纳米晶取向接合生长动力学研究及其在量子点发光性质调控中的应用

对晶体生长机制、动力学与微结构衍化的认识是实现纳米材料的尺寸和形貌可控制备的基础．以表面溶解沉积为特征的奥斯特瓦尔德熟化（0R）理论常用来解释传统的晶体生长过程．在该生长模式下,纳米晶体的生长呈现出小颗粒溶解而大颗粒逐渐长大的特征．在纳米材料体系,近来还发现了一种重要的新的晶体生长模式——“取向接合（OA）”机制,在该机制下,两个晶格取向一致的初级纳米颗粒可通过直接接合和结构调整,从而长成一个新的晶体．这一机制已被证实在许多纳米材料体系中广泛存在,并对所合成的纳米材料的形貌、微结构具有非常显著的影响,在构筑新型纳米结构方面具有潜在的优势．本文我们首先回顾了OA生长机制的认识历程和这一机制对材料科学的重大意义;进而,基于我们的研究工作系统介绍了OA生长动力学模型的建立与发展,进一步阐述了这一机制的微观过程及其对材料内部缺陷的特殊影响,深入地分析和讨论了表面包裹的强弱、表面作用的性质对OR机制和OA机制的抑制和调控作用;基于上述表面包裹可调控纳米材料的生长机制的认识,我们结合近期研究结果,从动力学角度分析了量子点的生长机制与其发光特性的内在关联,阐明了表面包裹调控量子点的发光性质的本质原因,为制备不同发光特征的量子点及理解其发光性质衍化规律提供了重要的理论指引．     

Mo覆盖层对MgO/CoFeB/Mo结构磁各向异性的影响

研究了Mo覆盖层厚度对MgO/CoFeB结构磁各向异性的影响. 研究发现, 加平行磁场生长出来的MgO/CoFeB/Mo样品表现为面内各向异性, 并且随着CoFeB的厚度减小, 面内各向异性逐渐减弱; 在CoFeB厚度减小到1.1 nm时, 仍可以保持面内各向异性, 垂直方向的外加饱和场逐渐减少; 厚度在0.9 nm及以下的情况下, 面内各向异性消失. 改变Mo覆盖层厚度, 当t_Mo= 1.6 nm时, 垂直方向的饱和场最小. 当生长过程的磁场变为垂直磁场时, 不同厚度的Mo覆盖层对MgO/CoFeB 的磁各向异性影响不同. Mo厚度在1 nm及以下时MgO/CoFeB/Mo样品表现为面内各向异性, Mo覆盖层厚度在1.2和5 nm之间时样品出现了垂直磁各向异性; 并且垂直方向的矫顽力也发生了变化, Mo覆盖层厚度为1.4 nm时样品的磁滞损耗会大一些.     

Influence of annealing temperature on the photoluminescence property of ZnO thin film covered by TiO2 nanoparticles

In this work, ZnO thin films covered by TiO₂ nanoparticles (labeled as TiO₂-ZnO thin films) were prepared by electron beam evaporation. The influence of annealing temperature on the photoluminescence property of the samples was studied. The structures and surface morphologies of the samples were analyzed by X-ray diffraction (XRD) and atomic force microscope, respectively. The photoluminescence was used to investigate the fluorescent properties of the samples. The measurement results show that the ultraviolet emission of ZnO thin films is largely enhanced after they are covered by TiO₂ nanoparticles, while the green emission is suppressed. However, when the annealing temperature is relatively high (≥500 °C), the intensity of ultraviolet emission drops off and a violet emission peak along with a blue emission peak appears. This is probably connected with the atomic interdiffusion between TiO₂ nanoparticles and ZnO thin film. Therefore, selecting a suitable annealing temperature is a key factor for obtaining the most efficient ultraviolet emission from TiO₂-ZnO thin films.     

Facile Hydrogenation of Acenapthylenes and Azulenes on the Face of a Triruthenium Carbonyl Moiety: Discovery of Specific Reactions on the Cluster Framework Providing Unique Insight for Cluster Catalysis

Summary.  Activation of molecular hydrogen by triruthenium carbonyl clusters bearing acenaphthylene or aceanthrylene as the face-capping ligand results in partial hydrogenation of these polyaromatic ligands, giving the corresponding hydride carbonyl clusters bound to hydrogenated acenaphthylene or aceanthrylene. The first isolation of 4,5-dihydroacenaphthylene or 4,5-dihydroaceanthrylene was achieved by treatment of the resulting hydride carbonyl clusters with CO. Similarly, triruthenium carbonyl species bearing substituted azulenes as the face-capping moiety gives the corresponding hydride carbonyl cluster bearing partially hydrogenated azulenes at room temperature; the corresponding partial hydrogenation of azulenes does not occur with di- or tetraruthenium homologues. Hydrogenation of di-, tri-, and tetraruthenium carbonyl clusters bearing substituted azulenes at elevated temperatures furnishes hydrogenative cluster fragmentation to mononuclear ruthenium hydrides; the stereochemistry of these complexes suggests that the reaction takes place through the activation of H₂ by the multinuclear species. The roles of the acenaphthylene or azulene ligands as hemilabile μ₃-ligands for triruthenium carbonyl clusters are discussed. Received April 28, 2000. Accepted May 9, 2000     

Mechanical Reinforcement of Molecular Hydrogel by Co‐assembly of Short Peptide‐based Gelators with Different Aromatic Capping Groups

We demonstrated in this study that mixing two short peptide‐based gelators with different aromatic capping groups would result in molecular hydrogels with enhanced mechanical property. We selected gelators of PTZ‐GFFY and Nap‐GFFY for the study. Both PTZ‐GFFY and Nap‐GFFY could independently form molecular hydrogel by a heating‐cooling process. However, the mechanical property of gels of PTZ‐GFFY and Nap‐GFFY was relatively weak with storage moduli (G′) of about 500 and 150 Pa, respectively. A two‐component gel of PTZ‐GFFY and Nap‐GFFY could also form by a heating‐cooling process. Surprisingly, the G′ value of the two‐component gel was about 5000 Pa , which was at least ten times bigger than that of each single‐component gel. This is a novel and simple strategy to improve the mechanical property of molecular hydrogels.     

Microwave-assisted synthesis of water-soluble styrylpyridine dye-capped zinc oxide nanoparticles for antibacterial applications

ZnO nanoparticles were successfully synthesized using a microwave method, whose surface was modified with {4-[(E)-2-(furan-2-yl)ethenyl]pyridin-1-ium-1-yl}acetate as a capping agent (1 and 3%). Their structural properties were investigated using FTIR, XRD, SEM, EDS, and UV–visible spectroscopy. XRD confirmed the Wurtzite structure for all compounds, a size of 30.6 nm for uncapped and 22.9 nm for 3% dye-capped nanoparticles were calculated from Scherer's equation. Hexagonal wurtzite shape of nanoparticles can be clearly seen in the SEM images. The DFT calculations were carried out using quantum espresso. These dye-capped ZnO nanoparticles were proved to be potential antibacterial agents, the minimum concentrations of dye-capped ZnO nanoparticles that inhibit the growth of bacteria are 1.5 mg/mL for Escherichia coli and 0.78 mg/mL for Bacillus subtilis, which are much lower than those of uncapped ZnO. The bioactivity data suggest these organic–inorganic hybrid nanoparticles emerged as a new class of antibacterial agents.     

Surface Capping Agents and Their Roles in Shape‐Controlled Synthesis of Colloidal Metal Nanocrystals

Surface capping agents have been extensively used to control the evolution of seeds into nanocrystals with diverse but well‐controlled shapes. Here we offer a comprehensive review of these agents, with a focus on the mechanistic understanding of their roles in guiding the shape evolution of metal nanocrystals. We begin with a brief introduction to the early history of capping agents in electroplating and bulk crystal growth, followed by discussion of how they affect the thermodynamics and kinetics involved in a synthesis of metal nanocrystals. We then present representative examples to highlight the various capping agents, including their binding selectivity, molecular‐level interaction with a metal surface, and impacts on the growth of metal nanocrystals. We also showcase progress in leveraging capping agents to generate nanocrystals with complex structures and/or enhance their catalytic properties. Finally, we discuss various strategies for the exchange or removal of capping agents, together with perspectives on future directions.     

DBS包覆TiO2纳米粒子的表面光伏及光致发光性能

采用溶胶-水热法合成了十二烷基苯磺酸钠(DBS)包覆的TiO2纳米粒子,并利用X射线衍射仪、透射电镜、表面光电压谱(SPS)和光致发光光谱(PL)等对样品进行表征.重点探讨了DBS包覆的适宜条件及DBS包覆对TiO2光伏和发光等性质的影响.结果表明,进釜前pH值在4.5~5.5,DBS用量为TiO2质量的1.0%~3.0%时,能够获得理想包覆.在水热过程中,DBS的引入对锐钛矿型TiO2微晶的生长有抑制作用.由于DBS的包覆,使TiO2的SPS和PL信号强度显著下降,这可能与磺酸基的吸电子性以及表面缺陷等的减少有关.     

High color rendering index and chromatic stability of top‐emitting white organic light‐emitting diodes capped with a supplementary green color conversion layer

We have demonstrated high color rendering index (CRI) and chromatic stability of top‐emitting white organic light‐emitting diodes (TEWOLEDs) by capping a supplementary green color conversion layer (CCL) on the cathode of single blue emitter based TEWOLEDs. By employing CCLs, blue photon energy is absorbed and converted to green emission efficiently, resulting in an improvement of CRI from 72 to 86. We attribute the increased high CRI to the broadening of the out‐coupled spectrum and an appropriate intensity match among the three primary colors. Meanwhile, the TEWOLEDs show extremely high chromatic stability. The results indicate that this method provides a new avenue to improve the CRI of TEWOLEDs.

     

The Crystal Structure of Tetraphenyldichloro(μ-hydroxo)- Distannate·quinoline

Hydrolysis of diphenyltin dichloride in the presence of quinoline and diethyl ether proceeds via formation of a monomeric diorganodistannoxane compound. The single crystal X-ray diffraction study of [Sn(C₆H₅)₂Cl(μ-OH)]₂ · quin is reported together with IR and H-NMR data. The dimer consists of five-coordinate tin(IV) units with di-μ-hydroxo bridging. The coordination geometry of the tin unit is a distorted trigonal bipyramid with two phenyl groups and one μ-hydroxo in equatorial positions and the other μ-hydroxo and chlorine atoms in axial positions.