Time resolved absorption spectroscopy has been used to study photoinduced electron injection and charge recombination in Zn-porphyrin sensitized nanostructured TiO(2) electrodes. The electron transfer dynamics is correlated to the performance of dye sensitized solar cells based on the same electrodes. We find that the dye/semiconductor binding can be described with a heterogeneous geometry where the Zn-porphyrin molecules are attached to the TiO(2) surface with a distribution of tilt angles. The binding angle determines the porphyrin-semiconductor electron transfer distance and charge transfer occurs through space, rather than through the bridge connecting the porphyrin to the surface. For short sensitization times (1 h), there is a direct correlation between solar cell efficiency and amplitude of the kinetic component due to long-lived conduction band electrons, once variations in light harvesting (surface coverage) have been taken into account. Long sensitization time (12 h) results in decreased solar cell efficiency because of decreased efficiency of electron injection.

Solar cells based on conjugated polymer and fullerene blends have been developed as a low-cost alternative to silicon. For efficient solar cells, electron-hole pairs must separate into free mobile charges that can be extracted in high yield. We still lack good understanding of how, why and when carriers separate against the Coulomb attraction. Here we visualize the charge separation process in bulk heterojunction solar cells by directly measuring charge carrier drift in a polymer:fullerene blend with ultrafast time resolution. We show that initially only closely separated (o1 nm) charge pairs are created and they separate by several nanometres during the first several picoseconds. Charge pairs overcome Coulomb attraction and form free carriers on a subnanosecond time scale. Numerical simulations complementing the experimental data show that fast three-dimensional charge diffusion within an energetically disordered medium, increasing the entropy of the system, is sufficient to drive the charge separation process.

Several Zn-porphyrin (ZnP) derivatives were designed to build highly efficient dye-sensitized solar cells (DSC). It was found that solar cell efficiencies normalized for surface coverage (η rel ) are affected by the molecular spacer connecting the porphyrin core to the TiO 2 surface, the sensitization conditions (solvent and time), and, to a lesser extent, the nature of the terminal group of the ZnP. Ultrafast transient absorption spectroscopy shows that electron transfer rates are strongly dependent on spacer and sensitization conditions. To understand this behavior at a molecular level, surface-sensitive vibrational spectroscopy, sum frequency generation (SFG), has been employed to investigate the adsorption geometries of these ZnP derivatives on the TiO 2 surface for the first time. The average tilt angles and adsorption ordering of the ZnP molecules on the TiO 2 surface were measured. A simple linear correlation between adsorption geometry of the adsorbed ZnP molecules, η rel , and the concentration of long-lived electrons in the conduction band of TiO 2 was shown to exist. The more perpendicular the orientation of the adsorbed ZnP (relative to the TiO 2 surface), the higher the concentration of long-lived electrons in the conduction band, which contributes to the increase of photocurrent and solar cell efficiency. This result indicates that the electron transfer between ZnP and TiO 2 occurs "through-space" rather than "through the molecular spacer". It is also revealed that the sensitization solvent (methanol) may affect adsorption geometry and adsorption ordering through coadsorption and modify the electron transfer dynamics and consequently solar cell efficiency. Aggregation effects, which were observed for the longer sensitization times, are also discussed in relation to adsorption geometry and radiationless quenching processes. With the work reported here we demonstrate a novel strategy for DSC material characterization that can lead to design and manufacturing of photoactive materials with predictable and controlled properties.

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In this paper we studied carrier drift dynamics in APFO3:PC61BM solar cells of varied stoichiometry (2:1, 1:1, and 1:4 APFO3:PC61BM) over a wide time range, from subpicoseconds to microseconds with a combination of ultrafast optical electric field probing and conventional transient integrated photocurrent techniques. Carrier drift and extraction dynamics are strongly stoichiometry dependent: the speed of electron or hole drift increases with higher concentration of PC61BM or polymer, respectively. The electron extraction from a sample with 80% PC61BM takes place during hundreds of picoseconds, but slows down to sub-microseconds in a sample with 33% PC61BM. The hole extraction is less stoichiometry dependent: it varies form sub-nanoseconds to tens of nanoseconds when the PC61BM concentration changes from 33% to 80%. The electron extraction rate correlates with the conversion efficiency of solar cells, leading to the conclusion that fast electron motion is essential for efficient charge carrier separation preventing their geminate recombination.