ABSTRACT
We report the direct and unambiguous determination of electron transfer rates and efficiencies from PbSe quantum dots (QDs) to mesoporous SnO2 films. We monitor the time-dependent electron density within the oxide with picosecond time resolution using Terahertz spectroscopy, following optical excitation of the QDs using a femtosecond laser pulse. QD-oxide electron transfer occurs with efficiencies of â¼2% in our samples under 800 nm pumping with a marked dependence on QD size, ranging from â¼100 ps injection times for the smallest, â¼2 nm diameter QDs, to â¼1 ns time scale for â¼7 nm QDs. The size-dependent electron transfer rates are modeled within the framework of Marcus theory and the implications of the results for device design are discussed.
ABSTRACT
In aqueous solutions at room temperature, poly( N-methyl-2-vinyl pyridinium iodide)- block-poly(ethylene oxide), P2MVP 38- b-PEO 211 and poly(acrylic acid)- block-poly(isopropyl acrylamide), PAA 55- b-PNIPAAm 88 spontaneously coassemble into micelles, consisting of a mixed P2MVP/PAA polyelectrolyte core and a PEO/PNIPAAm corona. These so-called complex coacervate core micelles (C3Ms), also known as polyion complex (PIC) micelles, block ionomer complexes (BIC), and interpolyelectrolyte complexes (IPEC), respond to changes in solution pH and ionic strength as their micellization is electrostatically driven. Furthermore, the PNIPAAm segments ensure temperature responsiveness as they exhibit lower critical solution temperature (LCST) behavior. Light scattering, two-dimensional 1H NMR nuclear Overhauser effect spectrometry, and cryogenic transmission electron microscopy experiments were carried out to investigate micellar structure and solution behavior at 1 mM NaNO 3, T = 25, and 60 degrees C, that is, below and above the LCST of approximately 32 degrees C. At T = 25 degrees C, C3Ms were observed for 7 < pH < 12 and NaNO 3 concentrations below approximately 105 mM. The PEO and PNIPAAm chains appear to be (randomly) mixed within the micellar corona. At T = 60 degrees C, onion-like complexes are formed, consisting of a PNIPAAm inner core, a mixed P2MVP/PAA complex coacervate shell, and a PEO corona.