Key Structure Parameters for Designing High-Performance Substrates of Surface-Enhanced Infrared Absorption...

Attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) plays a crucial role in understanding the interfacial reaction mechanisms at the molecular level, achieving an enhancement factor (EF) of up to 10³. However, when this technique is integrated with electrochemistry (EC-ATR-SEIRAS), the EF is significantly reduced by ten- to hundred-fold. Thus, understanding of the key parameters that contribute to the EF is of great importance in designing high-performance substrates and extending the application for EC-SEIRAS. In this study, we propose that the structure of the substrate for EC-ATR-SEIRAS consists of an enhancement unit (EU) supported on a conductivity unit (CU). The CU will screen the incident IR light reaching and interacting with the EU, resulting in a smaller EF as the CU thickness increases. Then, we introduce a strategy to optimize the performance of the EC-SEIRAS substrate by assembling a plasmonic antenna array as the EU that is supported on IR-transparent and conductive monolayer graphene as the CU. The established plasmon-enhanced EC-SEIRAS substrate demonstrates much higher IR enhancement, repeatability, and stability.