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Ferromagnetic metal–organic semiconductor (FM‐OSC) hybrid interfaces have been shown to play an important role for spin injection in organic spintronics. Here, 11,11,12,12‐tetracyanonaptho‐2,6‐quinodimethane (TNAP) is introduced as an interfacial layer in Co‐OSCs heterojunctions with an aim to tune the spin injection. The Co/TNAP interface is investigated by use of X‐ray and ultraviolet photoelectron spectroscopy (XPS/UPS), near edge X‐ray absorption fine structure (NEXAFS) and X‐ray magnetic circular dichroism (XMCD). Hybrid interface states (HIS) are observed at Co/TNAP interfaces, resulting from chemical interactions between Co and TNAP. The energy level alignment at the Co/TNAP/OSCs interface is also obtained, and a reduction of the hole injection barrier is demonstrated. XMCD results confirm sizeable spin polarization at the Co/TNAP hybrid interface.
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