Prof Laura Herz FRS

Abstract:

An understanding of aggregation effects in semiconducting polymers is essential for their use in optoelectronic devices; however, the dynamic evolution of such interchain states is not well understood. Here, we have investigated a blend of semiconducting poly(3-hexylthiophene) (P3HT) with an electronically inert ultrahigh-molecular-weight polyethylene (UHMW-PE) matrix that is shown to allow precise control over the extent to which the P3HT chains aggregate. We determined the singlet exciton population within isolated and aggregated P3HT regions using femtosecond time-resolved photoluminescence measurements and found a strong ultrafast decay pathway in the aggregated case only. Comparison of the emission from the two lowest vibronic bands demonstrates a changeover from an initial vibrationally "hot" photoexcited state to a geometrically relaxed aggregate state within ∼13 ps, corresponding to time scales for torsional relaxation in these materials. We conclude that formation of an aggregate excited state in conjugated polymers is mediated by vibrational relaxation from a low-symmetry to a high-symmetry ordered state for the ensemble. © 2010 American Chemical Society.

Abstract:

We have investigated the anisotropic dynamic dielectric response of aligned and well-isolated single-walled carbon nanotubes using optical-pump terahertz (THz)-probe techniques. The polarization anisotropy measurements demonstrate that the THz radiation interacts only with radiation polarized parallel to the nanotubes which have been selectively excited by a polarized pump pulse thus allowing controlled THz polarization to be achieved from unaligned nanotubes. © 2010 The American Physical Society.

Abstract:

We have used optical-pump terahertz-probe spectroscopy to explore the photoinduced conductivity dynamics in mesoporous anatase TiO2 films, commonly employed as the electron-transporting electrode in dye-sensitized solar cells. We find an intrinsic mobility value of 0.1 cm2/(V s) and diffusion length of ∼20 nm for electron motion through the TiO2 matrix. The photoconductivity dynamics in TiO2 films, both before and after sensitization with a ruthenium bypyridyl complex termed Z907, were examined in order to study the charge injection, trapping, and recombination time scales. We observe a biphasic charge injection from Z907, with a fast sub-500 fs component, followed by a slower 70-200 ps component. This is followed by photoconductivity decay over the first few nanoseconds, predominantly reflecting charge carrier trapping. In addition, we have utilized terahertz spectroscopy to investigate the influence of treating the titania surface with TiCl4 on early-time charge dynamics. In the solar cells, surface treatment of the mesoporous TiO2 with TiCl4 is critical to enable efficient operation. Here, we find that neither early-time charge mobility nor charge injection rate or decay times are significantly affected by the treatment, which suggests that it may, instead, have an impact on phenomena occurring on longer time scales. © 2010 American Chemical Society.