Design and synthesis of stable indigo polymer semiconductors for organic field-effect transistors with high fluoride sensitivity and selectivity.

We report the design and synthesis of two novel indigo donor-acceptor (D-A) polymers, PIDG-T-C20 and PIDG-BT-C20, comprising an indigo moiety that has intramolecular hydrogen-bonds as the acceptor building block and thiophene (T) and bithiophene (BT) as the donor building block, respectively. PIDG-T-C20 and PIDG-BT-C20 exhibited characteristic p-type semiconductor performance, achieving hole mobilities of up to 0.016 and 0.028 cm V s, respectively, which are highest values reported for indigo-based polymers. The better performing PIDG-BT-C20 was used for the fabrication of water-gated organic field-effect transistors (WGOFETs), which showed excellent stability at ambient conditions. The PIDG-BT-C20-based WGOFETs exhibited rapid response when fluoride ions were introduced to the water gate dielectric, achieving a limit of detection (LOD) of 0.40 mM. On the other hand, the devices showed much lower sensitivities towards other halide ions with the order of relative response: F ≫ Cl > Br > I. The high sensitivity and selectivity of PIDG-BT-C20 to fluoride over other halides is considered to be realized through the strong interaction of the hydrogen atoms of the N-H groups in the indigo unit with fluoride ions, which alters the intramolecular hydrogen-bonding arrangement, the electronic structures, and thus the charge transport properties of the polymer.