ORIENTATION AND BONDING OF BENZOIC-ACID, PHTHALIC-ANHYDRIDE AND PYROMELLITIC DIANHYDRIDE ON CU(110)

The interaction of the polyimide precursor pyromellitic dianhydride (P MDA), and the related compounds benzoic acid and phthalic anhydride, w ith Cu(110) has been studied by high resolution electron energy loss s pectroscopy (HREELS). For benzoic acid, deprotonation of the carboxyli c acid group occurs on adsorption leading to the formation of a surfac e benzoate species (C6H5COO-). Bonding to the surface occurs through a carboxylate linkage via two equivalent oxygen atoms. The HREEL spectr um is characterised by an intense dipole active band, the symmetric O- C-O stretching vibration, at approximately 1420 cm-1. The plane of the carboxylate group is aligned perpendicular to the surface as is the p lane of the benzene ring. A similar species is found following exposur e of Cu(110) to phthalic anhydride. The carboxylate linkage results fr om disruption of the anhydride ring with loss of the C=O character (C6 H4COO-). In the case of the dianhydride species PMDA, only one of the anhydride units is used in bonding to the surface; the second unit poi nts away from the surface and is characterised by the symmetric anhydr ide stretch at 1255 cm-1 and weak C=O stretching vibrations at approxi mately 1850 cm-1. In both cases, changes in the intensity of some of t he bands compared with benzoic acid suggest that the carboxylate group is tilted away from the surface normal due to an interaction between one of the carbons of the aromatic ring and the copper surface. This i mplies that the plane of the aromatic ring is now twisted out of the p lane of the carboxylate group and, although still perpendicular to the surface, the axis is tilted to.allow one of the beta-carbon atoms to interact with the surface. In all cases, off-specular measurements at a primary electron energy of approximately 8 eV are dominated by the i ntense C-H stretching vibration. Measurements of the intensity of this mode, in the surface benzoate species, as a function of incident elec tron energy suggest that excitation of this mode occurs via a resonanc e scattering mechanism.