The formation of CdS quantum dots and Au nanoparticles

Abstract

Abstract We report on microsecond-resolved in-situ SAXS experiments of the early nucleation and growth behavior of both cadmium sulfide (CdS) quantum dots in aqueous solution including the temperature dependence and of gold (Au) nanoparticles. A novel free-jet setup was developped to access reaction times as early as 20 μs. As the signal in particular in the beginning of the reaction is weak the containment-free nature of this sample environment prooved crucial. The SAXS data reveal a two-step pathway with a surprising stability of a structurally relaxed cluster with a diameter of about 2 nm. While these develop rapidly by ionic assembly, a further slower growth is attributed to cluster attachment. WAXS diffraction confirms, that the particles at this early stage are not yet crystalline. This growth mode is confirmed for a temperature range from 25°C to 45°C. An energy barrier for the diffusion of primary clusters in water of 0.60 eV was experimentally observed in agreement with molecular simulations. To access reaction times beyond 100 ms, a stopped-drop setup -again contaiment- free is introduced. SAXS experiments on the growth of Au nanoparticles on an extended time scale provide a much slower growth with one population only. Further, the influence of ionizing X-ray radiation on the Au particle fromation and growth is discussed.