Inverse Photoemission Experiments Research Articles

Mapping the evolution of Bi/Ge(111) empty states: From the wetting layer to pseudo-cubic islands

Semiconductors interfaced with heavy elements possessing a strong atomic spin–orbit coupling are important building blocks for the development of new spintronic devices. Here, we present a microscopic and spin-resolved spectroscopic investigation of ultrathin Bi films grown onto a Ge(111) substrate. At monolayer coverage, a Bi wetting layer is formed, characterized by a semiconducting behavior and a (3×3)R30° superstructure. The wetting layer supports the subsequent growth of Bi islands with a pseudo-cubic structure similar to that of Bi(110), showing a well-defined orientation with respect to the substrate high-symmetry directions. We performed photoemission and spin-resolved inverse photoemission experiments at off-normal electron emission and incidence, respectively, along the substrate Γ¯K¯ direction. Inverse photoemission, in particular, highlights the presence of a spin-polarized empty Bi state, not reported so far, due to the strong spin–orbit effects characteristic of the Bi surface and thin layers. Finally, scanning tunneling spectroscopy is employed to link the observed spectroscopic features to either the wetting layer or the Bi islands.

Visualizing the multifractal wave functions of a disordered two-dimensional electron gas

The wavefunctions of a disordered two-dimensional electron gas at the quantum-critical Anderson transition are predicted to exhibit multifractal scaling in their real space amplitude. We experimentally investigate the appearance of these characteristics in the spatially resolved local density of states of a two-dimensional mixed surface alloy Bi_xPb_{1-x}/Ag(111), by combining high-resolution scanning tunneling microscopy with spin and angle-resolved inverse-photoemission experiments. Our detailed knowledge of the surface alloy electronic band structure, the exact lattice structure and the atomically resolved local density of states enables us to construct a realistic Anderson tight binding model of the mixed surface alloy, and to directly compare the measured local density of states characteristics with those from our model calculations. The statistical analyses of these two-dimensional local density of states maps reveal their log-normal distributions and multifractal scaling characteristics of the underlying wavefunctions with a finite anomalous scaling exponent. Finally, our experimental results confirm theoretical predictions of an exact scaling symmetry for Anderson quantum phase transitions in the Wigner-Dyson classes.

Many-body effects on Cr(001) surfaces: An LDA+DMFT study

The electronic structure of the Cr(001) surface with its sharp resonance at the Fermi level is a subject of controversial debate of many experimental and theoretical works. To date, it is unclear whether the origin of this resonance is an orbital Kondo or an electron-phonon coupling effect. We have combined ab initio density functional calculations with dynamical mean-field simulations to calculate the orbitally resolved spectral function of the Cr(001) surface. The calculated orbital character and shape of the spectrum is in agreement with data from (inverse) photoemission experiments. We find that dynamic electron correlations crucially influence the surface electronic structure and lead to a low energy resonance in the ${d}_{{z}^{2}}$ and ${d}_{xz/yz}$ orbitals. Our results help to reconvene controversial experimental results from (I)PES and STM measurements.

Electronic structure of Mott-insulator CaCu 3 Ti 4 O 12 : Photoemission and inverse photoemission study

We have performed the photoemission and inverse photoemission experiments to elucidate the origin of Mott insulating states in A-site ordered perovskite CaCu$_3$Ti$_4$O$_{12}$ (CCTO). Experimental results have revealed that Cu 3$d$-O 2$p$ hybridized bands, which are located around the Fermi level in the prediction of the local-density approximation (LDA) band calculations, are actually separated into the upper Hubbard band at $\sim$ 1.5 eV and the lower Hubbard band at $\sim$ $-$1.7 eV with a band gap of $\sim$ 1.5-1.8 eV. We also observed that Cu 3$d$ peak at $\sim$ $-$3.8 eV and Ti 3$d$ peak at $\sim$ 3.8 eV are further away from each other than as indicated in the LDA calculations. In addition, it is found that the multiplet strucutre around $-$9 eV includes a considerable number of O 2$p$ states. These observations indicate that the Cu 3$d$ and Ti 3$d$ electrons hybridized with the O 2$p$ states are strongly correlated, which originates in the Mott-insulating states of CCTO.

Thin line of a Rashba-type spin texture: Unoccupied surface resonance of Tl/Si(111) alongΓ¯M¯

The Tl/Si(111)-$(1\ifmmode\times\else\texttimes\fi{}1)$ surface features outstanding properties with a unique spin pattern in momentum space. Along $\overline{\ensuremath{\Gamma}}\overline{K}$ $(\overline{\ensuremath{\Gamma}}{\overline{K}}^{\ensuremath{'}})$, surface states with rotating spin had been observed. Here, the focus is put on the unoccupied surface electronic structure along the $\overline{\ensuremath{\Gamma}}\overline{M}$ high-symmetry direction. Spin- and angle-resolved inverse-photoemission experiments with sensitivity to the in-plane and out-of-plane components of the spin-polarization vector are conducted with the help of our recently developed rotatable spin-polarized electron source (ROSE). In agreement with our theoretical findings, we identify a surface resonance with giant spin-orbit-induced spin splitting, which exhibits an exclusive Rashba-type spin texture, i.e., a pure in-plane spin polarization perpendicular to $\overline{\ensuremath{\Gamma}}\overline{M}$, in compliance with the mirror-plane symmetry of the $\overline{\ensuremath{\Gamma}}\overline{M}$ direction. Notably, for slight deviations from the high-symmetry line, this constraint is lifted and additional spin-polarization components emerge. This highlights the importance of a correct alignment of the experiment when investigating samples with spin textures that are more complex than in simple Rashba systems or in ferromagnets.

Ambiguity of experimental spin information from states with mixed orbital symmetries.

The spin texture of the unoccupied bands of the surface alloy Bi/Ag(111) is investigated with spin- and angle-resolved inverse photoemission and first-principles calculations. Surprisingly, the measured spin character does not always reflect the calculated spin texture of the bands. With the help of photoemission calculations within the one-step model, however, the discrepancy is traced back to the influence of the orbital symmetry of the respective states in combination with the experimental geometry. In particular, the calculations show that the spin texture of a surface band with mixed orbital symmetries may neither be recovered with s- nor p- nor unpolarized light. In general, spin information from direct or inverse photoemission experiments on electronic states with mixed orbital symmetries at spin-orbit-influenced surfaces has to be taken with a pinch of salt, while it remains reliable for states with pure symmetry.

Rotatable spin-polarized electron source for inverse-photoemission experiments

We present a ROtatable Spin-polarized Electron source (ROSE) for the use in spin- and angle-resolved inverse-photoemission (SR-IPE) experiments. A key feature of the ROSE is a variable direction of the transversal electron beam polarization. As a result, the inverse-photoemission experiment becomes sensitive to two orthogonal in-plane polarization directions, and, for nonnormal electron incidence, to the out-of-plane polarization component. We characterize the ROSE and test its performance on the basis of SR-IPE experiments. Measurements on magnetized Ni films on W(110) serve as a reference to demonstrate the variable spin sensitivity. Moreover, investigations of the unoccupied spin-dependent surface electronic structure of Tl/Si(111) highlight the capability to analyze complex phenomena like spin rotations in momentum space. Essentially, the ROSE opens the way to further studies on complex spin-dependent effects in the field of surface magnetism and spin-orbit interaction at surfaces.

Direct observation of a highly spin-polarized organic spinterface at room temperature

Organic semiconductors constitute promising candidates toward large-scale electronic circuits that are entirely spintronics-driven. Toward this goal, tunneling magnetoresistance values above 300% at low temperature suggested the presence of highly spin-polarized device interfaces. However, such spinterfaces have not been observed directly, let alone at room temperature. Thanks to experiments and theory on the model spinterface between phthalocyanine molecules and a Co single crystal surface, we clearly evidence a highly efficient spinterface. Spin-polarised direct and inverse photoemission experiments reveal a high degree of spin polarisation at room temperature at this interface. We measured a magnetic moment on the molecule's nitrogen π orbitals, which substantiates an ab-initio theoretical description of highly spin-polarised charge conduction across the interface due to differing spinterface formation mechanisms in each spin channel. We propose, through this example, a recipe to engineer simple organic-inorganic interfaces with remarkable spintronic properties that can endure well above room temperature.

Electronic structure of copper phthalocyanine fromG0W0calculations

We present all-electron G0W0 calculations for the electronic structure of the organic semiconductor copper phthalocyanine, based on semilocal and hybrid density-functional theory (DFT) starting points. We show that G0W0 calculations improve the quantitative agreement with high resolution photoemission and inverse photoemission experiments. However, the extent of the improvement provided by G0W0 depends significantly on the choice of the underlying DFT functional, with the hybrid functional serving as a much better starting point than the semilocal one. In particular, strong starting-point dependence is observed in the energy positions of highly localized molecular orbitals. This is attributed to self-interaction errors (SIE), due to which the orbitals obtained from semilocal DFT do not approximate the quasi-particle (QP) orbitals as well as those obtained from hybrid DFT. Our findings establish the viability of the G0W0 approach for describing the electronic structure of metal-organic systems, given a judiciously chosen DFT-based starting point.

Testing variations of the GW approximation on strongly correlated transition metal oxides: hematite (α-Fe2O3) as a benchmark

Quantitative characterization of low-lying excited electronic states in materials is critical for the development of solar energy conversion materials. The many-body Green's function method known as the GW approximation (GWA) directly probes states corresponding to photoemission and inverse photoemission experiments, thereby determining the associated band structure. Several versions of the GW approximation with different levels of self-consistency exist in the field. While the GWA based on density functional theory (DFT) works well for conventional semiconductors, less is known about its reliability for strongly correlated semiconducting materials. Here we present a systematic study of the GWA using hematite (α-Fe(2)O(3)) as the benchmark material. We analyze its performance in terms of the calculated photoemission/inverse photoemission band gaps, densities of states, and dielectric functions. Overall, a non-self-consistent G(0)W(0) using input from DFT+U theory produces physical observables in best agreement with experiments.

Quasiparticle and optical properties of rutile and anataseTiO2

Quasiparticle excitation energies and optical properties of ${\text{TiO}}_{2}$ in the rutile and anatase structures are calculated using many-body perturbation-theory methods. Calculations are performed for a frozen crystal lattice; electron-phonon coupling is not explicitly considered. In the GW method, several approximations are compared and it is found that inclusion of the full frequency dependence as well as explicit treatment of the Ti semicore states are essential for accurate calculation of the quasiparticle energy-band gap. The calculated quasiparticle energies are in good agreement with available photoemission and inverse photoemission experiments. The results of the GW calculations, together with the calculated static screened Coulomb interaction, are utilized in the Bethe-Salpeter equation to calculate the dielectric function ${ϵ}_{2}(\ensuremath{\omega})$ for both the rutile and anatase structures. The results are in good agreement with experimental observations, particularly the onset of the main absorption features around 4 eV. For comparison to low-temperature optical-absorption measurements that resolve individual excitonic transitions in rutile, the low-lying discrete excitonic energy levels are calculated with electronic screening only. The lowest energy exciton found in the energy gap of rutile has a binding energy of 0.13 eV. In agreement with experiment, it is not dipole allowed but the calculated exciton energy exceeds that measured in absorption experiments by about 0.22 eV and the scale of the exciton binding energy is also too large. The quasiparticle energy alignment of rutile is calculated for nonpolar (110) surfaces. In the GW approximation, the valence-band maximum is 7.8 eV below the vacuum level, showing a small shift from density-functional theory results.

Combined experimental setup for spin- and angle-resolved direct and inverse photoemission

We present a combined experimental setup for spin- and angle-resolved direct and inverse photoemission in the vacuum ultraviolet energy range for measurements of the electronic structure below and above the Fermi level. Both techniques are installed in one ultrahigh-vacuum chamber and, as a consequence, allow quasisimultaneous measurements on one and the same sample preparation. The photoemission experiment consists of a gas discharge lamp and an electron energy analyzer equipped with a spin polarization detector based on spin-polarized low-energy electron diffraction. Our homemade inverse-photoemission spectrometer comprises a GaAs photocathode as spin-polarized electron source and Geiger-Muller counters for photon detection at a fixed energy of 9.9 eV. The total energy resolution of the experiment is better than 50 meV for photoemission and better than 200 meV for inverse photoemission. The performance of our combined direct and inverse-photoemission experiment with respect to angular and energy resolutions is exemplified by the Fermi-level crossing of the Cu(111) L-gap surface state. Spin-resolved measurements of Co films on Cu(001) are used to characterize the Sherman function of the spin polarization detector as well as the spin polarization of our electron source.

Spin-Polarized Tunneling Spectroscopy in Tunnel Junctions with Half-Metallic Electrodes

We have studied the magnetoresistance (TMR) of tunnel junctions with electrodes of La(2/3)Sr(1/3)MnO3 and we show how the variation of the conductance and TMR with the bias voltage can be exploited to obtain precise information on the spin and energy dependence of the density of states. Our analysis leads to a quantitative description of the band structure of La(2/3)Sr(1/3)MnO3 including the energy gap delta between the Fermi level and the bottom of the t(2g) minority-spin band, in good agreement with data from spin-polarized inverse photoemission experiments. This shows the potential of magnetic tunnel junctions with half-metallic electrodes for spin-resolved spectroscopic studies.

Electron correlation effects on SiC(111) and SiC(0001) surfaces

The possibility is discussed that, independent of the polytype, large electronic correlationeffects give rise to semiconducting SiC surfaces with [111] or [0001] orientations. The mostimportant surface translational symmetries and 3 × 3 are considered. The discussion is based on the detailed knowledge of the surfaceatomic geometries and the electronic structures derived for these geometries usinga local density approximation for exchange and correlation. It is argued thatthe resulting half-filled, weakly dispersive dangling-bond bands within thefundamental gaps are split according to a Hubbard interaction parameterU, and that the surface systems undergo a Mott–Hubbard transition. Such a physical pictureprovides a qualitatively correct account of the single-particle excitation spectra eitherinferred from angle-resolved photoemission and inverse photoemission experiments orobtained from scanning tunnelling spectroscopy. The gap opening and hence the HubbardU parameter are discussed in terms of their dependence on the surface reconstruction as wellas the SiC polytype.

Photon detection with n-propanol and C2H6O isomers

We demonstrate that a Geiger–Müller-type bandpass photon detector, suitable for inverse photoemission experiments, can be constructed from a MgF2 entrance window that has a high-energy transmission threshold of 10.97 eV, and ethanol, a detection gas with an ionization potential of 10.48 eV. The photon detector has a mean detection energy of ℏωd=(10.89±0.07) eV and a bandpass of Δℏωd=(0.37±0.05) eV. A photon detector can also be constructed from n-propanol/MgF2 with a mean detection energy of ℏωd=(10.76±0.07) eV and a bandpass Δℏωd=(0.41±0.05) eV. These two new detection gas/window combinations have a higher detection energy and a narrower bandpass than the dimethylether/MgF2 detector [Δℏωd=(0.71±0.04) eV and ℏωd=10.60 eV]. Since all three detectors utilize a MgF2 entrance window, the photon bandpass can be changed straightforwardly by changing the detection gas. For systems that can be easily damaged by electron beams, having the freedom to open up the detector bandpass is an advantage because it can reduce the total electron exposure time.

Parameter-free calculation of single-particle electronic excitations inYH3

In recent optical experiments for ${\mathrm{YH}}_{3},$ a large band gap of almost 3 eV has been observed. In contrast, calculations within the local density approximation (LDA) result in a semimetallic band structure with a band overlap near the Fermi level of more than 1 eV. This unusually large discrepancy between the LDA results and experiment has led to suggestions that strong local correlation effects, similar to those found in transition metal oxides, are important in ${\mathrm{YH}}_{3}.$ Here we conclude from parameter-free quasi-particle calculations within the GW approximation that ${\mathrm{YH}}_{3}$ is essentially a conventional semiconductor. We argue that the experimental results can be fully understood in band structure terms without invoking strong local correlations. The unusually large error in the band structure made by LDA is traced to its poor description of the electronic structure of the hydrogen atom. Our GW results predict a fundamental band gap of only 1 eV and an optical gap of 2.6 eV, the difference being due to vanishing matrix elements for optical transitions at lower energies. Our prediction of a small fundamental gap could be experimentally confirmed by a combination of photoemission and inverse photoemission experiments.

Quasiparticle Electronic Structure of Copper in theGWApproximation

We show that the results of photoemission and inverse photoemission experiments on bulk copper can be quantitatively described within band-structure theory, with no evidence of effects beyond the single-quasiparticle approximation. The well-known discrepancies between the experimental band structure and the Kohn-Sham eigenvalues of density functional theory are almost completely corrected by self-energy effects. Exchange-correlation contributions to the self-energy arising from 3s and 3p core levels are shown to be crucial.

Threshold electronic structure at the oxygenKedge of3d-transition-metal oxides: A configuration interaction approach

It has been generally accepted that the threshold structure observed in the oxygen K edge X-ray absorption spectrum in 3d transition metal oxides represents the electronic structure of the 3d transition metal. There is, however, no consensus about the correct description. We present an interpretation, which includes both ground state hybridization and electron correlation. It is based on a configuration interaction cluster calculation using a MO6 cluster. The oxygen K edge spectrum is calculated by annihilating a ligand hole in the ground state and is compared to calculations representing inverse photoemission experiments in which a 3d transition metal electron is added. Clear differences are observed related to the amount of ligand hole created in the ground state. Two "rules" connected to this are discussed. Comparison with experimental data of some early transition metal compounds is made and shows that this simple cluster approach explains the experimental features quite well.

Non-Abelian Electrons: SO(5) Superspin Regimes for Correlated Electrons on a Two-Leg Ladder

We analyze critical and massive SO(5) superspin regimes for correlated electrons on a two-leg ladder. We identify fundamental low energy excitations, which carry the quantum numbers of a free electron and can be probed in (inverse) photoemission experiments. These excitations do not obey the usual Pauli principle but are governed by specific forms of the so-called non-Abelian exclusion statistics.

Electronic structure of 3d-transition-metal oxides: on-site Coulomb repulsion versus covalency

We have performed photoemission and inverse photoemission experiments on a series of 3d-transition-metal oxides with formal ionic configuration from to . The photoemission core-level spectra are analysed in terms of a simple cluster model leading to estimates for the charge-transfer energy , the Coulomb correlation energy , and the hybridization strength V. It is found that the ratio of the correlation energy to the hybridization energy significantly decreases from the late to the early transition metal oxides. This trend is attributed mostly to the increasing number of empty d states in the early transition metals which enhances the effective metal-ligand hybridization. We also compare the experimental valence band spectra with densities of states (DOS) from band-structure calculations. The rather good agreement between the theoretical DOS and the measured single-particle excitation spectra of the early 3d-transition-metal oxides as opposed to the failure of the one-electron description for most of the late transition metal oxides supports the results of the cluster model analysis.