Synergistic Resonances and Charge Transfer in Double-Shelled ZnO Hollow Microspheres for High-Performance Semiconductor-Based SERS Substrates

The main contribution of semiconductor nanomaterials to surface-enhanced Raman scattering (SERS) comes from charge transfer (CT) between the absorbing molecules and the semiconductor. However, it is still challenging to realize the combined effects of the electromagnetic mechanism (EM) and the chemical mechanism (CM) for semiconductor-based SERS substrates. Herein, we demonstrate and design double-shelled ZnO (ZnO-DS) hollow microspheres by a modified hydrothermal/solvothermal process. SERS experiments and theoretical simulations proved that the excellent SERS activity is mainly attributed to the combined effect of Mie resonances generated by the nanocavities in the unique hollow double-shell nanoparticles and the CT effect excited by special structure ZnO. Particularly, the produced ZnO-DS SERS substrates exhibited a low limit of detection (LOD, 1 × 10^-7 M for 4-MPY), outstanding sensitivity (EF = 1.2 × 10⁴), and high stability (RSD = 10.4%, over 30 days of storage at room temperature). Furthermore, benefiting from the matching of energy levels of the ZnO-DS substrate and probe molecules, the sulfhydryl molecules with similar structures could be selectively distinguished in complex environments. We visualize that this work will resolve the current dilemma between sensitivity and selective detection of SERS substrates and expect to enable the monitoring of target molecules in the environment containing complex mixtures such as food safety and environmental protection.