XPS and SERS study of silicon phthalocyanine monolayers: Umbrella vs octopus design strategies for formation of oriented SAMs

Two strategies are compared for the formation of self-assembled monolayers (SAMs) of silicon phthalocyanines on gold. Silicon plithalocyanines were synthesized with thiol anchoring groups in either eight peripheral side chains (the "octopus") or with one short thiol in an axial position (the "umbrella"). Both approaches gave phthalocyanines capable of forming SAMs on gold surfaces. The orientation and coverage of the plithalocyanines were compared using ellipsometry, X-ray photoelectron spectroscopy (XPS), and surface-enhanced Raman scattering (SERS). The octopus silicon plithalocyanines form poorly organized SAMs in which the phthalocyanine (Pc) rings are strongly tilted with respect to the gold surface. On average, between 3 and 4 of the thiol "arms" fail to bind to the gold surface, even when limiting coverage is achieved after 7 days of soaking. The film thickness is 22 +/- 5 Angstrom. In contrast, the umbrella silicon phthalocyanine produces close-packed SAMs within 1 h in which the Pc rings lie parallel to the gold surface. The average thickness of the later SAMs is 11 +/- 3 Angstrom, and each phthalocyanine ring occupies an average area of 284 Angstrom (2).