Control of self-assembly in micro- and nano-scale systems

Control of self-assembling systems at the micro- and nano-scale provides new opportunities for the engineering of novel materials in a bottom-up fashion. These systems have several challenges associated with control including high-dimensional and stochastic nonlinear dynamics, limited sensors for real-time measurements, limited actuation for control, and kinetic trapping of the system in undesirable configurations. Three main strategies for addressing these challenges are described, which include particle design (active self-assembly), open-loop control, and closed-loop (feedback) control. The strategies are illustrated using a variety of examples such as the design of patchy and Janus particles, the toggling of magnetic fields to induce the crystallization of paramagnetic colloids, and high-throughput crystallization of organic compounds in nanoliter droplets. An outlook of the future research directions and the necessary technological advancements for control of micro- and nano-scale self-assembly is provided.     

Fabrication of Schottky barrier MOSFETs using self-assembly CoSi2 nanopatterning and spacer gate technologies

A self-assembly patterning method for generation of epitaxial CoSi₂ nanostructures was used to fabricate 50 nm channel-length MOSFETs. The transistors have either a symmetric structure with Schottky source and drain or an asymmetric structure with n⁺-source and Schottky drain. The patterning technique is based on anisotropic diffusion of Co/Si atoms in a strain field during rapid thermal oxidation. The strain field is generated along the edges of a mask consisting of 20 nm SiO₂ and 300 nm Si₃N₄. During rapid thermal oxinitridation (RTON) of the masked silicide structure, a well-defined separation of the silicide layer forms along the edge of the mask. These highly uniform gaps define the channel region of the fabricated device. The separated silicide layers act as metal source and drain. A poly-Si spacer was used as the gate contact. The asymmetric transistor was fabricated by ion implantation into the unprotected CoSi₂ layer and a subsequent out-diffusion process to form the n⁺-source. I–V characteristics of both the symmetric and asymmetric transistor structures have been investigated.     

Evaporation induced self-assembly of zeolite A micropatterns due to the stick-slip dynamics of contact line

In this study, a new surfactant-solvent system was described for the preparation of periodic stripe patterns of zeolite A on solid substrates. The evaporation induced self-assembly of zeolite A particles was due to the stick-slip dynamics of the three-phase contact line of the colloid solutions in acetone containing 10% (v/v) poly(dimethylsiloxane) (PDMS) fluid (2 cst.). In order to investigate the possible effects of particle size and the particle concentration on the stick-slip dynamics, three types of zeolite A samples with different particle sizes (zeolite A-I: 250-500 nm, zeolite A-II: 100-250 nm and zeolite A-III: 0-100 nm) were utilized to prepare 0.007-0.06% (w/v) colloidal dispersions. Zeolite A micropatterns were self-assembled on the surface of glass, high density polyethylene (HDPE) and poly(tetrafluoroethylene) (PTFE) substrates, which were placed vertically inside the colloid solutions and held against the wall of the cylindrical vial during the evaporation of acetone. The stripe patterns of zeolite A particles were analyzed with field emission scanning electron microscope (FE-SEM) and optical microscope. The widths of microstripes and the distance between the stripes were found as 2-20 μm and 40-60 μm respectively depending on the particle concentration. By using the stick-slip dynamics of colloids, the linear micropatterns of zeolite A nanocrystals were prepared with low cost and low energy.     

Self-assembly of highly oriented palladium-based nanowires on mica surface

The self-assembly of various nanostructures is recently attracting a great deal of research attention. In this paper, we demonstrate that a palladium chloride aqueous solution, mixed with a proper ammonia solution, can produce Tetra-amminepalladous chloride (Pd(NH₃)₄Cl₂·H₂O) nanowires. These nanowires can spontaneously form the two-dimensional hexagon-oriented Pd(NH₃)₄Cl₂·H₂O arrays on mica surfaces. We can control the length and height of these nanowires by adjusting their deposit time on the mica substrate. This method can be potentially used in making sensors or in making templates to wire and position nanodevices.     

Synthesis and self-assembly of hyperbranched polyester peripherally modified by touluene-4-sulfonyl groups

In this paper, hyperbranched polyesters (HPs) were synthesized in the molten state from 2,2-bis(hydroxymethyl) propionic acid (bis-MPA) and 2-ethyl-2-hydroxymethyl-1,3-propanediol (TMP) using acid catalysis. The modified hyperbranched polyesters were obtained through the chemical modification of the hyperbranched polyester cores by substituting a controlled fraction of the terminal hydroxyl groups with touluene-4-sulfonyl chloride using triethylamine (TEA) as an acceptor of HCl. The resultant polyesters were characterized by ¹H NMR, ¹³C NMR, FT-IR, UV and GPC and their self-assembly behaviors were investigated. The results revealed that self-assembled structures could be formed in selected solvents (trichloromethane/acetone or trichloromethane/n-hexane).     

Marvelous self-assembly of hierarchically nanostructured porous zirconium phosphate solid acids with high thermal stability

A hierarchical structure of thermally stable macroporous zirconium phosphate solid acids with supermicroporous walls was prepared by a simple self-assembly process from the precursors of zirconium propoxide and orthophosphoric acid solution. The macroporous structures are uniform with the diameters ranging from 300 to 800 nm, one-dimensional channel-like. The effect of surfactant Brij 56 on the formation of macroporous structures has been studied. The frameworks of the synthesized hierarchical zirconium phosphates are amorphous with Zr–O–P bonding, exhibiting remarkably high thermal stability (at least 800 °C), on the basis of the X-ray diffraction (XRD), N₂ adsorption, X-ray photoelectron spectroscopy (XPS) analysis, Fourier transform infrared (FT-IR) and ³¹P nuclear magnetic resonance (NMR) spectra. Larger quantities of Zr–OH and P–OH groups are observed besides surface hydroxyl groups, suggesting the presence of acidity and the possibility of surface functionalization for practical applications including catalysis. The macroporous zirconium phosphates with hierarchical structures could also be the potential and efficient catalyst supports for the design of the structured catalysts and reactors.     

靶向壳聚糖基因载体与水溶性量子点的自组装

将透明质酸(HA)接枝到四种不同分子量的壳聚糖(CS)上,获得了靶向壳聚糖基因载体。将CS及接枝CS分别与水溶性量子点(QDs)自组装,研究发现,相对于纯QDs,CS/QDs复合物及接枝CS/QDs复合物的荧光强度均明显增强,荧光发射峰位发生红移。复合物呈核/壳结构,QDs被包裹在核内。和CS/QDs复合物相比,接枝CS/QDs复合物的尺寸更小,分布更为均一。     

Multiple morphologies of self-assembled star aggregates of amphiphilic PEO-b-PNPMA diblock copolymers in solution, synthesis and micellization

Novel amphiphilic block copolymers, poly(ethylene oxide)-b-poly(p-nitrophenyl methacrylate) (PEO-b-PNPMA) with controlled molecular weights and narrow molecular weight distribution were successively synthesized by ATRP of NPMA using PEO-Br as initiator. Self-assembling of the diblock copolymer PEO₁₁₃-b-PNPMA₂₈ in the different solvent mixtures yielded various morphologies of star micelle-like aggregates, such as spheres, vesicles, cauliflower-like aggregates and rod-like aggregates, which are determined by the nature of the common solvents and the selective solvents. Thus the critical selective solvent contents and the solvent contents in PNPMA-rich phase were measured, and they have the following order: ethanol > methanol > water, and THF > CH₃NO₂ > DMSO. The probable self-assembling mechanism is discussed. This method is convenient for preparation of multiple morphological star micelle-like aggregates in solution, especially from the amphiphilic block copolymers with relatively longer block shell.     

Nanoparticle induced network self-assembly in polymer-carbon black composites

A novel percolation phenomenon with inorganic nanoparticle loading in polyamide 6-carbon based nanoparticle hybrids was identified. Percolation threshold substantially shifts to lower carbon black (CB) volume fractions in the presence of optimum concentration of chemically modified montmorillonite (organoclay) while the effective organoclay concentration can be optimized to lower the slope of percolation curve maintaining electrical conductivity within static dissipative 10⁻⁶-10⁻⁹ S cm⁻¹ range. Organoclay/CB ‘nano-unit’ morphology was found in polyamide 6 ternary hybrids. It is composed of stacked organo-montmorillonite platelets that deform to wrap partially around one or two primary CB aggregates. This elementary nano-unit structure induces CB network self-assembly within polyamide 6 matrices. The structure was found to be prevalent throughout the polymer matrix. This morphology remains robust under wide range of thermal-deformation histories due to the strong preferred organoclay/polyamide 6/CB interactions that partially blocks the electron conduction and hopping mechanisms with clay ‘walls’ thereby reducing the slope of the percolation curve. Organoclay can be used as a dispersion control agent in these polymer-carbon systems to induce self-assembly of CB network at low CB content, simultaneously, partial blocking the electron hopping pathways to level the slope of percolation curves. High order exfoliation and nano-scale dispersion of organoclay is essential to induce this advanced percolation phenomenon.     

Self-reorganization of mixed poly(methyl methacrylate)/polystyrene brushes on planar silica substrates in response to combined selective solvent treatments and thermal annealing

This article reports reversible changes in surface morphology and surface wettability of mixed poly(methyl methacrylate) (PMMA)/polystyrene (PS) brushes with PS M_n slightly lower than that of PMMA in response to combined selective solvent treatments and thermal annealing. The mixed brushes were synthesized from asymmetric difunctional initiator-terminated monolayers by controlled radical polymerizations. Two sets of experiments were performed. The first set involved treating the samples with glacial acetic acid (AA), a selective solvent for PMMA, followed by treatment with cyclohexane, a selective solvent for PS, or thermal annealing. The surfaces were rough and composed of relatively ordered nanodomains after AA treatment. Subsequent cyclohexane treatment or thermal annealing made the surfaces flattened and surface analysis indicated that the outermost layers were occupied by PS. The second set of experiments involved treating the samples with cyclohexane or thermal annealing, followed by AA treatment. The surfaces were smooth after cyclohexane treatment or thermal annealing and became very rough in the subsequent AA treatment. The nanodomains formed in AA treatment were speculated to be micelles with PS forming the core shielded by PMMA chains.