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Further characterization suggests that the reaction mechanism is associated with Ullmann-type coupling to form the ordered chains as well as Ullmann-type and dehydrogenative C-C coupling to fabricate cross-linked polymer networks. Compared with the on-surface synthesis process of DBTT on the Cu(111) surface, it can be confirmed that the Au adatoms are vital to synthesize polythiophene. These findings provide important insight into the reaction mechanism of on-surface synthesized pure polythiophene and on-surface coupling can potentiall