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  1. We investigated the enhanced vapor responses and altered response ratios of a series of thiophene (co)polymers with oxygenated side chains (CH 2 OH, linear polyethylene glycol, and crown ether), including the novel poly(3-hydroxymethylthiophene) (PTOH) and other newly synthesized polymers. Hydroxymethyl-containing copolymers had higher mobility compared to poly(3-hexylthiophene) (P3HT). The larger crown ether moiety promotes transistor characteristics of P3HT while the smaller one impairs them. Incorporating different oxygen bearing functionalities increased responses of thiophene polymers to NO 2 , NH 3 , and acetone. For example a polyether side chain increases the NO 2 response sensitivity of copolymers of both P3HTmore »and PTOH, but sensitivity towards gas analytes was more prominent for glycol-based functionalities rather than the crown ethers. PTOH is very sensitive to NO 2 and the response likely includes a contribution from conductive protons on the OH group. The lack of correlation among the rank-ordered gas sensitivities imparted by each functional group was found to be useful for designing a selective sensor array. We specifically showed high classification accuracy for all the polymer responses to NO 2 and acetone vapors, both of which gave increased device currents but with response ratios different enough to allow highly classifying discriminant functions to be derived.« less
    Free, publicly-accessible full text available February 10, 2023
  2. The improvement of conjugated polymer-based gas sensors involves fine tuning the backbone electronic structure and solid-state microstructure to combine high stability and sensitivity. We had previously developed a series of diketopyrrolopyrrole (DPP)-based polymer semiconductors by introducing a variety of fluorene linkers to study the trends and mechanisms governing gas sensitivities and electronic stability in air and under gate and drain bias stress. The proportional on-current change of organic field-effect transistors (OFETs) using a dithienyl DPP–fluorene polymer reached ∼600% for a sequential exposure from 0.5–20 ppm of NO 2 for 5 minutes and also a high response-to-drift ratio under dynamic biasmore »stress. In the present work we specify the roles of static bias stress and traps in the sensing process for the first time. Apart from electronic structure, defects at the molecular and microstructural levels govern the ability to form and sustain traps and subsequent backbone dopability. A polymer with a twisted backbone was observed to be capable of creating an energetically broad trap distribution while a polymer with a high degree of solid-state order shows a tendency to form an energetically narrow trap distribution and a fast passivation of traps on exposure to air. The stability and energetic distribution of traps on subjecting the polymers to bias stress was related to electronic structure and solid-state packing; and the ability of NO 2 and NH 3 to fill/create traps further was evaluated. At a bias stress condition of V G = V D = −80 V, the polymers retain their NO 2 sensitivity both post NO 2 -aided recovery and air-aided recovery. In order to verify the ability of NH 3 to create traps, traps were erased from the OFET sensors by charging with the aid of a positive gate voltage leading to an increase in the NH 3 response when compared to air controls. This work demonstrates that the charge-trap filling and generation response mechanism is predominant and can even be leveraged for higher responses to vapors. Backbone dopability appears to be a minor contributor to responses in this category of polymeric semiconductors with engineered defects. Finally, bias stress generally does not preclude this category of OFET vapor sensors from recovering their original sensitivities.« less
  3. A carboxylated thiophene polymer-based chemiresistive device in a field-effect transistor (FET) configuration with unusual and enhanced responses to the widespread pollutants nitrogen dioxide (NO 2 ) and ammonia (NH 3 ) is described. The device based on a polymeric thiophene carboxylic acid showed a dramatic and superlinear increase in drain current ( I D ) of over 15 000% to a ramped exposure to 10 ppm NO 2 over several minutes, while its ethyl ester counterpart had significantly lower response. Devices incorporating either an ester or carboxylic acid displayed comparable and previously unreported increases in I D from 10 ppm rampedmore »NH 3 exposure of 200–300%. Conventional poly(alkylthiophenes) showed the expected current decreases from similar NH 3 exposures. Using threshold voltage shifts in silicon transistors coupled to our recently reported remote gate (RG) platform with thiophene polymer coatings, we determined that two differing response mechanisms are associated with the two gas exposures. By calculating the charge density induced in the polymers by NO 2 exposure using the silicon transistor voltage shifts, we conclude that proton conduction contributes significantly to the high sensitivity of the carboxylic acid to NO 2 , in addition to doping that was observed for all four polymers. Furthermore, hydrogen bonding moieties of the carboxylic acid and ester may be able to physisorb NH 3 and thus alter the charge distribution, rearrange polymer chains, and/or create a proton transfer network leading to the I D increase that is the opposite of the response obtained from non-carboxylated thiophene polymers.« less
  4. We summarize our recent results on material, device, and circuit structures for detection of volatile analytes in the atmosphere and proteins in aqueous solution. Common to both types of sensing goals is the design of materials that respond more strongly to analytes of interest than to likely interferents, and the use of chemical and electronic amplification methods to increase the ratio of the desired responses to the drift (signal/noise ratio). Printable materials, especially polymers, are emphasized. Furthermore, the use of multiple sensing elements, typically field-effect transistors, increases the selectivity of the information, either by narrowing the classes of compounds providingmore »the responses, distinguishing time-dependent from dose-dependent responses, and increasing the ratio of analyte responses to environmental drifts. To increase the stability of systems used to detect analytes in solution, we sometimes separate the sensing surface from the output device in an arrangement known as a remote gate. We show that the output device may be an organic-based or a silicon-based transistor, and can respond to electrochemical potential changes at the sensing surface arising from a variety of chemical interactions.« less