Highly Aligned Iontronics Microarchitectures for Multithreading Electrochemical Biomonitoring

Conductive polymers have attracted considerable interest in electrochemical biosensing, due to their customizable multifunctionality, effective ionic-electronic charge transport, biocompatibility, and solution processability. Solution processing represents their prevailing large-area fabrication strategy, yet inevitably yielding disorder stacking of polymer chains due to their inter-chain entanglement. The inhibition of electron and ion transport caused by disordered assembly limits the applications of conductive polymers in electronic and electrochemical devices. Here, we present a multi-interface-induced confined assembly strategy for the programmable construction of PEDOT:PSS iontronics microarchitectures with high alignment. The interfacial hydrogen-bond-induced assembly and shrinkage control of three-phase contact lines (TPCLs) facilitate the lamellar stacking of polymer chains, thereby enhancing the transport of ions and holes. The precise alignment and tunable size of the microarchitectures result in high-performing electrochemical transistors, exhibiting a high figure of merit μC * of 622.48 F cm -1 V -1 s -1 , rapid response, and prolonged durability. A multithreading biosensing chip with high performance and reproducibility is integrated by 96 individual iontronics-microarchitecture devices modified with electrodes and working channels. The biosensing chip with selective detection of seven metabolites demonstrates clinical testing for on-demand blood monitoring. Our strategy offers novel insights into organic bioelectronics for supporting diagnoses and treatments.