Highly Sensitive Flexible NH₃ Sensors Based on Printed Organic Transistors with Fluorinated Conjugated Polymers

Understanding the sensing mechanism in organic chemical sensors is essential for improving the sensing performance such as detection limit, sensitivity, and other response/recovery time, selectivity, and reversibility for real applications. Here, we report a highly sensitive printed ammonia (NH₃) gas sensor based on organic thin film transistors (OTFTs) with fluorinated difluorobenzothiadiazole-dithienosilole polymer (PDFDT). These sensors detected NH₃ down to 1 ppm with high sensitivity (up to 56%) using bar-coated ultrathin (<4 nm) PDFDT layers without using any receptor additives. The sensing mechanism was confirmed by cyclic voltammetry, hydrogen/fluorine nuclear magnetic resonance, and UV/visible absorption spectroscopy. PDFDT-NH₃ interactions comprise hydrogen bonds and electrostatic interactions between the PDFDT polymer backbone and NH₃ gas molecules, thus lowering the highest occupied molecular orbital levels, leading to hole trapping in the OTFT sensors. Additionally, density functional theory calculations show that gaseous NH₃ molecules are captured via cooperation of fluorine atoms and dithienosilole units in PDFDT. We verified that incorporation of functional groups that interact with a specific gas molecule in a conjugated polymer is a promising strategy for producing high-performance printed OTFT gas sensors.