Plasmonic Nanocrystal Arrays on Photonic Crystals with Tailored Optical Resonances

[Image: see text] Hierarchical plasmonic–photonic microspheres (PPMs) with high controllability in their structures and optical properties have been explored toward surface-enhanced Raman spectroscopy. The PPMs consist of gold nanocrystal (AuNC) arrays (3rd-tier) anchored on a hexagonal nanopattern (2nd-tier) assembled from silica nanoparticles (SiO(2)NPs) where the uniform microsphere backbone is termed the 1st-tier. The PPMs sustain both photonic stop band (PSB) properties, resulting from periodic SiO(2)NP arrangements of the 2nd-tier, and a surface plasmon resonance (SPR), resulting from AuNC arrays of the 3rd-tier. Thanks to the synergistic effects of the photonic crystal (PC) structure and the AuNC array, the electromagnetic (EM) field in such a multiscale composite structure can tremendously be enhanced at certain wavelengths. These effects are demonstrated by experimentally evaluating the Raman enhancement of benzenethiol (BT) as a probe molecule and are confirmed via numerical simulations. We achieve a maximum SERS enhancement factor of up to ∼10(8) when the resonances are tailored to coincide with the excitation wavelength by suitable structural modifications.