All-Inorganic and Hybrid Capping of Nanocrystals as Key to Their Application-Relevant Processing

The design of the surface chemistry of colloidal semiconductor nanocrystals (NCs) presents a powerful synthetic approach that allows to tune the optical and electronic properties of the particles in independent and precisely desired manner, to provide chemical and colloidal stability in diverse media, and, finally, to control their targeted applicability ranging from catalysis, medicine to advanced electronic devices. In this article, we summarize the successful functionalization of colloidal NCs with specifically chosen ligands using a novel ligand-exchange strategy. To transform diverse colloidal NCs into a competitive class of solution-processed semiconductors for electronic applications, we replaced the pristine, insulating ligands with tiny inorganic and hybrid inorganic/organic species. The surface modification with inorganic ions modulates the charge carrier density in NC units and guarantees enhanced interparticle interactions. The subsequent functionalization of the all-inorganic-capped NCs with organic molecules leads to the formation of hybrid inorganic/organic-capped NCs. For example, the introduction of short amine molecules enables to preserve the optical and electronic characteristics of their all-inorganic counterparts, while extending the solubility range and improving the ability to form long-range ordered 2D and 3D superstructures. Moreover, these short amines can be further used as convenient axillary co-ligands facilitating the surface functionalization of all-inorganic NCs with other biocompatible molecules, such as polyethylene glycol (PEG). This opens further perspectives for NCs not only in optoelectronic but also in biological and medical applications.