Size-Dependent Spectroscopy of MoS₂ Nanoclusters

The synthesis and characterization of 3.5, 4.5, and 8 nm diameter MoS2 nanoclusters are described. Each size is characterized by TEM images, electron diffraction, and optical spectroscopy. These nanoclusters can be synthesized directly or may be synthesized from samples of polydisperse nanoclusters. Obtaining larger or smaller discrete sizes from polydisperse samples indicates that these nanocluster sizes are thermodynamically favored, that is, these sizes correspond to free-energy minima. Electron diffraction and static spectroscopic results indicate that the particles are three atoms thick, specifically, single S−Mo−S trilayer disks. Static and time-resolved absorption and emission spectroscopy were used to determine the polarizations of the lowest energy allowed transitions in each case. We find that the 8 nm particles have a lowest energy absorption maximum at 473 nm that has mixed x − y and z polarizations, 4.5 nm particles have absorption maxima at 400 and 440 nm that are x − y and z polarized, respectively, and 3.5 nm particles have an absorption maximum at 362 nm that is z polarized. These results indicate that the polarization of the lowest observed transition is size-dependent and that the ordering of the lowest excited states changes as the particle size decreases.