Engineering atomic and molecular nanostructures at surfaces

The fabrication methods of the microelectronics industry have been refined to produce ever smaller devices, but will soon reach their fundamental limits. A promising alternative route to even smaller functional systems with nanometre dimensions is the autonomous ordering and assembly of atoms and molecules on atomically well-defined surfaces. This approach combines ease of fabrication with exquisite control over the shape, composition and mesoscale organization of the surface structures formed. Once the mechanisms controlling the self-ordering phenomena are fully understood, the self-assembly and growth processes can be steered to create a wide range of surface nanostructures from metallic, semiconducting and molecular materials.     

Folding DNA to create nanoscale shapes and patterns

'Bottom-up fabrication', which exploits the intrinsic properties of atoms and molecules to direct their self-organization, is widely used to make relatively simple nanostructures. A key goal for this approach is to create nanostructures of high complexity, matching that routinely achieved by 'top-down' methods. The self-assembly of DNA molecules provides an attractive route towards this goal. Here I describe a simple method for folding long, single-stranded DNA molecules into arbitrary two-dimensional shapes. The design for a desired shape is made by raster-filling the shape with a 7-kilobase single-stranded scaffold and by choosing over 200 short oligonucleotide 'staple strands' to hold the scaffold in place. Once synthesized and mixed, the staple and scaffold strands self-assemble in a single step. The resulting DNA structures are roughly 100 nm in diameter and approximate desired shapes such as squares, disks and five-pointed stars with a spatial resolution of 6 nm. Because each oligonucleotide can serve as a 6-nm pixel, the structures can be programmed to bear complex patterns such as words and images on their surfaces. Finally, individual DNA structures can be programmed to form larger assemblies, including extended periodic lattices and a hexamer of triangles (which constitutes a 30-megadalton molecular complex).     

Hierarchical self-assembly of DNA into symmetric supramolecular polyhedra

DNA is renowned for its double helix structure and the base pairing that enables the recognition and highly selective binding of complementary DNA strands. These features, and the ability to create DNA strands with any desired sequence of bases, have led to the use of DNA rationally to design various nanostructures and even execute molecular computations. Of the wide range of self-assembled DNA nanostructures reported, most are one- or two-dimensional. Examples of three-dimensional DNA structures include cubes, truncated octahedra, octohedra and tetrahedra, which are all comprised of many different DNA strands with unique sequences. When aiming for large structures, the need to synthesize large numbers (hundreds) of unique DNA strands poses a challenging design problem. Here, we demonstrate a simple solution to this problem: the design of basic DNA building units in such a way that many copies of identical units assemble into larger three-dimensional structures. We test this hierarchical self-assembly concept with DNA molecules that form three-point-star motifs, or tiles. By controlling the flexibility and concentration of the tiles, the one-pot assembly yields tetrahedra, dodecahedra or buckyballs that are tens of nanometres in size and comprised of four, twenty or sixty individual tiles, respectively. We expect that our assembly strategy can be adapted to allow the fabrication of a range of relatively complex three-dimensional structures.     

Self-directed self-assembly of nanoparticle/copolymer mixtures

The organization of inorganic nanostructures within self-assembled organic or biological templates is receiving the attention of scientists interested in developing functional hybrid materials. Previous efforts have concentrated on using such scaffolds to spatially arrange nanoscopic elements as a strategy for tailoring the electrical, magnetic or photonic properties of the material. Recent theoretical arguments have suggested that synergistic interactions between self-organizing particles and a self-assembling matrix material can lead to hierarchically ordered structures. Here we show that mixtures of diblock copolymers and either cadmium selenide- or ferritin-based nanoparticles exhibit cooperative, coupled self-assembly on the nanoscale. In thin films, the copolymers assemble into cylindrical domains, which dictate the spatial distribution of the nanoparticles; segregation of the particles to the interfaces mediates interfacial interactions and orients the copolymer domains normal to the surface, even when one of the blocks is strongly attracted to the substrate. Organization of both the polymeric and particulate entities is thus achieved without the use of external fields, opening a simple and general route for fabrication of nanostructured materials with hierarchical order.     

Complex shapes self-assembled from single-stranded DNA tiles

Programmed self-assembly of strands of nucleic acid has proved highly effective for creating a wide range of structures with desired shapes. A particularly successful implementation is DNA origami, in which a long scaffold strand is folded by hundreds of short auxiliary strands into a complex shape. Modular strategies are in principle simpler and more versatile and have been used to assemble DNA or RNA tiles into periodic and algorithmic two-dimensional lattices, extended ribbons and tubes, three-dimensional crystals, polyhedra and simple finite two-dimensional shapes. But creating finite yet complex shapes from a large number of uniquely addressable tiles remains challenging. Here we solve this problem with the simplest tile form, a 'single-stranded tile' (SST) that consists of a 42-base strand of DNA composed entirely of concatenated sticky ends and that binds to four local neighbours during self-assembly. Although ribbons and tubes with controlled circumferences have been created using the SST approach, we extend it to assemble complex two-dimensional shapes and tubes from hundreds (in some cases more than one thousand) distinct tiles. Our main design feature is a self-assembled rectangle that serves as a molecular canvas, with each of its constituent SST strands--folded into a 3 nm-by-7 nm tile and attached to four neighbouring tiles--acting as a pixel. A desired shape, drawn on the canvas, is then produced by one-pot annealing of all those strands that correspond to pixels covered by the target shape; the remaining strands are excluded. We implement the strategy with a master strand collection that corresponds to a 310-pixel canvas, and then use appropriate strand subsets to construct 107 distinct and complex two-dimensional shapes, thereby establishing SST assembly as a simple, modular and robust framework for constructing nanostructures with prescribed shapes from short synthetic DNA strands.     

3D DNA origami designed with caDNAno

For about three decades, DNA-based nanotechnology has been undergoing development as an assembly method for nanostructured materials. The DNA origami method pioneered by Rothemund paved the way for the formation of 3D structures using DNA self assembly. The origami approach uses a long scaffold strand as the input for the self assembly of a few hundred staple strands into desired shapes. Herein, we present a 3D origami "roller" (75 nm in length) designed using caDNAno software. This has the potential to be used as a template to assemble nanoparticles into different pre-defined shapes. The "roller" was characterized with agarose gel electrophoresis, atomic force microscopy (AFM) and transmission electron microscopy (TEM).     

Assembly and Characterization of Coordination Polymer Nanostructural Materials at Interfaces

1 Results Molecular self-assembly of one-/two-dimensional (1D/2D) nanostructures has recently received great interest because the specific structures of crystals determine their unique physical and chemical properties. Coordination polymers contain two central components, connectors and linkers. Transition metal ions are often used as versatile connectors, with coordination numbers ranging from 2 to 7 dependant on the oxidation states of the metal ions. Multidentate ligands are often used as linkers, wh...     

DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response

Matter structured on a length scale comparable to or smaller than the wavelength of light can exhibit unusual optical properties. Particularly promising components for such materials are metal nanostructures, where structural alterations provide a straightforward means of tailoring their surface plasmon resonances and hence their interaction with light. But the top-down fabrication of plasmonic materials with controlled optical responses in the visible spectral range remains challenging, because lithographic methods are limited in resolution and in their ability to generate genuinely three-dimensional architectures. Molecular self-assembly provides an alternative bottom-up fabrication route not restricted by these limitations, and DNA- and peptide-directed assembly have proved to be viable methods for the controlled arrangement of metal nanoparticles in complex and also chiral geometries. Here we show that DNA origami enables the high-yield production of plasmonic structures that contain nanoparticles arranged in nanometre-scale helices. We find, in agreement with theoretical predictions, that the structures in solution exhibit defined circular dichroism and optical rotatory dispersion effects at visible wavelengths that originate from the collective plasmon-plasmon interactions of the nanoparticles positioned with an accuracy better than two nanometres. Circular dichroism effects in the visible part of the spectrum have been achieved by exploiting the chiral morphology of organic molecules and the plasmonic properties of nanoparticles, or even without precise control over the spatial configuration of the nanoparticles. In contrast, the optical response of our nanoparticle assemblies is rationally designed and tunable in handedness, colour and intensity-in accordance with our theoretical model.     

Self-assembly of mesoscopically ordered chromatic polydiacetylene/silica nanocomposites

Nature abounds with intricate composite architectures composed of hard and soft materials synergistically intertwined to provide both useful functionality and mechanical integrity. Recent synthetic efforts to mimic such natural designs have focused on nanocomposites, prepared mainly by slow procedures like monomer or polymer infiltration of inorganic nanostructures or sequential deposition. Here we report the self-assembly of conjugated polymer/silica nanocomposite films with hexagonal, cubic or lamellar mesoscopic order using polymerizable amphiphilic diacetylene molecules as both structure-directing agents and monomers. The self-assembly procedure is rapid and incorporates the organic monomers uniformly within a highly ordered, inorganic environment. Polymerization results in polydiacetylene/silica nanocomposites that are optically transparent and mechanically robust. Compared to ordered diacetylene-containing films prepared as Langmuir monolayers or by Langmuir-Blodgett deposition, the nanostructured inorganic host alters the diacetylene polymerization behaviour, and the resulting nanocomposite exhibits unusual chromatic changes in response to thermal, mechanical and chemical stimuli. The inorganic framework serves to protect, stabilize, and orient the polymer, and to mediate its function. The nanocomposite architecture also provides sufficient mechanical integrity to enable integration into devices and microsystems.     

Self-directed growth of molecular nanostructures on silicon

Advances in techniques for the nanoscale manipulation of matter are important for the realization of molecule-based miniature devices with new or advanced functions. A particularly promising approach involves the construction of hybrid organic-molecule/silicon devices. But challenges remain--both in the formation of nanostructures that will constitute the active parts of future devices, and in the construction of commensurately small connecting wires. Atom-by-atom crafting of structures with scanning tunnelling microscopes, although essential to fundamental advances, is too slow for any practical fabrication process; self-assembly approaches may permit rapid fabrication, but lack the ability to control growth location and shape. Furthermore, molecular diffusion on silicon is greatly inhibited, thereby presenting a problem for self-assembly techniques. Here we report an approach for fabricating nanoscale organic structures on silicon surfaces, employing minimal intervention by the tip of a scanning tunnelling microscope and a spontaneous self-directed chemical growth process. We demonstrate growth of straight molecular styrene lines--each composed of many organic molecules--and the crystalline silicon substrate determines both the orientation of the lines and the molecular spacing within these lines. This process should, in principle, allow parallel fabrication of identical complex functional structures.     

Channel plasmon subwavelength waveguide components including interferometers and ring resonators

Photonic components are superior to electronic ones in terms of operational bandwidth, but the diffraction limit of light poses a significant challenge to the miniaturization and high-density integration of optical circuits. The main approach to circumvent this problem is to exploit the hybrid nature of surface plasmon polaritons (SPPs), which are light waves coupled to free electron oscillations in a metal that can be laterally confined below the diffraction limit using subwavelength metal structures. However, the simultaneous realization of strong confinement and a propagation loss sufficiently low for practical applications has long been out of reach. Channel SPP modes--channel plasmon polaritons (CPPs)--are electromagnetic waves that are bound to and propagate along the bottom of V-shaped grooves milled in a metal film. They are expected to exhibit useful subwavelength confinement, relatively low propagation loss, single-mode operation and efficient transmission around sharp bends. Our previous experiments showed that CPPs do exist and that they propagate over tens of micrometres along straight subwavelength grooves. Here we report the design, fabrication and characterization of CPP-based subwavelength waveguide components operating at telecom wavelengths: Y-splitters, Mach-Zehnder interferometers and waveguide-ring resonators. We demonstrate that CPP guides can indeed be used for large-angle bending and splitting of radiation, thereby enabling the realization of ultracompact plasmonic components and paving the way for a new class of integrated optical circuits.     

高密度有序银纳米球阵列的模板辅助退火制备

纳米结构的有序性对表面拉曼增强光谱（SERS）的均匀性起决定性作用,然而如何大面积制备有序的超高密度贵金属纳米结构依旧是个挑战. 文中提出了一种通过模板辅助退火方法,用于大面积制备结构可控、高密度有序的银纳米球阵列,研究了退火温度、压强和银膜厚度对银纳米球阵列形貌结构的影响. 制备的高密度有序银纳米球阵列可以进一步应用于SRES基底.     

Swollen liquid-crystalline lamellar phase based on extended solid-like sheets

Ordering particles at the nanometre length scale is a challenging and active research area in materials science. Several approaches have so far been developed, ranging from the manipulation of individual particles to the exploitation of self-assembly in colloids. Nanometre-scale ordering is well known to appear spontaneously when anisotropic organic moieties form liquid-crystalline phases; this behaviour is also observed for anisotropic mineral nanoparticles resulting in the formation of nematic, smectic and hexagonal mesophases. Here we describe a lyotropic liquid-crystalline lamellar phase comprising an aqueous dispersion of planar solid-like sheets in which all the atoms involved in a layer are covalently bonded. The spacing of these phosphatoantimonate single layers can be increased 100-fold, resulting in one-dimensional structures whose periodicity can be tuned from 1.5 to 225 nanometres. These highly organized materials can be mechanically or magnetically aligned over large pH and temperature ranges, and this property can be used to measure residual dipolar couplings for the structure determination of biomolecules by liquid-state NMR. We also expect that our approach will result in the discovery of other classes of mineral lyotropic lamellar phases.     

间苯三酚/甲醛和三嵌段共聚物F127一步合成介孔炭材料

以间苯三酚/甲醛为碳前体,三嵌段共聚物F127为模板剂,采用有机-有机自组装法制备有序介孔炭（OMC）材料,系统研究了乙醇和水混合溶剂的极性及合成温度对介孔炭结构的影响,并利用N2吸-脱附和小角X-射线衍射技术对合成的OMC材料进行了表征.结果表明：混合溶剂中乙醇的摩尔分数较高时,合成的OMC样品孔径和孔容较大,具有有序的介孔结构;而当溶剂中乙醇的摩尔分数较低时,合成材料的孔径和孔容明显减小,且介孔孔隙率和有序度都降低;在纯乙醇及乙醇-水混合溶剂中,随着反应温度的升高,合成OMC材料的BET比表面积、孔容和孔径均减小,微孔比例增加,且反应温度对乙醇-水混合溶剂中合成的OMC材料的结构影响更明显.     

切削大塑性变形制备纳米材料

长期以来，切屑都被看成是金属切削过程中产生的废物。最新研究表明在一定切削条件下形成的切屑几乎全部为纳米结构材料。首先分析了切削加工中材料的塑性变形特征，然后将切削大塑性变形制备纳米结构材料工艺与其他传统的剧烈塑性变形工艺进行比较，发现切削法具有工艺简单，价格低廉，生产效率高，对高强度材料同样适用等优点，同时还可以减少切屑回收过程对环境造成的污染。     

三嵌段共聚物自组装结构的分子调控

 利用耗散粒子动力学方法研究三嵌段共聚物的链构型对其在本体中自组装行为产生的影响. 通过系统调节共聚物的链构型, 得到了形态各异的嵌段共聚物相态结构, 如规则层状结构、 小尺寸相区无规堆积结构以及扭曲阶梯状结构等. 为使体系总的自由能降低, 不同链构型的嵌段共聚物会自发产生各种有序相态结构.     

Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates

Parallel processes for patterning densely packed nanometre-scale structures are critical for many diverse areas of nanotechnology. Thin films of diblock copolymers can self-assemble into ordered periodic structures at the molecular scale (approximately 5 to 50 nm), and have been used as templates to fabricate quantum dots, nanowires, magnetic storage media, nanopores and silicon capacitors. Unfortunately, perfect periodic domain ordering can only be achieved over micrometre-scale areas at best and defects exist at the edges of grain boundaries. These limitations preclude the use of block-copolymer lithography for many advanced applications. Graphoepitaxy, in-plane electric fields, temperature gradients, and directional solidification have also been demonstrated to induce orientation or long-range order with varying degrees of success. Here we demonstrate the integration of thin films of block copolymer with advanced lithographic techniques to induce epitaxial self-assembly of domains. The resulting patterns are defect-free, are oriented and registered with the underlying substrate and can be created over arbitrarily large areas. These structures are determined by the size and quality of the lithographically defined surface pattern rather than by the inherent limitations of the self-assembly process. Our results illustrate how hybrid strategies to nanofabrication allow for molecular level control in existing manufacturing processes.     

A 1.7-kilobase single-stranded DNA that folds into a nanoscale octahedron

Molecular self-assembly offers a means of spontaneously forming complex and well-defined structures from simple components. The specific bonding between DNA base pairs has been used in this way to create DNA-based nanostructures and to direct the assembly of material on the subnanometre to micrometre scale. In principle, large-scale clonal production of suitable DNA sequences and the directed evolution of sequence lineages towards optimized behaviour can be realized through exponential DNA amplification by polymerases. But known examples of three-dimensional geometric DNA objects are not amenable to cloning because they contain topologies that prevent copying by polymerases. Here we report the design and synthesis of a 1,669-nucleotide, single-stranded DNA molecule that is readily amplified by polymerases and that, in the presence of five 40-mer synthetic oligodeoxynucleotides, folds into an octahedron structure by a simple denaturation-renaturation procedure. We use cryo-electron microscopy to show that the DNA strands fold successfully, with 12 struts or edges joined at six four-way junctions to form hollow octahedra approximately 22 nanometres in diameter. Because the base-pair sequence of individual struts is not repeated in a given octahedron, each strut is uniquely addressable by the appropriate sequence-specific DNA binder.     

两亲性嵌段共聚物自组装形成平头胶束

高度不对称的两亲性嵌段共聚物可以通过自组装形成平头胶束聚集体.文中综述了嵌段共聚物的聚合方法,嵌段共聚物平头胶束的结构、类型和制备方法,平头胶束的形成机理及对其形貌的主要影响因素.     

A nanometre-scale electronic switch consisting of a metal cluster and redox-addressable groups

So-called bottom-up fabrication methods aim to assemble and integrate molecular components exhibiting specific functions into electronic devices that are orders of magnitude smaller than can be fabricated by lithographic techniques. Fundamental to the success of the bottom-up approach is the ability to control electron transport across molecular components. Organic molecules containing redox centres-chemical species whose oxidation number, and hence electronic structure, can be changed reversibly-support resonant tunnelling and display promising functional behaviour when sandwiched as molecular layers between electrical contacts, but their integration into more complex assemblies remains challenging. For this reason, functionalized metal nanoparticles have attracted much interest: they exhibit single-electron characteristics (such as quantized capacitance charging) and can be organized through simple self-assembly methods into well ordered structures, with the nanoparticles at controlled locations. Here we report scanning tunnelling microscopy measurements showing that organic molecules containing redox centres can be used to attach metal nanoparticles to electrode surfaces and so control the electron transport between them. Our system consists of gold nanoclusters a few nanometres across and functionalized with polymethylene chains that carry a central, reversibly reducible bipyridinium moiety. We expect that the ability to electronically contact metal nanoparticles via redox-active molecules, and to alter profoundly their tunnelling properties by charge injection into these molecules, can form the basis for a range of nanoscale electronic switches.