Dissipative Self‐Assembly of Anisotropic Nanoparticle Chains with Combined Electrodynamic and Electrostatic Interactions

Dissipative self‐assembly of colloidal nanoparticles offers the prospect of creating reconfigurable artificial materials and systems, yet the phenomenon only occurs far from thermodynamic equilibrium. Therefore, it is usually difficult to predict and control. Here, a dissipative colloidal solution system, where anisotropic chains with different interparticle separations in two perpendicular directions transiently arise among largely disordered silver nanoparticles illuminated by a laser beam, is reported. The optical field creates a nonequilibrium dissipative state, where a disorder‐to‐order transition occurs driven by anisotropic electrodynamic interactions coupled with electrostatic interactions. Investigation of the temporal dynamics and spatial arrangements of the nanoparticle system shows that the optical binding strength and entropy of the system are two crucial parameters for the formation of the anisotropic chains and responsible for adaptive behaviors, such as self‐replication of dimer units. Formation of anisotropic nanoparticle chains is also observed among colloidal nanoparticles made from other metal (e.g., Au), polymer (e.g., polystyrene), ceramic (e.g., CeO2), and hybrid materials (e.g., SiO2@Au core–shell), suggesting that light‐driven self‐organization will provide a wide range of opportunities to discover new dissipative structures under thermal fluctuations and build novel anisotropic materials with nanoscale order. A disorder‐to‐order transition in a dissipative silver nanoparticle colloidal system illuminated by a linearly polarized optical field is demonstrated. Anisotropic chains spontaneously form inside the electrodynamically bound yet thermally fluctuating silver nanoparticles. The anisotropic chains are produced by anisotropic electrodynamic interactions combined with electrostatic interactions.