Charge-transfer dynamics in van der Waals heterojunctions formed by thiophene-based semiconductor polymers and exfoliated franckeite investigated from resonantly core-excited electrons

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Physical Chemistry Chemical Physics
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Garcia-Basabe Y.
Steinberg D.
Daminelli L.M.
Mendoza C.D.
De Souza E.A.T.
Vicentin F.C.
G. Larrude D.
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© the Owner Societies.Organic/inorganic van der Waals heterojunctions formed by a combination of 2D materials with semiconductor polymer films enable the fabrication of new device architectures that are interesting for electronic and optoelectronic applications. Here, we investigated the charge-transfer dynamics at the interface between 2D layered franckeite (Fr) and two thiophene-based conjugated polymers (PFO-DBT and P3HT) from the resonantly core-excited electron. The unoccupied electronic states of PFO-DBT/Fr and P3HT/Fr heterojunctions were studied using near-edge X-ray absorption fine structure (NEXAFS) and resonant Auger (RAS) synchrotron-based spectroscopies. We found evidence of ultrafast (subfemtosecond charge-transfer times) interfacial electron delocalization pathways from specific electronic states. For the interface between the PFO-DBT polymer and exfoliated franckeite, the most efficient interfacial electron delocalization pathways were found through π∗(S-N) and π∗(S-C) electronic states corresponding to the benzothiadiazole and thiophene units. On the other hand, for the P3HT polymer, we found that electrons excited to π-π∗ and S1s-π∗(C-C) electronic states of the P3HT polymer are the most affected by the presence of exfoliated franckeite and consequently are the main interfacial electron-transfer pathways in this heterojunction. Our results have important implications in understanding how ultrafast electron delocalization is taking place in organic/inorganic van der Waals heterojunctions, which is relevant information in designing new devices involving these systems. This journal is
Assuntos Scopus
Based conjugated polymers , Charge-transfer dynamics , Electron delocalization , Interfacial electron transfer , Near edge x ray absorption fine structure , Optoelectronic applications , Semiconductor polymers , Unoccupied electronic state
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