Controlling the size of hot injection made nanocrystals by manipulating the diffusion coefficient of the solute.

We investigate the relation between the chain length of ligands used and the size of the nanocrystals formed in the hot injection synthesis. With two different CdSe nanocrystal syntheses, we consistently find that longer chain carboxylic acids result in smaller nanocrystals with improved size dispersions. By combining a more in-depth experimental investigation with kinetic reaction simulations, we come to the conclusion that this size tuning is due to a change in the diffusion coefficient and the solubility of the solute. The relation between size tuning by the ligand chain length and the coordination of the solute by the ligands is further explored by expanding the study to amines and phosphine oxides. In line with the weak coordination of CdSe nanocrystals by amines, no influence of the chain length on the nanocrystals is found, whereas the size tuning brought about by phosphine oxides can be attributed to a solubility change. We conclude that the ligand chain length provides a practical handle to optimize the outcome of a hot injection synthesis in terms of size and size dispersion and can be used to probe the interaction between ligands and the actual solute.

Utilizing self-exchange to address the binding of carboxylic acid ligands to CdSe quantum dots.

We use solution NMR techniques to analyze the organic/inorganic interface of CdSe quantum dots (Q-CdSe) synthesized using oleic acid as a surfactant. It is shown that the resulting Q-CdSe are stabilized by tightly bound oleic acid species that only exchange upon addition of free oleic acid. The NMR analysis points toward a two-step exchange mechanism where free ligands are initially physisorbed within the ligand shell to end up as bound, chemisorbed ligands in a second step. Importantly, we find that every ligand is involved in this exchange process. By addition of oleic acid with a deuterated carboxyl headgroup, we demonstrate that the bound ligands are oleate ions and not oleic acid molecules. This explains why a dynamic adsorption/desorption equilibrium only occurs in the presence of excess free oleic acid, which donates the required proton. Comparing the number of oleate ligands to the excess cadmium per CdSe quantum dot, we find a ratio of 2:1. This completes the picture of Q-CdSe as organic/inorganic entities where the surface excess of Cd(2+) is balanced by a double amount of oleate ligands, yielding overall neutral nanoparticles.

Langmuir-Schaefer deposition of quantum dot multilayers.

The application of colloidal nanocrystals in various devices requires their assembly into well-defined mono- or multilayers. We explore the possibilities of the Langmuir-Schaefer technique to make such layers, using CdSe quantum dots as a model system. The layer quality is assessed using atomic force microscopy, transmission electron microscopy, and UV-vis absorption spectroscopy. For hydrophobic substrates, we find that the Langmuir-Schaefer technique is an excellent tool for controlled multilayer production. With hydrophilic substrates, dewetting induces a cellular superstructure. Combination with photolithography leads to micropatterned multilayers, and combination of different nanocrystal sizes allows for the formation of 2D binary superstructures.

Reaction chemistry/nanocrystal property relations in the hot injection synthesis, the role of the solute solubility.

Various literature studies show that increasing the concentration of free acid in the hot injection synthesis of colloidal nanocrystals raises the diameter of the resulting nanocrystals. We analyze this reaction chemistry/nanocrystal property relation by combining reaction simulations with an experimental study on a particular CdSe nanocrystal synthesis. We find that increasing the free acid concentration has the same effect on a real synthesis as raising the solute solubility in the simulations. Both lead to larger sizes and a deterioration of the size dispersion at constant reaction rate. Since free acids are used to coordinate the cation precursors in these syntheses, this leads to a meaningful link between a parameter in reaction simulations and the composition of an experimental reaction mixture. We thus explain the increase of the nanocrystal size with the acid concentration as resulting from an enhanced consumption of the solute by nanocrystal growth, which reduces the number of nanocrystals formed. This link between a simulation parameter and the composition of the reaction mixture provides a rational basis to further explore and understand reaction chemistry/nanocrystal property relations in the hot injection synthesis.

Tuning of electronic properties in IV-VI colloidal nanostructures by alloy composition and architecture.

Colloidal lead chalcogenide (IV-VI) quantum dots and rods are of widespread scientific and technological interest, owing to their size tunable energy band gap at the near-infrared optical regime. This article reviews the development and investigation of IV-VI derivatives, consisting of a core (dot or rod) coated with an epitaxial shell, when either the core or the shell (or both) has an alloy composition, so the entire structure has the chemical formula PbSexS1-x/PbSeyS1-y (0 ≤ x(y) ≤ 1). The article describes synthesis procedures and an examination of the structures' chemical and temperature stability. The investigation of the optical properties revealed information about the quantum yield, radiative lifetime, emission's Stokes shift and electron-phonon interaction, on the variation of composition, core-to-shell division, temperature and environment. The study reflected the unique properties of core-shell heterostructures, offering fine electronic tuning (at a fixed size) by changing their architecture. The optical observations are supported by the electronic band structure theoretical model. The challenges related to potential applications of the colloidal lead chalcogenide quantum dots and rods are also briefly addressed in the article.