Tunable two-dimensional non-close-packed microwell arrays using colloidal crystals as templates

In this paper we demonstrate a facile and efficient way to fabricate poly(dimethylsiloxane) (PDMS) molds with hexagonal non-close-packed (ncp) arrangements of microwells by casting PDMS prepolymer onto two-dimensional (2D) ncp colloidal crystals. The templates of the 2D ncp colloidal crystals were fabricated via coupling lift-up soft lithography and solvent-swelling. We found that the depths of the microwells together with the lattice spacing can be adjusted by the sphere interstices and chemical composition of the 2D ncp colloidal crystals. The relationship of the surface character of the templates with the depths of the microwells can be explained by the wetting behavior of PDMS prepolymer on the rough surface. Contact angle measurements are consistent with the experimental results of the microwells in depth and agree well with the Cassie-Baxter theory. There are at least three advantages of the approach. First, the depth and distance of the microwells can be controlled. Second, PDMS molds can be easily peeled from the surfaces of the templates, which results in reusing the original templates to make new molds. Third, this method can be applied to other materials, such as photopolymerizable resin or thermosetting resin. The potential application of the microwells is as microlenses to make a pattern or as microvials in bioanalytical techniques.     

Direct deposition and assembly of gold colloidal particles using a nanofountain probe

We report the direct delivery and assembly of negatively charged gold colloidal particles atop positively charged amino-terminated silicon oxide surfaces using a nanofountain atomic force microscopy probe. The experimental results and fluid simulations indicate that the flow of nanoparticles is confined to the core tip region of the probe. This leads to the assembly of high-resolution submicron patterns (200 nm) on the substrate with feature sizes dependent on the tip-substrate contact time. A diffusion mechanism for the patterning is proposed and discussed.     

Patterned assembly of colloidal particles by confined dewetting lithography

We report the assembly of colloidal particles into confined arrangements and patterns on various cleaned and chemically modified solid substrates using a method which we term "confined dewetting lithography" or CDL for short. The experimental setup for CDL is a simple deposition cell where an aqueous suspension of colloidal particles (e.g., polystyrene spheres) is placed between a floating deposition template (i.e., metal microgrid) and the solid substrate. The voids of the deposition template serve as an array of micrometer-sized reservoirs where several hydrodynamic processes are confined. These processes include water evaporation, meniscus formation, convective flow, rupturing, dewetting, and capillary-bridge formation. We discuss the optimal conditions where the CDL has a high efficiency to deposit intricate patterns of colloidal particles using polystyrene spheres (PS; 4.5, 2.0, 1.7, 0.11, 0.064 microm diameter) and square and hexagonal deposition templates as model systems. We find that the optimization conditions of the CDL method, when using submicrometer, sulfate-functionalized PS particles, are primarily dependent on minimizing attractive particle-substrate interactions. The CDL methodology described herein presents a relatively simple and rapid method to assemble virtually any geometric pattern, including more complex patterns assembled using PS particles with different diameters, from aqueous suspensions by choosing suitable conditions and materials.     

Cooperativity in the adsorption of magnetic colloidal particles

In this paper we investigate the adsorption of magnetic particles onto magnetically patterned substrates. We find that the adsorption process is cooperative, where the probability of adsorption decreases with increasing substrate occupancy (namely, density of adsorbed particles). The effect of cooperativity can be accounted for by a simple modification of the adsorption probability as manifested by the binomial distribution. The negative cooperativity found in the magnetic particle adsorption is not due to direct repulsion between particles, but to screening of the surface's magnetic field by previously adsorbed particles. Thus, the adsorption of magnetic colloids on magnetic substrates is a self-limiting process.     

2-D assembly of colloidal particles on a planar electrode

Electrical voltage externally applied between parallel-plate electrodes can cause colloidal particles located near one of the electrodes to aggregate; thus monodisperse particles can be driven to form hexagonally close-packed arrays which can be useful in the fabrication of photonic materials. The mechanism for lateral motion of particles on the electrode surface is electroosmotic flow driven by the action of the applied electric field acting either on the equilibrium charges in the diffuse layer of the particles (ECEO) or on charge induced by the electric field on the surface of the electrode (ICEO). For steady currents, ECEO dominates whereas ICEO dominates for high-frequency alternating current. For intermediate frequencies (10 Hz to 1 kHz) both mechanisms are active. This critical review attempts to integrate concepts from electrochemistry and colloid chemistry to understand this electrokinetic phenomenon.     

Preparation and colloidal stability of monodisperse magnetic polymer particles

A previously proposed method was examined for producing monodisperse, submicrometer-sized magnetic polymer particles. The method applies soap-free emulsion polymerization during which Fe3O4 magnetic nanoparticles are heterocoagulated onto precipitated polymer nuclei. To chemically fix the magnetic particles to the polymer nuclei, vinyl groups were introduced on the Fe3O4 particles in a preliminary surface modification reaction with methacryloxypropyltrimethoxysilane, and methacryloxypropyldimethoxysilane (MPDMS) was added to reaction systems of the soap-free emulsion polymerization. The colloidal dispersion stability of magnetic polymer particles was improved by the addition of an ionic monomer, sodium p-styrenesulfonate (NaSS), during the polymerization. The polymerizations were carried out with styrene monomer and potassium persulfate initiator in ranges of NaSS concentrations (0-2.4 x 10(-3) M), NaSS addition times (60-80 min), and monomer concentrations (0.3-0.6 M) at fixed concentrations of 1.6 x 10(-2) M initiator and 1.3 x 10(-2) M MPDMS for pH 4.5 adjusted with a buffer system of [CH3COOH]/[NaOH]. The addition of NaSS during the polymerization could maintain the dispersion stability of magnetic polymer particles during the polymerization. Selection of the reaction conditions enabled the preparation of colloidally stable, submicrometer-sized magnetic polymer particles that had coefficients of variation of distribution smaller than the standard criterion for monodispersity, 10%.     

Colloidal assembly: the road from particles to colloidal molecules and crystals

Colloidal particles may be considered as building blocks for materials, just like atoms are the bricks of molecules, macromolecules, and crystals. Periodic arrays of colloids (colloidal crystals) have attracted much interest over the last two decades, largely because of their unique photonic properties. The archetype opal structures are based on close-packed arrays of spheres of submicrometer diameter. Interest in structuring materials at this length scale, but with more complex features and ideally by self-assembly processes, has led to much progress in controlling features of both building blocks and assemblies. The necessary ingredients include colloids, colloidal clusters, and colloidal "molecules" which have special shapes and the ability to bind directionally, the control over short-range and long-range interactions, and the capability to place and orientate these bricks. This Review highlights recent experimental and theoretical progress in the assembly of colloids larger than 50 nm.     

Size selective assembly of colloidal particles on a template by directed self-assembly technique

We report a simple and effective approach to organize micron- and submicron-sized particles in a size selective manner. This approach utilizes the template assisted directed self-assembly technique. A topographically patterned photoresist surface is fabricated and used to create an ordered array of colloidal particles from their aqueous suspensions. Assembly of particles on this template is then achieved by using a conventional spin coating technique. Feasibility of this technique to form a large area of patterned particle assemblies has been investigated. To arrange the particles on the template, the physical confinement offered by the surface topography must overcome a joint effect of centrifugal force and the hydrophobic nature of the photoresist surface. This concept has been extended to the size selective sorting of colloidal particles. The capability of this technique for sorting and organizing colloidal particles of a particular diameter from a mixture of microspheres is demonstrated.     

Branched networks by directed assembly of shape anisotropic magnetic particles

The directed assembly of shape anisotropic magnetic particles into targeted macrostructures requires judicious particle design. We present a framework to understand the self-assembly of magnetic non-Brownian H-shaped particles and the formation of branched networks under an applied magnetic field. A finite element integration (FEI) method is developed to identify the preferred particle orientation (relative to the applied field) at different values of the geometric parameters defining H shapes, and used to construct a phase diagram to generalize the results. Theoretical predictions are validated by comparing with experiments performed using magnetic hydrogels synthesized using stop-flow lithography (SFL). We demonstrate the ability of H-shaped particles to form chains parallel to the field that can thicken in a direction orthogonal to the field, and in some cases with branching. The assembly of a suspension containing H-shaped particles, or rods, or a combination of both, is reported.     

Magnetic click colloidal assembly

We introduce a new class of spherical colloids that reversibly self-assemble into well-defined nonlinear structures by virtue of "magnetic patches". This assembly is driven by tunable magnetostatic binding forces that originate from microscopic permanent magnets embedded underneath the surface of the particles. The resulting clusters form spontaneously in the absence of external magnetizing fields, and their geometry is determined by an interplay between magnetic, steric, and electrostatic interactions. Imposing an external magnetic field enables the clusters to unbind or change their geometry allowing, in principle, the creation of materials with a reconfigurable structural arrangement.     

Analysis of colloidal particles V. size-exclusion chromatography of colloidal semiconductor particles

An HPLC technique for the size determination of colloidal cadmium sulphide and zinc sulphide in a diameter range from 20 down to 2 nm using silica with pore sizes from 30 to 100 nm is described. The growth of the particles during the run was suppressed by the addition of stabilizers to the eluent and by the use of reversed-phase silica as the stationary phase for inorganic stabilizers. The calibration of the column sets by electron microscopy resulted in a linear relationship between the logarithm of the particle diameter and the elution time. The analysis was carried out within 4–10 min. The lateral resolution lay between 1.3% for larger particles and 1.9% for smaller particles. Below a diameter of 13 nm these values were better than those found from electron microscopy. From the comparison of the calibration lines for various colloidal materials, the differences in their electrical double layers could be estimated. The limitations of the method are discussed and the size-exclusion chromatographic and electron microscopic methods are compared.     

Graphitized pitch-based carbons with ordered nanopores synthesized by using colloidal crystals as templates

A highly graphitized ordered nanoporous carbon (ONC) was synthesized by using commercial mesophase pitch as carbon precursor and siliceous colloidal crystal as template. Since silica colloids of different sizes (above 6 nm) and narrow particle size distribution are commercially available, the pore size tailoring in the resulting ONCs is possible.     

Directed assembly of particles using directional DNA interactions

The use of synthetic DNA to direct the spontaneous self-assembly of synthetic particles into surprisingly complex structures is a rapidly maturing field. Notable recent breakthroughs involve the use of DNA to realize well-controlled interactions between particles that are both chemically specific and directional in nature, the use of hierarchical self-assembly approaches, as well as computational studies to map out the broad palette of accessible structures and assemblies.     

Large-scale fabrication of periodic nanostructured materials by using hexagonal non-close-packed colloidal crystals as templates

This letter reports a versatile nonlithographic technique for mass fabricating three types of technologically important materials-polymer microwell arrays, 2D-ordered magnetic nanodots, and semiconductor nanopillar arrays, each with high crystalline qualities and wafer-scale sizes. Spin-coated hexagonal non-close-packed silica colloidal crystals embedded in a polymer matrix are used as starting templates to create 2D polymeric microwell arrays. These through-hole arrays can then be used as second-generation templates to make periodic magnetic nanodots and semiconductor nanopillars. This self-assembly approach is compatible with standard semiconductor microfabrication, and complex micropatterns can be created for potential device applications. The wafer-scale technique may find important applications in biomicroanalysis, high-density magnetic recording media, and microphotonics.     

Formation and drying of colloidal crystals using nanosized silica particles

Much interest has been generated in the fabrication of colloidal crystals from suspensions because of the promise of photonic band gap applications. However, since the case of small, nonsedimenting colloidal particles indeed remains rather rarely treated, spherical silica particles with diameters varying from 75 down to 20 nm have been used in the present work to fabricate colloidal crystals by drying the suspending liquid. Typical events that take place during the drying process of a particulate film, such as cracking, compaction and penetration of air into a porous network, have been evaluated using existing theories, and the maximum stress in the drying film could be approximated. Investigation on the dry film structure by scanning electron microscopy showed the arrangement of particles in a close-packed system. To interpret the formation of such crystals, the amplitudes of the interparticle and capillary forces have been estimated from existing models. The repulsive interparticle forces allow the particles to remain stable and thus rearrange up to fairly high particle concentration. These modeling results showed the dominance of the capillary contribution at the end of the drying process. Nitrogen adsorption/desorption measurements gave very coherent results regarding both pore volume and pore size of the dry particulate films when compared to the expected ordered packing arrangements.     

Tailoring the interfacial assembly of colloidal particles by engineering the mechanical properties of the interface

Fluid interfaces can be used as a platform for promoting the direct and spontaneous self-assembly of colloidal particles, where the driving force is the reduction in interfacial energy. In addition, fluid interfaces allow fine-tuning of the particles ensemble by an external force, such as the presence of an imposed interfacial flow, or by engineering the interparticle interactions dictated by the interplay of interfacial forces. As a consequence, a wide-ranging set of interfacial structures can be achieved from liquid-like layers, which can flow under stress, to amorphous solids that are able to sustain static stress. Here, far from a comprehensive overview of the interfacial assembly of colloidal particles, different ways of tailoring it by rationally designing the rheological properties of the interface are provided, with a focus on experimental and theoretical methods and model systems that have been recently exploited. In particular, ligand-coated nanoparticles, with a strong emphasis on the effect of the ligands on the interfacial structure and the rheological properties, and soft nanogel particles, in which an environmental factor, such as the temperature, drives to different interfacial structures and mechanical responses will be further discussed.     

Fabrication of anisotropic silica hollow microspheres using polymeric protrusion particles as templates

Anisotropic polystyrene/poly(styrene-co-divinylbenzene) (PS/P(S-DVB)) protrusion particles with various morphologies such as eyeball-like, snowman-like, and raspberry-like were synthesized using a modified seeded polymerization method by dynamically controlling and stabilizing the phase separation. The effects of swelling agent, crosslinker, and monomer concentrations on the particle morphologies were studied. Using the PS/P(S-DVB) protrusion particles as templates, anisotropic silica (SiO₂) hollow microspheres were fabricated facilely. The obtained anisotropic silica hollow spheres had a potential application in rapid waste removal and detoxification extraction with a very simple procedure.