Unraveling the Co-Crystallization-Charge Transport Relation in Conjugated Polymer Blends via Meniscus-Assisted Solution-Shearing.

The ability to craft the co-crystallization in conjugated polymer blends represents an important endeavor for the enhancement of charge transport. However, simple and efficient approaches to co-crystallization have yet to be realized. Herein, for the first time, a robust meniscus-assisted solution-shearing (MASS) strategy is reported to achieve co-crystallization in the poly(2,5-bis(3-hexylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT-C6) and poly(2,5-bis(3-decylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT-C10) blended films, and correlate this co-crystalline structure to the charge transport properties. The as-cast PBTTT-C6/PBTTT-C10 blends exhibit co-crystalline or phase-separated structures influenced by their molecular weights. Interestingly, confined-shearing of the initial phase-separated blended solution to MASS produces the formation of their co-crystallization. The co-crystallization kinetics accompanied by the chain packing change and optical properties are scrutinized. Finally, the resulting organic field-effect transistors (OFETs) signify the cocrystal-facilitated charge transport in the blends. Conceptually, this efficient MASS strategy in rendering the co-crystallization in conjugated polymer blends can be readily extended to other conjugated polymer blends of interest for a variety of device applications.