Unoccupied surface states and surface barrier in metals

Recent progress in the spectroscopy of empty electronic states at metal surfaces allows for measuring the energy vs. momentum dispersion of both crystal-induced and image-potential surface states with high precision. This allows for deriving the effective barrier potential for an electron near a metal surface with considerable accuracy by comparing the experimental data with corresponding calculations based on the one-step model of inverse photoemission. The method is demonstrated for Cu(100) where four empty surface states are known experimentally.     

Surface states,local bonding,and surface reconstruction: Na on Cu(110)

Occupied and unoccupied surface states on Na/Cu(110) have been investigated by photoemission and inverse photoemission. By measuring surface state positions at the same adsorbate coverage on the reconstructed and the unreconstructed surface it is demonstrated that the surface states contribute to the total energy balance of the Na induced missing row reconstruction. During the onset of the reconstruction an up-shift of the surface states depopulates an initially occupied CuCu bonding surface state and consequently destabilizes the topmost Cu atoms. The surface state wavefunctions are qualitatively analyzed in a thight-binding LCAO picture.     

Spectroscopy of image-potential states by two-photon photoemission

Unoccupied electronic states in solids and at solid surfaces are usually studied by inverse photoemission. An alternative method is two-photon photoemission. It is superior in resolution but limited to states of sufficiently long lifetime below the vacuum level. So far this method has mainly been applied to image-potential states on metal surfaces. On Ag(111) and Cu(111) a narrow surface state below the Fermi level serves as the initial state, which results in a pronounced resonance in the two-photon photoemission. Ni(111) shows similar results. In the resonance the image-potential state is so highly populated that electron-electron interaction leads to an Auger-type process. Nevertheless, the system is not so greatly disturbed as to show deviations from the one-photon photoemission results concerning the occupied states. Ag(100) and Cu(100) have a smooth continuum of initial states. Consequently, no resonance occurs. The binding energy does not depend on the material but changes with surface orientation: it is about 0.80 eV at the (111) surfaces and about 0.55 eV at the (100) surfaces. The effective mass is free electron like except on Ag(111), where it is 30% heavier. The lifetime on Ag(100) is about 20 fs. The agreement with theory is excellent in some cases and only fair in others.     

Momentum-resolved inverse photoemission

Inverse photoemission including isochromat spectroscopy is shown to be a versatile technique to probe empty electronic states in solids and at clean and adsorbate covered surfaces. The complete set of quantum numbers of an electronic state can be determined and examples will be discussed for bulk and surface electronic states. For sufficiently low kinetic energy of the primary electrons, inverse photoemission is shown to be applicable to adsorbates also. This allows one to assess directly the unoccupied electronic states of the adsorbate which play an important role in the formation of the surface chemical bond. Examples are discussed for atomic and molecular chemisorption as well as adsorption on alkali promoted surfaces.     

Photon- and electron-induced surface voltage in electron spectroscopies on ZnSe(0 0 1)

The surface band bending in ZnSe(0 0 1), as a function of the temperature, is investigated both in the valence band (by photoemission) and in the conduction band (by inverse photoemission and absorbed current spectroscopies). Two different mechanisms are invoked for interpreting the experimental data: the band bending due to surface states, and the surface voltage induced by the incident beam. While the latter is well known in photoemission (surface photovoltage), we demonstrate the existence of a similar effect in inverse photoemission and absorbed current spectroscopies, induced by the incident electrons instead of photons. These results point to the importance of considering the surface voltage effect even in electron-in techniques for a correct evaluation of the band bending.     

One-dimensional metal structures at decorated steps

It is shown how wire structures a few nanometers wide can be fabricated by decorating step edges at vicinal surfaces. Their growth modes and electronic states are studied using Scanning Tunneling Microscopy (STM) and inverse photoemission. The observed growth modes are two-dimensional analogs of Stranski-Krastanov growth and layer-by-layer growth in three dimensions, e.g., for Cu on stepped Mo(1 1 0) and W(1 1 0), respectively. Contrast between different metals is achieved in STM pictures by resonant tunneling via surface states and image states, with the latter providing a map of the work function. The limit of single atomic rows decorating step edges is studied by inverse photoemission, and an energy shift of 0.4 eV is found for electronic states of step atoms. We expect stripe structures to become useful for the study of two- vs one-dimensional magnetism, for magnetoresistive films, and in the design of anisotropic materials.     

Realization of a spin-polarized two-dimensional electron gas via image-potential-induced surface states

Electrons in image-potential-induced surface states form a two-dimensional electron gas in front of the surfaces. In the case of ferromagnets, their binding energies as well as lifetimes depend on the orientation of their spin magnetic moment with respect to the magnetization direction. Various experiments with inverse photoemission and two-photon photoemission to detect the spin dependence of image states are reviewed. A new and successful approach to achieve and detect a spin-polarized two-dimensional electron gas is presented, namely polarization-dependent and spin-resolved two-photon photoemission. Additional time resolution opens the way to study spin-dependent electron dynamics.     

Electronic surface states of Cu(1 1 0) surface

Surface states are a unique and important class of quantum states that shave an important effect on the electronic properties of Cu(1 1 0) surface. The Cu(1 1 0) surface has been studied using ultraviolet photoemission spectroscopy (PES), inverse photoemission spectroscopy (IPES), and reflection anisotropy spectroscopy (RAS), and shows a resonance in the RAS spectra at 2.1 eV due to a transition between occupied and unoccupied surface states. The unoccupied surface state involved in the RAS transition at an energy of 1.7 eV at the point of the surface Brillouin zone has been investigated using IPES and the occupied surface state is seen in PES spectra at 0.45 eV below the Fermi level. The energy difference of the surface states, 2.15 eV, is a good match to the transition energy found in the RAS experiments.     

Quantum well and quantum wire states at metal surfaces

Novel effects in magnetic multilayer structures, such as oscillatory magnetic coupling and "giant" magnetoresistance, have created new materials that allow for an order of magnitude higher sensitivity in the detection of magnetically-recorded data. Determination of their electronic and magnetic structures with angle-resolved photoemission and inverse photoemission reveals quantized states in the noble metal spacer layers which are connected with oscillatory magnetic coupling and have implications on magnetoresistance. These states can be understood by a simple interferometer model, including the spin-dependent interface reflectivity that polarizes them and transmits the magnetic coupling through the noble metal spacer.Current efforts are discussed, which aim towards fabricating quantum wires and lateral superlattices on metals by decorating steps at vicinal surfaces. STM work on the growth mode of such structures is presented, which uses spectroscopic contrast to distinguish different metals. Specific electronic states at decorated step edges are found with inverse photoemission.     

Theory of satellites in photoemission and inverse photoemission spectra of 4 f materials

We present calculations of the relative intensities and peak separations of the f derived spectral density for the, integer valent, light rare earths. We consider both f derived photoemission and inverse photoemission spectra. In these types of experiments, the final states has either an excess or a deficiency of charge residing on the screened by the conduction electrons. If the screening interaction is This may give rise to the appearance of satellites in both photoemission and inverse photoemission spectra. However, the calculations indicate that the relative intensity of the f derived satellite in the inverse photoemission spectrum should be extremely weak, when compared to the intensity of the satellites in the photoemission experiment.     

Subthreshold photoemission from copper nanoclusters on the SiO2 surface

Subthreshold photoemission from copper nanoclusters formed on the SiO₂ surface has been observed under irradiation of the surface by photons in the 3.1–6.5-eV energy range. The average size of copper nanoclusters on the silicon oxide surface is 250–500 nm. Besides the conventional photoemission from the filled Shockley surface state (SS), strong photoemission has been recorded at incident photon energies of 0.5 eV below the work function of the copper surface. This emission is assumed to be generated in direct electron transitions from the SS state to the unfilled electron surface states formed by the Coulomb image potential, followed by escape from these states into vacuum.     

Angle-resolved photoemission from surface states

The role of the evanescent part of the unoccupied complex band structure in photoemission from surface states is revealed. The frequency dependence of the emission intensity from two surface states on the (100) and (111) surfaces of Al in the photon energy range from 40 to 110 eV is explained within an ab initio one-step theory of photoemission. A novel embedding method to determine surface states is presented. A high sensitivity of surface states spectra to details of the surface potential barrier is predicted, which offers a way to efficiently monitor surface properties.     

Quantum-well states and spin polarization in thin Ni films on Cu(0 0 1)

The unoccupied quantum-well states in thin Ni films on Cu(0 0 1) have been studied by spin- and angle-resolved inverse photoemission. Three quantum-well features are clearly resolved with exchange splittings of up to 70 meV. As a function of the wave vector parallel to the surface, the quantum-well states follow the corresponding sp band dispersion and evolve into surface resonances upon approaching the band-gap boundary.     

Bulk,surface and thermal effects in inverse photoemission spectra from Cu(100), Cu(110) and Cu(111)

We have performed a study of empty electronic bulk and surface states on the three low indexed copper surfaces employing momentum resolved inverse photoemission. The bulk electronic features may be well understood in the frame work of the bulk direct transition model using state of the art band structure calculations. Surface states of both, the crystal derived and the image potential induced type have been identified and were found to agree with previous work. Several radiative transitions into unoccupied bands were also investigated at elevated temperatures. Characteristic temperatures of an exponential attenuation law are distinctly different between surface and bulk transitions. However, no systematic behaviour of bulk transitions at different points of the Brillouin zone could be established.     

Angle-resolved photoemission study of Ag nanofilms grown on fcc transition-metal (111) substrates

A comparative study of the electronic structures of Ag nanofilms on the pseudomorphic metastable fcc Fe(111) and bulk-like fcc Co(111) substrates has been carried out to investigate their quantized electronic structures. The photoemission spectra of both Ag nanofilms exhibit the fine structures derived from the quantized sates of Ag sp valence electron. The nanofilm-thickness dependences of the binding energy of the quantized states are reproduced by the calculated results based on the phase accumulation model. From the angle-resolved photoemission measurements, the effective masses of the quantized electronic states along the direction parallel to the nanofilm surface were directly determined. We discuss the electronic hybridization effect between quantized states in Ag nanofilm and 3d-derived electronic states in transition-metal substrates.     

Surface states at the clean surfaces of cleaved Si(111) and GaAs(110)

A combination of ellipsometric data on the electronic transitions from occupied to unoccupied surface states and published photoemission data on the energy distribution of the occupied surface states has been used to construct models of the surface states densities at the cleaved Si (111) and GaAs (110) surfaces.     

Haloform adsorption on crystalline copolymer films of vinylidene fluoride with trifluoroethylene

Reversible bromoform adsorption on crystalline polyvinylidene fluoride with 30% of trifluoroethylene, P(VDF-TrFE 70:30) was examined by photoemission and inverse photoemission spectroscopies. The adsorption of bromoform on this polymer surface is associative and reversible. Molecular bromoform adsorption appears to be an activated process at 120 K with enhanced adsorption following the initial adsorption of bromoform. Strong intermolecular interactions are also implicated in the presence of a weak shake off or screened photoemission final state, whose intensity scales with the unscreened photoemission final state.     

Lifetime broadening in angle-resolved photoemission

The register line formalism of angle-resolved photoemission is applied to the special case where electrons are excited from sp surface states. By considering lifetime broadening alone, it is demonstrated that it is possible to explain why photoemission linewidths increase as the initial states disperse towards the Fermi level. Favourable comparisons are made between the theory and with measurements of the surface state widths on Cu(111) and Al(001).     

Electronic structure of semiconductor surfaces

Our present understanding of the electronic structure of semiconductor surfaces is reviewed. It is shown that photoemission and inverse photoemission are ideal techniques for probing occupied and unoccupied electronic states, respectively. All quantum numbers of an electron can be determined, i.e., energy, momentum, spin and angular symmetries. For simple systems, such as clean ordered surfaces with a small unit cell it is possible to understand the electronic structure from first-principles calculations. For complex systems, such as encountered during oxidation and dry etching one is restricted to measuring the properties determined by short-range order. Core level spectroscopy with synchrotron radiation is able to determine the oxidation state and the local bonding of surface and interface atoms.     

Observation of a warped helical spin texture in Bi2Se3 from circular dichroism angle-resolved photoemission spectroscopy

A differential coupling of topological surface states to left- versus right-circularly polarized light is the basis of many optospintronics applications of topological insulators. Here we report direct evidence of circular dichroism from the surface states of Bi(2)Se(3) using laser-based time-of-flight angle-resolved photoemission spectroscopy. By employing a novel sample rotational analysis, we resolve unusual modulations in the circular dichroism photoemission pattern as a function of both energy and momentum, which perfectly mimic the predicted but hitherto unobserved three-dimensional warped spin texture of the surface states. By developing a microscopic theory of photoemission from topological surface states, we show that this correlation is a natural consequence of spin-orbit coupling. These results suggest that our technique may be a powerful probe of the spin texture of spin-orbit coupled materials in general.