Morphology-induced phonon spectra of CdSe/CdS nanoplatelets: core/shell vs. core-crown

Recently developed two-dimensional colloidal semiconductor nanocrystals, or nanoplatelets (NPLs), extend the palette of solution-processable free-standing 2D nanomaterials of high performance. Growing CdSe and CdS parts subsequently in either side-by-side or stacked manner results in core-crown or core/shell structures, respectively. Both kinds of heterogeneous NPLs find efficient applications and represent interesting materials to study the electronic and lattice excitations and interaction between them under strong one-directional confinement. Here, we investigated by Raman and infrared spectroscopy the phonon spectra and electron-phonon coupling in CdSe/CdS core/shell and core-crown NPLs. A number of distinct spectral features of the two NPL morphologies are observed, which are further modified by tuning the laser excitation energy E_exc between in- and off-resonant conditions. The general difference is the larger number of phonon modes in core/shell NPLs and their spectral shifts with increasing shell thickness, as well as with E_exc. This behaviour is explained by strong mutual influence of the core and shell and formation of combined phonon modes. In the core-crown structure, the CdSe and CdS modes preserve more independent behaviour with only interface modes forming the phonon overtones with phonons of the core.