Ultrafast core-excited electron dynamics in model crystalline organic semiconductors

Electron transfer is key to the operation of devices based on molecular (organic) semiconductors. Others have shown that electron transfer in the solid state often proceeds on sub-50 fs timescales, the details of which can be difficult to temporally resolve using pump-probe spectroscopy. A popular technique to measure average time scales for such rapid electron-transfer events is the core-hole clock implementation of resonant Auger electron spectroscopy at a single X-ray absorption edge. This is often done on relatively small molecules with core-excited states that are highly localized. We have used resonant Auger spectroscopy to probe sub-50 fs electron dynamics of two relatively large model organic semiconductors: Cu phthalocyanine (CuPc) along with its fluorinated analog, F₁₆CuPc. We have interrogated electron dynamics simultaneously at N and C K-edges, along with calculations of initial and final states participating in the core-excited states. Our measurements show that the electron dynamics differ substantially across the two absorption edges for a given molecule, and that there are significant differences at a given edge between the two derivatives. X-ray spectroscopy calculations suggest that the extension of π-electron density onto peripheral F atoms in F₁₆CuPc is implicated in the large change in ultrafast electron dynamics upon fluorination. We believe our results have important implications for analysis of core-hole clock measurements on relatively large organic semiconductors.