2D Molecular Crystal Bilayer p–n Junctions: A General Route toward High‐Performance and Well‐Balanced Ambipolar Organic Field‐Effect Transistors

Ambipolar organic field‐effect transistors (OFETs) are vital for the construction of high‐performance all‐organic digital circuits. The bilayer p–n junction structure, which is composed of separate layers of p‐ and n‐type organic semiconductors, is considered a promising way to realize well‐balanced ambipolar charge transport. However, this approach suffers from severely reduced mobility due to the rough interface between the polycrystalline thin films of p‐ and n‐type organic semiconductors. Herein, 2D molecular crystal (2DMC) bilayer p–n junctions are proposed to construct high‐performance and well‐balanced ambipolar OFETs. The molecular‐scale thickness of the 2DMC ensures high injection efficiency and the atomically flat surface of the 2DMC leads to high‐quality p‐ and n‐layer interfaces. Moreover, by controlling the layer numbers of the p‐ and n‐type 2DMCs, the electron and hole mobilities are tuned and well‐balanced ambipolar transport is accomplished. The hole and electron mobilities reach up to 0.87 and 0.82 cm² V^?1 s^?1, respectively, which are the highest values among organic single‐crystalline double‐channel OFETs measured in ambient air. This work provides a general route to construct high‐performance and well‐balanced ambipolar OFETs based on available unipolar materials.