TiO2 Thickness-dependent charge transfer effect in p-aminothiophenol molecules chemisorbed on TiO2/Ni substrates

Semiconductors have been modulated in thickness to optimize their surface-enhanced Raman scattering (SERS) activity in noble metal/semiconductor SERS substrates. However, the charge transfer (CT) resonance mechanism caused by the change of the semiconductor thickness has not been fully clarified yet, due to the influence of the strong surface plasmon resonance (SPR) effect from the noble metals. Here, systems of p-aminothiophenol (PATP) molecules chemisorbed on TiO2/Ni nanopillar array films with precisely controlled TiO2 thicknesses (PATP/TiO2/Ni) were developed to systematically evaluate the TiO2 thickness-dependent CT mechanism on the premise of minimizing the SPR influence. Ultraviolet–visible, photoluminescence and X-ray photoelectron spectroscopy results demonstrated that four parts that ascribed to the SERS enhancement, photo-induced CT from Ni to TiO2, resonance excitation of TiO2, CT from TiO2 surface states to PATP molecules, and the molecular resonance of PATP molecules, are highly TiO2-thickness dependent. Hence the whole system exhibits a strong TiO2-thickness-dependent CT effect (at the two interfaces of Ni-TiO2 and TiO2-PATP) and SERS activity with a maximum SERS intensity at a TiO2 thickness of 40 nm. This work shall be valuable for future developing an optimal metal/semiconductor SERS substrates and obtaining an in-depth understanding of the semiconductor-thickness-dependent charge transfer mechanism for SERS applications.