We present the synthesis of nonspherical magnetic microparticles with multiple functionalities, shapes, and chemistries. Particle synthesis was performed in two steps: polymeric microparticles functionalized homogenously with carboxyl groups were generated using stop-flow lithography, and then in situ coprecipitation was used to grow magnetic nanoparticles at these carboxyl sites. With successive growth of magnetic nanoparticles, we obtained polymeric particles with saturation magnetizations of up to 42 emu/g microparticle. The growth in the magnetic nanoparticle mean size and polydispersity was determined from the magnetization curves obtained following each growth cycle; nanoparticle sizes were limited by the physical constraint of the effective mesh within the hosting gel microparticle. Particles with spatially segregated domains of varying magnetic properties (e.g., Janus particles, particles with step changes in magnetite concentration, etc.) can be synthesized readily using this approach.
The sonochemical synthesis of nanosized surface-dissymmetrical (Janus) particles is described. The Janus particles were composed of silica and polystyrene, with the polystyrene portion loaded with nanosized magnetite particles. It is shown that the Janus particles can be used to form kinetically stable oil-in-water emulsions that can be spontaneously broken on application of an external magnetic field. The one-pot synthetic process used to prepare the Janus particles has several advantages over other conventional methods of producing such particles.
The emulsion droplet solvent evaporation method has been used to prepare nanoclusters of monodisperse magnetite nanoparticles of varying morphologies depending on the temperature and rate of solvent evaporation and on the composition (solvent, presence of polymer, nanoparticle concentration, etc.) of the emulsion droplets. In the absence of a polymer, and with increasing solvent evaporation temperatures, the nanoparticles formed single- or multidomain crystalline superlattices, amorphous spherical aggregates, or toroidal clusters, as determined by the energetics and dynamics of the solvent evaporation process. When polymers that are incompatible with the nanoparticle coatings were included in the emulsion formulation, monolayer- and multilayer-coated polymer beads and partially coated Janus beads were prepared; the nanoparticles were expelled by the polymer as its concentration increased on evaporation of the solvent and accumulated on the surfaces of the beads in a well-ordered structure. The precise number of nanoparticle layers depended on the polymer/magnetic nanoparticle ratio in the oil droplet phase parent emulsion. The magnetic nanoparticle superstructures responded to the application of a modest magnetic field by forming regular chains with alignment of nonuniform structures (e.g., toroids and Janus beads) that are in accord with theoretical predictions and with observations in other systems.
Recent advances in quantum dot surface passivation have led to a rapid development of high-efficiency solar cells. Another critical element for achieving efficient power conversion is the charge neutrality of quantum dots, as charge imbalances induce electronic states inside the energy gap. Here we investigate how the simultaneous introduction of metal cations and halide anions modifies the charge balance and enhances the solar cell efficiency. The addition of metal salts between QD deposition and ligand exchange with 1,3-BDT results in an increase in the short-circuit current and fill factor, accompanied by a distinct reduction in a crossover between light and dark current density-voltage characteristics.
We report on modeling and experimental studies of the synthesis of opaque microparticles made via stop-flow lithography. Opaque magnetic beads and UV-absorbing dyes incorporated into hydrogel microparticles during synthesis changed the height and the degree of cross-linking of the polymer matrices formed. The effect of the concentration of these opaque materials on the particle height was determined experimentally and agreed well with model predictions based on the photopolymerization process over a wide range of UV absorbance. We also created particles with two independent anisotropies, magnetic and geometric, by applying magnetic fields during particle synthesis. Our work provides a platform for rational design of lithographic patterned opaque particles and also a new class of structured magnetic microparticles.
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