N-doping plays an irreplaceable role in controlling the electron concentration of organic semiconductors thus to improve performance of organic semiconductor devices. However, compared with many mature p-doping methods, n-doping of organic semiconductor is still of challenges. In particular, dopant stability/processability, counterion-semiconductor immiscibility and doping induced microstructure non-uniformity have restricted the application of ndoping in high-performance devices. Here, we report a computer-assisted screening approach to rationally design of a triaminomethane-type dopant, which exhibit extremely high stability and strong hydride donating property due to its thermally activated doping mechanism. This triaminomethane derivative shows excellent counterion-semiconductor miscibility (counter cations stay with the polymer side chains), high doping efficiency and uniformity. By using triaminomethane, we realize a record n-type conductivity of up to 21 S cm −1 and power factors as high as 51 μW m −1 K −2 even in films with thicknesses over 10 μm, and we demonstrate the first reported all-polymer thermoelectric generator.

Molecular doping plays an important role in the modification of carrier density of organic semiconductors thus enhancing their optoelectronic performance. However, efficient n‐doping remains challenging, especially owing to the lack of strongly reducing and air‐stable n‐dopants. Herein, an N‐heterocyclic carbene (NHC) precursor, DMImC, is developed as a thermally activated n‐dopant with the excellent stability in air. Its thermolysis in situ regenerates free NHC and subsequently dopes typical organic semiconductors. In sequentially doped FBDPPV films, DMImC does not disturb the π–π packing of the polymer and achieves good miscibility with the polymer. As a result, a high electrical conductivity of up to 8.4 S cm−1 is obtained. Additionally, the thermally activated doping and the excellent air stability permit DMImC to be noninteractively co‐processed with polymers in air. Our results reveal that DMImC can be served as an efficient n‐dopant suitable for various organic semiconductors.

Molecular doping plays an important role in the modification of carrier density of organic semiconductors thus enhancing their optoelectronic performance. However, efficient n‐doping remains challenging, especially owing to the lack of strongly reducing and air‐stable n‐dopants. Herein, an N‐heterocyclic carbene (NHC) precursor, DMImC, is developed as a thermally activated n‐dopant with the excellent stability in air. Its thermolysis in situ regenerates free NHC and subsequently dopes typical organic semiconductors. In sequentially doped FBDPPV films, DMImC does not disturb the π–π packing of the polymer and achieves good miscibility with the polymer. As a result, a high electrical conductivity of up to 8.4 S cm−1 is obtained. Additionally, the thermally activated doping and the excellent air stability permit DMImC to be noninteractively co‐processed with polymers in air. Our results reveal that DMImC can be served as an efficient n‐dopant suitable for various organic semiconductors.