Resolving Artifacts and Improving the Detection Limit in Circular Differential Scattering Measurement of Chiral and...

Circular differential scattering (CDS) spectroscopy has been developed as a powerful method for the characterization of the optical activity of individual plasmonic nanostructures and their complexes with chiral molecules. However, standard measurement setups often result in artifacts that have long raised concerns on the interpretation of spectral data. In fact, the detection limit of CDS setups is constrained by the high level of artifacts, to ±10%. We address this issue by means of a detailed theoretical description of changes in the polarization state when circularly polarized light is reflected at a dark-field condenser. As a result, we propose a modified CDS configuration based on sequentially placing the quarter-wave plate and linear polarizer within the detection optical path, to analyze the circular polarization state of the light scattered by individual particles. Extensive analysis demonstrates a detection limit of ±1.5% for the modified configuration, which is significantly lower than that for the conventional setup. As a standard system for CDS measurements, both achiral and chiral gold nanorods (AuNRs) were characterized using both setups. With achiral AuNRs, linear dichroism (LD) artifacts in the conventional setup are found to originate from LD present in the excitation light and are only present if anisotropic excitation is produced as a result of the misalignment of the excitation light to the condenser. With chiral AuNRs, CDS spectra recorded with the conventional setup depend on the orientation of the chiral AuNRs with respect to the x-axis of the microscope and are reversed compared to those on the colloid and measured in the modified configuration. The results are in good agreement with theoretical simulations for both configurations.