We present an in operando near-edge x-ray absorption fine structure (NEXAFS) study on p-type [11-(benzo[b]benzo[4,5]thieno[2,3-d]thiophen-2-yl)dodecyl)] BTBT-based self-assembled monolayer (BTBT-SAM) films. As a 2D-model system, the BTBT-SAM offers direct insight into the active organic semiconductor layer without interfering bulk materials. This allows for the observation of polaronic states caused by charged species at the dielectric/organic interface. Linear NEXAFS dichroism is employed to derive the molecular orientation of the BTBT subunit. Field-induced modifications in the unoccupied molecular orbitals are observed in the NEXAFS spectra. The spectral changes in the on- and off-states are discussed in the context of polaron formation due to charge accumulation induced by the applied electric field.
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