Chloroform is a general solvent for poly(3-hexylthiophene) (P3HT) active layers in field-effect transistors. However, its low boiling point and rapid evaporation limit the time for crystallization during the spin-coating process, and field-effect mobilities achieved for P3HT films spin-coated from chloroform are typically on the order of 0.01 cm2/(V s). Here we investigate a range of solvents with higher boiling points. We find that 1,2,4-trichlorobenzene with good solubility and a high boiling point significantly improves the field-effect mobilities up to 0.12 cm2/(V s) with on:off ratios of 106. By controlling the microstructure through the choice of solvent while keeping the molecular weight fixed, we observe a clear correlation between the field-effect mobility and the degree of microcrystalline order as measured by X-ray diffraction, as well as the strength of polaronic relaxation of charge carriers in the accumulation layer as measured by optical spectroscopy of field-induced charge.

This work describes a new design methodology that allows the preparation of air stable, semiconducting thiophene polymers with high charge carrier mobilities. The incorporation of thieno[2,3-b]thiophene into a polythiophene backbone introduces cross-conjugated double bonds that disfavor full delocalization, leading to high ionization potential in comparison to a fully conjugated polythiophene, with no reduction in charge carrier mobility. The resulting solution processable polymers exhibit charge carrier mobilities up to 0.15 cm2/V s and on/off ratios greater than 105 when measured in air. Transistors exhibit lifetimes of several months in air with no encapsulation necessary.

Bioelectronics enables the study of the aqueous media that host soft tissues and interfaces for their proper function, as well as of the connections between various cells and/or organs, which communicate by exchanging specific ions and biomolecules 1 . The fundamental properties of the biological systems set the requirements of the electronics counterpart. Electrolyte-gated transistors (EGTs) have emerged as important building blocks for enhanced bioelectronics because they are stable in an aqueous environment, operate at low voltages and can transduce and amplify biological signals into electronic signals [2][3][4][5] .EGTs are three-terminal devices where the conductivity of a semiconducting material connected to two electrodes, classified as the source and the drain, is modulated by a third electrode known as the gate. In a basic EGT, the gate electrode and the semiconducting channel are in direct contact with the electrolyte. A voltage V G and V D is applied at the gate and drain electrode, respectively (Fig. 1a). V G and V D are referenced to the source voltage, which is typically set to ground, V S = 0 V. The polarity and magnitude of the voltage applied to the gate electrode result in a drift of cations or anions from the electrolyte to the semiconducting channel. The ionic charges can enhance or deplete the electronic charges residing in the semiconductor channel. This ionicelectronic modulation gives rise to a large variation of the channel conductivity that, in turn, manifests in a large modulation of the electronic source to drain current flowing through the transistor channel. Upon application of the gate, source and drain voltages, ions drift into the electrolyte and accumulate at the gate and semiconductor. The sign of the gate voltage controls the charge type of these ions (cations or anions), whereas its magnitude controls their density. For example, when a positive gate voltage is applied, the anion concentration increases at the gate and the cation concentration increases at the semiconducting channel. The sub-nanometre scale dimension of the ions interacting with the gate and channel materials results in a large electrostatic interaction at the gate/electrolyte and electrolyte/channel interfaces, which yields the low-voltage operation of EGTs that can range from a few volts to even less than 1 V, depending on the specific materials used. The low-voltage operation is critically important for electrophysiology and in the case of a large variety of biosensors. In addition, in contrast to the conventional thin-film field-effect transistors, in EGTs the gate is not required to be positioned in front of the channel as the charge modulation is due to the accumulation or depletion of ions transported within