ）及其它],并对各种配合物的存储行为和存储机理进行了探讨. 过渡金属配合物具有清晰可逆的氧化还原过程,通过改变配体的结构和金属的种类可以很方便地调节材料的前线轨道能级和能隙,利于形成电学双稳态或多稳态,达到二进制或多进制存储的目的,具有潜在应用价值.     

吡唑啉衍生物的电化学性质及其能带结构

有机 /聚合物电致发光是当今世界上的热门研究领域[1 ,2 ] ,因而有机 /聚合物电致发光材料的能带结构成为非常重要的研究课题[3] .目前 ,确定有机 /聚合物电致发光材料的能带结构的方法主要有电化学法[4] ,光谱法[5] ,量子化学计算法[6] ,紫外光电子能谱法[7] ,光电子发射法[8] 等 .这些方法中 ,由于电化学方法操作简单 ,对仪器设备要求不高 ,故被广泛使用 .虽然不同的测试方法测得的能带数据存在一定的系统误差 ,但由于电发光器件中考虑的是材料间的能带匹配 ,因此 ,在不同的条件下测定的能带数据相对来说是可信的 .吡唑啉化合物具有较高的…     

CdTe纳米晶与蛋白相互作用研究

当半导体纳米晶的直径小于其电子的玻尔直径时 ,半导体纳米晶对电子具有量子限域效应 ,其发光波长与纳米晶的尺寸相关 .与有机荧光分子相比 ,荧光半导体纳米晶具有以下优点 :(1 )其激发谱在吸收阈值以上几乎是连续的 ,利于多波长激发 ;(2 )高强荧光发射 ,谱峰窄 ,峰形对称 ;(3 )发射波长随着粒径的增大而有规律地红移 ,只需改变粒径即可获得多色发光 ;(4)纳米晶的发光稳定性好 ,不易被光分解和漂白 .因此 ,半导体纳米晶作为新一代荧光生物标记物已有研究[1～ 6] .荧光生物标记要求使用水溶性的纳米粒子 ,水相合成半导体纳米晶操作简便、重复…     

无机材料的仿生合成

生物矿化重要的特征之一是细胞分泌的有机基质调制无机矿物的成核和生长, 形成具有特殊组装方式和多级结构特点的生物矿化材料(如骨、牙和贝壳)。仿生合成就是将生物矿化的机理引入无机材料合成, 以有机物的组装体为模板, 去控制无机物的形成,制备具有独特显微结构特点的无机材料, 使材料具有优异的物理和化学性能。仿生合成已成为无机材料化学的研究前沿。本文综述了无机材料仿生合成的发展现状。     

Peptide‐Based Methods for the Preparation of Nanostructured Inorganic Materials

With their unique sequence‐specific self‐assembly and their substrate recognition properties, peptides play critical roles in controlling the biomineralization of inorganic nanostructures in natural systems and in directing the assembly of important soft matter. These attributes render them particularly useful molecules for the fabrication of new materials. Researchers from many scientific disciplines now use peptides to direct the synthesis of new inorganic nanostructures and the assembly of soft biomaterials. In this Review we describe the developments in this field and focus on the versatility of peptides and their ability to direct the composition and structure of new inorganic materials.     

Rational synthesis of covalently bonded organic-inorganic hybrids

Hybrid materials based on covalently linked inorganic polyoxometalates (POMs) and organic species containing a delocalized pi system have drawn increasing attention. These hybrids, traditionally prepared by cluster assembly approaches that lack predictability and controllability, can now be synthesized through common organic reactions by using organically functionalized POM clusters as building blocks. This minireview highlights some of the most recent advances on a particular type of hybrids where the organic and inorganic components are connected by an imido linkage.     

具有聚集诱导发光效应的咔唑基三苯乙烯衍生物单体及聚合物

合成了一类新的咔唑基三苯乙烯衍生物单体及其聚合物.利用示差扫描量热法(DSC)、热重分析法(TGA)、紫外可见分光光度法和荧光分光光度法等对单体和聚合物的性能进行了初步的表征.实验结果表明,该单体和聚合物具有较高的玻璃化转变温度(Tg),分别为210℃和229℃;单体和聚合物均具有很高的热稳定性,热失重5%的温度分别为466℃和467℃;单体具有明显的聚集诱导发光性能(AIE),而聚合物则具有聚集诱导增强发光性能(AIEE);所合成的单体和聚合物有望在OLED器件以及化学传感器上得到应用.     

Influence of the alkyl side chain length on the room-temperature phosphorescence of organic copolymers

Pure organic room-temperature phosphorescence(RTP) materials have attracted wide attention owing to their excellent luminescent properties and great potential in various applications. In this work, iminostilbene and its analogues are applied to realize RTP emission by copolymerizing with acrylamide. It can be concluded that the growth of alkane chain in monomers can enhance the lifetime and photoluminescence quantum yield of RTP emission, and polymers with the larger conjugated structure of the ...     

Multinuclear PtII Complexes: Why Three is Better Than Two to Enhance Photophysical Properties

The self-assembly of platinum complexes is a well-documented process that leads to interesting changes of the photophysical and electrochemical behavior as well as to a change in reactivity of the complexes. However, it is still not clear how many metal units must interact in order to achieve the desired properties of a large assembly. This work aimed to clarify the role of the number of interacting Pt^II units leading to an enhancement of the spectroscopic properties and how to address inter- versus intramolecular processes. Therefore, a series of neutral multinuclear Pt^II complexes were synthesized and characterized, and their photophysical properties at different concentration were studied. Going from the monomer to dimers, the growth of a new emission band and the enhancement of the emission properties were observed. Upon increasing the platinum units up to three, the monomeric blue emission could not be detected anymore and a concentration independent bright-yellow/orange emission, due to the establishment of intramolecular metallophilic interactions, was observed.     

Lanthanide/zinc centered photoactive hybrids with functional sulfonamide linkage: Coordination bonding assembly,characterization and photophysical properties

In this paper, two novel kinds of organic–inorganic monomer, SUA-APEMS and SUA-APS, have been achieved by modifying 5-sulfosalicylic acid (SUA) with 3-aminopropyl-methyl-diethoxylsilane (APEMS) and 3-aminopropyl trimethoxysilane (APS). These two organic–inorganic monomers were used as multi-functional bridged components, which can coordinate to metal ions (Tb³⁺/Eu³⁺/Zn²⁺) with carbonyl groups, strongly absorb ultraviolet and effectively transfer energy to metal ions through their triplet excited state, as well as involve in the sol–gel process with inorganic host precursor tetraethoxysilane (TEOS), resulting two series of molecular hybrid materials (named as SUA-APEMS/APS-RE) with double chemical bond (RE(Zn)–O coordination bond and Si–O covalent bond). The effective intra-molecular energy transfer process gives rise to the characteristic emission of metal ions and the chemical bond make the hybrid materials owning better properties.     

Polarized near-edge x-ray-absorption fine structure spectroscopy of C60-functionalized 11-amino-1-undecane thiol self-assembled monolayer: molecular orientation and evidence for C60 aggregation

Near-edge x-ray-absorption fine structure (NEXAFS) spectroscopy was adopted to probe the unoccupied electronic states of C60 anchored onto an organized assembly of 11-amino-1-undecane thiol on Au(111). The polarization dependence of the intensity of pi* resonance associated with C60 pi network revealed the self-assembled monolayer (SAM) system to be oriented with an average molecular tilt angle of 57 degrees with respect to the surface normal. Invoking the absence of solid-state band dispersion effects and in comparison to solid C60 and /or 1-ML C60/Au(111), the electronic structure of the resulting assembly was found dominated by spectral position shift and linewidth and intensity changes of the lowest unoccupied molecular orbital (LUMO), LUMO+1, and LUMO+2 orbitals. The latter implied hybridization between N Pz of -NH2 group of thiolate SAM and pi levels of C60, resulting in a nucleophilic addition with a change in the symmetry of C60 from Ih to C1 in the SAM. Occurrence of a new feature at 285.3 eV in the NEXAFS spectrum, assigned previously to pi* graphitic LUMO, signified the formation of aggregated clusters, (C60)n of C60 monomer. Low tunneling current scanning tunneling microscopy confirmed them to be spherical and stable aggregates with n approximately 5.     

Fluorescence Emission from 2,6‐Naphthylene‐Bridged Mesoporous Organosilicas with an Amorphous or Crystal‐Like Framework

We report that 2,6‐naphthylene‐bridged periodic mesoporous organosilicas exhibit unique fluorescence behavior that reflects molecular‐scale periodicities in the framework. Periodic mesoporous organosilicas consisting of naphthalene–silica hybrid frameworks were synthesized by hydrolysis and condensation of a naphthalene‐derived organosilane precursor in the presence of a template surfactant. The morphologies and meso‐ and molecular‐scale periodicities of the organosilica materials strongly depend on the synthetic conditions. The naphthalene moieties embedded within the molecularly ordered framework exhibited a monomer‐band emission, whereas those embedded within the amorphous framework showed a broad emission attributed to an excimer band. These results suggest that the naphthalene moieties fixed within the crystal‐like framework are isolated in spite of their densely packed structure, different from conventional organosilica frameworks in which only excimer emission was observed for both the crystal‐like and amorphous frameworks at room temperature. This key finding suggests a potential to control interactions between organic groups and thus the optical properties of inorganic/organic hybrids.     

无机多孔材料的合成及其在环境催化领域的应用

无机多孔材料因其具有特殊的物化性能在化工、能源、环保等相关领域被广泛应用。本文总结了无机多孔材料的当前研究进展,详细介绍了微孔、介孔、大孔材料和大孔-介孔、大孔-微孔、介孔-微孔以及大孔-介孔-微孔等复合孔材料的制备方法,并介绍了无机多孔材料在室内、外等环保催化领域的应用,特别介绍了多孔材料对于消除移动源污染的应用。最后,对当前无机多孔材料在制备方面存在的问题进行了总结,并对今后无机多孔材料的制备方法和研究方向进行了展望。