from colloidal CdSe
quantum dots excited by UV light. CdSe-derived
nanoparticles with sizes below 10 nm exhibit a property known as
quantum confinement. Quantum confinement results when the electrons in a material are confined to a very small volume. Quantum confinement is size dependent, meaning the properties of CdSe nanoparticles are tunable based on their size. One type of CdSe nanoparticle is a CdSe
quantum dot. This discretization of energy states results in electronic transitions that vary by quantum dot size. Larger quantum dots have closer electronic states than smaller quantum dots which means that the energy required to excite an electron from HOMO to the LUMO is lower than the same electronic transition in a smaller quantum dot. This quantum confinement effect can be observed as a red shift in absorbance spectra for nanocrystals with larger diameters. Quantum confinement effects in quantum dots can also result in
fluorescence intermittency, called "blinking." CdSe quantum dots have been implemented in a wide range of applications including solar cells, light emitting diodes, and biofluorescent tagging. CdSe-based materials also have potential uses in biomedical imaging. Human tissue is permeable to near
infra-red light. By injecting appropriately prepared CdSe nanoparticles into injured tissue, it may be possible to image the tissue in those injured areas. CdSe quantum dots are usually composed of a CdSe core and a ligand shell. Ligands play important roles in the stability and solubility of the nanoparticles. During synthesis, ligands stabilize growth to prevent aggregation and precipitation of the nanocrystals. These capping ligands also affect the quantum dot's electronic and optical properties by passivating surface electronic states. An application that depends on the nature of the surface ligands is the synthesis of CdSe thin films. The density of the ligands on the surface and the length of the ligand chain affect the separation between nanocrystal cores which in turn influence
stacking and
conductivity. Understanding the surface structure of CdSe quantum dots in order to investigate the structure's unique properties and for further functionalization for greater synthetic variety requires a rigorous description of the ligand exchange chemistry on the quantum dot surface. A prevailing belief is that
trioctylphosphine oxide (TOPO) or
trioctylphosphine (TOP), a neutral ligand derived from a common precursor used in the synthesis of CdSe dots, caps the surface of CdSe quantum dots. However, results from recent studies challenge this model. Using NMR, quantum dots have been shown to be nonstoichiometric meaning that the cadmium to selenide ratio is not one to one. CdSe dots have excess cadmium cations on the surface that can form bonds with anionic species such as carboxylate chains. The CdSe quantum dot would be charge unbalanced if TOPO or TOP were indeed the only type of ligand bound to the dot. The CdSe ligand shell may contain both X type ligands which form
covalent bonds with the metal and L type ligands that form
dative bonds. It has been shown that these ligands can undergo exchange with other ligands. Examples of X type ligands that have been studied in the context of CdSe nanocrystal surface chemistry are sulfides and thiocyanates. Examples of L type ligands that have been studied are amines and phosphines (ref). A ligand exchange reaction in which tributylphosphine ligands were displaced by primary alkylamine ligands on chloride terminated CdSe dots has been reported. Stoichiometry changes were monitored using proton and phosphorus NMR.
Photoluminescence properties were also observed to change with ligand moiety. The amine bound dots had significantly higher photoluminescent
quantum yields than the phosphine bound dots. ==Applications==