Molecular conformation and electronic properties of protoporphyrin-IX self-assembled monolayers adsorbed on a Pt(111) surface

Monolayers of protoporphyrin-IX molecules are prepared on a Pt(111) surface by a self-assembly process in order to manufacture organic devices with controlled electronic properties. Scanning tunnelling microscopy (STM) and two-colour sum-frequency generation (2C-SFG) are performed ex situ in ambient air, in order to characterize their molecular conformation and electronic properties at the monolayer level, respectively. STM measurements performed with functionalized gold tips reveal a high covering rate of the metal surface. 2C-SFG measurements highlight CH stretching modes of vinyl substituted groups (R-CH=CH2) in the 2800–3200 cm-1 infrared spectral range and particular electronic features in the visible spectral range, i.e. a Soret band red shift and band separation compared to the liquid phase. Moreover, similar measurements are performed on Zn(II)Protoporphyrin-IX and 5-[p-(6-mercaptohexoxy)-phenyl]-10,15,20-triphenylporphin films for comparison. These results suggest a film conformation with the molecules having different tilt angles
with respect to the substrate normal, depending on the ion metal presence or the chain length bonded to the porphyrin moiety.