High‐Performance Room Temperature Ammonia Sensors Based on Pure Organic Molecules Featuring B‐N Covalent Bond

Exploring organic semiconductor gas sensors with high sensitivity and selectivity is crucial for the development of sensor technology. Herein, for the first time, a promising chemiresistive organic polymer P‐BNT based on a novel π‐conjugated triarylboron building block is reported, showcasing an excellent responsivity over 30 000 (Ra/Rg) against 40 ppm of NH3, which is ≈3300 times higher than that of its B‐N organic small molecule BN‐H. More importantly, a molecular induction strategy to weaken the bond dissociation energy between polymer and NH3 caused by strong acid‐base interaction is further executed to optimize the response and recovery time. As a result, the BN‐H/P‐BNT system with rapid response and recovery times can still exhibit a high responsivity of 718, which is among the highest reported NH3 chemiresistive sensors. Supported by in situ FTIR spectroscopy and theoretical calculations, it is revealed that the N‐H fractions in BN‐H small molecule promoted the charge distribution on phenyl groups, which increases charge delocalization and is more conducive to gas adsorption in such molecular systems. Notably, these distinctive small molecules also promoted charge transfer and enhanced electron concentration of the P‐BNT sensing polymer, thus achieving superior B‐N‐containing organic molecules with excellent sensing performance. A novel strategy to investigate the definite conjugated polymers and sensing activity for chemiresistive‐based organic semiconductor gas sensors by introducing B‐N covalent bond is reported. The as‐fabricated sensing device based on P‐BNT exhibited the highest response of 32 000 against 40 ppm of NH3 at room temperature. Importantly, the small molecule BN‐H with active N‐H can regulate P‐BNT to exhibit excellent stability, selectivity, and relative humidity resistance.