The photochemical instability of CdSe nanocrystals coated by hydrophilic thiols was studied nondestructively and systematically in water. The results revealed that the photochemical instability of the nanocrystals actually included three distinguishable processes, namely the photocatalytic oxidation of the thiol ligands on the surface of nanocrystals, the photooxidation of the nanocrystals, and the precipitation of the nanocrystals. At first, the thiol ligands on the surface of a nanocrystal were gradually photocatalytically oxidized using the CdSe nanocrystal core as the photocatalyst. This photocatalytic oxidation process was observed as a zero-order reaction in terms of the concentration of the free thiols in the solution. The photogenerated holes in a nanocrystal were trapped onto the thiol ligands bound on the surface of the nanocrystal, which initiated the photooxidation of the ligands and protected the nanocrystal from any photooxidation. After nearly all of the thiol ligands on the surface of the nanocrystals were converted into disulfides, the system underwent several different pathways. If the disulfides were soluble in water, then all of the disulfides fell into the solution at the end of this initial process, and the nanocrystals precipitated out of the solution without much variation over their size and size distribution. When the disulfides were insoluble in water, they likely formed a micelle-like structure around the nanocrystal core and kept it soluble in the solution. In this case, the nanocrystals only precipitated after severe oxidation, which took a long period of time. If the system contained excess free thiol ligands, they replaced the photochemically generated disulfides and maintained the stability and solubility of the nanocrystals. The initiation stage of the photooxidation of CdSe nanocrystals themselves increased as the thickness and packing density of the ligand shell increased. This was explained by considering the ligand shell on the surface of a nanocrystal as the diffusion barrier of the oxygen species from the bulk solution into the interface between the nanocrystal and the surface ligands. Experimental results clearly indicated that the initiation stage of the photooxidation was not caused by the chemical oxidation of the system kept in air under dark conditions or the hydrolysis of the cadmium-thiol bonds on the surface of the nanocrystals, both of which were magnitudes slower than the photocatalytic oxidation of the surface ligands if they occurred at all. The results described in this contribution have already been applied for designing new types of thiol ligands which dramatically improved the photochemical stability of CdSe nanocrystals with a ligand shell that is as thin as approximately 1 nm.
A method, pseudo steady-state titration, is introduced for determining the precipitation pH of nanocrystals coated by electron-donating ligands. CdSe nanocrystals coated with hydrophilic deprotonated thiol (thiolate) ligands were studied systematically. For comparison, CdTe and CdS nanocrystals coated with the same types of ligands were also examined. The results show that the precipitation of the nanocrystals is caused by the dissociation of the nanocrystal-ligand coordinating bonds from the nanocrystal surface. The ligands are removed from the surface due to protonation in a relatively low pH range, between 2 and 7 depending on the size, approximately within the quantum confinement size regime, and chemical composition (band gap) of the nanocrystals. In contrast, the redispersion of the nanocrystals was found to be solely determined by the deprotonation of the ligands. The size-dependent dissociation pH of the ligands was tentatively used as a means for determining the size-dependent free energy associated with the formation of a nanocrystal-ligand coordinating bond.
Amine ligands were identified to bond on the surface of CdSe nanocrystals in a dynamic fashion under elevated temperatures in the reproducible growth domain of the specific designed growth reactions. The surface ligand dynamics was found to strongly depend on the growth temperature, the ligand concentration, and the ligand chain length. The strong chain-length dependence was originated from the interligand interactions in the ligand monolayer of a nanocrystal, provided fatty amines being weak ligands for CdSe nanocrystals. When the growth reaction was above the boiling point of an amine ligand, the surface ligand dynamics was violent, a quasi-gas-phase state, indicated by strong temperature-dependent and fast growth rates of the nanocrystals. Approximately below its boiling point, a significantly weak temperature dependence of the growth rate of the nanocrystals associated with the quasi-liquid state of the surface ligands was observed. A direct result of studying the surface ligand dynamics of this well-established nanocrystal system was the formation of high-quality CdSe nanocrystals under much reduced temperature, 150 degrees C, in comparison to the standard 250-350 degrees C temperature range. This was achieved by using fatty amines with a short hydrocarbon chain at a low ligand concentration in the solution. Preliminary results indicate that a similar temperature (160 degrees C) also worked for the growth of InP nanocrystals.
Efficient photoluminescence ͑PL͒ up-conversion has been observed in colloidal CdTe quantum dots with an energy gain of as high as 360 meV. Compared with the normal PL, the peak energy of this up-converted PL ͑UCPL͒ shows a redshift of about 80 meV, and the corresponding radiative lifetime becomes nearly twice as long. This UCPL is attributed to the carrier recombination involving surface states mainly through a thermal excitation process.
CdTe quantum dots have unique characteristics that are promising for applications in photoluminescence, photovoltaics or optoelectronics. However, wide variations of the reported quantum yields exist and the influence of ligand-surface interactions that are expected to control the excited state relaxation processes remains unknown. It is important to thoroughly understand the fundamental principles underlying these relaxation processes to tailor the QDs properties to their application. Here, we systematically investigate the roles of the surface atoms, ligand functional groups and solvent on the radiative and non-radiative relaxation rates. Combining a systematic synthetic approach with X-ray photoelectron, quantitative FT-IR and time-resolved visible spectroscopies, we find that CdTe QDs can be engineered with average radiative lifetimes ranging from nanoseconds up to microseconds. The non-radiative lifetimes are anticorrelated to the radiative lifetimes, although they show much less variation. The density, nature and orientation of the ligand functional groups and the dielectric constant of the solvent play major roles in determining charge carrier trapping and excitonic relaxation pathways. These results are used to propose a coupled dependence between hole-trapping on Te atoms and strong ligand coupling, primarily via Cd atoms, that can be used to engineer both the radiative and non-radiative lifetimes.
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