Electronic and structural studies of immobilized thiol-derivatized cobalt porphyrins on gold surfaces

• Published in: Applied surface science Vol. 253; no. 18; pp. 7540 - 7548
• Main Authors: Berner, Simon, Lidbaum, Hans, Ledung, Greger, Åhlund, John, Nilson, Katharina, Schiessling, Joachim, Gelius, Ulrik, Bäckvall, Jan-E., Puglia, Carla, Oscarsson, Sven
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 2007; Elsevier Science
• Subjects: Chemistry; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Fysik; Immobilization; Kemi; NATURAL SCIENCES; NATURVETENSKAP; Physics; Porphyrin; Scanning tunnelling microscopy; TECHNOLOGY; TEKNIKVETENSKAP; Thiol-functionalized; X-ray photoelectron spectroscopy; 81.16.Dn; Porphyrin; 79.60.Dp; Scanning tunnelling microscopy; Immobilization; 68.43.Hn; 68.37.Ef; Thiol-functionalized; X-ray photoelectron spectroscopy; Gold; Cobalt; Scanning tunneling microscopy; Transition elements; X-ray photoelectron spectra
• ISSN: 0169-4332; 1873-5584; 1873-5584
• DOI: 10.1016/j.apsusc.2007.03.066

The immobilisation of thiol-derivatized cobalt porphyrins on gold surfaces has been studied in detail by means of combined scanning tunnelling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). S-thioacetyl has been used as a protective group for the thiol. Different routes for deprotection of the acetyl groups were performed in acidic and in basic conditions. The results show the formation of monolayer films for the different preparation schemes. The immobilisation of the molecules on the gold surface takes place through the thiol-linkers by the formation of multiple thiolate bonds. In the case of layers formed with protected porphyrins approximately 60% of the linkers are bonded to the gold surface whereas for deprotected layers the amount of bonded linkers is increased up to about 80%. STM measurements revealed that the molecules arrange in a disordered overlayer and do not exhibit mobility on the gold surface. Annealing experiments have been performed in order to test the stability of the porphyrin layers. Disordered patterns have been observed in the STM images after annealing at T = 400 °C. XPS revealed that the sulphur content disappeared completely after annealing at T = 180 °C and that the molecules did undergo significant modifications.