Reversible Attraction-Mediated Colloidal Crystallization on Patterned Substrates
Abstract
In this dissertation we used tunable particle-particle and particle-substrate attraction to achieve reversible two-dimensional crystallization of colloids on homogeneous and patterned substrates. Total internal reflection and video microscopy techniques were used to quantify the interparticle and particle-substrate interactions in these colloidal systems. Equilibrium and dynamic simulations were then utilized to link these colloidal interactions to the experimental colloidal phase behaviour. The importance of the nature of the attractive interaction in successfully crystallizing colloids has also been documented. The first set of experiments demonstrates the use of temperature and specific ion effects to reversibly control the net particle-substrate van der Waals (vdW) attraction. Colloidal stabilization was achieved via the use of adsorbed polymer brush layers. By using evanescent wave microscopy, we directly and precisely measured how temperature and specific ion effects control the dimensions of adsorbed polymer layers and hence the net van der Waals attraction in between the colloids and the substrate. However, the magnitude of the van der Waals attraction decays very rapidly with increasing surface separation and is therefore not conducive to the self assembly of colloidal crystals. We successfully used thermoresponsive polymer nanoparticles to control the depletion attraction between micron sized silica particles and thereby induced reversible crystallization of the micron sized silica colloids on homogeneous substrates. Video and evanescent wave microscopy techniques were used to measure the nanoparticle-induced attractive interaction as a function of temperature. The experimentally observed phase behaviour was verified via simulations that utilized knowledge of the measured colloidal depletion interactions. Finally, patterned surface topologies were used to position attractive colloidal crystals. Simulations were used to link the measured colloidal interactions to experimental phase behaviour as well as substrate topology. An extension of the concepts developed in this dissertation might suggest a general strategy to assemble colloidal particles into robust and annealable crystals contributing to the fabrication of photonic bandgap materials.