Thin films of silicon-doped Fe2O3 were deposited by APCVD (atmospheric pressure chemical vapor deposition) from Fe(CO)5 and TEOS (tetraethoxysilane) on SnO2-coated glass at 415 degrees C. HRSEM reveals a highly developed dendritic nanostructure of 500 nm thickness having a feature size of only 10-20 nm at the surface. Real surface area determination by dye adsorption yields a roughness factor of 21. XRD shows the films to be pure hematite with strong preferential orientation of the [110] axis vertical to the substrate, induced by silicon doping. Under illumination in 1 M NaOH, water is oxidized at the Fe2O3 electrode with higher efficiency (IPCE = 42% at 370 nm and 2.2 mA/cm2 in AM 1.5 G sunlight of 1000 W/m2 at 1.23 VRHE) than at the best reported single crystalline Fe2O3 electrodes. This unprecedented efficiency is in part attributed to the dendritic nanostructure which minimizes the distance photogenerated holes have to diffuse to reach the Fe2O3/electrolyte interface while still allowing efficient light absorption. Part of the gain in efficiency is obtained by depositing a thin insulating SiO2 interfacial layer between the SnO2 substrate and the Fe2O3 film and a catalytic cobalt monolayer on the Fe2O3 surface. A mechanistic model for water photooxidation is presented, involving stepwise accumulation of four holes by two vicinal iron or cobalt surface sites.

Photoanodes consisting of nanostructured hematite prepared by atmospheric pressure chemical vapor deposition (APCVD) have previously set a benchmark for solar water splitting. Here, we fully investigate this promising system by varying critical synthetic parameters and probing the photoanode performance to determine the major factors that influence operation. By varying the film thickness, we show film growth to be linear with an incubation time. We find no concern with electron transport for films up to 600 nm, but a higher recombination rate of photogenerated carriers in the hematite near the interface with the fluorine-doped tin oxide, as compared to the bulk section of the film. The mechanism for the formation of the thin film’s nanoporous dendritic structure is discussed on the basis of the results from varying the substrate growth temperate. The observed feature sizes of the film are found to depend strongly on this temperature and the presence of silicon dopant precursor (TEOS). Raman and Mössbauer experiments reveal how temperature and doping affect the crystallinity and ultimately the photoperformance. We also use impedance spectroscopy to find evidence for an unusually high donor density, which allows the formation of a space-charge field inside the nanosized features of the polycrystalline hematite photoanode.

Thin, silicon-doped nanocrystalline alpha-Fe2O3 films have been deposited on F-doped SnO2 substrates by ultrasonic spray pyrolysis and chemical vapor deposition at atmospheric pressure. The photocatalytic activity of these films with regard to photoelectrochemical water oxidation was measured at pH 13.6 under simulated AM 1.5 global sunlight. The photoanodes prepared by USP and APCVD gave 1.17 and 1.45 mA/cm2, respectively, at 1.23 V vs RHE. The morphology of the alpha-Fe2O3 was strongly influenced by the silicon doping, decreasing the feature size of the mesoscopic film. The silicon-doped alpha-Fe2O3 nano-leaflets show a preferred orientation with the (001) basal plane normal to the substrate. The best performing photoanode would yield a solar-to-chemical conversion efficiency of 2.1% in a tandem device using two dye-sensitized solar cells in series.

Carbon black was employed as the catalyst for triiodide reduction on fluorine-doped tin oxide glass substrates ͑FTO-glass͒ used as counter electrodes in platinum-free dye-sensitized solar cells. The fill factors were strongly dependent on the thickness of the carbon layer, and the light energy conversion efficiency also increased up to a thickness of 10 m. The charge-transfer resistance ͑R ct ͒ of the carbon counter electrode decreased with the thickness of the carbon layer. The R ct for the thicker carbon layer is less than three times that for the platinized FTO-glass. The highest cell efficiency was 9.1% under 100 mW cm −2 light intensity ͑1 sun AM 1.5 light, J sc = 16.8 mA cm −2 , V oc = 789.8 mV, fill factor = 0.685͒.