Surface-enhanced hyper-Raman and Raman hyperspectral mapping.

We investigate distributions of crystal violet and malachite green on plasmonic surfaces by principal component analysis (PCA) imaging of surface-enhanced hyper-Raman scattering (SEHRS) data. As a two-photon excited Raman scattering process, SEHRS provides chemical structure information based on molecular vibrations, but follows different selection rules than the normal, one-photon excited surface-enhanced Raman scattering (SERS). Therefore, simultaneous hyperspectral mapping using SEHRS excited at 1064 nm and SERS excited at 532 nm improves spatially resolved multivariate discrimination based on complementary vibrational information. The possibility to map distributions of the structurally similar dyes crystal violet and malachite green demonstrates the potential of this approach for multiplex imaging of complex systems.