Second order directed positioning of nanoparticles induced by the main terminal meniscus shape in irregular template cavities

Directed self-assembly of nanoparticles using topographical templates has demonstrated great capabilities of ordering particles at their maximum packing fraction resulting from template confinement effects and free energy minimization. However, to self-assemble nanostructures at a lower packing fraction with a precise control over particle's positioning is challenging due to the high entropy of such a system. Here, by fabricating templates of irregular cavities together with appropriate choice of solvent, we demonstrate the positioning of 8 nm Au nanoparticles within individual cavities at a low filling factor. In addition to the first-order of ordering dictated by the template topography, there is a second-order of ordering induced by the interplay between the evaporation of the residual solvent trapped within the cavities and their intrinsic geometries. The experimental results show that the cavities shaped as equilateral triangles exhibit a random positioning of the particles at the corners; in comparison, right-angled scalene (or irregular) triangles show a more controllable positioning of the particles within the corners of the smallest angle. Finally, this technique has been successfully used to fabricate arrays of dimers with a controllable center-to-center distances at sub-5 nm length scales.