Passivation of Molecular n-Doping: Exploring the Limits of Air Stability

• Published in: Advanced functional materials 2016-06, Vol.26 (21), p.3730-3737
• Main Authors: Tietze, Max L., Rose, Bradley D., Schwarze, Martin, Fischer, Axel, Runge, Steffen, Blochwitz-Nimoth, Jan, Lüssem, Björn, Leo, Karl, Brédas, Jean-Luc
• Format: Article
• Language: English
• Subjects: Degradation; DFT; Dopants; Doping; Electronics; Field effect transistors; molecular n-doping; Organic semiconductors; Passivation; Semiconductors; UPS
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.201505092

Molecular doping is a key technique for flexible and low‐cost organic complementary semiconductor technologies that requires both efficient and stable p‐ and n‐type doping. However, in contrast to molecular p‐dopants, highly efficient n‐type dopants are commonly sensitive to rapid degradation in air due to their low ionization energies (IEs) required for electron donation, e.g., IE = 2.4 eV for tetrakis(1,3,4,6,7,8‐hexahydro‐2H‐pyrimido[1,2‐a]pyrimidinato)ditungsten(II) (W2(hpp)4). Here, the air stability of various host:W2(hpp)4 combinations is compared by conductivity measurements and photoemission spectroscopy. A partial passivation of the n‐doping against degradation is found, with this effect identified to depend on the specific energy levels of the host material. Since host‐W2(hpp)4 electronic wavefunction hybridization is unlikely due to confinement of the dopant highest occupied molecular orbital (HOMO) to its molecular center, this finding is explained via stabilization of the dopant by single‐electron transfer to a host material whose energy levels are sufficiently low for avoiding further charge transfer to oxygen–water complexes. Our results show the feasibility of temporarily handling n‐doped organic thin films in air, e.g., during structuring of organic field effect transistors (OFETs) by lithography. The air sensitivity of various n‐doped organic thin films is investigated using the inherently air unstable W2(hpp)4. Air stable n‐type conductive films are achieved as long as the electron affinity (EA) of the host material lies deep enough to prevent reduction of O2(H2O)n complexes, i.e., if EA > 3.6 eV. On the basisof DFT‐ωB97X‐D3 calculations, there is a further ability to exclude formation of electronic host‐dopant hybrid orbitals for these systems.