Cubic Silver Nanoparticles Fixed on TiO₂ Nanotubes as Simple and Efficient Substrates for Surface Enhanced Raman...

In this work we show that ordered freestanding titanium oxide nanotubes (TiO₂ NT) may be used as substrates for the simple and efficient immobilization of anisotropic plasmonic nanoparticles. This is important because anisotropic plasmonic nanostructures usually give greater spectral enhancement than spherical nanoparticles. The size of the pores in a layer of titanium oxide nanotubes can be easily fitted to the size of many silver plasmonic nanoparticles highly active in SERS (surface-enhanced Raman scattering) spectroscopy (for example, silver nanocubes with an edge length of ca. 45 nm), and hence, the plasmonic nanoparticles deposited can be strongly anchored in such a titanium oxide substrate. The tubular morphology of the TiO₂ substrate used allows a specific arrangement of the silver plasmonic nanoparticles that may create many so-called SERS hot spots. The SERS activity of a layer of cubic Ag nanoparticles (AgCNPs) deposited on a tubular TiO₂ substrate (AgCNPs@TiO₂ NT) is about eight times higher than that of the standard electrochemically nanostructured surface of a silver electrode (produced by oxidation reduction cycling). Furthermore, a super hydrophilic character of the TiO₂ nanotubes surface allows for a uniform distribution of AgCNPs, which are deposited from an aqueous suspension. The new AgCNPs@TiO₂ NT hybrid layer ensures a good reproducibility of SERS measurements and exhibits a higher temporal stability of the achievable total SERS enhancement factor-one that is far better than standard SERS silver substrates. To characterize the morphology and chemical composition of such evidently improved SERS platforms thus received, we applied microscopic techniques (SEM, and scanning transmission electron microscopy (STEM)) and surface analytical techniques (Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS)).