Crystallinity-Controlled Naphthalene-<i>alt</i>-diketopyrrolopyrrole Copolymers for High-Performance Ambipolar Field Effect Transistors

Abstract

We report high-performance of ambipolar organic field-effect transistors (FETs) based on the low band gap copolymers of pDPPT2NAP-HD and pDPPT2NAP-OD. The polymers are composed of electron-rich 2,6-di(thienyl)naphthalene (T2NAP) and electron-deficient diketopyrrolopyrrole (DPP) units with branched alkyl chains of 2-hexyldecyl (HD) or 2-octyldodecyl (OD). The polymers were polymerized via Suzuki coupling, yielding optical band gaps of ∼1.4 eV. In the transistor performance test, we observed good ambipolar transport behavior in both polymer films, and pDPPT2NAP-OD displayed hole and electron mobilities 1 order of magnitude higher than the corresponding properties of pDPPT2NAP-HD. Thermal annealing of the polymer films increased the carrier mobilities. Annealing at 150 °C provided optimal conditions yielding saturated film crystallinity and maximized carrier mobility. The highest hole and electron mobilities achieved in these polymers were 1.3 and 0.1 cm2/(V s), respectively, obtained from pDPPT2NAP-OD. The polymer structure and thermal annealing affected the carrier mobility, and this effect was investigated by fully characterizing the polymer films by grazing incidence X-ray diffraction (GIXD), atomic force microscopy (AFM), and transmission electron microscopy (TEM) experiments. The GIXD data revealed that both polymers formed highly crystalline films with edge-on orientation. pDPPT2NAP-OD, which included longer alkyl chains, showed a higher tendency to form long-range order among the polymer chains. Thermal annealing up to 150 °C improved the polymer film crystallinity and promoted the formation of longer-range lamellar structures. AFM and TEM images of the films were consistent with the GI-XD data. Theoretical calculations of the polymer structures provided a rationale for the relationship between the torsional angle between aromatic rings and the carrier mobility. From the intensive electrical measurements and full characterizations, we find that the chemical structure of polymer backbone and side alkyl chain has a profound effect on film crystallinity, morphology, and transistor properties.