Towards controlled growth of carbon nanotubes from germanium on nanoindented silicon substrates

In this paper, we report on a metal-catalyst-free synthesis of carbon nanotubes (CNTs) on a pre-patterned Si(001) surface. Arrays of triangular-shaped holes were created by nanoindentation in specific sites of the sample. After germanium deposition and chemical vapor deposition (CVD) of acetylene, a few CNTs nucleated and grew from germanium nanoparticles. These results illustrate that it is possible to control the growth of CNTs without the use of any metal catalyst. By leading the assembly of Ge nanoparticles with a patterning technique, a precise control over the growth order is also attainable.

Synthesis and characterisation of metal oxyhydroxide and oxide nanomaterials

In this work, a range of nanomaterials have been synthesised based on metal oxyhydroxides MO(OH), where M=Al, Co, Cr, etc. Through a self-assembly hydrothermal route, metal oxyhydroxide nanomaterials with various morphologies were successfully synthesised: one dimensional boehmite (AlO(OH)) nanofibres, zero dimensional indium hydroxide (In(OH)3) nanocubes and chromium oxyhydroxide (CrO(OH)) nanoparticles, as well as two dimensional cobalt hydroxide and oxyhydroxide (Co(OH)2 & CoO(OH)) nanodiscs. In order to control the synthetic nanomaterial morphology and growth, several factors were investigated including cation concentration, temperature, hydrothermal treatment time, and pH. Metal ion doping is a promising technique to modify and control the properties of materials by intentionally introducing impurities or defects into the material. Chromium was successfully applied as a dopant for fabricating doped boehmite nanofibres. The thermal stability of the boehmite nanofibres was enhanced by chromium doping, and the photoluminescence property was introduced to the chromium doped alumina nanofibres. Doping proved to be an efficient method to modify and functionalize nanomaterials. The synthesised nanomaterials were fully characterised by X-ray diffraction (XRD), transmission electron microscopy (TEM) combined with selected area electron diffraction (SAED), scanning electron microscopy (SEM), BET specific surface area analysis, X-ray photoelectron spectroscopy (XPS) and thermo gravimetric analysis (TGA). Hot-stage Raman and infrared emission spectroscopy were applied to study the chemical reactions during dehydration and dehydroxylation. The advantage of these techniques is that the changes in molecular structure can be followed in situ and at the elevated temperatures.

Towards a controlled growth of self-assembled nanostructures: shaping, ordering and localization in Ge/Si heteroepitaxy.

The strain-induced self-assembly of suitable semiconductor pairs is an attractive natural route to nanofabrication. To bring to fruition their full potential for actual applications, individual nanostructures need to be combined into ordered patterns in which the location of each single unit is coupled with others and the surrounding environment. Within the Ge/Si model system, we analyze a number of examples of bottom-up strategies in which the shape, positioning, and actual growth mode of epitaxial nanostructures are tailored by manipulating the intrinsic physical processes of heteroepitaxy. The possibility of controlling elastic interactions and, hence, the configuration of self-assembled quantum dots by modulating surface orientation with the miscut angle is discussed. We focus on the use of atomic steps and step bunching as natural templates for nanodot clustering. Then, we consider several different patterning techniques which allow one to harness the natural self-organization dynamics of the system, such as: scanning tunneling nanolithography, focused ion beam and nanoindentation patterning. By analyzing the evolution of the dot assembly by scanning probe microscopy, we follow the pathway which leads to lateral ordering, discussing the thermodynamic and kinetic effects involved in selective nucleation on patterned substrates.

Mussel-inspired bioceramics with self-assembled Ca-P/polydopamine composite nanolayer : preparation, formation mechanism, improved cellular bioactivity and osteogenic differentiation of bone marrow stromal cells

The nanostructured surface of biomaterials plays an important role in improving their in vitro cellular bioactivity as well as stimulating in vivo tissue regeneration. Inspired by the mussel’s adhesive versatility, which is thought to be due to the plaque–substrate interface being rich in 3,4-dihydroxy-L-phenylalamine (DOPA) and lysine amino acids, in this study we developed a self-assembly method to prepare a uniform calcium phosphate (Ca-P)/polydopamine composite nanolayer on the surface of b-tricalcium phosphate (b-TCP) bioceramics by soaking b-TCP bioceramics in Tris–dopamine solution. It was found that the addition of dopamine, reaction temperature and reaction time are three key factors inducing the formation of a uniform Ca-P/polydopamine composite nanolayer. The formation mechanism of a Ca-P/polydopamine composite nanolayer involved two important steps: (i) the addition of dopamine to Tris–HCl solution decreases the pH value and accelerates Ca and P ionic dissolution from the crystal boundaries of b-TCP ceramics; (ii) dopamine is polymerized to form self-assembled polydopamine film and, at the same time, nanosized Ca-P particles are mineralized with the assistance of polydopamine, in which the formation of polydopamine occurs simultaneously with Ca-P mineralization (formation of nanosized microparticles composed of calcium phosphate-based materials), and finally a self-assembled Ca-P/polydopamine composite nanolayer forms on the surface of the b-TCP ceramics. Furthermore, the formed self-assembled Ca-P/polydopamine composite nanolayer significantly enhances the surface roughness and hydrophilicity of b-TCP ceramics, and stimulates the attachment, proliferation, alkaline phosphate (ALP) activity and bone-related gene expression (ALP, OCN, COL1 and Runx2) of human bone marrow stromal cells. Our results suggest that the preparation of self-assembled Ca-P/polydopamine composite nanolayers is a viable method to modify the surface of biomaterials by significantly improving their surface physicochemical properties and cellular bioactivity for bone regeneration application.

Hyperbranched polymer-gold nanoparticle assemblies : role of polymer architecture in hybrid assembly formation and SERS activity

Plasmonic gold nano-assemblies that self-assemble with the aid of linking molecules or polymers have the potential to yield controlled hierarchies of morphologies and consequently result in materials with tailored optical (e.g. localized surface plasmon resonances (LSPR)) and spectroscopic properties (e.g. surface enhanced Raman scattering (SERS)). Molecular linkers that are structurally well-defined are promising for forming hybrid nano-assemblies which are stable in aqueous solution and are increasingly finding application in nanomedicine. Despite much ongoing research in this field, the precise role of molecular linkers in governing the morphology and properties of the hybrid nano-assemblies remains unclear. Previously we have demonstrated that branched linkers, such as hyperbranched polymers, with specific anchoring end groups can be successfully employed to form assemblies of gold NPs demonstrating near-infrared SPRs and intense SERS scattering. We herein introduce a tailored polymer as a versatile molecular linker, capable of manipulating nano-assembly morphologies and hot-spot density. In addition, this report explores the role of the polymeric linker architecture, specifically the degree of branching of the tailored polymer in determining the formation, morphology and properties of the hybrid nano-assemblies. The degree of branching of the linker polymer, in addition to the concentration and number of anchoring groups, is observed to strongly influence the self-assembly process. The assembly morphology shifts primarily from 1D-like chains to 2D plates and finally to 3D-like globular structures, with increase in degree of branching. Insights have been gained into how the morphology influences the SERS performance of these nano-assemblies with respect to hot-spot density. These findings supplement the understanding of the morphology determining nano-assembly formation and pave the way for the possible application of these nano-assemblies as SERS bio-sensors for medical diagnostics.

Simulation and visualization of self-assembled nanodevice networks synthesized via plasma–surface interaction

Using advanced visualization techniques, a comprehensive visualization of all the stages of the self-organized growth of internetworked nanostructures on plasma-exposed surface has been made. Atomistic kinetic Monte Carlo simulation for the initial stage of deposition, with 3-D visualization of the whole system and half-tone visualization of the density field of the adsorbed atoms, makes it possible to implement a multiscale predictive modeling of the development of the nanoscale system.

Deterministic control of plasma-assembled self-organized Ge/Si quantum dot arrays

Self-assembly of size-uniform and spatially ordered quantum dot (QD) arrays is one of the major challenges in the development of the new generation of semiconducting nanoelectronic and photonic devices. Assembly of Ge QD (in the ∼5-20 nm size range) arrays from randomly generated position and size-nonuniform nanodot patterns on plasma-exposed Si (100) surfaces is studied using hybrid multiscale numerical simulations. It is shown, by properly manipulating the incoming ion/neutral flux from the plasma and the surface temperature, the uniformity of the nanodot size within the array can be improved by 34%-53%, with the best improvement achieved at low surface temperatures and high external incoming fluxes, which are intrinsic to plasma-aided processes. Using a plasma-based process also leads to an improvement (∼22% at 700 K surface temperature and 0.1 MLs incoming flux from the plasma) of the spatial order of a randomly sampled nanodot ensemble, which self-organizes to position the dots equidistantly to their neighbors within the array. Remarkable improvements in QD ordering and size uniformity can be achieved at high growth rates (a few nms) and a surface temperature as low as 600 K, which broadens the range of suitable substrates to temperature-sensitive ultrathin nanofilms and polymers. The results of this study are generic, can also be applied to nonplasma-based techniques, and as such contributes to the development of deterministic strategies of nanoassembly of self-ordered arrays of size-uniform QDs, in the size range where nanodot ordering cannot be achieved by presently available pattern delineation techniques.

Nanosphere monolayer-templated, ion-assisted nanofeature etching in dielectric materials : a numerical simulation of nanoscale ion flux topography

The results of numerical simulations of nanometer precision distributions of microscopic ion fluxes in ion-assisted etching of nanoscale features on the surfaces of dielectric materials using a self-assembled monolayer of spherical nanoparticles as a mask are presented. It is shown that the ion fluxes to the substrate and nanosphere surfaces can be effectively controlled by the plasma parameters and the external bias applied to the substrate. By proper adjustment of these parameters, the ion flux can be focused onto the areas uncovered by the nanospheres. Under certain conditions, the ion flux distributions feature sophisticated hexagonal patterns, which may lead to very different nanofeature etching profiles. The results presented are generic and suggest viable ways to overcome some of the limitations of the existing plasma-assisted nanolithography.

Self-organized nanoarrays : plasma-related controls

The paper presents an investigation of self-organizational and -assembly processes of nanostructure growth on surfaces exposed to low-temperature plasmas. We have considered three main growth stages-initial, or sub-monolayer growth stage, separate nanostructure growth stage, and array growth stages with the characteristic sizes of several nm, several tens of nm, and several hundreds of nm, respectively, and have demonstrated, by the experimental data and hybrid multiscale numerical simulations, that the plasma parameters can strongly influence the surface processes and hence the kinetics of self-organization and -assembly. Our results show that plasma-controlled self-organization is a promising way to assemble large regular arrays of nanostructures. © 2008 IUPAC.

Low-temperature assembly of ordered carbon nanotip arrays in low-frequency, high-density inductively coupled plasmas

High-density inductively coupled plasma (ICP)-assisted self-assembly of the ordered arrays of various carbon nanostructures (NS) for the electron field emission applications is reported. Carbon-based nano-particles, nanotips, and pyramid-like structures, with the controllable shape, ordering, and areal density are grown under remarkably low process temperatures (260-350 °C) and pressures (below 0.1 Torr), on the same Ni-based catalyst layers, in a DC bias-controlled floating temperature regime. A high degree of positional and directional ordering, elevated sp2 content, and a well-structured graphitic morphology are achieved without the use of pre-patterned or externally heated substrates.

Structure and assembly of immature HIV

The major structural components of HIV are synthesized as a 55-kDa polyprotein, Gag. Particle formation is driven by the self-assembly of Gag into a curved hexameric lattice, the structure of which is poorly understood. We used cryoelectron tomography and contrast-transfer-function corrected subtomogram averaging to study the structure of the assembled immature Gag lattice to approximate to 17-angstrom resolution. Gag is arranged in the immature virus as a single, continuous, but incomplete hexameric lattice whose curvature is mediated without a requirement for pentameric defects. The resolution of the structure allows positioning of individual protein domains. High-resolution crystal structures were fitted into the reconstruction to locate protein-protein interfaces involved in Gag assembly, and to identify the structural transformations associated with virus maturation. The results of this study suggest a concept for the formation of nonsymmetrical enveloped viruses of variable sizes.

Investigations of an electrochemical platform based on the layered MoS2-graphene and horseradish peroxidase nanocomposite for direct electrochemistry and electrocatalysis

The self-assembly of layered molybdenum disulfide–graphene (MoS2–Gr) and horseradish peroxidase (HRP) by electrostatic attraction into a novel hybrid nanomaterial (HRP–MoS2–Gr) is reported. The properties of the MoS2–Gr were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (TEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). UV–vis and Fourier transform infrared spectroscopy (FT-IR) indicate that the native structure of the HRP is maintained after the assembly, implying good biocompatibility of MoS2–Gr nanocomposite. Furthermore, the HRP–MoS2–Gr composite is utilized as a biosensor, which displays electrocatalytic activity to hydrogen peroxide (H2O2) with high sensitivity (679.7 μA mM−1 cm−2), wide linear range (0.2 μM–1.103 mM), low detection limit (0.049 μM), and fast amperometric response. In addition, the biosensor also exhibits strong anti-interference ability, satisfactory stability and reproducibility. These desirable electrochemical properties are attributed to the good biocompatibility and electron transport efficiency of the MoS2–Gr composite, as well as the high loading of HRP. Therefore, this biosensor is potentially suitable for H2O2 analysis in environmental, pharmaceutical, food or industrial applications.

Synthesis of mesoporous TiO2/SiO2 hybrid films as an efficient photocatalyst by polymeric micelle assembly

Thermally stable mesoporous TiO2/SiO2 hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle-assembly method. A triblock copolymer, poly(styrene-b-2-vinyl pyridine-b-ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles. The effective interaction of titanium tetraisopropoxide (TTIP) and tetraethyl orthosilicate (TEOS) with the polymeric micelles enabled us to fabricate stable mesoporous films. By changing the molar ratio of TEOS and TTIP, several mesoporous TiO2/SiO2 hybrid films with different compositions can be synthesized. The presence of amorphous SiO2 phase effectively retards the growth of anatase TiO2 crystal in the pore walls and retains the original mesoporous structure, even at higher temperature (650 °C). These TiO2/SiO2 hybrid films are of very high quality, without any cracks or voids. The addition of SiO2 phase to mesoporous TiO2 films not only adsorbs more organic dyes, but also significantly enhances the photocatalytic activity compared to mesoporous pure TiO2 film without SiO2 phase.

Improved photovoltaic performance of dye-sensitized solar cells with modified self-assembling highly ordered mesoporous TiO 2 photoanodes

Strategies for improving the photovoltaic performance of dye-sensitized solar cells (DSSCs) are proposed by modifying highly transparent and highly ordered multilayer mesoporous TiO 2 photoanodes through nitrogen-doping and top-coating with a light-scattering layer. The mesoporous TiO 2 photoanodes were fabricated by an evaporation-induced self-assembly method. In regard to the modification methods, the light-scattering layer as a top-coating was proved to be superior to nitrogen-doping in enhancing not only the power conversion efficiency but also the fill factor of DSSCs. The optimized bifunctional photoanode consisted of a 30-layer mesoporous TiO 2 thin film (4.15 μm) and a Degussa P25 light-scattering top-layer (4 μm), which gives rise to a ∼200% higher cell efficiency than for unmodified cells and a fill factor of 0.72. These advantages are attributed to its higher dye adsorption, better light scattering, and faster photon-electron transport. Such a photoanode configuration provides an efficient way to enhance the energy conversion efficiency of DSSCs.

Peripherally η1-Platinated Organometallic Porphyrins as Building Blocks for Multiporphyrin Arrays

The modification of peripherally metalated meso-η1-platiniometalloporphyrins, such as trans-[PtBr(NiDAPP)(PPh3)2] (H2DAPP = 5-phenyl-10,20-bis(3‘,5‘-di-tert-butylphenyl)porphyrin), leads to the analogous platinum(II) nitrato and triflato electrophiles in almost quantitative yields. Self-assembly reactions of these meso-platinioporphyrin tectons with pyridine, 4,4‘-bipyridine, or various meso-4-pyridylporphyrins in chloroform generate new multicomponent organometallic porphyrin arrays containing up to five porphyrin units. These new types of supramolecular arrays are formed exclusively in high yields and are stable in solution or in the solid state for extended periods. They were characterized by multinuclear NMR and UV−visible spectroscopy as well as high-resolution electrospray ionization mass spectrometry.