Fundamentals of perovskite formation for photovoltaics

Perovskite solar cells have become strong contenders in the arena of photovoltaics due to the stunning rise in their efficiency from 3 % to over 20 % in just seven years. In this time, numerous device architectures and thin film deposition methods have been explored. The sequential deposition and anti-solvent methods are among the most widely used for preparing perovskite solar cells.

Optimizing these perovskite deposition processes to tune the perovskite film morphology plays a key role in the race for the highest efficiencies as homogeneity of the film correlates with superior photovoltaic performance. To date, the factors controlling perovskite film formation in various deposition methods and the precise mechanism are little understood. In light of this, the aim of the thesis is to unravel the salient aspects of perovskite film formation.

I first study the formation of methylammonium lead iodide in sequential deposition using confocal laser scanning fluorescence microscopy (CLSM) and scanning electron microscopy (SEM). I discover that illumination during film formation is a major factor in the reaction as it greatly accelerates perovskite formation and tunes the final film morphology by controlling nucleation of lead iodide. The nucleation density increases logarithmically with the illumination intensity. I uncover the mechanism behind this effect and demonstrate that it is a quantum phenomenon and not merely a heating effect. I posit that absorbed light lowers the surface tension, thereby facilitating nucleation. Not only is this effect present in the main deposition methods â sequential deposition and the anti-solvent methods, but also in perovskites of more complex compositions that are employed in state-of-the-art solar cells.

Second, I scrutinize the individual stages in the formation of methylammonium lead iodide perovskite in sequential deposition. SEM-cathodoluminescence imaging identifies the presence of mixed crystalline aggregates composed of methylammonium lead iodide perovskite and lead iodide in forming perovskite films. Using cross-sectional CLSM for the first time, I identify the directionality of perovskite formation. Kinetic monitoring and model fitting bring forward the Avrami models as the most suitable to quantify and represent the formation of perovskite under different conditions of temperature, film thickness and illumination.

Finally, I identify a maturation effect in the perovskite film in solar cells stored in the dark and investigate the dynamic spontaneous coalescence of crystals in the film. During maturation, small crystals merge to form larger ones and this reduces the number of grain boundaries and the associated trap states, supressing non-radiative recombination. The photovoltaic performance of high efficiency solar cells thus increases and it is accompanied by a reduction in the hysteresis.

Overall, apart from providing insights into the dynamic nature of deposited films, I present a fundamental und