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Abstract As an indispensable constituent of plasmonic materials/dielectrics for surface enhanced Raman scattering (SERS) effects, dielectrics play a key role in excitation and transmission of surface plasmons which however remain more elusive relative to plasmonic materials. Herein, different roles of vertical dielectric walls, and horizontal and vertical dielectric layers in SERS via 3D periodic plasmonic materials/dielectrics structures are studied. Surface plasmon polariton (SPP) interferences can be maximized within dielectric walls besieged by plasmonic layers at the wall thicknesses of integral multiple half‐SPPplasmonic material‐dielectric‐wavelength which effectively excites localized surface plasmon resonance to improve SERS effects by one order of magnitude compared to roughness and/or nanogaps only. The introduction of extra Au nanoparticles on thin dielectric layers can further enhance SERS effects only slightly. Thus, the designed Au/SiO2 based SERS chips show an enhancement factor of 8.9 × 1010, 265 times higher relative to the chips with far thinner SiO2 walls. As many as 1200 chips are batch fabricated for a 4 in wafer using cost‐effective nanoimprint lithography which can detect trace Hg ions as low as 1 ppt. This study demonstrates a complete generalized platform from design to low‐cost batch‐fabrication to applications for novel high performance SERS chips of any plasmonic materials/dielectrics.

Abstract Accurate design of high‐performance 3D surface‐enhanced Raman scattering (SERS) probes is the desired target, which is possibly implemented with a prerequisite of quantifying formidable multiple coupling effects involved. Herein, by combining theory and experiments on 3D periodic Au/SiO2 nanogrid models, a generalized methodology of accurately designing high performance 3D SERS probes is developed. Structural symmetry, dimensions, Au roughness, and polarization are successfully correlated quantitatively to intrinsic localized electromagnetic field (EMF) enhancements by calculating surface plasmon polariton (SPP), localized surface plasmon resonance (LSPR), optical standing wave effects, and their couplings theoretically, which is experimentally verified. The hexagonal SERS probes optimized by this methodology realize over two orders of magnitudes (405 times) improvement of detection limit for Rhodamine 6G model molecules (2.17 × 10−11 m) compared to the unoptimized probes with the same number density of hot spots, an enhancement factor of 3.4 × 108, a uniformity of 5.52%, and are successfully applied to the detection of 5 × 10−11 m Hg ions in water. This unambiguously results from the Au roughness‐independent extra 144% contribution of LSPR effects excited by SPP interference waves as secondary sources, which is very unusual to be beyond the conventional recognition.