Plasmonic Trapping-Induced Crystallization of Acetaminophen

We demonstrate that plasmonic trapping can control crystallization of acetaminophen from its aqueous solution. Irradiation of a focused continuous-wave near-infrared laser to a plasmonic Au nanolattice supporting a thin film of a saturated solution allowed acetaminophen molecules to crystallize in annular distribution with the center of the focal spot. The annularly distributed crystals can be spatially manipulated by changing the position of the laser focal spot. The annular pattern is rationalized by competition between electrical field gradient force as an attractive force to the focal spot and thermophoretic force as a repulsive force. It is also found that, upon stopping the laser irradiation, the crystals first transformed to highly concentrated droplets rather than directly dissolving to the solution. Relaxation of the droplets by self-diffusion to the solution followed to the crystal/droplet transformation. These two-step dissociation dynamics indicate that not only plasmonic trapping of the molecules but also the enhanced electrical field by surface plasmon contributes to drive the crystallization, and it has a possibility to show the reverse process of the two-step nucleation model. Our demonstration highlights the possibility that plasmonic trapping by designed near-field and temperature distribution can manipulate not only molecular assembly but also creation of functional crystalline materials in nanoscale.