Antenna array-enhanced attenuated total reflection IR analysis in an aqueous solution

Attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) is a powerful technique that provides structural and functional information during dynamic reactions in aqueous solutions. One existing limitation is the sensitivity to extract the signals of trace-level analytes from the background water in situ and in real time. Here, we proposed a novel ATR-SEIRAS platform that integrated a large-scale triangle gold antenna array onto a conventional ATR-IR platform to increase the sensitivity of this analytical technique. A square centimeter level well-ordered gold antenna array was fabricated onto an Si prism via nanosphere lithography. The size-dependent antenna array resonance had weak correlation with the incident polarization and antenna orientation, allowing antenna array-enhanced IR detection without the requirement of a microscope. In addition, the antenna resonance shift that occurred due to analyte adsorption-induced refractive index variation could be minimized benefiting from the high refractive index of Si (3.4). As a demonstration, we dynamically monitored the adsorption of the trace levels of proteins on top of the antenna array with a real signal enhancement factor larger than 300. Our platform opens an avenue to apply antenna array-enhanced IR spectroscopy in an aqueous environment measured via commercial IR instruments, which is extremely promising for the interfacial applications that require signal enhancement.