Enhanced charge-transfer induced by conduction band electrons in aluminum-doped zinc oxide/molecule/Ag sandwich structures observed by surface-enhanced Raman spectroscopy.

In the semiconductor/molecule/metal system, enhancing the efficiency of the charge-transfer (CT) plays a pivotal role in improving the sensitivity of semiconductor-based surface-enhanced Raman scattering (SERS). In this work, use of SERS for detection of an enhanced CT in a chemically-etched Al-doped ZnO (AZO), 4-mercaptopyridine (MPy) molecule, and Ag nanoparticles (NPs) (AZO/MPy/Ag) sandwich structure is reported. A series of CT routes are proposed in the energy level diagram of AZO/MPy/Ag assemblies under the excitation line at 633 nm. Very interestingly, for the first of its kind, a significant CT route from the conduction band (CB) of AZO to the lowest unoccupied molecular orbital (LUMO) of MPy molecule is detected. This route can remarkably improve the degree of CT in the AZO/MPy/Ag system by about 48% compared with that of the ZnO/MPy/Ag system. Furthermore, the uniquely enhanced CT route is also further confirmed by alternative probe molecules like p-aminothiophenol (PATP) and 4-mercaptobenzoic acid (MBA). The discovery of this extra CT route will inevitably play an irreplaceable role in SERS enhancement through its participating in the CT enhancement mechanism.