Multidirectional, Multicomponent Electric Field Driven Assembly of Complex Colloidal Chains

External fields (magnetic and electric) present a simple, robust and efficient route to manipulate and assemble colloidal particles. We report how biparticle dispersions can be assembled into well-defined arrays of tunable morphology using external AC electric field. Binary dispersions of strongly and weakly charged colloidal particles were arranged into linear composite chains via dipole-dipole attraction. The frequency of the applied electric field was the first control parameter for reversibly tuning the biparticle attraction from longitudinal assembly (in the direction of field) to the traverse one (perpendicular to the field). We show that in addition to frequency, spatial limitations play a key role in the assembly process and may assist in the formation of short bidirectional chain-like clusters or characteristic highly structured strings of colloidal triplets. Thus, we control the long-range organization through a combination of particle size ratio, concentration ratio and field frequency. The new strategy to reconfigure the microstructures can find application in better control of the field driven colloidal assembly processes and may be extended to the formation of more complex and precisely arranged particle networks.