有机自组装低维圆偏振发光材料的研究进展

具有圆偏振发光(CPL)性质的材料由于在3D显示、光学存储以及光学防伪等领域的重要应用,近年来越来越受到研究人员的关注。超分子策略能够将不同类型的分子组装成具有独特功能的低维(零维、一维和二维等)结构,因而成为构筑CPL活性有机低维材料的最有效方法之一。本文从超分子自组装驱动力的角度综述了近几年自组装CPL活性有机低维材料的研究进展。首先,本文系统地总结了现阶段设计自组装CPL活性有机低维材料的策略,其次重点讨论了这类材料的性能及应用,最后探讨了这一领域未来的发展机遇和挑战。     

Self-assembled structures of 4′-([2,2′:6′,2″-terpyridine]-4′-yl)-[1,1′-phenyl]-4-carboxylic acid molecules induced by metal atoms on ag(111) surface

The self-assembled supramolecular structures of 4′-([2,2′:6′,2″-terpyridine]-4′-yl)-[1,1′-phenyl]-4-carboxylic acid (Y) molecules on Ag(111) surface induced by metal elements have been studied by scanning tunneling microscopy. After annealing, the as-deposited monolayer of Y molecules shows four kinds of well-ordered structures due to the competition between dipole interaction, hydrogen bonding and Van der Waals interaction. Introduced Cu atoms drive ordered monolayer into a self-assembled supramolecular structure with bright spots. Deposited Ag atoms cause the monolayer change to a windmill shape self-assembled supramolecular structure. Though the Cu and Ag are in the same group of the periodic table, a Cu atom connects two COOH groups and an Ag atom trends to bind to three COOH groups during the formation of metal-organic bonding within both induced structures. Such result suggests that the self-assembled structures formed by metal-organic coordination bonding can be controlled by choosing the number of metal-organic coordination bonds, which can be helpful to design metal-organic molecular architectures comprising functional building blocks.     

Two-dimensional self-assembly of DNA base molecules on Cu(111) surfaces

We present scanning tunneling microscope images of the self-assembled nucleic-acid base molecules on the surfaces of Cu(111). The images reveal that the chemical inertness of the Cu(111) substrate allows the molecules to diffuse over the surface to self-assemble themselves spontaneously into their own unique structure: adenine into one-dimensional (1D) molecular chains, thymine into 2D islands, guanine into 2D square lattices, and cytosine into 1D zig-zag molecule-cluster networks. We find that molecular orbital calculations reproduce some of the observed self-assembly, and suggest that base-base interaction induced by hydrogen bonding is essential to this phenomenon.     

A direct observation on the surface assembling and ordering of coumarin derivatives on the graphite surface

The 2D monolayer structures of two coumarin derivatives, 4-heptadecyl-7-hydroxycoumarin (HHC) 1 and 3-(2-benzo thiazolyl)-7-octadecyloxy-coumarin (BOC) 2, have been studied by STM and different sensitivity to thermal annealing for these two systems has been observed. The results show that the arrangements of these two molecules are obviously different in the self-assembled monolayer at 20 °C on the graphite surface. Furthermore, only BOC is sensitive to thermal annealing. The assembly of BOC becomes more stable and ordered after annealing at 65 °C for 1 h.     

Device applications of self-assembled monolayers and monolayer-protected nanoclusters

The present status of self-assembled monolayers (SAMs) on different surfaces (2D systems) as well as monolayer formation on metallic and semiconducting cluster surfaces (3D SAM) to form monolayer-protected nanoclusters (MPCs) and their assemblies is reviewed briefly. Attention is focused mainly on the potential electronic and photonic applications of SAMs, MPCs and their 2D and 3D structures fabricated using covalent and hydrophobic interactions in contrast to the usual electrostatic assemblies. These examples illustrate the rational use of organic molecules and nanoclusters using the concept of self-assembly, where subtle systems of double tunnel junctions, hetero junctions and single-electron transition devices could be developed based on the structure and chemistry of multifunctional molecules. The tailoring of cluster size and cluster–cluster spacing to reveal interesting transitions in electronic properties is also demonstrated using the low temperature behavior of the 3D network of nanoclusters as an example. These devices are believed to play an important role in the coming years as the chip functions and clock frequencies reach orders of magnitude beyond those extrapolated from Moore’s law.     

Self-assembly of 5-octadecyloxyisophthalic acid and its coadsorption with terephthalic acid

The structure of the self-assembled monolayer of pure 5-octadecyloxyisophthalic acid (5OIA), and the coadsorption monolayer of 5OIA and terephthalic acid, is investigated using scanning tunneling microscopy (STM) at the liquid-solid interface. 5OIA self-assembles into a monolayer comprised of different structures. For the major phase, 5OIA molecules alternately pack with opposite enantiotopic faces in a lamella, giving lamellae with a chain-to-trough angle of ∼88°. Two adjacent lamellae are assembled together by a hydrogen-bonding network between two carboxylic acid groups from each lamella. In the self-assembled monolayer of the mixture solution of 5OIA and terephthalic acid, 5OIA molecules coadsorb with terephthalic acid and therefore form two stoichiometric multi-component domains. Each domain has a molar ratio of 2:1 for 5OIA and terephthalic acid. For each component (5OIA or terephthalic acid), the two coadsorption structures exhibit opposite chirality.     

Self-assembly of nanoparticles on the surface of ionic crystals: Structural properties

With a suitable combination of ligand-stabilised nanoparticle suspension and ionic salt solutions, it is possible to produce microcrystals that are coated with nanoparticles. The self-assembly process of coating microcrystals by gold nanoparticles (NP) is mediated by the crystal lattice. This is the so-called CLAMS process - a generic process for self-organisation of nanoparticles on the surface of crystals [M. Murugeshan, D. Cunningham, J.-L. Martnez-Albertos, R. Vrcelj, B.D. Moore, Chem. Commun. (2005) 2677]. We are exploring here the structural properties of these self-assembled structures by using different imaging techniques.     

What orchestrates the self-assembly of glycine molecules on Cu(100)?

The structures of two competing phases and their interrelationship in the self-organization of glycine molecules on a Cu(100) surface were clarified. Despite their similar structural energies predicted using first-principles calculation, completely different mechanisms were found to stabilize the two phases. The balance and coordination of the two mechanisms that induce a variety of self-assembled structures in this attractive system were revealed. Furthermore, the importance of the microscopic arrangement of the molecules in designing the macroscopic electronic structures was directly demonstrated.     

Understanding formation of molecular rotor array on Au(111) surface

The motion of single molecules on surfaces plays an important role in nanoscale engineering and bottom-up construction of complex devices at single molecular scale. In this article, we review the recent progress on single molecular rotors self-assembled on Au(111) surfaces. We focus on the motion of single phthalocyanine molecules on the reconstructed Au(111) surface based on the most recent results obtained by scanning tunneling microscopy (STM). An ordered array of single molecular rotors with large scale is self-assembled on Au(111) surface. Combined with first principle calculations, the mechanism of the surface-supported molecular rotor is investigated. Based on these results, phthalocyanine molecules on Au (111) are a promising candidate system for the development of adaptive molecular device structures.     

Assembly of quantum dots on peptide nanostructures and their spectroscopic properties

We present a chemical process for the decoration of self-assembled two-dimensional peptide fibrils with two different sizes of CdSe@ZnS core–shell quantum dots (Qdots) capped with trioctylphosphine oxide molecules. The attachment of the semiconducting nanoparticles to the fibrils is directed via disulfide bond between the quantum dot and cysteine aminoacids that are deliberately impeded in the peptide structures. A significant red shift in the emission spectra of the quantum dots is observed and attributed to the synergistic interaction between adjacent nanoparticles arranged on peptide film templates extending over hundreds of nanometers.     

Anisotropic water chain growth on Cu(110) observed with scanning tunneling microscopy

We report a novel structure of water aggregate by means of scanning tunneling microscopy. Water molecules are self-assembled into one-dimensional chains on Cu(110) at 78 K. The chain exhibits a zigzag structure with a period of 7.2 A and grows to a length of approximately 1000 A. We propose that water hexamers are arranged alternately along the chain. Interchain repulsion due to dipole interaction facilitates the 1D chain growth. A two-dimensional overlayer develops only at high coverage.     

Self-assembly of C60 into highly ordered chain-like structures on HOPG observed at ambient conditions

The observation of chain-like structures of self-assembled C₆₀ molecules on HOPG surfaces at room temperature in aerial atmosphere by means of scanning tunneling microscopy is reported. The ca. 2.5 nm center-to-center distance between two fullerene molecules is much larger than in the close-packed layered or film structures of C₆₀ usually found on HOPG surfaces.     

The simplest model of adsorption of molecules with different orientations in adlayer on the stepped surface

In this article we have constructed and studied using the Monte Carlo and transfer-matrix techniques the simple lattice gas models of self-assembled monolayer, which consists of molecules with different orientations in the adlayer on the stepped surfaces. It was shown that in the case of adsorption of complex molecules the surface heterogeneity of stepped type leads to a great variety of ordered structures comparatively with homogeneous one. The constructed models fairly well reproduce the main features of real SAMs consisting of molecules with different orientations with respect to interface and the model ordered phases are also analogues to the structures of real SAMs.     

透射式扫描近场光学显微镜探针光场分布及其受激荧光分子光场分布研究

通过利用经Grober发展的Bethe模型,计算了透射式近场光学显微镜探针针尖附近及进入样 品后的光场分布,研究了它的横向分辨率、透射深度、透射系数等问题.模拟在光学近场激 发下生物荧光分子成像的过程,研究了荧光分子的极化方向和入射光偏振方向对信号收集的影响,发现荧光图像是偏振极性和荧光分子极性共同作用的结果. 关键词： 近场光学 光场分布 荧光分子成像     

On the interaction of self-assembled C<Subscript>60</Subscript>F<Subscript>18</Subscript> polar molecules with the Ni(100) surface

The current work is dedicated to investigation of the interaction between self-assembled polar molecules of fullerene fluoride C₆₀F₁₈ with the chemically active surface Ni(100) under radiation and heat treatments. X-ray photoelectron spectroscopy is used in combination with quantum-chemical simulation. For the first time, the transformation of an as-deposited dielectric continuous 2D thin film to a 3D island-type assembly with molecular ordering within the islands is shown to take place. The degree of coverage of the Ni surface by C₆₀F₁₈ islands (0.6–0.7) and their height (~6 nm) are estimated. Quantum-chemical simulation shows that the chemisorption energy of the C₆₀F₁₈ molecule on the Ni surface equals ~6.6 eV and fluorine atoms are located at a distance of 1.9 Å above the Ni surface. The results of the investigation provide an opportunity to create nanoscale ordered structures with local changes in the work function.     

Self-assembly,optical and electrical properties of fork-tailed perylene bisimides

Effect of side-chain length on self-assembly, optical and electrochemical properties of N,N′-di(1-pentylbutyl)perylene-3,4,9,10-tetracarboxylic bisimide and N,N′-di(1-hexylpentyl)perylene-3,4,9,10-tetracarboxylic bisimide has been studied. The photo-physical, thermal and electrochemical properties were studied using UV–Vis and fluorescence, differential scanning calorimetry, and cyclic voltammetry, respectively. The molecules self-assembled as 1D – rods and molecular bundles, self-assembly was studied using SEM, optical and fluorescence microscopic techniques. The results concluded that the compound with short tail exhibits low solubility and self-assembled faster. The photo-physical properties of the compounds were not much affected by varying the alkyl chain length. The compounds geometries were optimized at 6-31G^∗ using DFT and the potentials were correlated with molecular orbitals.     

Rewritable self-assembled long-period gratings in photonic bandgap fibers using microparticles

We report the demonstration of rewritable self-assembled long-period gratings in air-core photonic bandgap fibers. The long-period gratings are written by filling the air-core region of the fiber with a solution containing polystyrene microspheres. The microspheres are self-assembled into a periodic structure as the liquid inside the fiber evaporates, forming the long-period grating. The formed grating can then be easily erased for rewriting purposes by connecting the end of the fiber to a microfluidic pump through a microfluidic channel and washing out the microparticles with an appropriate liquid. The same microfluidic system can also be used to fine control the writing process of the gratings. This technique creates possibilities for writing various different filtering functions in air-core photonic bandgap fibers by varying the composition and/or the shape of the used microparticles. The presented technique is potentially applicable to solid-core photonic crystal fibers as well.     

Surface state control of III–V semiconductors using molecular modification

An attempt to control surface electronics of III–V semiconductor using wet chemical processes has been performed. Here, we report results on the use of self-assembled monolayers (SAMs) of organic molecules on (0 0 1) GaAs surface. Octadecanethiol (ODT) and benzenethiol (BT) have been the choice in the present study.GaAs wafers were modified by thiol molecules on the flat surface after the native oxide layers are removed by chemical etching under optimized conditions. The change in the electronic properties was measured in terms of transport properties via the SAM layer by conductive probe atomic force microscopy. The current–voltage characteristics thus obtained show that ODT functions as a tunnel barrier while BT is conductive due to the presence of π-electrons. As a result, we can control the electronic states of GaAs–molecule interface for realizing novel device structures by the selection of functional molecules.     

Influence of tapering process on changes of optical fiber refractive index distribution along a structure

Investigations of internal structure changes along an optical fiber during the manufacture of biconical taper have been described. Basing on the constant volume theory, classification of biconical structures manufactured on a special set-up is presented and discussed. The interferometric tomography method has been used for determination of 3D geometry and refractive index distribution in manufactured optical fiber tapers. The experiments provide detailed information on external (diameter of cladding) as well as internal (core diameter and refractive index profile) changes along the taper region. The results have been discussed in relation to the parameters of the manufacturing process.