Nanoscale Insights into Enhanced Raman Spectroscopy

Abstract

Enhanced Raman spectroscopies, such as surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS), are based on the amplification of intrinsically weak Raman signals of a molecule by metallic nanostructures. The main enhancement is attributed to electromagnetic enhancement. Chemical effects, such as formation of a surface complex, or a charge-transfer complex, co-adsorbed anion effect, also add to the enhancement of the signal. Using SERS, it has been difficult to study details of chemical enhancement and polarization effects due to limited optical resolution of the technique and usage of roughened metal surfaces. These obstacles were overcome with the development of the TERS technique. TERS has extended Raman spectroscopy into the nanoscale region. In this chapter, nanoscale insights into surface chemistry that lead to Raman signal enhancement are described. The effect of molecular binding and orientation as well as commonly used in SERS chloride activation of metal surfaces is discussed. Finally, we describe the future prospects of TERS and the challenges that keep us from harnessing the full potential of the technique.