Self-passivation of molecular n-type doping during air exposure using a highly efficient air-instable dopant

In contrast to p-dopants, highly efficient molecular n-dopants are prone to degradation in air due to their low ionization potentials, limiting the processing conditions of doped functional organic devices. In this contribution, we investigate the air-stability of pure films of the n-dopant tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)ditungsten(II) (W2(hpp)4) and of C60 layers doped by W2(hpp)4. We find that 1/3 of the initial conductivity of the doped C60 thin films can be restored by thermal annealing in vacuum after a drop by 5 orders of magnitude upon air exposure. Furthermore, we show by ultraviolet photoelectron spectroscopy (UPS) and Seebeck measurements that the Fermi level shift toward the lowest unoccupied molecular orbital (LUMO) of C60 remains after air exposure, clearly indicating a conservation of n-doping. We explain these findings by a down-shift of the W2(hpp)4 energy levels upon charge-transfer to a host material with deeper lying energy-levels, facilitating a protection against oxidation in air. Consequently, the observed recovery of the conductivity can be understood in terms of a self-passivation of the molecular n-doping. Hence, an application of highly efficient n-doped thin films in functional organic devices handled even under ambient conditions during fabrication is feasible. © 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim

Performance and lifetime of vacuum deposited organic light-emitting diodes:Influence of residual gases present during device fabrication

Understanding the influence of residual gases present during vacuum deposition of organic light-emitting diodes (OLEDs) and their effect on the device lifetime and the electrical characteristics of OLEDs is crucial for advancing industrial fabrication. In order to gain a more in-depth understanding, the influence of residual nitrogen, oxygen, and water vapor on lifetime and electrical characteristics is investigated. This is achieved by introducing the residual gases into the evaporation chamber through a needle valve while monitoring the partial pressures with the help of a mass spectrometer. We find that water vapor introduces a series resistance to the OLED while the other gases do not influence the electric characteristics. The presence of oxygen or nitrogen impacts the lifetime of the OLEDs by the same amount. Water vapor introduces an additional, even faster degradation process within the first hours of OLED operation. The electrically stressed OLEDs are analyzed by laser desorption/ionization time-of-flight mass spectroscopy. We identify the dimerisation of BPhen as well as the complexation reaction of α-NPD with an Ir(piq) fragment as sources of device degradation

Self-passivation of molecular n-type doping during air exposure using a highly efficient air-instable dopant

In contrast to p-dopants, highly efficient molecular n-dopants are prone to degradation in air due to their low ionization potentials, limiting the processing conditions of doped functional organic devices. In this contribution, we investigate the air-stability of pure films of the n-dopant tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)ditungsten(II) (W2(hpp)4) and of C60 layers doped by W2(hpp)4. We find that 1/3 of the initial conductivity of the doped C60 thin films can be restored by thermal annealing in vacuum after a drop by 5 orders of magnitude upon air exposure. Furthermore, we show by ultraviolet photoelectron spectroscopy (UPS) and Seebeck measurements that the Fermi level shift toward the lowest unoccupied molecular orbital (LUMO) of C60 remains after air exposure, clearly indicating a conservation of n-doping. We explain these findings by a down-shift of the W2(hpp)4 energy levels upon charge-transfer to a host material with deeper lying energy-levels, facilitating a protection against oxidation in air. Consequently, the observed recovery of the conductivity can be understood in terms of a self-passivation of the molecular n-doping. Hence, an application of highly efficient n-doped thin films in functional organic devices handled even under ambient conditions during fabrication is feasible. © 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim