Colloidal n-Doped CdSe and CdSe/ZnS Nanoplatelets

J Phys Chem Lett. 2021 Nov 25;12(46):11259-11266. doi: 10.1021/acs.jpclett.1c02856. Epub 2021 Nov 12.

Abstract

Colloidal semiconductor nanoplatelets (NPLs) are chemical versions of well-studied quantum wells (QWs). For QWs, gating and carrier doping are standard tools to manipulate their optical, electric, or magnetic properties. It would be highly desirable to use pure chemical methods to dope extra charge carriers into free-standing colloidal NPLs to achieve a similar level of manipulation. Here we report colloidal n-doped CdSe and CdSe/ZnS NPLs achieved through a photochemical doping method. The extra electrons doped into the conduction band edges are evidenced by exciton absorption bleaches recoverable through dedoping and the appearance of new intersub-band transitions in the near-infrared. A high surface ligand coverage is the key to successful doping; otherwise, the doped electrons can be depleted likely by unpassivated surface cations. Large trion binding energies of 20-30 meV are found for the n-doped CdSe NPLs, which, in contrast, are reduced by 1 order of magnitude in CdSe/ZnS core/shell NPLs due to dielectric screening. Furthermore, we identify a long-lived negative trion with a lifetime of 1.5-1.6 ns that is likely dominated by radiative recombination.