Laurence M. Peter

Dye-Sensitized Solar Cells Based on Oriented TiO2 Nanotube Arrays: Transport, Trapping, and Transfer of Electrons

Dye-sensitized solar cells fabricated using ordered arrays of titania nanotubes (tube lengths 5, 10, and 20 microm) grown on titanium have been characterized by a range of experimental methods. The collection efficiency for photoinjected electrons in the cells is close to 100% under short circuit conditions, even for a 20 microm thick nanotube array. Transport, trapping, and back transfer of electrons in the nanotube cells have been studied in detail by a range of complementary experimental techniques. Analysis of the experimental results has shown that the electron diffusion length (which depends on the diffusion coefficient and lifetime of the photoinjected electrons) is of the order of 100 microm in the titania nanotube cells. This is consistent with the observation that the collection efficiency for electrons is close to 100%, even for the thickest (20 microm) nanotube films used in the study. The study revealed a substantial discrepancy between the shapes of the electron trap distributions measured experimentally using charge extraction techniques and those inferred indirectly from transient current and voltage measurements. The discrepancy is resolved by introduction of a numerical factor to account for non-ideal thermodynamic behavior of free electrons in the nanostructured titania.

Dye-sensitized nanocrystalline solar cells

The basic physical and chemical principles behind the dye-sensitized nanocrystalline solar cell (DSC: also known as the Grätzel cell after its inventor) are outlined in order to clarify the differences and similarities between the DSC and conventional semiconductor solar cells. The roles of the components of the DSC (wide bandgap oxide, sensitizer dye, redox electrolyte or hole conductor, counter electrode) are examined in order to show how they influence the performance of the system. The routes that can lead to loss of DSC performance are analyzed within a quantitative framework that considers electron transport and interfacial electron transfer processes, and strategies to improve cell performance are discussed. Electron transport and trapping in the mesoporous oxide are discussed, and a novel method to probe the electrochemical potential (quasi Fermi level) of electrons in the DSC is described. The article concludes with an assessment of the prospects for future development of the DSC concept.

A novel charge extraction method for the study of electron transport and interfacial transfer in dye sensitised nanocrystalline solar cells

Abstract A novel charge extraction method has been developed to study the transport, trapping and back reaction of photogenerated electrons in dye sensitised nanocrystalline cells (Gratzel cells). The cell is illuminated at open circuit until a steady state is reached in which the rates of photogeneration and of back reaction of electrons with tri-iodide are equal. The illumination is then interrupted, and the electron density is allowed to decay for a given time in the dark before short circuiting the cell using a solid state switch. For high efficiency cells, the integrated current measured at short circuit corresponds closely to the remaining electronic charge in the film. Small corrections are required to account for back reaction and substrate charging. The delay time between interruption of the illumination and short circuit charge extraction is varied systematically to follow the decay of electron concentration. Analysis of the time dependence of the electron charge indicates that the back reaction of electrons with I 3 − is second order in electron density, which is consistent with the formation of I 2 −. as an intermediate. Simultaneous measurement of the charge and photovoltage decay curves shows that the density of trap states decreases exponentially with trap depth.

Electron transport and back reaction in dye sensitised nanocrystalline photovoltaic cells

The transport and back reaction of electrons in dye sensitised nanocrystalline solar cells (DSNC) has been studied by frequency resolved optical perturbation techniques. Intensity modulated photocurrent spectroscopy (IMPS) has been used to obtain values of the electron diffusion coefficient, Dn, as a function of illumination intensity. It was found that Dn increased with intensity (Dn∝I−0.5). Intensity-modulated photovoltage spectroscopy (IMVS) has been used to measure the electron lifetime, τn, which is determined by the rate of back reaction with I3− ions in the electrolyte. It was found that τn decreased with light intensity (τn∝I−0.5). The electron diffusion length, Ln=(Dnτn)1/2, is therefore only weakly dependent on light intensity. The values of Ln were used to calculate the theoretical IPCE of the cell. Experimental measurements confirmed the prediction that the IPCE should remain almost constant over five orders of magnitude of light intensity. Possible reasons for the opposite trends in Dn and τn are discussed and related to the fundamental processes taking place in the DSNC.

Towards sustainable photovoltaics: the search for new materials

The opportunities for photovoltaic (PV) solar energy conversion are reviewed in the context of projected world energy demands for the twenty-first century. Conventional single-crystal silicon solar cells are facing increasingly strong competition from thin-film solar cells based primarily on polycrystalline absorber materials, such as cadmium telluride (CdTe) and copper indium gallium diselenide (CIGS). However, if PVs are to make a significant contribution to satisfy global energy requirements, issues of sustainability and cost will need to be addressed with increased urgency. There is a clear need to expand the range of materials and processes that is available for thin-film solar cell manufacture, placing particular emphasis on low-energy processing and sustainable non-toxic raw materials. The potential of new materials is exemplified by copper zinc tin sulphide, which is emerging as a viable alternative to the more toxic CdTe and the more expensive CIGS absorber materials.

Kinetics of oxygen evolution at α-Fe2O3 photoanodes: a study by photoelectrochemical impedance spectroscopy

Photoelectrochemical Impedance Spectroscopy (PEIS) has been used to characterize the kinetics of electron transfer and recombination taking place during oxygen evolution at illuminated polycrystalline α-Fe(2)O(3) electrodes prepared by aerosol-assisted chemical vapour deposition from a ferrocene precursor. The PEIS results were analysed using a phenomenological approach since the mechanism of the oxygen evolution reaction is not known a priori. The results indicate that the photocurrent onset potential is strongly affected by Fermi level pinning since the rate constant for surface recombination is almost constant in this potential region. The phenomenological rate constant for electron transfer was found to increase with potential, suggesting that the potential drop in the Helmholtz layer influences the activation energy for the oxygen evolution process. The PEIS analysis also shows that the limiting factor determining the performance of the α-Fe(2)O(3) photoanode is electron-hole recombination in the bulk of the oxide.

Kinetics of light-driven oxygen evolution at alpha-Fe2O3 electrodes.

The kinetics of light-driven oxygen evolution at polycrystalline alpha-Fe2O3 layers prepared by aerosol-assisted chemical vapour deposition has been studied using intensity modulated photocurrent spectroscopy (IMPS). Analysis of the frequency-dependent IMPS response gives information about the competition between the 4-electron oxidation of water by photogenerated holes and losses due to electron-hole recombination via surface states. The very slow kinetics of oxygen evolution indicates the presence of a kinetic bottleneck in the overall process. Surface treatment of the alpha-Fe2O3 with dilute cobalt nitrate solution leads to a remarkable improvement in the photocurrent response, but contrary to expectation, the results of this study show that this is not due to catalysis of hole transfer but is instead the consequence of almost complete suppression of surface recombination.

Thermodynamic aspects of the synthesis of thin-film materials for solar cells.

A simple and useful thermodynamic approach to the prediction of reactions taking place during thermal treatment of layers of multinary semiconductor compounds on different substrates has been developed. The method, which uses the extensive information for the possible binary compounds to assess the stability of multinary phases, is illustrated with the examples of Cu(In,Ga)Se(2) and Cu(2)ZnSnSe(4) as well as other less-studied ternary and quaternary semiconductors that have the potential for use as absorbers in photovoltaic devices.

Intensity dependence of the electron diffusion length in dye-sensitised nanocrystalline TiO2 photovoltaic cells

Abstract The efficiency of dye-sensitised nanocrystalline solar cells is limited in part by the back reaction of photo-injected electrons with tri-iodide ions present in the electrolyte. Competition between this back reaction and the collection of electrons by diffusion to the substrate contact can be described in terms of the electron diffusion length Ln=(Dnτn)1/2, where Dn is the electron diffusion coefficient and τn is the electron lifetime determined by the rate of reaction of electrons with tri-iodide. Dn and τn have been determined over five orders of magnitude of illumination intensity using intensity-modulated photocurrent and intensity-modulated photovoltage spectroscopy. It has been found that τn decreases with light intensity, whereas Dn increases. As a consequence, the electron diffusion coefficient Ln is only weakly intensity dependent, and the incident photon to current conversion efficiency (IPCE) is predicted to be almost independent of intensity. The experimental IPCE agrees well with the predicted values. The results suggest that the kinetics of the back reaction of electrons with tri-iodide couple may be second order in electron density.

Energetics and kinetics of light-driven oxygen evolution at semiconductor electrodes: the example of hematite

Light-driven water-splitting (photoelectrolysis) at semiconductor electrodes continues to excite interest as a potential route to produce hydrogen as a sustainable fuel, but surprisingly little is known about the kinetics and mechanisms of the reactions involved. Here, some basic principles of semiconductor photoelectrochemistry are reviewed with particular emphasis on the effects of slow interfacial electron transfer at n-type semiconductors in the case of light-driven oxygen evolution. A simple kinetic model is outlined that considers the competition between interfacial transfer of photogenerated holes and surface recombination. The model shows that, if interfacial charge transfer is very slow, the build-up of holes at the surface will lead to substantial changes in the potential drop across the Helmholtz layer, leading to non-ideal behavior (Fermi level pinning). The kinetic model is also used to predict the response of photoanodes to chopped illumination and to periodic perturbations of illumination and potential. Recent experimental results obtained for α-Fe2O3 (hematite) photoanodes are reviewed and interpreted within the framework of the model.