Tailoring Structure and Field-Effect Characteristics of Ultrathin Conjugated Polymer Films via Phase Separation

A phase-separation method has been developed to control the semiconductor thickness and molecular arrangement via the semiconducting/insulating polymer blend system. The thickness of the poly(3-hexylthiophene) film has been regulated from 10.5 ± 1.4 nm down to 1.9 ± 0.8 nm with a favorable self-assembly degree and the mobility ranging from 0.21 to 0.03 cm2 V–1 s–1. The ultrathin films show high bias stability and weak decay after 24 days with a bottom-gate configuration. Benefited from a good molecular order, the films have low activation energy and a 2D charge transport profile in semiconductor layers. Moreover, this blending process can be used as a general strategy of thickness control in flexible low-voltage devices and donor–acceptor-conjugated polymers.