Optical Nanocrystallography with Tip-Enhanced Phonon Raman Spectroscopy

Conventional phonon Raman spectroscopy is a powerful experimental technique for the study of crystalline solids that allows crystallography, phase and domain identification on length scales down to ∼1 μm. Here we demonstrate the extension of tip-enhanced Raman spectroscopy to optical crystallography on the nanoscale by identifying intrinsic ferroelectric domains of individual BaTiO3 nanocrystals through selective probing of different transverse optical phonon modes in the system. The technique is generally applicable for most crystal classes, and for example, structural inhomogeneities, phase transitions, ferroic order and related finite-size effects occurring on nanometre length scales can be studied with simultaneous symmetry selectivity, nanoscale sensitivity and chemical specificity.