The Colloidal Stabilization of Quantum Dots: Towards Manufacturable, Efficient Solution-Processed Solar Cells

Understanding colloidal stabilization can influence the design of optoelectronic devices and enable improvements to their performance and stability. For photovoltaics, important characteristics of the active layer material are high conductivity along with a minimum of recombination centers. In order to capitalize on the benefits of solution-processed materials, it is important to minimize the number of processing steps: ideally, to achieve a low-cost solution, materials would be deposited using a single process step compatible with roll-to-roll manufacturing. Prior to this work, the highest-performing colloidal quantum dots (CQD) solar cells have relied on several deposition steps that are repeated in a layer-by-layer (LBL) fashion. The purpose of these process steps has been to remove the long insulating ligands used in synthesis and replace them with short ligands that allow electrical conduction. The large number of steps combined, typically implemented via spin coating, leads to inefficient materials utilization and fails to show a path to a manufacturable solution. In this work, the first CQD solar cells were designed, built, and characterized combining state-of-art performance with scalable manufacture. Firstly, I report the first automated CQD synthesis to result in CQDs that form high-performance CQD solar cells. I analyze the CQD synthesis and by separating it into two phases - nucleation and growth phase - my insights are used to create higher-quality CQDs exhibiting enhanced monodispersity. I then proceed to develop a CQD ink: a CQD solution ready for direct deposition to form a semiconducting film exhibiting low trap state density. In early trials the CQD ink showed only limited power conversion efficiencies of 2%. I designed a new ink strategy, which I term cleavable hemiketal ligands. This novel two-component ligand strategy enables the combination of colloidal stabilization (via this longer two-component ligand) and cleavability (enabling excellent packing in film and, ultimately, excellent electronic properties). As capstone, I report CQD solar cells exhibiting 7.9% solar power conversion efficiencies. This is, by a wide margin, the most efficient class of CQD solar cells to be reported based on a manufacturable fabrication method. The advances in this work - from automated synthesis to synchrotron studies of CQD packing to novel cleavable ligands - pave the way for new sustainable energy harvesting strategies based on solution-processed nanomaterials.Ph.D