XPS characterization of self-assembled monolayers (SAMs) of tetraphenylporphyrin bearing a rigid tripodal linker by chemisorption of the thiol-derivatized terminal groups on gold substrate is described. The surface structure of the SAMs bearing tripodal linker were analyzed by X-ray photoelectron spectroscopy (XPS), and electrochemical cyclic voltammetry (CV) measurements. XPS confirms the formation of porphyrin SAMs on Au surface and identified bonding configurations of porphyrin molecules in the chemisorption of SAMs. The film thickness values (36 Å) obtained by XPS agree well with the estimated value by assuming the vertical orientation of the molecules on the gold surface. Using the Au4f7/2 as an internal standard, a lower binding energies shift (1.8 eV) of S2p in the SAMs reveals that the porphyrins were chemisorbed onto the surface via sulfurgold bonds. Electrochemical CV measurements suggest near monolayer coverage of the tripodal porphyrins with good stability of the redox SAMs, which have promising application in the development of molecular based electronic device and memory architectures.
