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Stable F-induced structures observed by STM; No Cu 2+ chemical states on surface after XPS; Strong chemisorption state of F; Eads > 4 eV; (2√2×√2)R45o 3F is identified on Cu(001); θ=0.75 ML with hollow and near hollow adsorption sites due to strong F-F repulsion; Kagomé structures p(5×5) 12F and p(7×7) 24F (0.48 ML and 0.49 ML coverage) are formed on Cu(111); Low diffusion barrier explains observation of fcc, hcp and bridge F atoms positions for p(5×5) and p(7×7) on Cu(111); Observed superstructures can be considered as a 2D copper fluoride with a “low” Cu valency; At higher fluorine coverage (θ=1 ML) structures become unstable with respect to CuF2 formation.