Unraveling the Origin of Elemental Chemical Shift and the Role of Atomic Hydrogen in a Surface Ullmann Coupling System

The Ullmann coupling of aryl halides is a powerful method in the on-surface synthesis of functional materials. Understanding its basic aspects and influencing factors can aid in the use of this tool for the fabrication of intriguing structures. In this study, we unveil (1) the origin of the shift in the elemental binding energy (BE) and (2) the functions of atomic hydrogen (AH) in a typical Ullmann coupling system using combined spectroscopy and microscopy techniques. During debromination of the aryl halide precursor, the work function (WF) alteration is correlated with the surface Br amount. The WF change instead of C–Ag formation is proposed to play a dominant role in the shift of the molecular C 1s BE. AH dosing onto organometallic chains leads to chain decomposition and surface Br removal. In contrast, AH dosing onto covalent poly( para- phenylene) (PPP) chains results in superhydrogenation in addition to Br removal. The C 1s BE shift is attributed to both WF change and superhydrogenation effects. Thermal annealing restores the PPP chains by eliminating superhydrogenation, which causes the C 1s BE to shift to a high BE. This study provides deep insights into the mechanisms of Ullmann coupling on surfaces, highlighting the significant role of WF alterations and AH treatments in these processes.