Electrostatic Interaction across a Single-Layer Carbon Shell.

Ions inside of fullerene molecules are model systems for the study of the electrostatic interaction across a single layer of carbon. For TbSc2N@C80 on h-BN/Ni(111), we observe with high-resolution X-ray photoelectron spectroscopy a splitting of the C 1s core level. The data may be explained quantitatively with density functional theory. The correlation of the C 1s eigenvalues and the Coulomb potential of the inside ions at the corresponding carbon sites indicates incomplete screening of the electric field due to the endohedral ions. The screening comprises anisotropic charge transfer to the carbon atoms and their polarization. This behavior is essential for the ordering of endohedral single-molecule magnets and is expected to occur in any single-layer material.

Charge-transfer excitons at organic semiconductor surfaces and interfaces.

When a material of low dielectric constant is excited electronically from the absorption of a photon, the Coulomb attraction between the excited electron and the hole gives rise to an atomic H-like quasi-particle called an exciton. The bound electron-hole pair also forms across a material interface, such as the donor/acceptor interface in an organic heterojunction solar cell; the result is a charge-transfer (CT) exciton. On the basis of typical dielectric constants of organic semiconductors and the sizes of conjugated molecules, one can estimate that the binding energy of a CT exciton across a donor/acceptor interface is 1 order of magnitude greater than k(B)T at room temperature (k(B) is the Boltzmann constant and T is the temperature). How can the electron-hole pair escape this Coulomb trap in a successful photovoltaic device? To answer this question, we use a crystalline pentacene thin film as a model system and the ubiquitous image band on the surface as the electron acceptor. We observe, in time-resolved two-photon photoemission, a series of CT excitons with binding energies < or = 0.5 eV below the image band minimum. These CT excitons are essential solutions to the atomic H-like Schrodinger equation with cylindrical symmetry. They are characterized by principal and angular momentum quantum numbers. The binding energy of the lowest lying CT exciton with 1s character is more than 1 order of magnitude higher than k(B)T at room temperature. The CT(1s) exciton is essentially the so-called exciplex and has a very low probability of dissociation. We conclude that hot CT exciton states must be involved in charge separation in organic heterojunction solar cells because (1) in comparison to CT(1s), hot CT excitons are more weakly bound by the Coulomb potential and more easily dissociated, (2) density-of-states of these hot excitons increase with energy in the Coulomb potential, and (3) electronic coupling from a donor exciton to a hot CT exciton across the D/A interface can be higher than that to CT(1s) as expected from energy resonance arguments. We suggest a design principle in organic heterojunction solar cells: there must be strong electronic coupling between molecular excitons in the donor and hot CT excitons across the D/A interface.

Formation of two-dimensional polarons that are absent in three-dimensional crystals.

We report the direct time domain observation of a many-body process in a two-dimensional system: small polaron formation from the localization of a conduction band electron in NaCl thin films of unit cell thickness. Contrary to theoretical prediction for bulk NaCl crystal where an electron polaron does not exist, time-resolved two-photon photoemission reveals small polaron formation from delocalized conduction band electrons in crystalline NaCl thin films. The increased deformability and the reduced electronic bandwidth of a crystalline lattice in the thin film format are both responsible for the formation of small polarons that are absent in bulk solids.

Electron dynamics at polyacene/Au(111) interfaces.

Two-photon photoemission (2PPE) spectroscopy is used to examine the excited electronic structure and dynamics at polyacene/Au(111) interfaces. Image resonances are observed in all cases (benzene, naphthalene, anthrathene, tetracene, and pentacene), as evidenced by the free-electron like dispersions in the surface plane and the dependences of these resonances on the adsorption of nonane overlayers. The binding energies and lifetimes of these resonances are similar for the five interfaces. Adsorption of nonane on top of these films pushes the electron density in the image resonance away from the metal surface, resulting in a decrease in the binding energy (-0.3 eV) and an increase in the lifetime (from <20 to approximately 110 fs). The insensitivity of the image resonances to the size of polyacene molecules and the absence of photoinduced electron transfer from the metal substrate to molecular states both suggest that the unoccupied molecular orbitals are not strongly coupled to the delocalized metal states or image potential resonances.

Delocalized electron resonance at the alkanethiolate self-assembled monolayer/Au(111) interface.

We probe the electronic structure of alkanethiolate self-assembled monolayers (SAMs) on Au(111) using two-photon photoemission spectroscopy. We observe a dispersive unoccupied resonance close to the vacuum level with a lifetime shorter than 30 fs. The short lifetime and the insensitivity of the energy level and dispersion to molecular length (and thus layer thickness) suggest that the probability density of the electron wave function is concentrated inside the molecular layer close to the SAM/Au interface. Such an interfacial resonance results from the image like potential at the SAM/Au interface.

Electron transport across the alkanethiol self-assembled monolayer/Au(111) interface: role of the chemical anchor.

Alkanethiol self-assembled monolayers (SAMs) on Au(111) are model systems for molecular electronics. We probe the role of the chemisorption bond on electron dynamics at the SAM/Au interface using time-resolved two-photon photoemission. Formation of the Au-S bond is evidenced by a localized sigma resonance, which broadens and shifts upward in energy when the lying-down chemisorbed molecules stand up. The localized chemisorption bond does not affect the electronic coupling between delocalized image resonances and the metal substrate. Instead, lifetimes of image resonances are decreased due to scattering with S atoms within the thiol or thiolate monolayer.

Localization of surface states in disordered step lattices.

The character of the surface state wave function on regularly stepped Cu(111) is reinvestigated. It is shown that the qualitative change at terrace lengths around 17 A observed previously by Ortega et al. [Phys. Rev. Lett. 84, 6110 (2000)]] must necessarily be described as a change from a propagating superlattice state to a terrace-confined quasi-one-dimensional state. This reconciles previous, apparently contradictory experimental results and sheds new light on the behavior of nearly free electrons in nanostructures. Possible mechanisms driving the localization are discussed on the basis of the surface state bulk penetration depth, which has been measured in both regimes.

Step-lattice-induced band-gap opening at the fermi level.

The interaction of the Shockley surface state with the step lattice of vicinal Cu(111) leads to the formation of an electronic superlattice state. On Cu(443), where the average terrace length forms a "shape resonance" with the Fermi wavelength, we find a step-lattice-induced band-gap opening at the Fermi level. A gap magnitude >200 meV is inferred from high resolution photoemission experiments and line shape analysis. The corresponding energy gain with respect to a gapless case is approximately 11 meV/unit cell, and is a substantial contribution to the stabilization of the step lattice.