Molecular junctions based on aromatic coupling

If individual molecules are to be used as building blocks for electronic devices, it will be essential to understand charge transport at the level of single molecules. Most existing experiments rely on the synthesis of functional rod-like molecules with chemical linker groups at both ends to provide strong, covalent anchoring to the source and drain contacts. This approach has proved very successful, providing quantitative measures of single-molecule conductance, and demonstrating rectification and switching at the single-molecule level. However, the influence of intermolecular interactions on the formation and operation of molecular junctions has been overlooked. Here we report the use of oligo-phenylene ethynylene molecules as a model system, and establish that molecular junctions can still form when one of the chemical linker groups is displaced or even fully removed. Our results demonstrate that aromatic pi-pi coupling between adjacent molecules is efficient enough to allow for the controlled formation of molecular bridges between nearby electrodes.     

Self‐Assembly of Functional Molecules into 1D Crystalline Nanostructures

Self‐assembled functional nanoarchitectures are employed as important nanoscale building blocks for advanced materials and smart miniature devices to fulfill the increasing needs of high materials usage efficiency, low energy consumption, and high‐performance devices. One‐dimensional (1D) crystalline nanostructures, especially molecule‐composed crystalline nanostructures, attract significant attention due to their fascinating infusion structure and functionality which enables the easy tailoring of organic molecules with excellent carrier mobility and crystal stability. In this review, we discuss the recent progress of 1D crystalline self‐assembled nanostructures of functional molecules, which include both a small molecule‐derived and a polymer‐based crystalline nanostructure. The basic principles of the molecular structure design and the process engineering of 1D crystalline nanostructures are also discussed. The molecular building blocks, self‐assembly structures, and their applications in optical, electrical, and photoelectrical devices are overviewed and we give a brief outlook on crucial issues that need to be addressed in future research endeavors.     

Peptide‐Based Nanotubes and Their Applications in Bionanotechnology

In nature, biological nanomaterials are synthesized under ambient conditions in a natural microscopic‐sized laboratory, such as a cell. Biological molecules, such as peptides and proteins, undergo self‐assembly processes in vivo and in vitro, and these monomers are assembled into various nanometer‐scale structures at room temperature and atmospheric pressure. The self‐assembled peptide nanostructures can be further organized to form nanowires, nanotubes, and nanoparticles via their molecular‐recognition functions. The application of molecular self‐assemblies of synthetic peptides as nanometer‐scale building blocks in devices is robust, practical, and affordable due to their advantages of reproducibility, large‐scale production ability, monodispersity, and simpler experimental methods. It is also beneficial that smart functionalities can be added at desired positions in peptide nanotubes through well‐established chemical and peptide syntheses. These features of peptide‐based nanotubes are the driving force for investigating and developing peptide nanotube assemblies for biological and non‐biological applications.     

Bottom-up realization of a porous metal-organic nanotubular assembly

Nanotubes are generally prepared from their constituent elements at high temperatures, and thus it is difficult to control their size, shape and electronic states. One useful approach for synthesizing well-defined nanostructures involves the use of building blocks such as metal ions and organic molecules. Here, we show the successful creation of an assembly of infinite square prism-shaped metal-organic nanotubes obtained from the simple polymerization of a square-shaped metal-organic frame. The constituent nanotube has a one-dimensional (1D) channel with a window size of 5.9×5.9 ?(2), and can adsorb water (H(2)O) and alcohol vapours, whereas N(2) and CO(2) do not adhere. It consists of four 1D covalent chains that constitute a unique electronic structure of 'charge-density wave (CDW) quartets' on crystallization. Moreover, exchanging structural components and guest molecules enables us to control its semiconductive bandgap. These findings demonstrate the possibility of bottom-up construction of new porous nanotubes, where their degrees of freedom in both pore space and framework can be used.     

Substrate-induced magnetic ordering and switching of iron porphyrin molecules

To realize molecular spintronic devices, it is important to externally control the magnetization of a molecular magnet. One class of materials particularly promising as building blocks for molecular electronic devices is the paramagnetic porphyrin molecule in contact with a metallic substrate. Here, we study the structural orientation and the magnetic coupling of in-situ-sublimated Fe porphyrin molecules on ferromagnetic Ni and Co films on Cu(100). Our studies involve X-ray absorption spectroscopy and X-ray magnetic circular dichroism experiments. In a combined experimental and computational study we demonstrate that owing to an indirect, superexchange interaction between Fe atoms in the molecules and atoms in the substrate (Co or Ni) the paramagnetic molecules can be made to order ferromagnetically. The Fe magnetic moment can be rotated along directions in plane as well as out of plane by a magnetization reversal of the substrate, thereby opening up an avenue for spin-dependent molecular electronics.     

Supramolecular Helices: Chirality Transfer from Conjugated Molecules to Structures

Different scales of chirality endow a material with many excellent properties and potential applications. In this review, using π‐conjugated molecules as functional building blocks, recent progress on supramolecular helices inspired by biological helicity is summarized. First, induced chirality on conjugated polymers and small molecules is introduced. Molecular chirality can be amplified to nanostructures, superstructures, and even macroscopic structures by a self‐assembly process. Then, the principles for tuning the helicity of supramolecular chirality, as well as formation of helical heterojunctions, are summarized. Finally, the potential applications of chiral structures in chiral sensing and organic electronic devices are critically reviewed. Due to recent progress in chiral structures, an interdisciplinary area called “chiral electronics” is expected to gain wide popularity in the near future.     

Nanopatterning the electronic properties of gold surfaces with self-organized superlattices of metallic nanostructures

The self-organized growth of nanostructures on surfaces could offer many advantages in the development of new catalysts, electronic devices and magnetic data-storage media. The local density of electronic states on the surface at the relevant energy scale strongly influences chemical reactivity, as does the shape of the nanoparticles. The electronic properties of surfaces also influence the growth and decay of nanostructures such as dimers, chains and superlattices of atoms or noble metal islands. Controlling these properties on length scales shorter than the diffusion lengths of the electrons and spins (some tens of nanometres for metals) is a major goal in electronics and spintronics. However, to date, there have been few studies of the electronic properties of self-organized nanostructures. Here we report the self-organized growth of macroscopic superlattices of Ag or Cu nanostructures on Au vicinal surfaces, and demonstrate that the electronic properties of these systems depend on the balance between the confinement and the perturbation of the surface states caused by the steps and the nanostructures' superlattice. We also show that the local density of states can be modified in a controlled way by adjusting simple parameters such as the type of metal deposited and the degree of coverage.     

Photocurrent imaging of nanocrystal quantum dots on single-walled carbon nanotube device

Semiconductor nanocrystal quantum dots (NQDs) are considered an attractive candidate for use in optoelectronic applications due to the ease of band gap control provided by varying the particle size. To increase the efficiency of NQDs when practically applied in devices, researchers have introduced the concept of coupling of NQDs to one-dimensional nanostructures such as single-walled carbon nanotubes (SWCNTs), which have a ballistic conducting channel. In the present study, NQDs of CdSe core and CdSe/ZnS are used as light absorbing building blocks. SWCNTs and functionalized NQDs are non-covalently coupled using pyridine molecules in order to maintain their electronic structures. To measure the electrical signals from the device, a NQDs-SWCNT hybrid nanostructure is fabricated as a field-effect transistor (FET) using the dielectrophoresis (DEP) method. A confocal scanning microscope was used to scan the devices using a diffraction-limited laser spot and the photocurrent was recorded as a function of the position of the laser spot. To improve the performance of detecting small electronic signal with high signal-to-noise ratio we used a lock-in technique with an intensity-modulated laser. In this paper, we have demonstrated that detection of local photoconductivity provides an efficient means to resolve electronic structure modulations along NQDs-SWCNT hybrid nanostructures.     

Biocatalytically Triggered Co‐Assembly of Two‐Component Core/Shell Nanofibers

For the development of applications and novel uses for peptide nanostructures, robust routes for their surface functionalization, that ideally do not interfere with their self‐assembly properties, are required. Many existing methods rely on covalent functionalization, where building blocks are appended with functional groups, either pre‐ or post‐assembly. A facile supramolecular approach is demonstrated for the formation of functionalized nanofibers by combining the advantages of biocatalytic self‐assembly and surfactant/gelator co‐assembly. This is achieved by enzymatically triggered reconfiguration of free flowing micellar aggregates of pre‐gelators and functional surfactants to form nanofibers that incorporate and display the surfactants’ functionality at the surface. Furthermore, by varying enzyme concentration, the gel stiffness and supramolecular organization of building blocks can be varied.     

Advances in Molecular Electronics: A Brief Review

The field of molecular electronics, also known as moletronics, deals with the assembly of molecular electronic components using molecules as the building blocks. It is an interdisciplinary field that includes physics, chemistry, materials science, and engineering. Moletronics mainly deals with the reduction of size of silicon components. Novel research has been performed in developing electrical-equivalent molecular components. Moletronics has established its influence in electronic and photonic applications, such as conducting polymers, photochromics, organic superconductors, electrochromics, and many more. Since there is a need to reduce the size of the silicon chip, attaining such technology at the molecular level is essential. Although the experimental verification and modeling of molecular devices present a daunting task, vital breakthroughs have been achieved in this field. This article combines an overview of various molecular components, such as molecular transistors, diodes, capacitors, wires, and insulators, with a discussion of the potential applications of different molecules suitable for such components. We emphasize future developments and provide a brief review of different achievements that have been made regarding graphene-based molecular devices.     

Exploring the transferability of large supramolecular assemblies to the vacuum-solid interface

We present an interplay of high-resolution scanning tunneling microscopy imaging and the corresponding theoretical calculations based on elastic scattering quantum chemistry techniques of the adsorption of a gold-functionalized rosette assembly and its building blocks on a Au(111) surface with the goal of exploring how to fabricate functional 3-D molecular nanostructures on surfaces. The supramolecular rosette assembly stabilized by multiple hydrogen bonds has been sublimed onto the Au(111) surface under ultra-high vacuum conditions; the resulting surface nanostructures are distinctly different from those formed by the individual molecular building blocks of the rosette assembly, suggesting that the assembly itself can be transferred intact to the surface by in situ thermal sublimation. This unanticipated result will open up new perspectives for growth of complex 3-D supramolecular nanostructures at the vacuum-solid interface. This article is published with open access at Springerlink.com     

Fabrication of Nanoreaction Clusters with Dual‐Functionalized Protein Cage Nanobuilding Blocks

Fabrication of functional nanostructures is a prominent issue in nanotechnology, because they often exhibit unique properties that are different from the individual building blocks. Protein cage nanoparticles are attractive nanobuilding blocks for constructing nanostructures due to their well‐defined symmetric spherical structures, polyvalent nature, and functional plasticity. Here, a lumazine synthase protein cage nanoparticle is genetically modified to be used as a template to generate functional nanobuilding blocks and covalently display enzymes (β‐lactamase) and protein ligands (FKBP12/FRB) on its surface, making dual‐functional nanobuilding blocks. Nanoreaction clusters are subsequently created by ligand‐mediated alternate deposition of two complementary building blocks using layer‐by‐layer (LbL) assemblies. 3D nanoreaction clusters provide enhanced enzymatic activity compared with monolayered building block arrays. The approaches described here may provide new opportunities for fabricating functional nanostructures and nanoreaction clusters, leading to the development of new protein nanoparticle‐based nanostructured biosensor devices.     

Novel bioinorganic nanostructures based on mesolamellar intercalation or single-molecule wrapping of DNA using organoclay building blocks

Nanosheets or nanoclusters of aminopropyl-functionalized magnesium phyllosilicate (AMP) were prepared in water by exfoliation and used as structural building blocks for the preparation of DNA-based hybrid nanostructures in the form of ordered mesolamellar nanocomposites or highly elongated nanowires, respectively. The former consisted of alternating layers of single sheets of AMP interspaced with intercalated monolayers of intact double-stranded DNA molecules of relatively short length ( approximately 700 base pairs) that were accessible to small molecules such as ethidium bromide. In contrast, the nanowires comprised isolated micrometer-long molecules of lambda-DNA or plasmid DNA that were sheathed in an ultrathin organoclay layer and which were either protected from or remained accessible to endonuclease-mediated clipping depending on the extent of biomolecule wrapping. Both types of hybrid nanostructures showed a marked increase in the DNA melting (denaturation) temperature, indicating significant thermal stabilization of the confined biomolecules. Our results suggest that nanoscale building blocks derived from organically modified inorganic clays could be useful agents for enhancing the chemical, thermal, and mechanical stability of isolated molecules or ensembles of DNA. Such constructs should have increased potential as functional components in bionanotechnology and nonviral gene transfection.     

A Nonconventional Approach to Patterned Nanoarrays of DNA Strands for Template‐Assisted Assembly of Polyfluorene Nanowires

DNA molecules have been widely recognized as promising building blocks for constructing functional nanostructures with two main features, that is, self‐assembly and rich chemical functionality. The intrinsic feature size of DNA makes it attractive for creating versatile nanostructures. Moreover, the ease of access to tune the surface of DNA by chemical functionalization offers numerous opportunities for many applications. Herein, a simple yet robust strategy is developed to yield the self‐assembly of DNA by exploiting controlled evaporative assembly of DNA solution in a unique confined geometry. Intriguingly, depending on the concentration of DNA solution, highly aligned nanostructured fibrillar‐like arrays and well‐positioned concentric ring‐like superstructures composed of DNAs are formed. Subsequently, the ring‐like negatively charged DNA superstructures are employed as template to produce conductive organic nanowires on a silicon substrate by complexing with a positively charged conjugated polyelectrolyte poly[9,9‐bis(6′‐N,N,N‐trimethylammoniumhexyl)fluorene dibromide] (PF2) through the strong electrostatic interaction. Finally, a monolithic integration of aligned arrays of DNA‐templated PF2 nanowires to yield two DNA/PF2‐based devices is demonstrated. It is envisioned that this strategy can be readily extended to pattern other biomolecules and may render a broad range of potential applications from the nucleotide sequence and hybridization as recognition events to transducing elements in chemical sensors.     

Vapor growth and photoconductivity of single-crystal nickel-phthalocyanine nanorods

Nickel-phthalocyanines (NiPc) with planar aromatic structures are ideal building blocks for organic nanostructures. They can self-assemble into stacks through π-π interaction, exhibit high thermal and chemical stabilities, and possess outstanding electrical and optical properties. Herein, single-crystal NiPc nanorods were synthesized by a facile vapor transfer deposition method. Their nanostructures and compositions were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) in detail. The deposited NiPc nanorods were found to be the β-phase single crystals. Moreover, the NiPc nanorod-based devices were fabricated and exhibited high photocurrent upon white-light illumination. This indicates that the NiPc nanorods can be considered as a candidate material for fabricating photoelectric devices.     

Single-Walled Carbon Nanotubes for Flexible Electronics and Sensors

This article reviews the use of electronic quality single-walled carbon nanotubes grown via chemical vapor deposition （CVD） approaches at high temperatures as building blocks for fabricating flexible field-effect devices, such as thin-film transistors （TFTs） and chemical sensors. Dry transfer printing technique is developed for forming films of CVD nanotubes on low-temperature plastic substrates. Examples of TFTs with the use of nanotubes and thin dielectrics and hydrogen sensors with the use of nanotubes decorated with palladium nanoparticles are discussed in detail to demonstrate the promising potentiality of single-walled carbon nanotubes for building high performance flexible devices, which can find applications where traditional devices on rigid substrates are not suitable.     

Synthesis and applications of one-dimensional semiconductors

Nanoscale inorganic materials such as quantum dots (0-dimensional) and one-dimensional (1D) structures, such as nanowires, nanobelts and nanotubes, have gained tremendous attention within the last decade. Among the huge variety of 1D nanostructures, semiconducting nanowires have gained particular interest due to their potential applications in optoelectronic and electronic devices. Despite the huge efforts to control and understand the growth mechanisms underlying the formation of these highly anisotropic structures, some fundamental phenomena are still not well understood. For example, high aspect-ratio semiconductors exhibit unexpected growth phenomena, e.g. diameter-dependent and temperature-dependent growth directions, and unusual high doping levels or compositions, which are not known for their macroscopic crystals or thin-film counterparts.This article reviews viable synthetic approaches for growing high aspect-ratio semiconductors from bottom-up techniques, such as crystal structure governed nucleation, metal-promoted vapour phase and solution growth, formation in non-metal seeded gas-phase processes, structure directing templates and electrospinning. In particular new experimental findings and theoretical models relating to the frequently applied vapour-liquid-solid (VLS) growth are highlighted. In addition, the top-down application of controlled chemical etching, using novel masking techniques, is described as a viable approach for generating certain 1D structures. The review highlights the controlled synthesis of semiconducting nanostructures and heterostructures of silicon, germanium, gallium nitride, gallium arsenide, cadmium sulphide, zinc oxide and tin oxide. The alignment of 1D nanostructures will be reviewed briefly. Whilst specific and reliable contact procedures are still a major challenge for the integration of 1D nanostructures as active building blocks, this issue will not be the focus of this paper. However, the promising applications of 1D semiconductors will be highlighted, particularly with reference to surface dependent electronic transduction (gas and biological sensors), energy generation (nanomechanical and photovoltaic) devices, energy storage (lithium storage in battery anodes) as well as nanowire photonics.     

Thin-film-based nanoarchitectures for soft matter: controlled assemblies into two-dimensional worlds

Controlling the organization of molecular building blocks at the nanometer level is of utmost importance, not only from the viewpoint of scientific curiosity, but also for the development of next-generation organic devices with electrical, optical, chemical, or biological functions. Self-assembly offers great potential for the manufacture of nanoarchitectures (nanostructures and nanopatterns) over large areas by using low-energy and inexpensive spontaneous processes. However, self-assembled structures in 3D media, such as solutions or solids, are not easily incorporated into current device-oriented nanotechnology. The scope of this review is therefore to introduce the expanding methodology for the construction of thin-film-based nanoarchitectures on solid surfaces and to try to address a general concept with emphasis on the availability of dynamic interfaces for the creation and manipulation of nanoarchitectures. In this review, the strategies for the construction of nanostructures, the control and manipulation of nanopatterns, and the application of nanoarchitectures are described; the construction strategies are categorized into three classes: i) π-conjugated molecular assembly in two dimensions, ii) bio-directed molecular assembly on surfaces, and iii) recent thin-film preparation technologies.     

Digital memory device based on tobacco mosaic virus conjugated with nanoparticles

Nanostructured viruses are attractive for use as templates for ordering quantum dots to make self-assembled building blocks for next-generation electronic devices. So far, only a few types of electronic devices have been fabricated from biomolecules due to the lack of charge transport through biomolecular junctions. Here, we show a novel electronic memory effect by incorporating platinum nanoparticles into tobacco mosaic virus. The memory effect is based on conductance switching, which leads to the occurrence of bistable states with an on/off ratio larger than three orders of magnitude. The mechanism of this process is attributed to charge trapping in the nanoparticles for data storage and a tunnelling process in the high conductance state. Such hybrid bio-inorganic nanostructures show promise for applications in future nanoelectronics.