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The study of optical and plasmonic properties of structures is an important step in the development of substrates for surface-enhanced Raman scattering (SERS) applications. In this work, structures based on a disordered array of hemispherical silver nanoparticles (AgNPs) on a single-crystal silicon (c-Si) substrate are studied. A simple and reproducible method is proposed in which an Ag island film obtained by chemical reduction of AgNO 3 is transformed after annealing at 350 °C into an array of hemispherical AgNPs on a thin SiO 2 layer. The average radii of AgNPs range from 30 to 130 nm, which can be varied due to the concentration of AgNO 3 in the initial deposition solution. Numerical calculations of the scattering, absorption, and extinction cross-sections are used to determine the positions of the localized surface plasmon resonance (LSPR) multipoles depending on the hemispherical AgNP size. The splitting of the LSPR dipole is found in the reflection spectra at oblique angles of incidence for p-polarization of light, which indicates the prolate shape of the hemispherical AgNPs. Finally, SERS shows reliable detection of 10−7 M (crystal violet) with the enhanced factor ∼ 6.2 × 10 5 and the relative standard deviation of signal ∼ 10 %. These studies suggest that hemispherical AgNPs on a SiO 2 @c-Si are promising candidates for detecting triphenylmethane dyes. [Display omitted] • SERS substrates based on hemispherical AgNPs on SiO 2 @c-Si have been fabricated. • FDTD calculations were used to determine LSPR multipoles as a function of AgNP size. • Splitting of the LSPR in the reflection spectra of p-polarized light was found. • Prolate shape of the AgNPs were confirmed by SEM method and optical investigations. • SERS substrates showed reliable CV detection of 10−7 M with EF ∼ 6.2 × 10 5 and RSD ∼ 10 %. [ABSTRACT FROM AUTHOR]