Image-potential States Research Articles

Nonvalence Correlation-Bound Anion States of Polycyclic Aromatic Hydrocarbons.

In this work, we characterize the nonvalence correlation-bound anion states of several polycyclic aromatic hydrocarbon (PAH) molecules. Unlike the analogous image potential states of graphene that localize the charge density of the excess electron above and below the plane of the sheet, we find that for PAHs, much of the charge distribution of the excess electron is localized around the periphery of the molecule. This is a consequence of the electrostatic interaction of the electron with the polar CH groups. By replacing the H atoms by F atoms or the CH groups by N atoms, the charge density of the excess electron shifts from the periphery to above and below the plane of the ring systems.

Resolubility of image-potential resonances

A theory of image-potential states is presented for the general case where these surface electronic states are resonant with a bulk continuum. The theory extends the multiple scattering approach of Echenique and Pendry into the strong coupling regime while retaining independence from specific forms of surface and bulk potentials. The theory predicts the existence of a well-resolved series of resonances for arbitrary coupling strengths. Surprisingly, distinct image-potential resonances are thus expected to exist on almost any metal surface, even in the limiting case of jellium.

Rashba Spin-Orbit Coupling in Image Potential States.

The search in two-dimensional condensed matter systems of Rashba-type spin-polarized electronic states is aimed by the possibility to control and manipulate the spin orientation. In this Letter, for the first time, we report on the experimental evidence of a Rashba-type spin splitting in the n=1 image potential state. The image potential state Rashba splitting here measured at the graphene/Ir(111) interface, as confirmed by theoretical considerations, can be detectable to any metal surface with a significant spin-orbit coupling.

Effect of surface plasmons at the Al/alumina interface on the formation of nanopores in Al anodization

We investigated the formation mechanism of nanoporous alumina in the electrochemical reaction of aluminium with oxalic acid solution in terms of the pinning effect of Fermi level at the metal–oxide interface. On the Al metal surface, the image potential state pins the standing mode of collectively excited surface electrons and the evanescent wave forms the plasmon mode, which can be reflected in oxide barrier formation. A nanoporous alumina thin film with an amorphous phase oxide layer on the Al surface can enhance light absorption at a shorter wavelength than 382 nm and provide strong Fabry–Perot oscillation in photoreflectance. The cathodoluminescence spectra show the surface plasmon mode as a consequence of the self-ordered oxide nanopores. The Kretschmann configuration of an attenuated total reflection set-up for prism/oxalic solution/Al interface, which also provides a prism-coupled surface plasmon and forms oxide nanopores on the Al surface via a laser-enhanced anodization process.

Surface states resonances at the single-layer graphene/Cu(111) interface

By tuning the laser photon energy in the non-linear two-photons photoemission at a single-layer graphene/Cu(111) interface, it is possible to observe a strong resonance at hυ=3.5eV along with a weaker one at hυ=3.85eV. The main resonance photon energy is consistent with a direct optical transition between the occupied Cu(111) Shockley surface state and the n=1 image potential state, located in the real gap-space between the single-layer graphene and the Cu(111) surface. The large amplitude of this resonance unveils a high value of the electric dipole matrix element integral that governs this transition. Furthermore, the Lorentzian shape of this resonance implies that these two states are decoupled from the continuum of states and the lifetime of the image potential state can be estimated.

Nature of the surface states at the single-layer graphene/Cu(111) and graphene/polycrystalline-Cu interfaces

Single-layer graphene supported on a metal surface has shown remarkable properties relevant for novel electronic and optoelectronic devices. However, the nature of the electronic states derived from unoccupied surface states and quantum well states, lying in the real-space gap between the graphene and the solid surface, has not been explored and exploited yet. Herein, we use ultraviolet nonlinear angle-resolved photoemission spectroscopy to unveil the coexistence at the graphene/Cu(111) interface of a highest occupied Shockley surface state (HOSS) and the two lowest unoccupied surface states (LUSS). The experimental results and electronic structure calculations, based on one-dimensional model potential, indicate that the two unoccupied states originate from the hybridization of an $n=1$ image potential state with a quantum well state. The hybridized nature of these unoccupied states is benchmarked by a similar experiment done on single-layer graphene grown on copper polycrystalline foil where only the image state survives being the quantum well state at this interface inhibited.

Modification of electronic surface states by graphene islands on Cu(111)

We present a study of graphene/substrate interactions on UHV-grown graphene islands with minimal surface contamination using \emph{in situ} low-temperature scanning tunneling microscopy (STM). We compare the physical and electronic structure of the sample surface with atomic spatial resolution on graphene islands versus regions of bare Cu(111) substrate. We find that the Rydberg-like series of image potential states is shifted toward lower energy over the graphene islands relative to Cu(111), indicating a decrease in the local work function, and the resonances have a much smaller linewidth, indicating reduced coupling to the bulk. In addition, we show the dispersion of the occupied Cu(111) Shockley surface state is influenced by the graphene layer, and both the band edge and effective mass are shifted relative to bare Cu(111).

Microspot two-photon photoemission spectroscopy for CuPc film on HOPG

Microspot two-photon photoemission (micro-2PPE) spectroscopy has been applied to measure the lateral distribution of unoccupied levels on copper phthalocyanine (CuPc) film on HOPG. In addition to the LUMO-derived level and the image potential state (IPS) on the film, we identified the modified IPS which is stabilized by the hole localized in a molecule. We show that modified IPS is observed only on bilayer area, reflecting the localization of the hole in a molecule. The modified IPS is absent on monolayer area, because the hole strongly interacts with substrate.

Excited states at interfaces of a metal-supported ultrathin oxide film

We report layer-resolved measurements of the \textit{unoccupied} electronic structure of ultrathin MgO films grown on Ag(001). The metal-induced gap states at the metal/oxide interface, the oxide band gap as well as a surface core exciton involving an image-potential state of the vacuum are revealed through resonant Auger spectroscopy of the Mg $KL_{23}L_{23}$ Auger transition. Our results demonstrate how to obtain new insights on \textit{empty} states at interfaces of metal-supported ultrathin oxide films.

Application of a time-of-flight spectrometer with delay-line detector for time- and angle-resolved two-photon photoemission

We describe the design and operation of a time-of-flight electron spectrometer which is capable of simultaneously acquiring the energy and momentum distribution of low-energy photoelectrons in two dimensions parallel to the surface. We discuss its capabilities and limitations in particular for time- and angle-resolved two-photon photoemission (2PPE) with pulsed lasers. The performance of the spectrometer is demonstrated by presenting 2PPE data on the momentum-dependent electron dynamics of the first (n=1) image-potential state on Cu(001). The data reveal a weak but systematic dependence of the decay dynamics on sample azimuth with one-fold symmetry which we attribute to a small residual step density on the nominal flat surface.

Image potential states at chevron-shaped graphene nanoribbons /Au(111) interfaces

Image potential states at chevron-shaped graphene nanoribbons /Au(111) interfaces

From two-dimensional electron gas to localized charge: Dynamics of polaron formation in organic semiconductors

Electronic transport in organic semiconductors is mediated by localized polarons. However, the dynamics on how delocalized electrons collapse into polarons through electron-nuclear interaction is not well known. In this work, we use time- and angle-resolved photoemission spectroscopy to study polaron formation in titanyl phthalocyanine deposited on $\mathrm{Au}(111)$ surfaces. Electrons are optically excited from the metal to the organic layer via the image potential state, which evolves from a dispersive to a nondispersive state after photoexcitation. The spatial size of the electrons is determined from the band structure using a tight-binding model. It is observed that the two-dimensional electron wave collapses into a wave packet of size \ensuremath{\sim}3 nm within 100 fs after photoexcitation.

Spontaneous doping of two-dimensional NaCl films with Cr atoms: aggregation and electronic structure.

Scanning tunneling microscopy (STM) experiments combined with density functional theory (DFT) calculations reveal that deposited Cr atoms replace either Na or Cl ions, forming substituting dopants in ultrathin NaCl/Au(111) films. The Cr dopants exchange electrons with the support thus changing the electronic properties of the film and in particular the work function. The Cr atoms spontaneously aggregate near the edges of the bilayer (2L) NaCl islands, forming a new phase in the insulator with a remarkably dense population of Cr dopants. The spectra of differential conductance yield evidence that, compared to the undoped or Cr-poor 2L NaCl films on Au(111), the Cr-rich region shows different interface states, shifted image-potential states, and a reduced work function. This demonstrates the potential of doping ultrathin films to modify their adsorption properties in a desired manner.

Quantum beats at the metal/organic interface

Time resolved two-photon photoemission (TPPE) is used to probe the unoccupied electronic structure of monolayer films of dicarbonitrile-quaterphenyl (NC-Ph4-CN) on Ag(111) and cobalt phthalocyanine (CoPc) on Ag(100). For both samples, photoelectron spectra show a well-formed series of electronic states near the vacuum level. These are assigned as the 1≤n≤4 image-potential states (IPS's) based on the scaling of their binding energies and lifetimes. Time domain measurements at energies near the vacuum level exhibit intensity oscillations (quantum beats) which are due to excitation of an electronic wave packet of the n≥4 IPS's. The wave packets remain coherent until population decay renders them unobservable. These measurements clearly demonstrate that the classical image-potential state structure is retained to high order (n∼6) in the presence of aromatic organic adlayers. This represents the first definitive observation via TPPE of quantum beats of electronic origin at the metal/organic interface.

Spin-dependent lifetime and exchange splitting of surface states on Ni(1 1 1)

We report on a spin-resolved two-photon photoemission study of the Ni(1 1 1) surface states. Nickel thin films were grown by molecular beam epitaxy on a W(1 1 0) substrate. The first image-potential state is used as a sensor to map the spin polarization of the occupied surface states. This allows us to identify the majority spin component of the Shockley surface state as well as a majority and minority d-derived surface resonance. The n = 1 image-potential state is found to be exchange split by 14 ± 3 meV. In spite of the fact that the band structure at the Fermi level exhibits a strongly discerned density of states in both spin channels, we observe low spin asymmetries in the decay and dephasing rates of the photoexcited electrons. Varying the sample preparation reveals that the Shockley surface state contributes about 40% to the spin-dependent decay rate.

Quantitative determination of a nano-object's atom density without atomic resolution

We outline a possibility to determine the adatom density of individual nano-objects via measurement of their electronic structure. For this aim, the nonlinear shift of image potential states measured on individual Cu nanoclusters on Ag(100) by low-temperature scanning tunneling spectroscopy is carefully analyzed. The quantitative analysis is confirmed by density-functional theory calculations. A peak width analysis furthermore reveals whether the clusters are purely metallic or alloyed.

Interplay of local and global interfacial electronic structure of a strongly coupled dipolar organic semiconductor

We investigate the consequences of strong electronic coupling at the organic semiconductor/metal interface in both the ground and excited state manifold for the case of chloro-boron subphthalocyanine on Cu(111). Using a combination of low-temperature scanning tunneling microscopy and ultraviolet photoelectron spectroscopy and angle-resolved two-photon photoemission, we are able to connect local electronic interactions at the interface with thin film structure despite complex growth in the submonolayer regime. We show that strong coupling leads to charge transfer from the surface to the molecule, and we are able to correlate this observation with the specific molecular adsorption geometry. Strong coupling further results in molecular excited state anion resonances and is responsible for autoionization of highly excited image potential states, relating to the heterogeneous electronic environment in these thin films. This study provides a step towards disentangling interfacial electronic interactions at complex organic/metal interfaces.

Unoccupied electronic states of icosahedral Al-Pd-Mn quasicrystals: Evidence of image potential resonance and pseudogap

We study the unoccupied region of the electronic structure of the fivefold symmetric surface of an icosahedral (i) Al-Pd-Mn quasicrystal. A feature that exhibits parabolic dispersion with an effective mass of (1.15±0.1)me and tracks the change in the work function is assigned to an image potential resonance because our density functional calculation shows an absence of band gap in the respective energy region. We show that Sn grows pseudomorphically on i-Al-Pd-Mn as predicted by density functional theory calculations, and the energy of the image potential resonance tracks the change in the work function with Sn coverage. The image potential resonance appears much weaker in the spectrum from the related crystalline Al-Pd-Mn surface, demonstrating that its strength is related to the compatibility of the quasiperiodic wave functions in i-Al-Pd-Mn with the free-electron-like image potential states. Our investigation of the energy region immediately above EF provides unambiguous evidence for the presence of a pseudogap, in agreement with our density functional theory calculations.

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.

Nonvalence correlation-bound anion states of spherical fullerenes.

We present a one-electron model Hamiltonian for characterizing nonvalence correlation-bound anion states of fullerene molecules. These states are the finite system analogs of image potential states of metallic surfaces. The model potential accounts for both atomic and charge-flow polarization and is used to characterize the nonvalence correlation-bound anion states of the C60, (C60)2, C240, and C60@C240 fullerene systems. Although C60 is found to have a single (s-type) nonvalence correlation-bound anion state, the larger fullerenes are demonstrated to have multiple nonvalence correlation-bound anion states.