Device Modelling of Perovskite Solar Cells

This thesis is primarily concerned with the electrical characterization and modelling of perovskite solar cells. Perovskite cells are a new player in the photovoltaic arena with several intriguing properties. One of these is the presence of intrinsic mobile ions which make these semiconductors simultaneously ionic conductors at room temperature. The presence of mobile ions is significant in that it leads to a number of transient behaviours in optoelectronic measurements, including nominally simple current-voltage measurements where the phenomena are broadly labelled as aspects of “I-V hysteresis”. The first two-thirds of this thesis describes our work on extended drift-diffusion models which incorporate the presence of mobile ions into the conventional equations of semiconductor physics. These allow us to uncover mechanistic explanations for a variety of transient behaviours which are broadly caused by coupling between electronic and ion dynamics. The first third (Chapter 2) deals with hysteresis in the form of rate-dependent I-V sweeps: a selection of unusual measurements of this type is presented including a temporary enhancement in open-circuit voltage following prolonged periods of negative bias, dramatically S-shaped current-voltage sweeps, decreased current extraction following positive biasing or “inverted hysteresis”, and non-monotonic transient behaviours in the dark and the light. This initial study is supplemented with a more in-depth investigation of inverted hysteresis and its correlation with band-alignment. The second third (Chapter 3) delves deeper into electrical characterization with a first-principles study of electrical impedance spectroscopy. We focus on accounting for features in the measured capacitance spectrum (sufficient for a full account of the total impedance due to the Kramers-Kronig relations) of standard-structure (non-inverted) perovskite cells. Here our models make clear the necessity of distinguishing fundamental contributions to the measured capacitance due to charging, from those due to currents delayed by slow processes such as ion migration. With this distinction clearly established we provide a detailed account of all the major features observed in impedance measurements of these cells, including the exotic and previously puzzling appearance of giant photo-induced capacitance, loop features and negative capacitance. The final part of this thesis in Chapter 4 concerns the integration of perovskite cells into tandem arrangements with a partner such as the crystalline silicon cell. Of relevance to any thin-film solar cell, and to 4-terminal tandem cells in particular, is the specifications of its transparent conductor layers. We analyze transparent conductor requirements under different regimes of metallization (the addition of metallic bus-bars or fingers). Here a key parameter is the minimal achievable wire width, which dictates the necessary trade-off between transparency and conductivity in the underlying transparent conductor. We identify 30 μm as a critical width below which many emerging transparent conducting layers such as carbon nanotubes and graphene become competitive with state-of-the-art transparent conductive oxides such as ITO for a stand-alone perovskite cell. We also discuss a novel strategy for integrating perovskite and Si cells into a single monolithic structure without the need for a tunnel junction or recombination layer. This is identified as being possible due to the presence of interfacial sub-gap states which can facilitate high-conductivity ohmic contact between TiO2 and p-type Si, and has significant advantages in terms of reducing optical losses and processing steps.