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The application of small perturbation frequency techniques to solar cells provides a great deal of information in terms of capacitive and resistive processes that are related to the photophysical mechanisms that lie at the basis of the photovoltaic operation. These methods can be exhaustively exploited to determine bulk and contact effects in the solar cells, and henceforth improve and optimize materials and interfaces. For photovoltaic devices, the main effects of interest in impedance spectroscopy are the capacitive charge storage and the resistive processes of transport and recombination. The combination of these parameters provides important information about properties such as conductivity, diffusion length and carrier lifetime. In this chapter, we provide an extensive review of the present status of knowledge about these aspects of solar cell operation for organic solar cells and hybrid organic–inorganic perovskite solar cells. We describe an exhaustive characterization of capacitive processes, including dielectric relaxation processes, and examine the interpretation of transport and recombination based on a variety of experimental techniques.

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