This thesis addresses the syntheses towards high quality CdSe and CdTe nanoparticles. Therefore, thermodynamic and kinetic aspects of the hot injection method are investigated. By means of the introduction of a thermodynamically less favored nuclei species the nucleation event of CdSe quantum dot synthesis is affected. Utilizing highly reactive tin or lithium silylamides, primarily formed SnSe or Li2Se nuclei undergo a cation exchange to the demanded CdSe particles. The further growth proceeds without the incorporation of the so called quasi-seed species. In this manner, the mechanism of the cation exchange-mediated nucleation is proven and optimized with respect to the required amount of the quasi-seed species. Furthermore, this protocol is applied to up-scaling attempts to reduce the efforts for optimization to a minimum. Following this, a successful laboratory batch up-scaling is achieved by increasing flask size as well as precursor concentrations by factors of 2 and 10, respectively. A further possibility to thermodynamically influence the hot injection synthesis is the activation of the precursor species. By altering the injection pathway, as compared to the standard synthesis, the precursor species are differently coordinated and hence possess different thermodynamic stabilities. Investigations on the system of CdTe quantum dots lead to the result of a cation activation by the use of the thermodynamically less stable carboxylate ligands instead of phosphonates. Additionally, anion activation is suggested due to a kind of aging of the phosphine ligands via their oxidation by phosphonic acids. Furthermore, it is found that the ratio of Cd-to-Te strongly influences the formation of so called magic-sized clusters. Following the results, the smallest detectable species is determined as a cluster species with a size of 1.8 nm. The role of the magic-sized clusters is not fully resolved, but the initial growth is assumed to occur via monomer deposition onto or the fusion of the observed clusters. On the other hand, cluster dissolution is thermodynamically forced by the decreasing monomer concentration and can simply be explained by the process of Ostwald ripening via the creation of a smaller cluster species. Mechanistically this is explained by the formation of configurational deviations from the ideal closed-shell structure. Finally the inorganic coating of the core quantum dots in investigated. Therefore, homoepitaxial coating is employed to overcome the limit in particle size by introducing additional monomer supply. As a result, following the classical crystallization theory, defined injections of precursor material during the diffusion limited growth regime allow a fine tuning of the final particle size. Nevertheless, homoepitaxial coating inevitably leads to photoluminescence quenching, whereas heteroepitaxial growth usually improves the optical quality. By means of a type I structure, CdSe/CdS/ZnS, the successive ion layer adsoption and reaction mechanism is discussed. Furthermore, alloy structures of CdSe/ZnSe with a radially gradated intermediate shell of CdZnSe are achieved by postsynthetic high temperature treatments. This annealing induces internal diffusion processes and allows exactly adjusting the emission wavelength due to defined shrinkage of the initial core size during the alloying process.

This thesis addresses the syntheses towards high quality CdSe and CdTe nanoparticles. Therefore, thermodynamic and kinetic aspects of the hot injection method are investigated. By means of the introduction of a thermodynamically less favored nuclei species the nucleation event of CdSe quantum dot synthesis is affected. Utilizing highly reactive tin or lithium silylamides, primarily formed SnSe or Li2Se nuclei undergo a cation exchange to the demanded CdSe particles. The further growth proceeds without the incorporation of the so called quasi-seed species. In this manner, the mechanism of the cation exchange-mediated nucleation is proven and optimized with respect to the required amount of the quasi-seed species. Furthermore, this protocol is applied to up-scaling attempts to reduce the efforts for optimization to a minimum. Following this, a successful laboratory batch up-scaling is achieved by increasing flask size as well as precursor concentrations by factors of 2 and 10, respectively. A further possibility to thermodynamically influence the hot injection synthesis is the activation of the precursor species. By altering the injection pathway, as compared to the standard synthesis, the precursor species are differently coordinated and hence possess different thermodynamic stabilities. Investigations on the system of CdTe quantum dots lead to the result of a cation activation by the use of the thermodynamically less stable carboxylate ligands instead of phosphonates. Additionally, anion activation is suggested due to a kind of aging of the phosphine ligands via their oxidation by phosphonic acids. Furthermore, it is found that the ratio of Cd-to-Te strongly influences the formation of so called magic-sized clusters. Following the results, the smallest detectable species is determined as a cluster species with a size of 1.8 nm. The role of the magic-sized clusters is not fully resolved, but the initial growth is assumed to occur via monomer deposition onto or the fusion of the observed clusters. On the other hand, cluster dissolution is thermodynamically forced by the decreasing monomer concentration and can simply be explained by the process of Ostwald ripening via the creation of a smaller cluster species. Mechanistically this is explained by the formation of configurational deviations from the ideal closed-shell structure. Finally the inorganic coating of the core quantum dots in investigated. Therefore, homoepitaxial coating is employed to overcome the limit in particle size by introducing additional monomer supply. As a result, following the classical crystallization theory, defined injections of precursor material during the diffusion limited growth regime allow a fine tuning of the final particle size. Nevertheless, homoepitaxial coating inevitably leads to photoluminescence quenching, whereas heteroepitaxial growth usually improves the optical quality. By means of a type I structure, CdSe/CdS/ZnS, the successive ion layer adsoption and reaction mechanism is discussed. Furthermore, alloy structures of CdSe/ZnSe with a radially gradated intermediate shell of CdZnSe are achieved by postsynthetic high temperature treatments. This annealing induces internal diffusion processes and allows exactly adjusting the emission wavelength due to defined shrinkage of the initial core size during the alloying process.