Surface dipole of F4TCNQ films: Collective charge transfer and dipole-dipole repulsion in submonolayers

Abstract: A charge transfer (CT) model is introduced for strong acceptors like A = F4TCNQ that are ionized on surfaces at low coverage {\theta}. Each A forms a CT dimer with a surface state S. Dipole-dipole repulsion grows as {\theta}^3/2 up to {\theta} = 1 in a full monolayer. Electron transfer {\rho}({\theta}) within dimers is found self-consistently and decreases with increasing coverage. The surface dipole and work function shift {\Delta}{\Phi} are proportional to {\theta}{\rho}({\theta}). The CT model has implications for photoemission and accounts for {\Delta}{\Phi}(d) profiles of F4TCNQ films of thickness d on Cu(1,1,1) or on hydrogenated diamond (1,0,0). The CT model also describes {\Delta}{\Phi}({\theta}) of organic donors on metals and is contrasted to previous treatments of dipoles on a surface.