In situ UV-visible absorption during spin-coating of organic semiconductors: a new probe for organic electronics and photovoltaics

Spin-coating is the most commonly used technique for the lab-scale production of solution processed organic electronic, optoelectronic and photovoltaic devices. Spin-coating produces the most efficient solution-processed organic solar cells and has been the preferred approach for rapid screening and optimization of new organic semiconductors and formulations for electronic and optoelectronic applications, both in academia and in industrial research facilities. In this article we demonstrate, for the first time, a spin-coating experiment monitored in situ by time resolved UV-visible absorption, the most commonly used, simplest, most direct and robust optical diagnostic tool used in organic electronics. In the first part, we successfully monitor the solution-to-solid phase transformation and thin film formation of poly(3-hexylthiophene) (P3HT), the de facto reference conjugated polymer in organic electronics and photovoltaics. We do so in two scenarios which differ by the degree of polymer aggregation in solution, prior to spin-coating. We find that a higher degree of aggregation in the starting solution results in small but measurable differences in the solid state, which translate into significant improvements in the charge carrier mobility of organic field-effect transistors (OFET). In the second part, we monitor the formation of a bulk heterojunction photoactive layer based on a P3HT-fullerene blend. We find that the spin-coating conditions that lead to slower kinetics of thin film formation favour a higher degree of polymer aggregation in the solid state and increased conjugation length along the polymer backbone. Using this insight, we devise an experiment in which the spin-coating process is interrupted prematurely, i.e., after liquid ejection is completed and before the film has started to form, so as to dramatically slow the thin film formation kinetics, while maintaining the same thickness and uniformity. These changes yield substantial improvements to the power conversion efficiency of solar cells without requiring additional thermal annealing, or the use of solvent additives. Through these simple examples, we demonstrate that gaining insight into the thin film formation process can inspire the development of new processing strategies. The insight into the inner workings of spin-coating may be increasingly important to improving the performance or efficiency of roll-to-roll manufactured devices.