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The dynamics of two-dimensional small-polaron formation at ultrathin alkane layers on a silver(111) surface have been studied with femtosecond time- and angle-resolved two-photon photoemission spectroscopy. Optical excitation creates interfacial electrons in quasi-free states for motion parallel to the interface. These initially delocalized electrons self-trap as small polarons in a localized state within a few hundred femtoseconds. The localized electrons then decay back to the metal within picoseconds by tunneling through the adlayer potential barrier. The energy dependence of the self-trapping rate has been measured and modeled with a theory analogous to electron transfer theory. This analysis determines the inter- and intramolecular vibrational modes of the overlayer responsible for self-trapping as well as the relaxation energy of the overlayer molecular lattice. These results for a model interface contribute to the fundamental picture of electron behavior in weakly bonded solids and can lead to better understanding of carrier dynamics in many different systems, including organic light-emitting diodes.

Two-photon photoemission is a promising new technique that has been developed for the study of electron dynamics at interfaces. A femtosecond laser is used to both create an excited electronic distribution at the surface and eject the distribution for subsequent energy analysis. Time- and momentum-resolved two-photon photoemission spectra as a function of layer thickness fully determine the conduction band dynamics at the interface. Earlier clean surface studies showed how excited electron lifetimes are affected by the crystal band structure and vacuum image potential. Recent studies of various insulator/metal interfaces show that the dynamics of excess electrons are largely determined by the electron affinity of the adsorbate. In general, electron dynamics at the interface are influenced by the substrate and adlayer band structures, dielectric screening, and polaron formation in the two-dimensional overlayer lattice.