Charge transfer dynamics in fully operational dye sensitised solar cells consisting of an electrolyte or organic spiroOMeTAD in contact with a highly porous electrodeposited ZnO film sensitised with a monolayer of the indoline dye DN216 were observed using ultrafast transient absorption spectroscopy. From the temporal evolution of spectral signatures assigned with the help of spectroelectrochemical experiments to the population and depopulation of initial, transient and final states, a model was completed for the multistep injection of photoexcited electrons from the molecular absorber to the ZnO acceptor. Injection was found to occur via three different paths with three characteristic rates: directly from the dye's lowest unoccupied molecular orbital into the ZnO conduction band (200 fs) and via intermediate molecular dominated and surface dominated hybrid states (2 ps and 10 ps, respectively).
Porous ZnO/EosinY films have been electrochemically deposited by oxygen reduction in the presence of a zinc salt from EosinY-containing aqueous solutions, with either chloride or perchlorate as the counter anion. EosinY was removed and the films were sensitised by D149. These electrodes were used for dye-sensitised solar cells (DSCs), and charge transport in the porous network was studied by intensity modulated current/voltage spectroscopy (IMVS/IMPS) and electrochemical impedance spectroscopy (EIS) under illumination. Doping of ZnO during the electrodeposition could be proven by changes in the charge transport in ZnO and could be shown to occur when chloride was used as the counter ion. By using perchlorate as the counter ion, on the other hand, a more reproducible occupation of trap levels was obtained at, however, slightly lower voltages in DSCs whose origin is discussed in detail.
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