Otimização e caracterização de nanoestruturas de ouro e prata recobertas com uma camada ultrafina de MnO2, SiO2 ou TiO2: uma alternativa para aplicações das técnicas espectroscópicas intensificadas por superfície

Abstract

The present work covers the syntheses and characterizations of gold nanorods (AuNR) and gold and silver spherical nanoparticles (AuSN and AgSN) coated with ultrathin layers of manganese, silicon or titanium oxide. Dielectric layers were characterized by UV-Vis, infrared absorption spectroscopy, X ray diffraction (XRD), cyclic voltammetry (CV) and transmission electron microscopy (TEM) techniques. Plasmonic nanostructures (PN) which are used as substrates in spectroscopic applications are unstable in the presence of many analytes, thus leading to aggregation and subsequent precipitation. This instability makes the characterization of the adsorbate much more challenging. Coating PN with dielectric layers strongly increases its structural stability, while retaining their plasmonic properties. To this end, the scope of this work was to cover AuNR by ultrathin layers of MnO2, SiO2 or TiO2 and AuNS or AgNS by TiO2 and verify its applicability in surface spectroscopic techniques. By means of displacement of the localized surface plasmon resonance band, it was possible to follow the formation and increase of the thickness of the dielectric layer adsorbed at the interface of the metal when compared to PN without coating, which are results of the changes in the local refractive index to PN. The XRD technique was used to confirm the formation of the hybrid materials. It was observed non-crystalline haloes attributed to the oxides and diffraction peaks characteristic of Au metallic nanostructures. Moreover, it was possible to characterize the Ag and Au PN with oxides by means of analysis by TEM, wherein was possible to confirm the presence of uniform layer coatings of MnO2, SiO2 or TiO2 surrounding the metallic core with a thickness below 6 nm. The use of the CV technique allowed verifying that the oxide shells did not have pinholes. The optimized hybrid materials were used as surface enhanced Raman scattering (SERS) and surface enhanced fluorescence (SEF) substrates for adsorption analysis of the IR-820 molecule. The SERS measurements using incident radiations at 633 and 1064 nm showed a significant increase in the relative intensities of some vibrational modes compared to the Raman spectrum of the free molecule, through which the assignments of the vibrational modes were performed. The SEF measurements obtained with the incident radiation 785 nm showed an increase in the SEF intensity for higher oxide thicknesses, which was attributed to the increase in the distance between adsorbate and the conductive surface of the metal. Moreover, adsorption of the 3-mercaptopropionic acid (MPA) and 4-mercaptobenzoic acid (MBA) molecules in these NP coated was studied using SERS. It was possible to identify and assign the most significant vibrational modes and confirm the adsorption site of MPA and MBA molecules. The results confirmed the successful formation of the oxide layers surrounding the metallic cores. Finally, the applications of the SERS and SEF effect have shown to be very promising for the synthesized substrates.