Batchwise growth of silica cone patterns via self-assembly of aligned nanowires

Silica-cone patterns self-assembled from well-aligned nanowires are synthesized using gallium droplets as the catalyst and silicon wafers as the silicon source. The cones form a triangular pattern array radially on almost the whole surface of the molten Ga ball. Detailed field-emission scanning electron microscopy (SEM) analysis shows that the cone-pattern pieces frequently slide off and are detached from the molten Ga ball surface, which leads to the exposure of the catalyst surface and the growth of a new batch of silicon oxide nanowires as well as the cone patterns. The processes of growth and detachment alternate, giving rise to the formation of a volcano-like or a flower-like structure with bulk-quantity pieces of cone patterns piled up around the Ga ball. Consequently, the cone-patterned layer grows batch by batch until the reaction is terminated. Different to the conventional metal-catalyzed growth model, the batch-by-batch growth of the triangular cone patterns proceeds on the molten Ga balls via alternate growth on and detachment from the catalyst surface of the patterns; the Ga droplet can be used continuously and circularly as an effective catalyst for the growth of amorphous SiO(x) nanowires during the whole growth period. The intriguing batchwise growth phenomena may enrich our understanding of the vapour-liquid-solid (VLS) growth mechanism for the catalyst growth of nanowires or other nanostructures and may offer a different way of self-assembling novel silica nanostructures.     

Preparation of nanoporous polyimide thin films via layer-by-layer self-assembly of cowpea mosaic virus and poly(amic acid)

Low dielectric (low-κ) materials are of key importance for the performance of microchips. In this study, we show that nanosized cowpea mosaic virus (CPMV) particles can be assembled with poly(amic acid) (PAA) in aqueous solutions via the layer-by-layer technique. Then, upon thermal treatment CPMV particles are removed and PAA is converted into polyimide in one step, resulting in a porous low-κ polyimide film. The multilayer self-assembly process was monitored by quartz crystal microbalance and UV-Vis spectroscopy. Imidization and the removal of the CPMV template was confirmed by Fourier transform infrared spectroscopy and atomic force microscopy respectively. The dielectric constant of the nanoporous polyimide film thus prepared was 2.32 compared to 3.40 for the corresponding neat polyimide. This work affords a facile approach to fabrication of low-κ polyimide ultrathin films with tunable thickness and dielectric constant.     

Large pore size nanoporous materials from the self-assembly of asymmetric bottlebrush block copolymers

Asymmetric polystyrene-polylactide (PS-PLA) bottlebrush block copolymers have been shown to self-assemble into a cylindrical morphology with large domain spacings. PLA cylinders can be selectively etched out of the shear-aligned polymer monoliths to generate nanoporous materials with an average cylindrical pore diameter of 55 nm. The remaining bottlebrush backbone provides a functional, hydrophilic coating inside the nanopores. This methodology significantly expands the range of pore sizes attainable in block copolymer based nanoporous materials.     

Controllable growth of highly ordered ZnO nanorod arrays via inverted self-assembled monolayer template

This article presents a facile and effective approach to the controllable growth of highly ordered and vertically aligned ZnO nanorod arrays on the GaN substrate via a hydrothermal route by using the TiO(2) ring template deriving from the polystyrene microsphere self-assembled monolayer. The size of TiO(2) ring template can be flexibly tuned from 50 to 400 nm for the 500 nm polystyrene microspheres by varying the time of reactive ion etching and the concentration of TiO(2) sol. As a result, the diameter of the individual ZnO nanorods can be potentially tuned over a wide range. The combination of several characterization techniques has demonstrated that the ordered ZnO nanorods are highly uniform in diameter and height with perfect alignment and are epitaxially grown along [0001] direction. This work provides a novel and accessible route to prepare oriented and aligned ZnO nanorod arrays with high crystalline quality.     

Synthesis of nanoporous silicon carbide via the preceramic polymer route

Nanoporous silicon carbide materials were prepared by the pyrolysis of the preceramic polymer, polycarbosilane (PCS), with and without the addition of an inert filler (nano- and micron-sized silicon carbide powders). Hydrosilylation crosslinking of PCS with divinylbenzene prior to pyrolysis appeared to have little influence on the development of micro- and mesoporosity. Maximum micropore volumes were 0.28 cm³ g^?1 for non-crosslinked PCS and 0.25, 0.33 and 0.32 cm³ g^?1 for PCS crosslinked with 2, 6 and 10 wt.% DVB respectively. Micropore volumes decreased under hydrothermal conditions to 0.03 cm³ g^?1 for non-crosslinked and 0 cm³ g^?1 for crosslinked PCS. Porosity was also lost at temperatures above 700 °C. The addition of nano-sized SiC powders to PCS prior to pyrolysis maintained mesoporosity to temperatures of 1200 °C, however, micron-sized SiC powders did not maintain porosity above 800 °C. The modal pore size in pellets formed by compressing micron-sized powders with the preceramic polymer was 5 μm compared to 30 nm when nano-sized powders were used.     

Influence of growth parameters on the fabrication of high-quality colloidal crystals via a controlled evaporation self-assembly method

A controlled evaporation self-assembly method with multiple controllable parameters was used to synthesize high-quality colloidal crystals. The environmental parameters, such as the relative humidity, evaporation temperature and pressure, were studied for the quality controls of colloidal crystals during the formation. In the experimental results, we show how these parameters influence the quality of colloidal crystals significantly. Moreover, it is found that, under the case of the relative humidity of 70%, evaporation temperature of 35 °C and pressure of 6.0 kPa, the fabricating high-quality colloidal crystals is optimal from aqueous solution of monodisperse polystyrene spheres with a diameter of 260 nm in a short time (less than 10 h). Highest possible crystal quality may be obtained after the natural drying in the vacuum chamber.     

Flux growth of rare earth silicates and aluminosilicates

Crystals of R₂SiO₅, R₂Si₂O₇, rare earth apatites, and square-faceted rare earth aluminium garnets containing silicon have been grown from fluxed melts. Silicon was provided in two ways: by vapour transport of a siliceous vapour species which diffused into the melts (vapour-flux method), and by including SiO₂ in the initial mixtures. The results of these two methods are compared.The materials have been characterized by X-ray diffraction and, in some cases, by EPMA. Powder pattern data for some of the rare earth apatites are included.     

Flux growth of silicates with vapour transported silicon

As a result of a proposed vapour transport mechanism, silicate crystals have been grown from fluxed melts which originally contained only trace amounts of silicon. The melts were contained in platinum crucibles in a sillimanite, Al₂SiO₅, muffle, and the flux consisted of PbF₂, or PbF₂ + PbO, occasionally with additional MoO₃. It is postulated that a volatile siliceous species resulted from the reaction of PbF₂ vapour with the muffle and that this species transported Si into the fluxed melts. The silicate crystals produced include Er₂SiO₅, Dy₂SiO₅, Mg₂SiO₄·MgF₂, a new material of formula Dy₄SiO₈, and several new rare earth compounds with the apatite structure.     

单壁碳纳米管/聚苯胺自组装薄膜的制备及性能研究

依靠化学键组装法在导电玻璃ITO表面制备了单壁碳纳米管/聚苯胺薄膜.通过VV-vis光谱证实了导电聚苯胺和单壁碳纳米管之间存在着电子相互作用,循环伏安测试表明,经过聚苯胺的化学共价修饰后,单壁碳纳米管薄膜的电化学稳定性得到了显著提升.     

Improving catalytic efficiency via tailoring macroscopic elasticity of nanoporous materials

Journal of Materials Science - Nanoporous materials with unique 3D interconnected networks have large specific surface area and high-density activate sites, making them ideal candidates for various...     

Biomimetic composites via molecular scale self-assembly and biomineralization

New composite material designs are being inspired by the light weight, mechanically robust and unique functions of material systems in Nature. To gain access to these designs, new insight into these structures and their functions, coupled with bottom-up or molecular scale designs, are being implemented. While the synthesis of biomimetic material composites based on these concepts is embryonic, the integration of these concepts into broader materials science and engineering needs will continue to grow.     

On the growth sequence of highly ordered nanoporous anodic aluminium oxide

Anodic aluminium oxide films were fabricated by well known two-step anodizing process in oxalic acid electrolyte. The ordering characteristics (ordered pore domains, average pore diameter size and through-pore arrangement) of anodic aluminium oxide films, obtained in different growth sequences, were identified by microscopic analysis such as ex situ contact-mode atomic force microcopy and scanning electron microscopy. Flattened areas in which some pits are seen mostly cover the electropolished surface of aluminium. Single anodizing of aluminium produces a broad distribution of nanopore size, whereas induces a highly ordered hemispherical pattern, which plays the ordered nucleation sites for the second anodizing step. Moreover, a quasi-linear growth behavior exists for the ordered domain growth versus the duration of first step anodizing. The through-pore arrangement of ideally grown membranes is not influenced by increasing the duration of second step anodizing.     

Visualization of the self-assembly of silica nanochannels reveals growth mechanism

Self-assembled mesoporous structures with well-ordered nanoscale channels could be used in applications such as molecular separation, nano-optics, molecular electronics, nanomedicine and catalysis. However, the domain sizes that can be created in such systems are limited by our lack of a detailed understanding of the relevant growth processes. Here we report the real-time observation of domain growth in the self-assembly of silica nanochannels using fluorescence polarization imaging and atomic force microscopy. We show that transient lamellar structures precede the formation of hexagonal layers, and that the layer growth follows two distinct pathways. In addition, the domains are grown on a mesoporous film substrate, which acts as a sieve and allows control of the delivery of the reactive species. We use these insights and capabilities to grow layers of well-ordered silica nanochannels with domain sizes of up to ～0.3 mm.     

Tailoring the vapor-liquid-solid growth toward the self-assembly of GaAs nanowire junctions

New insights into understanding and controlling the intriguing phenomena of spontaneous merging (kissing) and the self-assembly of monolithic Y- and T-junctions is demonstrated in the metal-organic chemical vapor deposition growth of GaAs nanowires. High-resolution transmission electron microscopy for determining polar facets was coupled to electrostatic-mechanical modeling and position-controlled synthesis to identify nanowire diameter, length, and pitch, leading to junction formation. When nanowire patterns are designed so that the electrostatic energy resulting from the interaction of polar surfaces exceeds the mechanical energy required to bend the nanowires to the point of contact, their fusion can lead to the self-assembly of monolithic junctions. Understanding and controlling this phenomenon is a great asset for the realization of dense arrays of vertical nanowire devices and opens up new ways toward the large scale integration of nanowire quantum junctions or nanowire intracellular probes.     

Optical fiber gas sensors based on hydrophobic alumina thin films formed by the electrostatic self-assembly monolayer process

Optical fiber gas sensors have been fabricated by deposition of Al/sub 2/O/sub 3/ and polymer ultra-thin films on the ends of optical fibers using the electrostatic self assembly monolayer process. These sensors are designed to operate at the standard transmission wavelengths with no cross sensitivity to temperature from at least 10 to 70/spl deg/C. Experimental results of the response of these sensors to organic volatile compounds such as acetone, dichloromethane, or ethanol, are presented. In addition, a thermal curing process is proposed for achieving a humidity cross sensitivity of less than 1.4% from 11% to 85% of relative humidity, this cross sensitivity was still negligible after one year of the thermal curing process.     

Surface modification of titanium thin film with chitosan via electrostatic self-assembly technique and its influence on osteoblast growth behavior

Chitosan (Chi) and poly (styrene sulfonate) (PSS) were employed to surface modify titanium thin film via electrostatic self-assembly (ESA) technique in order to improve its biocompatibility. The surface chemistry, wettability and surface topography of the coated films with different number of deposited layers were investigated by using X-ray photoelectron spectroscopy (XPS), water contact angle measurement and atomic force microscopy (AFM), respectively. The results indicated that a full surface coverage for the outmost layer was achieved at least after deposition of five layers, i.e., PEI/(PSS/Chi)₂ on the titanium films. The formed multi-layered structure of PEI(PSS/Chi) _x (x ≥ 2) on the titanium film was stable in air at room temperature and in phosphate buffered solution (PBS) for at least 3 weeks. Cell proliferation, cell viability, DNA synthesis as well as differentiation function (alkaline phosphatase) of osteoblasts on chitosan-modified titanium film (PEI/(PSS/Chi)₆) and control sample were investigated, respectively. Osteoblasts cultured on chitosan-modified titanium film displayed a higher proliferation tendency than that of control (p < 0.01). Cell viability, alkaline phosphatase as well as DNA synthesis measurements indicated that osteoblasts on chitosan-modified titanium films were greater (p < 0.01) than those for the control, respectively. These results suggest that surface modification of titanium film was successfully achieved via deposition of PEI/(PSS/Chi) _x layers, which is useful to enhance the biocompatibility of the titanium film.     

表面自组装改性石墨烯/环氧纳米复合材料的研究进展

二维石墨烯以其优异的性能广泛应用于制备聚合物纳米复合材料,而如何增强石墨烯与基体的界面相容性则至关重要。近年来,利用自组装技术在石墨烯表面负载功能化金属或非金属纳米粒子,赋予其良好的分散性和多功能特征的研究颇受关注。主要综述了近年来有关表面自组装改性石墨烯的途径及在改善环氧纳米复合材料的阻燃抑烟、摩擦磨损特性、热性能和耐腐蚀性等方面的应用进展。     

Electric-field assisted growth and self-assembly of intrinsic silicon nanowires

Electric-field assisted growth and self-assembly of intrinsic silicon nanowires, in-situ, is demonstrated. The nanowires are seen to respond to the presence of a localized DC electric field set up between adjacent MEMS structures. The response is expressed in the form of improved nanowire order, alignment, and organization while transcending a gap. This process provides a simple yet reliable method for enhanced control over intrinsic one-dimensional nanostructure placement and handling.     

Analysis of punctures in DNA self-assembly under forward growth

This paper deals with the characterization and analysis of intentionally induced punctures on a DNA self-assembly. Based on forward growth, punctures are utilized to remove errors in DNA tiles from the self-assembly. Initially, a Markov model is proposed by considering different types of punctures under various bonding conditions in the tiles. For different values of on and off rates (as corresponding to the parameters G(se) and G(mc)), it is shown that the proposed models can assess the types of puncture for removing mismatched tiles as errors. Subsequently, a novel model of puncturing is introduced to establish the condition by which a generic aggregate can utilize punctures for error resilience. It is proven that by using the correct puncture(s), errors as frozen mismatched tiles are moved toward the boundaries, thus ensuring the generation of the target assembly and ease in removal of the errors. As an example, the Sierpinski tile set is analyzed based on the proposed models to fully assess the appropriate type of puncture for this pattern. Simulation results are provided as evidence that the proposed models are effective.