Free‐Charge Carrier Generation in Homojunction Non‐Polymeric Organic Semiconductor Films – The Role of the Optical Frequency Dielectric Constant

Abstract Engineering the dielectric constant (ε) to lower the exciton binding energy of the light‐absorbing semiconductor can improve organic photovoltaic (OPV) device performance. Here, a series of materials are reported with 2‐(3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)malononitrile (INCN) acceptor end groups and a central glycolated bis(4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene) unit with large low‐frequency (ε_lf = 7.4–7.9 at 0.1–0.2 MHz) and optical‐frequency (ε_opt up to 6.6 at 2 × 10¹⁴ Hz) dielectric constants. The INCN end groups differed in whether they were protonated, chlorinated, or fluorinated, with the latter having the highest ε_opt. An ε_opt of 6.6 is predicted to lead to a low exciton binding energy of ≈0.04 eV. Time‐resolved microwave conductivity measurements showed a temperature‐dependent yield–mobility product, with it increasing linearly from 340 K. The onset temperature was near that required to overcome the calculated exciton binding energy and indicates increased free charge generation in a homojunction film. Room temperature transient absorption spectroscopy revealed that photoexcitation rapidly converted to a lower energy state that was consistent with the formation of polarons or a charge transfer state. This work provides experimental evidence of the importance of ε_opt for the generation of free charges, and a strategy for development of efficient single chromophore homojunction OPV devices.