Neck Barrier Engineering in Quantum Dot Dimer Molecules via Intra-Particle Ripening

Coupled colloidal quantum dot (CQD) dimers represent a new class of artificial molecules composed of fused core/shell semiconductor nanocrystals. The electronic coupling and wavefunction hybridization is enabled by the formation of an epitaxial connection with a coherent lattice between the shells of the two neighboring quantum dots where the shell material and its dimensions dictate the quantum barrier characteristics for the charge carriers. Herein we introduce a colloidal approach to control the neck formation at the interface between the two CQDs in such artificial molecular constructs. This allows the tailoring of the neck barrier in pre-linked homodimers formed via fusion of multifaceted wurtzite CdSe/CdS CQDs. The effects of reaction time, temperature and excess ligands is studied. The neck filling process follows an intraparticle ripening mechanism at relatively mild reaction conditions while avoiding inter-particle ripening. The degree of surface ligand passivation plays a key role in activating the surface atom diffusion to the neck region. The degree of neck filling strongly depends also on the initial relative orientation of the two CQDs, where homonymous plane attachment allows for facile neck growth, unlike the case of heteronymous plane attachment. Upon neck-filling, the observed red-shift of the absorption and fluorescence measured both for ensemble and single dimers, is assigned to enhanced hybridization of the confined wavefunction in CQD dimer molecules, as supported by quantum calculations. The fine tuning of the particle interface introduced herein provides therefore a powerful tool to further control the extent of hybridization and coupling in CQD molecules.
Comment: Article- 19 pages, 5 figures; SI- 18 pages, 12 figures. Journal of the American Chemical Society Article ASAP, 2021