RESUMO
The poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) film is a promising material for electrodes, biomolecular sensor channels, and probes for physiological signals because the electrical conduction of PEDOT:PSS is tuned simply through the electrochemical reaction with the target analyte. However, forming a specific morphology or nanostructure on PEDOT:PSS thin films immersed in an aqueous solution is still a challenge. Herein, we report the mechanism for the stepwise morphological change in the highly conductive PEDOT:PSS layer that successfully explains the electrical and structural modulations that occur after a soaking test in various pH conditions. The change in PEDOT:PSS begins with the rapid swelling and dissolution of PSS-rich domains and the simultaneous structural rearrangement of the remaining PEDOT chains within 1 s of dipping. Analysis confirms that the pH conditions of an aqueous solution govern the oxidation state and the form of the PEDOT chains. After removing the water molecules, additional PEDOT-rich grains were generated and accumulated on the surface of the film, which exhibited hydrophobic barrier characteristics. With the help of this intrinsic barrier on the PEDOT:PSS surface, the sheet resistance slightly increased from 72 to 144 Ω/sq even after dipping in a water bath for 350 h. We also demonstrate the usability of the proposed approach on a sensor to detect vitamin C in an aqueous medium. Utilizing the electrochemical reaction of PEDOT:PSS films, the simple resistor sensor showed a response time of less than 150 s, which is 10 times faster than that observed in a previous report. The soaked samples also showed a more reliable linear correlation between the current change and the amount of ascorbic acid compared with pristine PEDOT:PSS. Both the proposed mechanism and the role of accumulated PEDOT-rich regions illustrate the versatile potential of highly conductive PEDOT:PSS films in the field of bioelectronic applications, owing to the increased design architecture.
RESUMO
Recent advances in numerous biological applications have increased the accuracy of monitoring the level of biologically significant analytes in the human body to manage personal nutrition and physiological conditions. However, despite promising reports about costly wearable devices with high sensing performance, there has been a growing demand for inexpensive sensors that can quickly detect biological molecules. Herein, we present highly sensitive biosensors based on organic electrochemical transistors (OECTs), which are types of organic semiconductor-based sensors that operate consistently at low operating voltages in aqueous solutions. Instead of the gold or platinum electrode used in current electrochemical devices, poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) was used as both the channel and gate electrodes in the OECT. Additionally, to overcome the patterning resolution limitations of conventional solution processing, we confirmed that the irradiation of a high-power IR laser (λ = 1064 nm) onto the coated PEDOT:PSS film was able to produce spatially resolvable micropatterns in a digital-printing manner. The proposed patterning technique exhibits high suitability for the fabrication of all-PEDOT:PSS OECT devices. The device geometry was optimized by fine-tuning the gate area and the channel-to-gate distance. Consequently, the sensor for detecting ascorbic acid (vitamin C) concentrations in an electrolyte exhibited the best sensitivity of 125 µA dec-1 with a limit of detection of 1.3 µM, which is nearly 2 orders of magnitude higher than previous findings. Subsequently, an all-plastic flexible epidermal biosensor was established by transferring the patterned all-PEDOT:PSS OECT from a glass substrate to a PET substrate, taking full advantage of the flexibility of PEDOT:PSS. The prepared all-plastic sensor device is highly cost-effective and suitable for single-use applications because of its acceptable sensing performance and reliable signal for detecting vitamin C. Additionally, the epidermal sensor successfully obtained the temporal profile of vitamin C in the sweat of a human volunteer after the consumption of vitamin C drinks. We believe that the highly sensitive all-PEDOT:PSS OECT device fabricated using the accurate patterning process exhibits versatile potential as a low-cost and single-use biosensor for emerging bioelectronic applications.