Direct in situ determination of the polarization dependence of physisorption on ferroelectric surfaces

The ability to manipulate dipole orientation in ferroelectric oxides holds promise as a method to tailor surface reactivity for specific applications. As ferroelectric domains can be patterned at the nanoscale(1), domain-specific surface chemistries may provide a method for fabrication of nanoscale devices. Although studies over the past 50 yr have suggested that ferroelectric domain orientation may affect the energetics of adsorption, definitive evidence is still lacking(2-5). Domain-dependent sticking coefficients are observed using temperature-programmed desorption and scanning surface potential microscopy, supported by first-principles calculations of the reaction coordinate. The first unambiguous observations of differences in the energetics of physisorption on ferroelectric domains are presented here for CH(3)OH and CO(2) on BaTiO(3) and Pb(Ti(0.52)Zr(0.48))O(3) surfaces.