Nanoassembly of gold nanoparticles: An active substrate for size-dependent surface-enhanced Raman scattering.

Nanoassembly of gold nanoparticles has been achieved through a simple and facile process without using any surfactants or linkers. Atomic force microscopy confirmed assemblies of several tens of microns, whereas tiny interparticle gaps less than 5 nm was revealed by scanning electron microscopy. Such nanoassemblies with tiny interparticle gaps were found to be highly surface-enhanced Raman scattering (SERS)-active with enhancement factor in the order of 6 to 8. Contrary to usual trends in nanoparticles size dependent SERS enhancement, such 2D nanoassemblies of different sizes of nanoparticles showed relatively broadened SERS enhancement distribution. Finite difference time domain (FDTD) analysis was employed to highlight the EM-field distribution in connection to such giant SERS enhancement. In depth and hotsite-wise analysis on EM near-field distributions for monomers, dimers and septamers of 50 nm of gold nanoparticles were carried out at three specific incident polarizations (i.e. s-, 45° and p-polarizations). At s- and p-polarization the strongest hotsites were having the EM near-field distributions in the range of 124.8 and 133.3 V/m respectively with lower population of confined EM near-fields. Such correlated investigation will be indispensable to understand and interpret hierarchical and functional nanoassemblies from its unit nanoparticle blocks for the advances of technological breakthroughs.