Lattice dynamics of quasi-two-dimensional CdSe nanoplatelets and their Raman and infrared spectra

TL;DR

This study uses first-principles calculations to analyze the phonon, Raman, and infrared spectra of CdSe nanoplatelets, revealing that many observed spectral features are due to quasi-Lamb modes rather than surface optical modes.

Contribution

It provides a detailed theoretical analysis of phonon and spectral properties of CdSe nanoplatelets, challenging previous interpretations of experimental Raman spectra.

Findings

Lamb modes in nanoplatelets are optical, not acoustic.

Low-frequency modes originate from bulk TA phonons.

Reinterpretation of Raman spectra features as quasi-Lamb modes.

Abstract

Phonon spectra of CdSe nanoplatelets (2-6 ML) with the zinc-blende structure were calculated from first principles within the density-functional theory. It turned out that the Lamb modes in nanoplatelets are in fact optical rather than acoustic vibrations. Phonon spectra of the nanoplatelets show the appearance of a large number of low-frequency modes inherited from TA phonons in bulk CdSe. Calculations of the Raman spectra indicate a need to revise the interpretation of available experimental data. The largest contribution to the Raman spectra is provided by the quasi-Lamb modes with the $A_1$ symmetry. The $B_2$ modes whose frequencies depend on the environment of nanoplatelets and whose properties are closest to the properties of LO phonons explain the results obtained in the "nanoparticle-on-mirror" geometry. The features in Raman spectra previously attributed to surface optical (SO) modes should be interpreted as a manifestation of lower-order quasi-Lamb $A_1$ modes. Calculations of the infrared spectra find, in addition to the TO phonon line, the appearance of intense lines from surface modes originating from terminating F(Cl) atoms on the surface of nanoplatelets and true SO-modes.