skip to main content


Title: High Signal‐to‐Noise Chemical Sensors Based on Compensated Organic Transistor Circuits
Abstract

Operational stability and sensitivity are key issues for the practical application of organic field‐effect‐transistor (OFET)‐based sensors. Instability over time due to intrinsic device bias stress and conductance drift induced by the ambient environment can obscure responses to analytes of interest. These instabilities are well‐known hindrances to the practical application of OFET sensors. It is demonstrated for the first time that an innovative and simple two‐OFET circuit design can effectively compensate the drifts originating from bias stress and/or the environment while maintaining chemical sensitivity and increasing signal‐to‐noise ratio. This is enabled by illumination of one photosensitive OFET to compensate the drift of the other chemical‐sensing OFET, though in principle a pair of OFETs with opposing drifts generated by any mechanism could be used. The circuit, compared with individual OFET‐based sensors, achieves significantly increased environmental stability, and its enhanced response to chemical vapors is also demonstrated by detecting the representative pollutants nitrogen dioxide (NO2) and ammonia (NH3). This shows that OEFTs with drifts being compensated by any mechanism can lead to stabilized sensor circuits.

 
more » « less
Award ID(s):
1807293
NSF-PAR ID:
10459365
Author(s) / Creator(s):
 ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Materials Technologies
Volume:
4
Issue:
10
ISSN:
2365-709X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    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 bias 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. 
    more » « less
  2. Abstract

    Photonic sensors based upon high‐quality microcavities have found a wide variety of applications ranging from inertial sensing, electro‐ and magnetometry to chemical and biological sensing. These sensors have a dynamic range limited by the linewidth of the cavity mode transducing the input. This dynamic range not only determines the range of the signal strength that can be detected, but also affects the resilience of the sensor against large deteriorating external perturbations and shocks in a practical environment. Unfortunately, there is a general trade‐off between the detection sensitivity and the dynamic range, which undermines the performance of all microcavity‐based sensors. Here, an approach is proposed to extend the dynamic range significantly beyond the cavity linewidth limit by exploiting the periodic nature of the modulation signal, making measurements in the nonlinear transduction regime without degrading the detection sensitivity for weak signals. With a cavity optomechanical system, a dynamic range of over six times larger than the cavity linewidth is experimentally demonstrated, far beyond the conventional linear region of operation for such a sensor. This approach will help design microcavity‐based sensors to achieve high detection sensitivity and a large dynamic range at the same time, a crucial property for their use in a practical environment.

     
    more » « less
  3. Abstract

    Total alkalinity (AT) is an important parameter in the study of aquatic biogeochemical cycles, chemical speciation modeling, and many other important fundamental and anthropogenic (e.g., industrial) processes. We know little about its short‐term variability, however, because studies are based on traditional bottle sampling typically with coarse temporal resolution. In this work, an autonomous ATsensor, named the Submersible Autonomous Moored Instrument for Alkalinity (SAMI‐alk), was tested for freshwater applications. A comprehensive evaluation was conducted in the laboratory using freshwater standards. The results demonstrated excellent precision and accuracy (± 0.1%–0.4%) over the ATrange from 800 to 3000 μmol L−1. The system had no drift over an 8 d test and also demonstrated limited sensitivity to variations in temperature and ionic strength. Three SAMI‐alks were deployed for 23 d in the Clark Fork River, Montana, with a suite of other sensors. Compared to discrete samples, in situ accuracy for the three instruments were within 10–20 μmol L−1(0.3–0.6%), indicating good performance considering the challenges of in situ measurements in a high sediment, high biofouling riverine environment with large and rapid changes in temperature. These data reveal the complex ATdynamics that are typically missed by coarse sampling. We observed ATdiel cycles as large as 60–80 μmol L−1, as well as a rapid change caused by a runoff event. Significant errors in inorganic carbon system modeling result if these short‐term variations are not considered. This study demonstrates both the feasibility of the technology and importance of high‐resolution ATmeasurements.

     
    more » « less
  4. Abstract

    Chemical sensors based on solution‐processed 2D nanomaterials represent an extremely attractive approach toward scalable and low‐cost devices. Through the implementation of real‐time impedance spectroscopy and development of a three‐element circuit model, redox exfoliated MoS2nanoflakes demonstrate an ultrasensitive empirical detection limit of NO2gas at 1 ppb, with an extrapolated ultimate detection limit approaching 63 ppt. This sensor construct reveals a more than three orders of magnitude improvement from conventional direct current sensing approaches as the traditionally dominant interflake interactions are bypassed in favor of selectively extracting intraflake doping effects. This same approach allows for an all solution‐processed, flexible 2D sensor to be fabricated on a polyimide substrate using a combination of graphene contacts and drop‐casted MoS2nanoflakes, exhibiting similar sensitivity limits. Finally, a thermal annealing strategy is used to explore the tunability of the nanoflake interactions and subsequent circuit model fit, with a demonstrated sensitivity improvement of 2× with thermal annealing at 200 °C.

     
    more » « less
  5. Abstract

    A systematic analysis is used to understand electrical drift occurring in field‐effect transistor (FET) dissolved‐analyte sensors by investigating its dependence on electrode surface‐solution combinations in a remote‐gate (RG) FET configuration. Water at pH 7 and neat acetonitrile, having different dipoles and polarizabilities, are applied to the RG surface of indium tin oxide, SiO2, hexamethyldisilazane‐modified SiO2, polystyrene, poly(styrene‐co‐acrylic acid), poly(3‐hexylthiophene‐2,5‐diyl) (P3HT), and poly [3‐(3‐carboxypropyl)thiophene‐2,5‐diyl] (PT‐COOH). It is discovered that in some cases a slow reorientation of dipoles at the interface induced by gate electric fields causes severe drift and hysteresis because of induced interface potential changes. Conductive and charged P3HT and PT‐COOH increase electrochemical stability by promoting fast surface equilibrations. It is also demonstrated that pH sensitivity of P3HT (17 mV per pH) is an indication of proton doping. PT‐COOH shows further enhanced pH sensitivity (30 mV per pH). This combination of electrochemical stability and pH response in PT‐COOH are proposed as advantageous for polymer‐based biosensors.

     
    more » « less