Polyurethane-Based Stretchable Semiconductor Nanofilms with High Intrinsic Recovery Similar to Conventional Elastomers

Polymer semiconductors with large elastic recovery (ER) under high strain in thin film state are highly desirable for stretchable electronics. Here we report a type of stretchable semiconductor PU(DPP)x, by copolymerization of oligodiketopyrrolopyrrole-based conjugated block and hydrogenated polybutadiene flexible block via urethane linkage for intermolecular hydrogen bonding. By regulating block ratio, PU(DPP)35 with 35 wt % conjugated block exhibits high intrinsic ER > 80% under 175% strain (ε) in pseudo free-standing thin film state, comparable with commercial elastomers, and crack onset strain (COS) > 300% along with maximum hole mobility of 0.19 cm2 V–1 s–1 in organic thin film transistors to bring it to the best performing block copolymer-type stretchable semiconductors. Enhanced mobility is achieved using PU(DPP)35 as the binder for conjugated polymer PDPPT3. The 25 wt %-PDPPT3 blend displays mobility up to 1.28 cm2 V–1 s–1 along with COS ∼120%, and 10 wt %-PDPPT3 blend exhibits ER of 78% at ε = 150%, COS of ∼230%, modulus of 36.5 MPa, maximum mobility of 0.62 cm2 V–1 s–1 and no obvious degradation of mobility at ε = 150% after 100 cycles of strain. Moreover, the structural similarity enables the blend film uniform and stable microstructure against mechanical and thermal deformation. Notably, PU(DPP)35 and the blend are characterized by high mechanical performance similar to that of commercial elastomers in thin film state, and demonstrate their potential for high performance stretchable electronics.