Numerous studies have shown that the performance of hematite photoanodes for light-driven water splitting is improved substantially by doping with various metals, including tin. Although the enhanced performance has commonly been attributed to bulk effects such as increased conductivity, recent studies have noted an impact of doping on the efficiency of the interfacial transfer of holes involved in the oxygen evolution reaction. However, the methods used were not able to elucidate the origin of this improved efficiency, which could originate from passivation of surface electron-hole recombination or catalysis of the oxygen evolution reaction. The present study used intensity-modulated photocurrent spectroscopy (IMPS), which is a powerful small amplitude perturbation technique that can de-convolute the rate constants for charge transfer and recombination at illuminated semiconductor electrodes. The method was applied to examine the kinetics of water oxidation on thin solution-processed hematite model photoanodes, which can be Sn-doped without morphological change. We observed a significant increase in photocurrent upon Sn-doping, which is attributed to a higher transfer efficiency. The kinetic data obtained using IMPS show that Sn-doping brings about a more than tenfold increase in the rate constant for water oxidation by photogenerated holes. This result provides the first demonstration that Sn-doping speeds up water oxidation on hematite by increasing the rate constant for hole transfer.
The diffusion length of electrons in high efficiency liquid electrolyte dye-sensitized nanocrystalline solar cells has been investigated using two different approaches. The first method is based on measuring the rise and decay times of the small amplitude photovoltage increment generated by a short laser pulse superimposed on a range of steady-state illumination levels. The advantage of this technique is that it allows the simultaneous measurement of the diffusion coefficient and electron lifetime under identical conditions. In addition to transportcontrolled substrate charging, direct injection of electrons into the substrate from dye adsorbed at the contact interface was observed at the high laser pulse energies required for measurements at high dc photovoltages. The second method involves using intensity-modulated photocurrent and photovoltage spectroscopies (IMPS and IMVS, respectively) to measure the electron diffusion coefficient and electron lifetime at short circuit and open circuit, respectively, as a function of light intensity. The difference between the electron trap occupancies under open-circuit and short-circuit conditions must be accounted for in this case. The diffusion lengths derived from the study are in the range of 40-70 µm, which are at least an order of magnitude greater than the film thickness. This indicates that the electron collection efficiency in the cells is close to 100%.
Nanostructuring has proven to be a successful strategy in overcoming the trade-off between light absorption and hole transport to the solid/electrolyte interface in hematite photoanodes for water splitting. The suggestion that poor electron (majority carrier) collection hinders the performance of nanostructured hematite electrodes has led to the emergence of host-guest architectures in which the absorber layer is deposited onto a transparent high-surface-area electron collector. To date, however, state of the art nanostructured hematite electrodes still outperform their host-guest counterparts, and a quantitative evaluation of the benefits of the host-guest architecture is still lacking. In this paper, we examine the impact of host-guest architectures by comparing nanostructured tin-doped hematite electrodes with hematite nanoparticle layers coated onto two types of conducting macroporous SnO2 scaffolds. Analysis of the external quantum efficiency spectra for substrate (SI) and electrolyte side (EI) illumination reveals that the electron diffusion length in the host-guest electrodes based on an undoped SnO2 scaffold is increased substantially relative to the nanostructured hematite electrode without a supporting scaffold. Nevertheless, electron collection is still incomplete for EI illumination. By contrast, an electron collection efficiency of 100% is achieved by fabricating the scaffold using antimony-doped SnO2, showing that the scaffold conductivity is crucial for the device performance.
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