Topography-Correlated Confocal Raman Microscopy with Cylindrical Vector Beams for Probing Nanoscale Structural Order

Cylindrical vector beams, such as radially or azimuthally polarized doughnut beams, are combined with topography studies of pentacene thin films, allowing us to correlate Raman spectroscopy with intermolecular interactions depending on the particular pentacene polymorph. Polarization-dependent Raman spectra of the C-H bending vibrations are resolved layer by layer within a thin film of ∼20 nm thickness. The variation of the Raman peak positions indicates changes in the molecular orientation and in the local environment at different heights of the pentacene film. With the assistance of a theoretical model based on harmonic oscillator and perturbation theory, our method reveals the local structural order and the polymorph at different locations within the same pentacene thin film, depending mainly on its thickness. In good agreement with the crystallographic structures reported in the literature, our observations demonstrate that the first few monolayers grown in a structure are closer to the thin-film phase, but for larger film thicknesses, the morphology evolves toward the crystal-bulk phase with a larger tilting angle of the pentacene molecules against the substrate normal.