Alex J. Shearer

Metal/Phthalocyanine Hybrid Interface States on Ag(111)

A phthalocyanine/Ag(111) interface state is observed for the first time using time- and angle-resolved two-photon photoemission. For monolayer films of metal-free (H2Pc) and iron phthalocyanine (FePc) on Ag(111), the state exists 0.23 ± 0.03 and 0.31 ± 0.03 eV above the Fermi level, respectively. Angle-resolved spectra show the state to be highly dispersive with an effective mass of 0.50 ± 0.15 me for H2Pc and 0.67 ± 0.14 me for FePc. Density functional theory calculations on the H2Pc/Ag(111) surface allow us to characterize this state as being a hybrid state resulting from the interaction between the unoccupied molecular states of the phthalocyanine ligand and the Shockley surface state present on the bare Ag(111) surface. This work, when taken together with the extensive literature on the 3,4,9,10-perylene tetracarboxylic dianhydride/Ag interface state, provides compelling evidence that the hybridization of metal surface states with molecular electronic states is a general phenomenon.

Femtosecond Electron Solvation at the Ionic Liquid/Metal Electrode Interface

Electron solvation is examined at the interface of a room temperature ionic liquid (RTIL) and an Ag(111) electrode. Femtosecond two-photon photoemission spectroscopy is used to inject an electron into an ultrathin film of RTIL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Bmpyr](+)[NTf2](-)). While much of current literature highlights slower nanosecond solvation mechanisms in bulk ionic liquids, we observe only a femtosecond response, supporting morphology dependent and interface specific electron solvation mechanisms. The injected excess electron is found to reside in an electron affinity level residing near the metal surface. Population of this state decays back to the metal with a time constant of 400 ± 150 fs. Electron solvation is measured as a dynamic decrease in the energy with a time constant of 350 ± 150 fs. We observe two distinct temperature regimes, with a critical temperature near 250 K. The low temperature regime is characterized by a higher work function of 4.41 eV, while the high temperature regime is characterized by a lower work function of 4.19 eV. The total reorganizational energy of solvation changes above and below the critical temperature. In the high temperature regime, the electron affinity level solvates by 540 meV at 350 K, and below the critical temperature, solvation decreases to 200 meV at 130 K. This study will provide valuable insight to interface specific solvation of room temperature ionic liquids.

Femtosecond Trapping of Free Electrons in Ultrathin Films of NaCl on Ag(100).

We report the excited-state electron dynamics for ultrathin films of NaCl on Ag(100). The first three image potential states (IPSs) were initially observed following excitation. The electrons in the spatially delocalized n = 1 IPS decayed on the ultrafast time scale into multiple spatially localized states lower in energy. The localized electronic states are proposed to correspond to electrons trapped at defects in the NaCl islands. Coverage and temperature dependence of the localized states support the assignment to surface trap states existing at the NaCl/vacuum interface. These results highlight the importance of electron trapping in ultrathin insulating layers.

Electron dynamics of the buffer layer and bilayer graphene on SiC

Angle- and time-resolved two-photon photoemission (TPPE) was used to investigate electronic states in the buffer layer of 4H-SiC(0001). An image potential state (IPS) series was observed on this strongly surface-bound buffer layer, and dispersion measurements indicated free-electron-like behavior for all states in this series. These results were compared with TPPE taken on bilayer graphene, which also show the existence of a free-electron-like IPS series. Lifetimes for the n = 2, and n = 3 states were obtained from time-resolved TPPE; slightly increased lifetimes were observed in the bilayer graphene sample for the n = 2 the n = 3 states. Despite the large band gap of graphene at the center of the Brillouin zone, the lifetime results demonstrate that the graphene layers do not behave as a simple tunneling barrier, suggesting that the buffer layer and graphene overlayers play a direct role in the decay of IPS electrons.