29,31‑H Phthalocyanine Covalently Bonded Directly to a Si(111) Surface Retains Its Metalation Ability

The reaction of metal-free phthalocyanine molecules with a chlorine-terminated Si(111) surface is investigated to produce a phthalocyanine functionality directly attached to a semiconductor surface, without additional linkers or layers. The carefully prepared Cl–Si(111) surface provides an oxygen-free substrate that is reacted with 29,31-H phthalocyanine (H₂Pc) in a wet-chemistry process resulting in HCl elimination. The in situ metalation of this H₂Pc-modified silicon surface with cobalt is confirmed, suggesting that the produced functionality is chemically active. These processes are investigated by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and time-of-flight secondary ion mass spectrometry supplemented by density functional theory calculations. The morphology of the surface is monitored by atomic force microscopy. The combined spectroscopic, microscopic, and theoretical investigations demonstrate that additional linkers are not required for phthalocyanine attachment to occur, as the direct attachment can take place by forming Si–N bonds, and that the resulting surface species can participate in a metalation process.