- Kiefer, David;
- Kroon, Renee;
- Hofmann, Anna I;
- Sun, Hengda;
- Liu, Xianjie;
- Giovannitti, Alexander;
- Stegerer, Dominik;
- Cano, Alexander;
- Hynynen, Jonna;
- Yu, Liyang;
- Zhang, Yadong;
- Nai, Dingqi;
- Harrelson, Thomas F;
- Sommer, Michael;
- Moulé, Adam J;
- Kemerink, Martijn;
- Marder, Seth R;
- McCulloch, Iain;
- Fahlman, Mats;
- Fabiano, Simone;
- Müller, Christian
Molecular doping is a crucial tool for controlling the charge-carrier concentration in organic semiconductors. Each dopant molecule is commonly thought to give rise to only one polaron, leading to a maximum of one donor:acceptor charge-transfer complex and hence an ionization efficiency of 100%. However, this theoretical limit is rarely achieved because of incomplete charge transfer and the presence of unreacted dopant. Here, we establish that common p-dopants can in fact accept two electrons per molecule from conjugated polymers with a low ionization energy. Each dopant molecule participates in two charge-transfer events, leading to the formation of dopant dianions and an ionization efficiency of up to 200%. Furthermore, we show that the resulting integer charge-transfer complex can dissociate with an efficiency of up to 170%. The concept of double doping introduced here may allow the dopant fraction required to optimize charge conduction to be halved.