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Solution‐processable highly conductive polymers are of great interest in emerging electronic applications. For p‐doped polymers, conductivities as high a nearly 105 S cm−1 have been reported. In the case of n‐doped polymers, they often fall well short of the high values noted above, which might be achievable, if much higher charge‐carrier mobilities determined could be realized in combination with high charge‐carrier densities. This is in part due to inefficient doping and dopant ions disturbing the ordering of polymers, limiting efficient charge transport and ultimately the achievable conductivities. Here, n‐doped polymers that achieve a high conductivity of more than 90 S cm−1 by a simple solution‐based co‐deposition method are reported. Two conjugated polymers with rigid planar backbones, but with disordered crystalline structures, exhibit surprising structural tolerance to, and excellent miscibility with, commonly used n‐dopants. These properties allow both high concentrations and high mobility of the charge carriers to be realized simultaneously in n‐doped polymers, resulting in excellent electrical conductivity and thermoelectric performance.
Two conjugated polymers with rigid planar backbones, but with disordered crystalline structures, exhibit surprising structural tolerance to commonly used n‐dopants. These properties allow both high concentrations and high mobility of the charge carriers to be realized simultaneously in n‐doped polymers, resulting in excellent electrical conductivity of over 90 S cm−1 and thermoelectric performance up to 106 µW m−1 K−2.