Synthesis of Doped Semiconductor Nanocrystals and Conductive Coatings.

摘要

Semiconductor nanocrystals are an intriguing class of materials because of their size-tunable properties. This makes them promising for future optoelectronic devices such as solar cells and light emitting diodes. Realization of these devices, however, requires precise control of the flow of electricity through the particles. In bulk semiconductors, this is achieved by using materials with few unintentional defects, then intentionally adding particular defects or dopants to alter the semiconductor's electronic properties. In contrast, the addition of electrically active dopants has scarcely been demonstrated in semiconductor nanocrystals, and charge transport is hindered by the barrier of electron hopping between particles.;The goal of this thesis, therefore, is to discover new methods to control charge transport in nanocrystals. It divides into three major thrusts: 1) the investigation of the doping process in semiconductor nanocrystals, 2) the invention of new synthetic methods to incorporate electrically active dopants into semiconductor nanocrystals, and 3) the invention of a new nanocrystal surface coating that aids processing of nanocrystals into devices but can be removed to enhance charge transport between particles.;The first objective is achieved by the comparison of four different precursors that have been used to dope Mn into nanocrystals. Experiments show that dimethylmanganese incorporates efficiently into ZnSe nanocrystals while other precursors are less efficient and sometimes lower the quality of the nanocrystals produced.;The second goal is met by the application of a core-shell synthetic strategy to the incorporation of non-isovalent impurities (Al and In) into CdSe nanocrystals. By separating the three steps of nucleation, dopant binding, and growth, each step can be optimized so that doping is achieved and high quality particles are produced. Detailed characterization shows dopant incorporation and local environment, while transistor measurements reveal that the nanocrystal Fermi level rises with increasing Al content.;The third thrust is achieved by the use of primary dithiocarbamates as ligands to stabilize CdSe, and PbSe / CdSe core/shell nanoparticles. Primary dithiocarbamates bind well to metals but include a weak chemical bond that can be broken with gentle heating. This enables us to bind them to nanoparticles, process the particles into devices, then remove the ligand via gentle heating. Characterization of the ligand-particle interactions show excellent ligand binding to the particle surface and easy ligand removal with heating. After ligand removal, the inter-particle spacing shrinks. Transistor measurements reveal that this reduces the barrier to interparticle electron transport, enhancing the conductivity of the film.