Doping-Induced Dielectric Catastrophe Prompts Free-Carrier Release in Organic Semiconductors

The control over material properties attainable through molecular doping is essential to many technological applications of organic semiconductors, such as organic light-emitting diodes or thermoelectrics. These excitonic semiconductors typically reach the degenerate limit only at impurity concentrations of 5-10%, a phenomenon that has been put in relation with the strong Coulomb binding between charge carriers and ionized dopants, and whose comprehension remained elusive so far. This study proposes a general mechanism for the release of carriers at finite doping in terms of collective screening phenomena. A multiscale model for the dielectric properties of doped organic semiconductor is set up by combining first principles and microelectrostatic calculations. The results predict a large nonlinear enhancement of the dielectric constant (tenfold at 8% load) as the system approaches a dielectric instability (catastrophe) upon increasing doping. This can be attributed to the presence of highly polarizable host-dopant complexes, plus a nontrivial leading contribution from dipolar interactions in the disordered and heterogeneous system. The enhanced screening in the material drastically reduces the (free) energy barriers for electron-hole separation, rationalizing the possibility for thermal charge release. The proposed mechanism is consistent with conductivity data and sets the basis for achieving higher conductivities at lower doping loads.