In this work, the surface engineering method is used to produce Mn helical star-shaped (pine-tree-like) nanosculptured thin films with three-, four-, and fivefold symmetries on Cu substrates using an oblique angle deposition technique together with rotation of the sample holder at certain angles. Nano structure and morphologies of the produced samples were obtained by means of atomic force microscope and field emission scanning electron microscope. Raman spectroscopy of the Mn/Cu samples impregnated by 4,4′-bipyridine (C10H8N2) solution with different concentrations, zidovudine (C10H13N5O4), and L-histidine (C6H9N3O2) was performed using 532 nm laser wavelength. A high degree of enhancement is achieved on Raman spectroscopy of all of these specimens. Comparison of the surface-enhanced Raman spectroscopy (SERS) results for 4,4′ bipyridine (bipy) obtained in this work with the published literature using Ag and Au substrates in different shapes showed a significant enhancement improvement by using Mn sculptured structures. Reduction of the bipy concentration changed the enhancement factor. Enhancement factors of 107 and 105 were obtained for threefold symmetry sample using 2.885 × 10–2 and 10–3 mol L–1 bipy concentrations, respectively. Surface-enhanced Raman spectroscopy results of this work show that Mn nanostructures designed and engineered in this work can not only replace Ag and Au materials, but also provide a much higher enhancement factor.

Mn helical star-shaped (pine-tree-like) nano-sculptured thin films with three-, four-and fivefold symmetry on copper substrates were produced using oblique angle deposition method in conjunction with rotation of sample holder at certain angles. Raman spectroscopy of the samples which were subjected to impregnation by 4,4′-bipyridine (C 10 H 8 N 2) solution was carried out by 632.8 nm wavelength laser. The analysis of the Raman spectra showed enhancement for the 4,4′-bipyridine main bands (1592 and 1297 cm −1) belonging to the C=C stretching mode, aromatic ring stretching ring and in-plane ring mode of 4,4′-bipyridine, same as results obtained for Ag nano-structures. In addition, overtone and combined peaks are detected that may be related to the particular sculptured structure of the thin films fabricated in this work and the laser wavelength used for Raman spectroscopy. UV-Vis (absorption mode) spectra showed consistent observations with the SERS results leading to important role of surface electromagnetic selection rule in intensification of SERS, in addition pointing out the importance of the effect of the size of hot spots on the frequency of the localized surface plasmonic oscillations.