Photo-Gated Charge Transfer of Organized Assemblies of CdSe Quantum Dots

The electronic conductivity of tri-n-octylphosphineoxide (TOPO)-protected CdSe quantum dots (QDs) was studied at the air-water interface using the Langmuir technique within the context of photochemical and photophysical excitation. It was found that, upon photoirradiation with photon energies higher than that of the absorption threshold, the voltammetric currents increased rather substantially with a pair of voltammetric peaks at positive potentials. However, the photoconductivity profiles exhibited a dynamic transition, which was ascribed to the strong affinity of oxygen onto the CdSe surface and the consequent trapping of the photogenerated electrons. The resulting excess of holes led to photocorrosion of the particle cores. The oxygen adsorption and photoetching processes were found to be reversible upon cessation of the photoexcitation. In contrast, only featureless voltammetric responses were observed when the particle monolayers were deposited onto the electrode surface and the film conductance was measured in a vacuum (the overall profiles were analogous to that of a Coulomb blockade). A comparative study was also carried out with a CdSe dropcast thick film immersed in acetonitrile, where the photoconductivity profiles were reversible and almost linear. The latter was attributed to the separation of photogenerated electrons and holes which were subsequently collected at the electrodes under voltammetric control. In the dropcast system, the oxygen effects were minimal which was ascribed to the acetontrile medium that limited the access to oxygen and thus the particles were chemically intact. These studies suggest that chemical environment plays an important role in the determination of the chemical stability and electronic conductivity of CdSe QD thin films.