A new design of dye-sensitized solar cells involves colloidal semiconductor quantum dots that serve as antennas, funneling absorbed light to the charge separating dye molecules via nonradiative energy transfer. The colloidal quantum dot donors are incorporated into the solid titania electrode resulting in high energy transfer efficiency and significant improvement of the cell stability. This design practically separates the processes of light absorption and charge carrier injection, enabling us to optimize each of these separately. Incident photon-to-current efficiency measurements show a full coverage of the visible spectrum despite the use of a red absorbing dye, limited only by the efficiency of charge injection from the dye to the titania electrode. Time resolved luminescence measurements clearly relate this to Forster resonance energy transfer from the quantum dots to the dye. The presented design introduces new degrees of freedom in the utilization of quantum dot sensitizers for photovoltaic cells. In particular, it opens the way toward the utilization of new materials whose band offsets do not allow direct charge injection.
In this article, the physics of FRET is demonstrated for an architecture of dye‐sensitized solar cells, in which the quantum dot “antennas” that serve as donors are incorporated into the solid titania electrode, providing isolation from electrolyte quenching, and potentially increased photostability. The energy transferred to the dye acceptor from the quantum dot donor, in addition to the direct light absorption by the dye, finally induce dye excitation and electron injection to the metal oxide semiconductor electrode. We use time‐resolved photoluminescence measurements to directly show achievement of FRET efficiencies of up to 70%, corresponding to over 80% internal quantum efficiency when considering radiative energy transfer as well. The various parameters governing the FRET efficiency and the requirements for high efficiency FRET‐based cells are discussed. Since both buried donors inside the electrode and donors solubilized in the electrolyte have both been shown to achieve high energy transfer efficiencies, and as the two methods take advantage of different available volumes of the electrode to introduce donors providing the excess absorption, synergy of the two methods is highly promising for achieving panchromatic absorption within a thin electrode.
Preparation of pure and homogenous site specifically single- and double-labelled biopolymers suitable for spectroscopic determination of structural characteristics is a major current challenge in biopolymers chemistry. In particular, proper analysis of single-molecule Förster resonance energy transfer measurements is based on the spectral characteristics of the probes. Heterogeneity of any of the probes may introduce errors in the analysis, and hence, care must be taken to avoid preparation of inhomogeneous labelled biopolymer samples. When we prepared samples of Escherichia coli adenylate kinase (AK) mutants labelled with either Atto 488 or Atto 647N, the products were spectrally inhomogeneous and the composition of the mixture changed gradually over time. We show here that the inhomogeneity was not a result of variation in the dye interaction with neighbouring side chains. Rather, the slow drift of the spectral characteristics of the probes was a characteristic of an irreversible chemical transformation probably due to the hydrolysis of the succinimide ring of the attached dye into its succinamic acid form. Overnight incubation of the labelled protein in mild basic solution accelerated the interconversion, yielding homogeneous labelled samples. Using this procedure, we obtained stable homogenous AK mutant labelled at residues 142 and 188.
Single molecule studies make possible the characterization of molecular processes and the identification of biophysical sub‐populations that are not accessible through ensemble studies. We describe tethered particle motion, a method that allows one to study single molecules in their natural form without having to apply any external forces. The method combines darkfield microscopy with a metal nano‐bead. It permits the study of the biophysical properties of the tethered particles, as well as protein–DNA interactions. The method is not suitable for in vivo studies, and we therefore describe two other methods that are appropriate for live‐cell imaging
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