Water Effects on Colloidal Semiconductor Nanocrystals: Correlation of Photophysics and Photochemistry.

With high-quality CdSe/CdS core/shell nanocrystals as the main model system and under a controlled atmosphere, responses of photoexcited semiconductor nanocrystals to two active species (water and/or oxygen) in an ambient environment are studied systematically. Under photoexcitation, although high-quality semiconductor nanocrystals in either thin solid films or various solutions have a near-unity photoluminescence quantum yield, there is still a small probability (∼10-5 per photon absorbed) to be photoreduced by the water molecules efficiently accumulated in the highly hydrophilic nanocrystal-ligands interface. The resulting negatively charged nanocrystals are the starting point of most photophysical variations, and the hydroxyl radical─key photo-oxidation product of water─plays the main role for initiating various photochemical processes. Depending on the supplementation of water to the interface, accessibility to oxygen, photoirradiation power, type of matrices, type of measurement schemes, and solubility of nanocrystals in the solution, various photophysical/photochemical phenomena─either reported or not reported in the literature─are reproducibly observed. Results confirm that photophysical properties and photochemical reactions can be well-correlated, offering a unified and unique basis for fundamental studies and the design of processing techniques in industry.