Colloidal Multiscale Assembly via Photothermally Driven Convective Flow for Sensitive In‐Solution Plasmonic Detections

The assembly of metal nanoparticles and targets to be detected in a small light probe volume is essential for achieving sensitive in‐solution surface‐enhanced Raman spectroscopy (SERS). Such assemblies generally require either chemical linkers or templates to overcome the random diffusion of the colloids unless the aqueous sample is dried. Here, a facile method is reported to produce 3D multiscale assemblies of various colloids ranging from molecules and nanoparticles to microparticles for sensitive in‐solution SERS detection without chemical linkers and templates by exploiting photothermally driven convective flow. The simulations suggest that colloids sub 100 nm in diameter can be assembled by photothermally driven convective flow regardless of density; the assembly of larger colloids up to several micrometers by convective flow is significant only if their density is close to that of water. Consistent with the simulation results, the authors confirm that the photothermally driven convective flow is mainly responsible for the observed coassembly of plasmonic gold nanorods with either smaller molecules or larger microparticles. It is further found that the coassembly with the plasmonic nanoantennae leads to dramatic Raman enhancements of molecules, microplastics, and microbes by up to fivefold of magnitude compared to those measured in solution without the coassembly. A light‐induced, linker‐free and on‐spot 3D multiscale coassembly of plasmonic nanoparticles is developed to detect enhanced Raman signals of liquid samples including multiscale analytes from nano to micron. Using the photothermally driven 3D coassembly, a dramatic Raman enhancement of molecules, microplastics, and microbe is achieved by up to fivefold magnitude compared to the previous colloidal assembly methods.