金属配合物分子纳米结构构筑与调控的STM研究进展

金属配合物分子具有结构多样且可控以及功能丰富等特点,在催化、传感、分子识别、纳米器件等领域得到广泛应用, 对金属配合物分子的研究已是分子科学研究中的热点之一.同时, 利用配合物分子构筑表面分子纳米结构以及对配合物单分子性质的研究也日趋活跃. 近年来, 本研究组发展了配合物分子在固体表面的自组装技术, 并结合扫描隧道显微技术(STM)开展了一系列有关金属配合物分子表面纳米结构的研究工作, 在固体表面成功实现了对配体、配合物分子的高分辨STM成像、原位配合以及分子识别, 设计和构筑了多种功能配合物分子纳米结构,并系统研究了结构形成规律. 本文以本研究组近年来有关金属配合物分子组装的研究结果为主, 结合国内外相关研究小组的研究结果,综述有关金属配合物分子纳米结构的构筑与调控的STM研究进展, 介绍该类分子在固体表面的组装和分散规律, 为表面分子纳米结构的构筑和调控提供理论和实验基础.     

表面等离激元金属纳米粒子的多元化结构及应用

目前, 单一的金属纳米粒子结构已经难以满足多学科交叉发展的需求. 因此, 将多种金属纳米粒子(如不同尺寸、 形状、 组分等)集成在同一基底表面, 能够充分发挥不同金属纳米粒子的性质和优势, 极具研究价值和应用价值. 本文介绍了多元化表面等离激元纳米粒子结构的构筑方法, 以及其在信息编码、 光电器件、 能源催化等领域的应用. 最后, 提出了当前在多元化结构制备中存在的挑战, 并展望了利用多元化结构实现性能提升的前景.     

硅纳米结构对表面辅助激光解吸/电离质谱检测性能的提高

本文总结了多种构筑硅纳米结构的方法, 综述了近年来利用硅纳米结构提高表面辅助激光解吸/电离质谱(SALDI-MS)性能的研究工作, 展望了利用功能化的硅纳米结构表面进一步提高激光解吸/电离(LDI)效率的前景.     

高分子表面微纳米结构的构筑及应用

近年来,纳米科技在高分子材料上的应用给高分子科学和材料的发展注入了新的活力.高分子材料表面微纳米结构与材料的性能密切相关,其微纳米结构结合高分子材料本身丰富多彩的特性,在材料科学、微电子学以及细胞生物学等方面都有重要的科学意义和应用价值.目前关于高分子材料表面微纳米结构的构筑已有大量报道,涉及的实验方法和材料非常广泛,大体上可以分为模板法和非模版法.在运用中往往需要综合利用高分子的各种特性和多种实验方法.本文以构筑方法分类,综述了近十几年来在高分子表面构筑微纳米结构的研究进展,对其应用前景做了简要介绍.     

简易制备高整流比的异质纳米通道

生命体内的离子通道在各种生物功能调节过程及生命活动中具有重要的意义.模仿生物孔道的离子输运性质,构筑人工纳米通道,并研究人工纳米通道的离子输运性质是一项具有重大意义的研究课题.本文通过双面阳极氧化和原位扩孔结合的方法制备了对称结构的沙漏形氧化铝纳米通道.通过在对称结构的沙漏形氧化铝（AAO）纳米通道一侧粘贴一层透明胶带,经过热处理后,获得了一种具有高整流比的有机-无机异质纳米通道.基于非对称的结构和电荷分布,氧化铝纳米通道与有机纳米通道在复合区域形成异质结构.由于多孔AAO纳米通道和有机纳米通道的协同效应,异质纳米通道表现出独特的纳米流体二极管特性,即在比较宽的pH范围内具有单一的整流方向.在该体系中,氧化铝纳米通道内壁的羟基和有机纳米通道内壁的羧基在不同pH值下所带电荷性质不同,使异质结构纳米通道内壁表面电荷的性质和电荷密度发生改变,可以通过调节体系的pH来调控通道内的离子传输.     

ECSTM针尖诱导构筑Au表面有序Pd纳米粒子阵列

利用电化学扫描隧道显微镜(ECSTM)在温和的电化学和隧道偏压的条件下诱导电极表面发生特定的局域电化学反应, 在Au(111)单晶电极表面构筑了Pd纳米粒子的阵列. 研究了两种不同的溶液体系(PdCl2和PdSO4)构筑纳米粒子所需设定的不同参数, 同时探讨了选择不同参数的原因.     

基于水滴模板法的微纳复合超疏水结构制备的研究

利用粒子辅助水滴模板法的实施获得规则蜂窝状图案化多孔结构模板,并进一步利用聚二甲基硅氧烷(PDMS)复制转移技术获得表面具有微米尺寸蜂窝状突起阵列的反向图案化结构.以这种图案化突起结构作为微米尺寸所提供的微米级粗糙度为基础,设计了2种的简单的二次纳米结构的引入过程,最终实现了微米级阵列和纳米级粗糙度的复合.第一种方法借助银镜反应来实现纳米银结构的化学沉积,最终在PDMS阵列表面获得了致密的纳米银颗粒沉积层,并成功获得了表面接触角达166度的超疏水性质.第二种方法利用了聚电解质/二氧化硅粒子层层静电自组装的方法引入纳米结构,结果在仅仅进行了2个组装循环的条件下即可获得超疏水性质的表面复合结构.通过简单的实验设计试图提供一种基于水滴模板法的微纳复合超疏水结构的普适性制备方法.     

Armchair型石墨纳米带的电子结构和输运性质

利用第一性原理的电子结构和输运性质计算方法, 研究了扶手椅(armchair)型单层石墨纳米带(具有锯齿边缘)的电子结构和输运性质及其边缘空位缺陷效应. 研究发现, 完整边缘的扶手椅型石墨纳米带是典型的金属性纳米带, 边缘空位缺陷的存在对扶手椅型纳米带能带结构有一定的影响,但并不彻底改变其金属性特征.     

纳米粒子组装体系的研究进展

制备纳米粒子组装体系是构筑纳米结构的重要方法之一，本文综述了纳米粒子组装体系的制备方法及其性质和应用研究。     

石墨烯纳米带的可控制备研究进展

石墨烯纳米带是宽度为纳米尺度的石墨烯条带,根据其边缘构型的不同可以分为锯齿型石墨烯纳米带和扶手型石墨烯纳米带.纳米尺度导致的量子限域效应和边缘构型引起的边缘效应能够调节石墨烯纳米带的电子结构,打开石墨烯的带隙.而且,石墨烯纳米带具有极大的长宽比和极高比例的边缘原子,为通过结构裁剪实现功能定制提供了无限可能.这些几何和电子结构特性使得石墨烯纳米带在电子器件等诸多领域比石墨烯具有更大的应用潜力,因此,石墨烯纳米带的相关研究一直是纳米材料领域的热点.基于此,本综述首先介绍了石墨烯纳米带的结构和性质,全面介绍了石墨烯纳米带的制备方法,相应的制备方法可以分为两部分:(1)自上而下法:通过等离子体、离子束、扫描隧道显微镜和金属纳米颗粒对石墨烯和碳纳米管进行刻蚀和切割,制备石墨烯纳米带.该方法面临最大挑战在于如何提高刻蚀和切割精度.(2)自下而上法:利用含碳前驱体,如有机化合物、碳氢化合物气体以及碳化硅等,制备石墨烯纳米带.该方法利于实现原子精度的结构控制,尤其是化学气相沉积法有望实现低成本、规模化制备.最后展望石墨烯纳米带研究的挑战和前景.我们相信,随着材料和技术的创新发展,石墨烯纳米带必将成为一...     

Linear nanostructure formation of aldehydes by self-directed growth on hydrogen-terminated silicon(100)

The self-directed growth of organic molecules on silicon surfaces allows for the rapid, parallel production of hybrid organic-silicon nanostructures. In this work, the formation of benzaldehyde- and acetaldehyde-derived nanostructures on hydrogen-terminated H-Si(100)-2x1 surface is studied by scanning tunneling microscopy in ultrahigh vacuum and by quantum mechanical methods. The reaction is a radical-mediated process that binds the aldehydes, through a strong Si-O covalent bond, to the surface. The aldehyde nanostructures are generally composed of double lines of molecules. Two mechanisms that lead to double line growth are elucidated.     

Ordering of TiO2-based nanostructures on SrTiO3(001) surfaces

A class of nanostructured surface phases on SrTiO3(001) is reported and characterized through atomic-resolution scanning tunneling microscopy and Auger electron spectroscopy. These surface phases are created via argon ion sputtering and UHV annealing and form close-packed domains of highly ordered nanostructures. Depending on the type of nanostructures present, the domain ordering exhibit either (6 x 2), (9 x 2), (12 x 2), (6 x 8), or (7 x 4) surface patterning. The nanostructures are composed of TiO2-derived complexes surrounded by a TiO2 surface termination. Such surface ordering phenomena introduce another level of complexity in the chemistry of perovskite oxide surfaces and provide a basis from which potential photocatalytic and molecular-ordering applications may be developed.     

c(4 × 2) and related structural units on the SrTiO3(001) surface: scanning tunneling microscopy, density functional theory, and atomic structure

Density functional theory is used to simulate high-bias, constant-current scanning tunneling micrographs for direct comparison with experimental images. Coupled to previous spectroscopic data, these simulations are used to determine the atomic structure of Ti-rich nanostructures on strontium titanate (001) surfaces. These nanostructures have three consecutive TiO(x) surface layers and exploit the distinctive structural motif of the c(4 × 2) reconstruction as their main building block. A structural model of a characteristic triline defect is also proposed.     

Dispersion interactions enable the self-directed growth of linear alkane nanostructures covalently bound to silicon

Current interest in methods for controllably adding organic molecules to silicon surfaces relates to proposed hybrid silicon-organic devices. It was recently shown that a "self-directed" growth process, requiring only limited scanned probe intervention, has the potential to permit rapid, parallel production of ordered molecular nanostructures on silicon with predefined absolute position, structure, composition, and extent of growth. The hybrid organic-silicon structures formed are bound by strong covalent interactions. In this work, we use scanning tunneling microscopy and density functional theory techniques to show that molecule-surface dispersion interactions enable the growth process and play a crucial role in the final configurations of the nanostructures.     

Sexithiophene adlayer growth on vicinal gold surfaces

We have investigated the initial stages of vacuum-deposited sexithiophene (alpha-6T) adlayer formation on Au(111) vicinal surfaces at room temperature. The in situ scanning tunneling microscopy (STM) and photoemission spectroscopy (PES) reveal a step edge-driven growth of alpha-6T on the Au(111) vicinal surfaces that first leads to the formation of an ordered monolayer, comprising two phases with the molecular major axes aligned along the step edges. The monolayer formation is then followed by the appearance of a single-phase 2D superstructure at a two-monolayer coverage. The results highlight the potential of using vicinal metal surfaces as templates for generating organized organic nanostructures over macroscopic areas for applications in organic electronics and moletronics.     

Regulating the Interactions of Adsorbates on Surfaces by Scanning Tunneling Microscopy Manipulation

Scanning tunneling microscopy (STM) manipulation has received wide attention in the surface science community since the pioneering work of Eigler to construct surface nanostructures in an atom by atom fashion. Lots of scientists have been inspired and devoted to study the surface issues with the help of STM manipulations and great achievements have been obtained. In this Minireview, we mainly describe the recent progress in applying STM manipulations to regulate the inter‐adsorbate and adsorbate–substrate interactions on solid surfaces. It was shown that this technique could not only differentiate intermolecular interactions but also construct molecular nanostructures by regulating different kinds of inter‐adsorbate interactions or adsorbate–substrate interactions.     

枝状分子表面组装结构的形成与结构转变

本文是对近期有关枝状分子在石墨表面吸附组装研究的综述.利用扫描隧道显微技术,系统研究了5-甲氧基间苯二酸类枝状分子在石墨表面组装结构的形成及结构转变,发现虽然该类枝状分子大都可以在石墨表面自发有序组装,但是最终形成的组装结构不仅与分子本身结构例如烷基链的数目有关,与分子浓度有关,还与所用溶剂有关.分子浓度和溶剂的变化,影响组装体系内的相互作用力如分子与基底间的作用力、分子间氢键的作用力等,影响分子迁移和结构转变的动力学过程,从而影响枝状分子组装的最终结构.研究揭示了特定体系中枝状分子组装结构与分子浓度、所用溶剂的定量和定性关系.研究结果有助于认识和掌握枝状分子组装规律,进而可以通过改变相关技术参数,调控得到不同的枝状分子表面组装体,为实现可控构筑分子表面组装结构提供了新的思路.     

Self-organization of a self-assembled supramolecular rectangle, square, and three-dimensional cage on Au111 surfaces

The structure and conformation of three self-assembled supramolecular species, a rectangle, a square, and a three-dimensional cage, on Au111 surfaces were investigated by scanning tunneling microscopy. These supramolecular assemblies adsorb on Au111 surfaces and self-organize to form highly ordered adlayers with distinct conformations that are consistent with their chemical structures. The faces of the supramolecular rectangle and square lie flat on the surface, preserving their rectangle and square conformations, respectively. The three-dimensional cage also forms well-ordered adlayers on the gold surface, forming regular molecular rows of assemblies. When the rectangle and cage were mixed together, the assemblies separated into individual domains, and no mixed adlayers were observed. These results provide direct evidence of the noncrystalline solid-state structures of these assemblies and information about how they self-organize on Au111 surfaces, which is of importance in the potential manufacturing of functional nanostructures and devices.     

Scanning tunneling microscopy of functional nanostructures on solid surfaces: Manipulation,self-assembly,and applications

The manipulation, self-assembly, and application of functional nanostructures on solid surfaces are fundamental issues for the development of electronics and optoelectronics. For a future molecular electronics the fabrication of high-quality organic thin films on metal surfaces is crucial, which can be achieved by thermal evaporation for various organic/metal systems. The switching property of single molecules can be manipulated and measured, revealing a possibility to realize single molecular devices. Manipulation of a local conductance transition in organic thin films, used for ultra-high density data storage, has also been achieved based on several different mechanisms. The stability, reversibility, and repeatability of the local conductance transition have been improved by molecular design. In this article, we will summarize our recent scanning tunneling microscopy studies on these issues and discuss their perspectives.