Semiconductors group

Abstract:

Linear π-conjugated oligomers have been widely investigated, but the behavior of the corresponding cyclic oligomers is poorly understood, despite the recent synthesis of π-conjugated macrocycles such as [n]cycloparaphenylenes and cyclo[n]thiophenes. Here we present an efficient template-directed synthesis of a π-conjugated butadiyne-linked cyclic porphyrin hexamer directly from the monomer. Small-angle X-ray scattering data show that this nanoring is shape-persistent in solution, even without its template, whereas the linear porphyrin hexamer is relatively flexible. The crystal structure of the nanoring-template complex shows that most of the strain is localized in the acetylenes; the porphyrin units are slightly curved, but the zinc coordination sphere is undistorted. The electrochemistry, absorption, and fluorescence spectra indicate that the HOMO-LUMO gap of the nanoring is less than that of the linear hexamer and less than that of the corresponding polymer. The nanoring exhibits six one-electron reductions and six one-electron oxidations, most of which are well resolved. Ultrafast fluorescence anisotropy measurements show that absorption of light generates an excited state that is delocalized over the whole π-system within a time of less than 0.5 ps. The fluorescence spectrum is amazingly structured and red-shifted. A similar, but less dramatic, red-shift has been reported in the fluorescence spectra of cycloparaphenylenes and was attributed to a high exciton binding energy; however the exciton binding energy of the porphyrin nanoring is similar to those of linear oligomers. Quantum-chemical excited state calculations show that the fluorescence spectrum of the nanoring can be fully explained in terms of vibronic Herzberg-Teller (HT) intensity borrowing.

Abstract:

High-performance dye-sensitized solar cells are usually fabricated using nanostructured TiO(2) as a thin-film electron-collecting material. However, alternative metal-oxides are currently being explored that may offer advantages through ease of processing, higher electron mobility, or interface band energetics. We present here a comparative study of electron mobility and injection dynamics in thin films of TiO(2), ZnO, and SnO(2) nanoparticles sensitized with Z907 ruthenium dye. Using time-resolved terahertz photoconductivity measurements, we show that, for ZnO and SnO(2) nanoporous films, electron injection from the sensitizer has substantial slow components lasting over tens to hundreds of picoseconds, while for TiO(2), the process is predominantly concluded within a few picoseconds. These results correlate well with the overall electron injection efficiencies we determine from photovoltaic cells fabricated from identical nanoporous films, suggesting that such slow components limit the overall photocurrent generated by the solar cell. We conclude that these injection dynamics are not substantially influenced by bulk energy level offsets but rather by the local environment of the dye-nanoparticle interface that is governed by dye binding modes and densities of states available for injection, both of which may vary from site to site. In addition, we have extracted the electron mobility in the three nanoporous metal-oxide films at early time after excitation from terahertz conductivity measurements and compared these with the time-averaged, long-range mobility determined for devices based on identical films. Comparison with established values for single-crystal Hall mobilities of the three materials shows that, while electron mobility values for nanoporous TiO(2) films are approaching theoretical maximum values, both early time, short distance and interparticle electron mobility in nanoporous ZnO or SnO(2) films offer considerable scope for improvement.

Abstract:

Monodisperse DNA-templated one dimensional dye assemblies have been constructed in which the energy transfer can be directed. Fluorescence experiments suggest an optimum transfer efficiency for stacks of 30 bases long.

Abstract:

We have investigated the charge photogeneration dynamics at the interface formed between single-walled carbon nanotubes (SWNTs) and poly(3-hexylthiophene) (P3HT) using a combination of femtosecond spectroscopic techniques. We demonstrate that photoexcitation of P3HT forming a single molecular layer around a SWNT leads to an ultrafast (∼430 fs) charge transfer between the materials. The addition of excess P3HT leads to long-term charge separation in which free polarons remain separated at room temperature. Our results suggest that SWNT-P3HT blends incorporating only small fractions (1%) of SWNTs allow photon-to-charge conversion with efficiencies comparable to those for conventional (60:40) P3HT-fullerene blends, provided that small-diameter tubes are individually embedded in the P3HT matrix.