Colloidal self‐assembly provides one promising route to fabricate spatially periodic meta‐materials with novel properties important to a number of emerging technologies. However, colloidal assembly is generally initiated via irreversible step‐changes and proceeds along unspecified, non‐equilibrium kinetic pathways with little opportunity to manipulate defects or reconfigure microstructures. Here, a conceptually new approach that enables the use of feedback control to quantitatively and reversibly guide the dynamic evolution of colloid ensembles between disordered fluid and crystalline configurations is demonstrated. The key to this approach is the use of free energy landscape models to inform feedback control laws that close the loop between real‐time sensing (via order parameters) and actuation (via tunable electrical potentials). This approach, which demonstrates controlled assembly to create ordered materials and perform active reconfiguration, is based on chemical physics that suggest it can be generalized to other microscopic processes.

We fabricated chemically and shape-anisotropic colloids composed of silica rods coated with gold tips using a multistep process involving electric-field alignment and crystallization, microcontact printing, and selective metallization. Through direct observation, we found that these "Janus matchsticks" self-assemble into multipods (bi-, tri-, and tetrapods) of varying coordination number and patch angle in aqueous solution.

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We report video microscopy measurements and computer simulations of quasi-two-dimensional configurations of micron sized colloids in 1 MHz ac electric fields between coplanar thin film electrodes. Interactions of induced dipoles (IDs) with each other and inhomogeneous electric fields (IFs) as a function of concentration and field amplitude produced microstructures including confined hard disk fluids, oriented dipolar chains, and oriented hexagonal close packed crystals. Equilibrium measurements and analyses of single colloids within electric fields were used to directly measure ID-IF interactions in the absence of many body effects. Measurements of concentrated systems were characterized in terms of density profiles across the electrode gap and angular pair distribution functions. In concentrated measurements, an inverse Monte Carlo analysis was used to extract the ID-ID interaction. A single adjustable parameter consistently modified the ID-IF potential and the ID-ID potential to account for weakening of ID as the result of the local particle concentration and configuration.

We report nonintrusive optical microscopy measurements of single micrometer-sized silica and polystyrene colloids in inhomogeneous AC electric fields as a function of field amplitude and frequency. By using a Boltzmann inversion of the time-averaged sampling of single particles within inhomogeneous electric fields, we sensitively measure induced dipole-field interactions on the kT energy scale and fN force scale. Measurements are reported for frequencies when the particle polarizability is greater and less than the medium, as well as the crossover between these conditions when dipole-field interactions vanish. For all cases, the measured interactions are well-described by theoretical potentials by fitting a nondimensional induced dipole-field magnitude. While silica dipole-field magnitudes are well-described by existing electrokinetic models, the polystyrene results suggest an anomalously high surface conductance. Sensitive measurements of dipole-field interactions in this work provide a basis to understand dipole-dipole interactions in particle ensembles in the same measurement geometry in part II.

We report a feedback control method to precisely target the number of colloidal particles in quasi-2D ensembles and their subsequent assembly into crystals in a quadrupole electrode. Our approach relies on tracking the number of particles within a quadrupole electrode, which is used in a real-time feedback control algorithm to dynamically actuate competing electrokinetic transport mechanisms. Particles are removed from the quadrupole using DC-field mediated electrophoretic-electroosmotic transport, while high-frequency AC-field mediated dielectrophoretic transport is used to concentrate and assemble colloidal crystals. Our results show successful control of the size of crystals containing 20 to 250 colloidal particles with less than 10% error. Assembled crystals are characterized by their radius of gyration, crystallinity, and number of edge particles, and demonstrate the expected size-dependent properties. Our findings demonstrate successful ensemble feedback control of the assembly of different sized colloidal crystals using multiple actuators, which has broad implications for control over nano- and micro- scale assembly processes involving colloidal components.

We report nonintrusive optical microscopy measurements of ensembles of polystyrene colloids in inhomogeneous AC electric fields as a function of field frequency and particle size. By using an inverse Monte Carlo (MC) simulation analysis of time-averaged particle microstructures, we sensitively measure induced dipole-dipole interactions on the kT energy scale. Measurements are reported for frequencies when the particle polarizability is greater and less than the medium, as well as the crossover between these conditions when dipole-dipole interactions vanish. By using measured single dipole-field interactions and associated parameters from Part I as input in the inverse analysis, the dipole-dipole interactions in this work are accurately modeled with no adjustable parameters for conditions away from the crossover frequency (i.e., |f(CM)| > 0). As dipolar interactions vanish at the crossover, a single frequency-dependent parameter is introduced to account for microstructures that appear to result from weak AC electro-osmotic flow induced interactions. By connecting quantitative measures of equilibrium microstructures and kT-scale dipole-field and dipole-dipole interactions, our findings provide a basis to understand colloidal assembly in inhomogeneous AC electric fields.

We investigate the electric field-induced assembly of Janus colloids composed of silica rods patterned with gold patches in both side- and tip-coated motifs. These shape and chemically anisotropic particles assemble into reconfigurable chains, whose structure depends on patch location, AC electric field strength, and frequency.