Porous semiconductor film morphologies facilitate fluid diffusion and mass transport into the charge-carrying layers of diverse electronic devices. Here, we report the nature-inspired fabrication of several porous organic semiconductor-insulator blend films [semiconductor: P3HT (p-type polymer), C8BTBT (p-type small-molecule), and N2200 (n-type polymer); insulator: PS] by a breath figure patterning method and their broad and general applicability in organic thin-film transistors (OTFTs), gas sensors, organic electrochemical transistors (OECTs), and chemically doped conducting films. Detailed morphological analysis of these films demonstrates formation of textured layers with uniform nanopores reaching the bottom substrate with an unchanged solid-state packing structure. Device data gathered with both porous and dense control semiconductor films demonstrate that the former films are efficient TFT semiconductors but with added advantage of enhanced sensitivity to gases (e.g., 48.2%/ppm for NO₂ using P3HT/PS), faster switching speeds (4.7 s for P3HT/PS OECTs), and more efficient molecular doping (conductivity, 0.13 S/m for N2200/PS).

Organic thin film transistor (OTFT) based gas sensors have demonstrated promising applications, owing to their advantages of high selectivity and room temperature operation, accompanied by their low cost, large scale manufacture, and flexibility. However, the understanding of the sensing mechanism is far from clear. Herein, we reveal the sensing mechanism of an organic transistor sensor for ammonia (NH₃) detection through studying the recovery behavior in various atmospheres. Inspired by the significant difference in the recovery of the transistor sensor in N₂ and in air, we deduced that the operation mechanism should not only involve the NH₃–film interaction. Among a series of recovery processes, only upon exposure to wet air can the sensors completely recover in a certain time. Such a phenomenon, coupled with the transistor’s performance evolution under vacuum, directly evidenced the existence of a pre-doping effect in the transistor by water (H₂O) in ambient air. As a result, the response to the NH₃ analyte is actually a de-doping process via reaction with the H₂O. The full recovery in wet air is attributable to re-doping by H₂O. Density functional theory (DFT) calculations were employed to assist the understanding of such a sensing mechanism. This study could help in the understanding of the sensing processes in many organic semiconductor based sensors.