Colloidal quantum dot photovoltaic devices have improved from initial, sub-1% solar power conversion efficiency to current record performance of over 7%. Rapid advances in materials processing and device physics have driven this impressive performance progress. The highest-efficiency approaches rely on a fabrication process that starts with nanocrystals in solution, initially capped with long organic molecules. This solution is deposited and the resultant film is treated using a solution containing a second, shorter capping ligand, leading to a cross-linked, non-redispersible, and dense layer. This procedure is repeated, leading to the widely employed layer-by-layer solid-state ligand exchange. We will review the properties and features of this process, and will also discuss innovative pathways to creating even higher-performing films and photovoltaic devices.