Assembling quantum dots via critical Casimir forces

AbstractProgrammed assembly of colloidal inorganic nanocrystal superstructures is crucial for the realization of future artificial solids as well as present optoelectronic applications. Here, we present a new way to assemble quantum dots reversibly using binary solvents. By tuning the temperature and composition of the binary solvent mixture, we achieve reversible aggregation of nanocrystals in solution induced by critical Casimir forces. We study the temperature-sensitive quantum-dot assembly with dynamic light scattering. We show that careful screening of the electrostatic repulsion by adding salt provides a further parameter to tune the reversible assembly

Thermosensitive Molecular, Colloidal, and Bulk Interactions Using a Simple Surfactant

Efficient use of (nano)particle self-assembly for creating nanostructured materials requires sensitive control over the interactions between building blocks. Here, a very simple method for rendering the interactions between almost any hydrophobic nano- and microparticles thermoswitchable is described and this attraction is characterized using colloid probe atomic force microscopy (CP-AFM). In a single-step synthesis, a thermoresponsive surfactant is prepared that through physical adsorption generates a thermosensitive brush on hydrophobic surfaces. These surface layers can reversibly trigger gelation and crystallization of nano- and microparticles, and at the same time can be used to destabilize emulsions on demand. The method requires no chemical surface modification yet is universal, reproducible, and fully reversible

Temperature-triggered colloidal gelation through well-defined grafted polymeric surfaces

Sufficiently strong interparticle attractions can lead to aggregation of a colloidal suspension and, at high enough volume fractions, form a mechanically rigid percolating network known as a colloidal gel. We synthesize a model thermo-responsive colloidal system for systematically studying the effect of surface properties, grafting density and chain length, on the particle dynamics within colloidal gels. After inducing an attraction between particles by heating, aggregates undergo thermal fluctuation which we observe and analyze microscopically; the magnitude of the variance in bond angle is larger for lower grafting densities. Macroscopically, a clear increase of the linear mechanical behavior of the gels on both the grafting density and chain length arises, as measured by rheology, which is inversely proportional to the magnitude of local bond angle fluctuations. This colloidal system will allow for further elucidation of the microscopic origins to the complex macroscopic mechanical behavior of colloidal gels including bending modes within the network. View Full-Tex

Programmable co-assembly of oppositely charged microgels

Here we report the development of an aqueous, self-assembling system of oppositely charged colloids leading towards particle arrangements with controlled order. The colloidal system consists of two types of particles, each consisting of refractive index matched colloidal core–shell microgel particles, which are either negatively charged or amphoteric. By slowly decreasing the pH of our system below the isoelectric point of the amphoteric particles, changing their net charge from negative to positive, the co-assembly of the colloids is induced. By using different buffer concentrations, we gain temporal and kinetic control over the acidification process and thus the ability to program the co-assembly of the two particles species

Colloidal gelation of oppositely charged particles

Colloidal gelation has been extensively studied for the case of purely attractive systems, but little is understood about how colloidal gelation is affected by the presence of repulsive interactions. Here we demonstrate the gelation of a binary system of oppositely charged colloids, in which repulsive interactions compete with attractive interactions. We observe that gelation is controlled by varying the total volume fraction, the interaction strength, and the new tuning parameter of the mixing ratio of the two particle types, and present a state diagram of gelation along all these phase-space coordinates. Contrary to commonly studied purely attractive gels, in which weakly quenched gels are more compact and less tenuous, we find that particles in these binary gels form fewer contacts and the gels become more tenuous as we approach the gel point. This suggests that a different mechanism governs gel formation and ultimate structure in binary gelation: particles are unable to form additional favorable contacts through rearrangements, due to the competition of repulsive interactions between similarly charged colloids and attractive interactions between oppositely charged colloids