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Ishii, H. et al. Kelvin probe study of band bending at organic semiconductor/metal interfaces: examination of Fermi level alignment.
Ultraviolet photoemission spectroscopy (UPS) characterization of the NiOx film and its interface with the polymer shows Fermi level alignment of the polymer with the NiOx film.
UPS of the blend also demonstrates Fermi level alignment of the organic active layer with the HTL, consistent with the lack of correlation between Voc and HTL work-function.
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If ΔΦSAM became negative (positive) enough, the LUPS (HOPS) of 2P would be shifted below (above) the Fermi level for vacuum-level alignment.
Depending on the nature of the SAM, we observe clear transitions between Fermi level pinning and vacuum-level alignment regimes.
At equilibrium, the Fermi level of TiO2 aligns with the Fermi level of InP, inducing an inversion region in p-type InP close to the TiO2/InP interface.
We find that the level alignments can be organized in three regimes: Fermi level pinning close to the LUPS of 2P, vacuum-level alignment (i.e., the Schottky−Mott limit), and pinning close to the HOPS.
Assuming an aligned Fermi level in the NW and measuring the onset difference at the linear part yields the vacuum level difference for the segments.
The key question to be addressed here is how the SAM-induced work-function change affects the actual alignment of the electrode Fermi level relative to the energy levels of the subsequently deposited OSC, that is, the highest occupied and the lowest unoccupied π-states (HOPS/LUPS) of 2P.
Additionally, the a priori unexpected observation has been made that the substituent (and, thus, the molecular ionization potential) has no impact on the relative alignment of the metal Fermi level and the highest occupied π-states, 44) at least as long as the SAM packing density was sufficiently high.
Thus, the tunneling decay with iodine shows the lowest value among those anchoring groups with a trend βN (thiol) > βN (amine) > βN (carboxylic acid) > βN (iodine), which may be due to the difference in the alignment of molecular energy levels to the Fermi level of Au electrode [23, 31].
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