Tuning the Morphology of Solution-Sheared P3HT:PCBM Films.

Organic bulk heterojunction (BHJ) solar cells are a promising alternative for future clean-energy applications. However, to become attractive for consumer applications, such as wearable, flexible, or semitransparent power-generating electronics, they need to be manufactured by high-throughput, low-cost, large-area-capable printing techniques. However, most research reported on BHJ solar cells is conducted using spin coating, a single batch fabrication method, thus limiting the reported results to the research lab. In this work, we investigate the morphology of solution-sheared films for BHJ solar cell applications, using the widely studied model blend P3HT:PCBM. Solution shearing is a coating technique that is upscalable to industrial manufacturing processes and has demonstrated to yield record performance organic field-effect transistors. Using grazing incident small-angle X-ray scattering, grazing incident wide-angle X-ray scattering, and UV-vis spectroscopy, we investigate the influence of solvent, film drying time, and substrate temperature on P3HT aggregation, conjugation length, crystallite orientation, and PCBM domain size. One important finding of this study is that, in contrast to spin-coated films, the P3HT molecular orientation can be controlled by the substrate chemistry, with PEDOT: PSS substrates yielding face-on orientation at the substrate-film interface, an orientation highly favorable for organic solar cells.

Flow-enhanced solution printing of all-polymer solar cells.

Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a ∼90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhanced all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. We expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility.

Understanding polymorphism in organic semiconductor thin films through nanoconfinement.

Understanding crystal polymorphism is a long-standing challenge relevant to many fields, such as pharmaceuticals, organic semiconductors, pigments, food, and explosives. Controlling polymorphism of organic semiconductors (OSCs) in thin films is particularly important given that such films form the active layer in most organic electronics devices and that dramatic changes in the electronic properties can be induced even by small changes in the molecular packing. However, there are very few polymorphic OSCs for which the structure-property relationships have been elucidated so far. The major challenges lie in the transient nature of metastable forms and the preparation of phase-pure, highly crystalline thin films for resolving the crystal structures and evaluating the charge transport properties. Here we demonstrate that the nanoconfinement effect combined with the flow-enhanced crystal engineering technique is a powerful and likely material-agnostic method to identify existing polymorphs in OSC materials and to prepare the individual pure forms in thin films at ambient conditions. With this method we prepared high quality crystal polymorphs and resolved crystal structures of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), including a new polymorph discovered via in situ grazing incidence X-ray diffraction and confirmed by molecular mechanic simulations. We further correlated molecular packing with charge transport properties using quantum chemical calculations and charge carrier mobility measurements. In addition, we applied our methodology to a [1]benzothieno[3,2-b][1]1benzothiophene (BTBT) derivative and successfully stabilized its metastable form.