Influence of Semiconductor Thickness and Molecular Weight on the Charge Transport of a Naphthalenediimide-Based Copolymer in Thin-Film Transistors

The N-type semiconducting polymer, P(NDI2OD-T2), with different molecular weights (MW = 23, 72, and 250 kg/mol) was used for the fabrication of field-effect transistors (FETs) with different semiconductor layer thicknesses. FETs with semiconductor layer thicknesses from ∼15 to 50 nm exhibit similar electron mobilities (μ’s) of 0.2–0.45 cm2 V–1 s–1. Reduction of the active film thickness led to decreased μ values; however, FETs with ∼2 and ∼5 nm thick P(NDI2OD-T2) films still exhibit substantial μ’s of 0.01–0.02 and ∼10–4 cm2 V–1 s–1, respectively. Interestingly, the lowest molecular weight sample (P-23, MW ≈ 23 kg/mol, polydispersity index (PDI) = 1.9) exhibited higher μ than the highest molecular weight sample (P-250, MW ≈ 250 kg/mol, PDI = 2.3) measured for thicker devices (15–50 nm). This is rather unusual behavior because typically charge carrier mobility increases with MW where improved grain-to-grain connectivity usually enhances transport events. We attribute this result to the high crystallinity o...