Photo-induced-photo-catalytic SERS with silver-deposited TiO2 nanorods for ultrasensitive and sustainable detection of low Raman cross-section molecules

Abstract

Surface-enhanced Raman spectroscopy (SERS) offers significant advantages, including label-free, non-invasive analysis and ultrasensitivity down to the single-molecule level, making it widely applicable in analytical chemistry and biology. However, its effectiveness is limited when detecting molecules with inherently low Raman scattering cross-sections, restricting its broader applications. In this study, we apply the photo-induced-photo-catalytic SERS (PI-PC SERS) technique, utilizing an Ag-deposited TiO₂ nanorod (Ag/TiO₂ NR) substrate to overcome this limitation. The PI-PC SERS technique combines two optoelectronic effects: photo-induced enhanced Raman scattering (PIERS) and the photocatalytic activity of the metal/semiconductor substrate. PIERS amplifies Raman signals beyond normal SERS, while the photocatalytic effect facilitates the removal of residual analytes. The PI-PC SERS process follows three sequential irradiation steps: (i) pre-irradiation with 365 nm UV light to activate PIERS, (ii) laser excitation at 785 nm to capture the enhanced Raman signal, and (iii) post-irradiation with 365 nm UV light to trigger photocatalytic degradation. Two low Raman cross-section molecules, 4-nitrophenol (a widely used pesticide) and urea (an important biomarker), were selected to evaluate the performance of the PI-PC SERS technique on the Ag/TiO₂ NR substrate. The results demonstrated that PI-PC SERS not only enhanced detection sensitivity tenfold compared to normal SERS but also enabled self-cleaning by efficiently removing residual analytes after measurement, ensuring substrate reusability. These findings pave the way for advancing SERS-based techniques for detecting low Raman cross-section molecules while broadening their potential applications in chemical and biological sensing fields.