Modification of BaTiO3 thin films: adjustment of the effective surface work function

Sputter-deposited BaTiO3 thin films have been modified with an alkylphosphonic acid and a partially-fluorinated alkylphosphonic acid in order to model the surface composition of similarly modified BaTiO3 nanoparticles. We present here the surface characterization of these modified films by a combination of X-ray photoelectron spectroscopy (XPS) and UV-photoelectron spectroscopy (UPS). BaTiO3 layers of average thicknesses ca. 2 nm were prepared by radio frequency (rf) magnetron sputter deposition on Ag films, to avoid charging effects during XPS/UPS characterization. Octadecylphosphonic acid (ODPA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl phosphonic acid (perfluorohexyloctyl phosphonic acid, FHOPA), molecules with quite different molecular dipole moments, were chemisorbed from solution to the BaTiO3 surface. Polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) of the modified BaTiO3 films indicated bidentate bonding of the alkylphosphonic acid to the oxide. Modification of the BaTiO3 surface with the partially-fluorinated alkylphosphonic acid (versus the normal alkylphosphonic acid) significantly changes the BaTiO3 interface dipole as revealed by UPS/XPS measurements, which, in turn, changes the frontier orbital offsets between the oxide and the organic modifier.