Angle-resolved Two-photon Photoemission Research Articles

Ultrafast electron dynamics in a topological surface state observed in two-dimensional momentum space

We study ultrafast population dynamics in the topological surface state of Sb_2Te_3 in two-dimensional momentum space with time- and angle-resolved two-photon photoemission spectroscopy. Linearly polarized mid-infrared pump pulses are used to permit a direct optical excitation across the Dirac point. We show that this resonant excitation is strongly enhanced within the Dirac cone along three of the six {bar{Gamma }}–{bar{M}} directions and results in a macroscopic photocurrent when the plane of incidence is aligned along a {bar{Gamma }}–{bar{K}} direction. Our experimental approach makes it possible to disentangle the decay of transiently excited population and photocurent by elastic and inelastic electron scattering within the full Dirac cone in unprecedented detail. This is utilized to show that doping of Sb_2Te_3 by vanadium atoms strongly enhances inelastic electron scattering to lower energies, but only scarcely affects elastic scattering around the Dirac cone.

Band Formation at Interfaces Between N-Heteropolycycles and Gold Electrodes.

Efficient charge injection at organic semiconductor/metal interfaces is crucial for the performance of organic field effect transistors. Interfacial hybrid band formation between electronic states of the organic compound and the metal electrode facilitates effective charge injection. Here, we show that a long-range ordered monolayer of a flat-lying N-heteropolycyclic aromatic compound on Au(111) leads to dispersing occupied and unoccupied interfacial hybrid bands. Using angle-resolved two-photon photoemission we determine their energy level alignment and dispersion relations. We suggest that band formation proceeds via hybridization of a localized occupied molecular state with the d-bands of the Au substrate, where the large effective mass of the d-bands is significantly reduced in the hybrid band. Hybridization of an unoccupied molecular state with the Au sp-band leads to a band with an even smaller effective mass.

A combined laser-based angle-resolved photoemission spectroscopy and two-photon photoemission spectroscopy study of Td–WTe2

Laser-based angle-resolved photoemission spectroscopy and two-photon photoemission spectroscopy are employed to study the valence electronic structure of the Weyl semimetal candidate Td–WTe2 along two high symmetry directions and for binding energies between ≈ −1 eV and 5 eV. The experimental data show a good agreement with band structure calculations. Polarization dependent measurements provide further information on initial and intermediate state symmetry properties with respect to the mirror plane of the Td structure of WTe2.

Orbital-Driven Rashba Effect in a Binary Honeycomb Monolayer AgTe.

The Rashba effect is fundamental to the physics of two-dimensional electron systems and underlies a variety of spintronic phenomena. It has been proposed that the formation of Rashba-type spin splittings originates microscopically from the existence of orbital angular momentum (OAM) in the Bloch wave functions. Here, we present detailed experimental evidence for this OAM-based origin of the Rashba effect by angle-resolved photoemission (ARPES) and two-photon photoemission experiments for a monolayer AgTe on Ag(111). Using quantitative low-energy electron diffraction analysis, we determine the structural parameters and the stacking of the honeycomb overlayer with picometer precision. Based on an orbital-symmetry analysis in ARPES and supported by first-principles calculations, we unequivocally relate the presence and absence of Rashba-type spin splittings in different bands of AgTe to the existence of OAM.

Nonlinear Plasmonic Photoelectron Response of Ag(111).

Photons can excite collective and single-particle excitations in metals; the collective plasmonic excitations are of keen interest in physics, chemistry, optics, and nanotechnology because they enhance coupling of electromagnetic energy and can drive nonlinear processes in electronic materials, particularly where their dielectric function ϵ(ω) approaches zero. We investigate the nonlinear angle-resolved two-photon photoemission (2PP) spectroscopy of the Ag(111) surface through the ϵ(ω) near-zero region. In addition to the Einsteinian single-particle photoemission, the 2PP spectra report unequivocal signatures of nonlocal dielectric, plasmonically enhanced, excitation processes.

Negative Te spin polarization responsible for ferromagnetic order in the doped topological insulator V0.04(Sb1−xBix)1.96Te3

Ferromagnetic topological insulators have emerged as a promising platform for quantum anomalous Hall (QAH) effect with a dissipationless edge transport. However, the observation of QAH effect has so far been restricted to extremely low temperatures. We investigate the microscopic origin of ferromagnetism coupled with topological insulators in vanadium-doped (Sb, Bi)(2)Te-3 employing the x-ray magnetic circular dichroism, angle-resolved two-photon photoemission spectroscopy, combined with first-principles calculations. We found a negative spin polarization, and thus an antiparallel magnetic moment at the Te site with respect to that of the vanadium dopants, which plays the key role in the ferromagnetic order. We ascribe it to the hybridization between Te p and V d majority spin states at the Fermi energy (E-F), being supported by a Zener-type p-d exchange interaction scenario. The substitution of Bi at the Sb site suppresses the bulk ferromagnetism by introducing extra electron carriers in the majority spin channel of Te p states that compensates the antiparallel magnetic moment on the Te site. Our findings reveal important clues to designing magnetic topological insulators with higher Curie temperature that work under ambient conditions.

Relativistic theory of two-photon photoemission from ferromagnetic materials

A fully relativistic theory of angle-resolved two-photon photoemission for ferromagnetic materials is derived from the general theory of pump-probe photoemission that is based on the Keldysh formalism. Two-photon photoemission spectroscopy is a widely used analytical tool to study nonequilibrium phenomena in nonmagnetic as well as in magnetic solids, as for example ultrafast demagnetization processes. Our theoretical approach aims at a quantitative description of the time-dependent spectroscopic properties of specific solid systems under consideration, and it allows for the inclusion of static correlation effects via the local spin-density and dynamical mean-field theory electronic structure approach. To this end we follow Pendry's one-step theory of the photoemission process as closely as possible and make extensive use of concepts of relativistic multiple - scattering theory within the layer-Korringa-Kohn-Rostoker method in order to guarantee angular resolution in the spectroscopic calculations. As usual the final state of the two-photon photoemission process is represented by a time-reversed low-energy electron diffraction state. The formalism allows for a quantitative calculation of the time-dependent photocurrent for moderately correlated systems like simple ferromagnetic metals. A first application to the Fe(100) surface is discussed in detail.

Hybridization of an unoccupied molecular orbital with an image potential state at a lead phthalocyanine/graphite interface

The interaction of a molecular orbital with a surface state is important to understand the spatial distribution of the wave function at the molecule/substrate interface. In this study, we focus on hybridization of an unoccupied state of lead phthalocyanine (PbPc) with the image potential state (IPS) on a graphite surface. The hybridization modifies the energy-momentum dispersions of the IPS on PbPc films as observed by angle-resolved two-photon photoemission. On the PbPc 1 monolayer film, the IPS band forms a band gap and back-folding appears at the first Brillouin zone boundary due to the periodic potential by the adsorbate lattice. The modification of the dispersion is accompanied by the intensity enhancement of the IPS. We attributed the origin of the modified dispersion and intensity enhancement to a hybridization of the IPS with a molecule-derived unoccupied level. From the photon energy-dependent measurement on multilayer films, we have found the diffuse unoccupied molecular level in the vicinity of the IPS. The tail part of the IPS wave function in the substrate is enhanced by the hybridization with the unoccupied state, and thus strengthens the transition from the occupied substrate band to the hybridized IPS.

Structure and electronic properties of the (3×3)R30∘SnAu2/Au(111) surface alloy

We have investigated the atomic and electronic structure of the $(\sqrt{3}\ifmmode\times\else\texttimes\fi{}\sqrt{3})R{30}^{\ensuremath{\circ}}\phantom{\rule{4pt}{0ex}}\mathrm{SnA}{\mathrm{u}}_{2}\text{/}\mathrm{Au}(111)$ surface alloy. Low-energy electron diffraction and scanning tunneling microscopy measurements show that the native herringbone reconstruction of bare Au(111) surface remains intact after formation of a long-range ordered $(\sqrt{3}\ifmmode\times\else\texttimes\fi{}\sqrt{3})R{30}^{\ensuremath{\circ}}\mathrm{SnA}{\mathrm{u}}_{2}\text{/}\mathrm{Au}(111)$ surface alloy. Angle-resolved photoemission and two-photon photoemission spectroscopy techniques reveal Rashba-type spin-split bands in the occupied valence band with comparable momentum space splitting as observed for the Au(111) surface state, but with a hole-like parabolic dispersion. Our experimental findings are compared with density functional theory (DFT) calculation that fully support our experimental findings. Taking advantage of the good agreement between our DFT calculations and the experimental results, we are able to extract that the occupied Sn-Au hybrid band is of $(s,\phantom{\rule{0.28em}{0ex}}d)$-orbital character, while the unoccupied Sn-Au hybrid bands are of $(p,\phantom{\rule{0.28em}{0ex}}d)$-orbital character. Hence we can conclude that the Rashba-type spin splitting of the hole-like Sn-Au hybrid surface state is caused by the significant mixing of Au $d$ with Sn $s$ states in conjunction with the strong atomic spin-orbit coupling of Au, i.e., of the substrate.

Multistep and multiscale electron transfer and localization dynamics at a model electrolyte/metal interface.

The lifetime, coupling, and localization dynamics of electronic states in molecular films near metal electrodes fundamentally determine their propensity to act as precursors or reactants in chemical reactions, crucial for a detailed understanding of charge transport and degradation mechanisms in batteries. In the current study, we investigate the formation dynamics of small polarons and their role as intermediate electronic states in thin films of dimethyl sulfoxide (DMSO) on Cu(111) using time- and angle-resolved two-photon photoemission spectroscopy. Upon photoexcitation, a delocalized DMSO electronic state is initially populated two monolayers from the Cu surface, becoming a small polaron on a 200 fs time scale, consistent with localization due to vibrational dynamics of the DMSO film. The small polaron is a precursor state for an extremely long-lived and weakly coupled multilayer electronic state, with a lifetime of several seconds, thirteen orders of magnitude longer than the small polaron. Although the small polaron in DMSO has a lifetime of 140 fs, its role as a precursor state for long-lived electronic states could make it an important intermediate in multistep battery reactivity.

Complex manifold of Rashba and image-potential states on Bi/Ag(111)

Angle-resolved, mono- and bichromatic two-photon photoemission was used to study the electronic structure at the surface of the giant Rashba system Bi/Ag(111). The photoemission intensity maps are exceptionally rich in structure due to a large manifold of initial and intermediate states that allow for various resonant interband transitions. Using different photon energies, we succeeded in disentangling the complex experimental data. Close to the Fermi level the unoccupied, Rashba-split ${p}_{x}{p}_{y} ({m}_{j}=1/2)$ surface state can be identified with a Rashba parameter of $3.0\ifmmode\pm\else\textpm\fi{}0.2$ eV \AA{} and a lifetime of $26\ifmmode\pm\else\textpm\fi{}5$ fs. At higher energies the spin-split ${p}_{x}{p}_{y} ({m}_{j}=3/2)$ and ${p}_{z}$ bands as well as the first three members of a series of image-potential resonances were observed. Circular dichroism was used to gain information on the spin structure of both the initial and intermediate states and to corroborate the assignment to Rashba bands.

Revealing the Coulomb interaction strength in a cuprate superconductor

We study optimally doped Bi$_{2}$Sr$_{2}$Ca$_{0.92}$Y$_{0.08}$Cu$_{2}$O$_{8+\delta}$ (Bi2212) using angle-resolved two-photon photoemission spectroscopy. Three spectral features are resolved near 1.5, 2.7, and 3.6 eV above the Fermi level. By tuning the photon energy, we determine that the 2.7-eV feature arises predominantly from unoccupied states. The 1.5- and 3.6-eV features reflect unoccupied states whose spectral intensities are strongly modulated by the corresponding occupied states. These unoccupied states are consistent with the prediction from a cluster perturbation theory based on the single-band Hubbard model. Through this comparison, a Coulomb interaction strength U of 2.7 eV is extracted. Our study complements equilibrium photoemission spectroscopy and provides a direct spectroscopic measurement of the unoccupied states in cuprates. The determined Coulomb U indicates that the charge-transfer gap of optimally doped Bi2212 is 1.1 eV.

Extended Space Charge Region and Unoccupied Molecular Band Formation in Epitaxial Tetrafluorotetracyanoquinodimethane Films

Generating well-defined molecular structures at inorganic/organic interfaces and within molecular films is fundamental for charge carrier transport and thus the performance of organic molecule-based (opto)electronic devices. Here we show by means of low-energy electron diffraction that tetrafluorotetracyanoquinodimethane (F4TCNQ) grows in an epitaxial fashion on the Au(111) surface, resulting in a unit cell which consists of one molecule. In this well-ordered crystalline films we found the formation of an extended space charge region and a dispersing unoccupied electronic molecular state using energy- and angle-resolved two-photon photoemission. The latter finding is a clear proof for band formation in the crystalline molecular structure. We suggest that the high electron affinity of F4TCNQ and a bandlike electron transport are responsible for the formation of the space charge region. Using F4TCNQ as a hole injection layer may open the opportunity to manipulate the hole injection barrier in a controlled w...

Ultrafast energy- and momentum-resolved surface Dirac photocurrents in the topological insulator Sb2Te3

We present energy-momentum mapping of surface Dirac photocurrent in the topological insulator Sb$_2$Te$_3$ by means of time- and angle-resolved two-photon photoemission spectroscopy combined with polarization-variable mid-infrared pulse laser. It is demonstrated that the direct optical transition from the occupied to the unoccupied part of the surface Dirac-cone permits the linear and circular photogalvanic effect which thereby enables us to coherently control the surface electric-current by laser polarization. Moreover, the surface current mapping directly visualizes ultrafast current dynamics in the Dirac cone in the time domain. We unravel the ultrafast intraband relaxation dynamics of the inelastic scattering and momentum scattering separately. Our observations pave the pathway for coherent optical control over surface Dirac electrons in topological insulators.

Excitonic States in Narrow Armchair Graphene Nanoribbons on Gold Surfaces

Narrow graphene nanoribbons (GNRs) exhibit electronic and optical properties that are not present in extended graphene. Most importantly, they possess band gaps in the order of a few electron volts, which has been subject to numerous studies. Here we report on the experimental observation of exctionic states in the band gap of N = 7 armchair GNRs (7-GNR) on Au(111) and Au(788) using energy- and angle-resolved two-photon photoemission spectroscopy. Thereby, an exciton binding energy in the 7-GNR on Au(111) of 160 ± 60 meV has been determined. On the stepped Au(788) surface, the exciton binding energy is in the same range.

Intervalley scattering in MoS2 imaged by two-photon photoemission with a high-harmonic probe

We report on the direct mapping of electron transfer in the momentum space of bulk MoS2 by means of time- and angle-resolved two-photon photoemission with a high-harmonic probe. For this purpose, we have combined a high-repetition rate high-harmonic source with tunable femtosecond pump pulses and a 3D (kx,ky,E) electron spectrometer. We show that optical excitation slightly above the A exciton resonance results in an immediate occupation of the conduction band at K¯ followed by an ultrafast transfer (<50 fs) to the conduction band minimum at Σ¯. Both signals, at K¯ and Σ¯, do not vanish over the observed period of 400 fs. The technique described here enables direct access to the charge transfer dynamics in k-space and allows the study of decay times and decay channels in various systems with dependence on the excess energy or helicity of the excitation.

Rashba splitting in an image potential state investigated by circular dichroism two-photon photoemission spectroscopy

We have explored the band splitting and spin texture of the image potential state (IPS) on Au(001) derived from the Rashba-type spin-orbit interaction (SOI) by using angle-resolved bichromatic two-photon photoemission (2PPE) spectroscopy in combination with circular dichroism (CD). The Rashba parameter for the first $(n=1)$ IPS is determined to be ${48}_{\ensuremath{-}20}^{+8}\phantom{\rule{4pt}{0ex}}\mathrm{meV}\phantom{\rule{0.16em}{0ex}}\AA{}$, which is consistent with the spin-polarized band structure calculated from the embedded Green's function technique for semi-infinite crystals. The present results demonstrate that bichromatic CD-2PPE spectroscopy is powerful for mapping the spin-polarized unoccupied band structures originating from SOIs in various classes of condensed matter.

Generation of Transient Photocurrents in the Topological Surface State of Sb_{2}Te_{3} by Direct Optical Excitation with Midinfrared Pulses.

We combine tunable midinfrared (mid-IR) pump pulses with time- and angle-resolved two-photon photoemission to study ultrafast photoexcitation of the topological surface state (TSS) of Sb_{2}Te_{3}. It is revealed that mid-IR pulses permit a direct excitation from the occupied to the unoccupied part of the TSS across the Dirac point. The novel optical coupling induces asymmetric transient populations of the TSS at ±k_{∥}, which reflects a macroscopic photoexcited electric surface current. By observing the decay of the asymmetric population, we directly investigate the dynamics of the long-lived photocurrent in the time domain. Our discovery promises important advantages of photoexcitation by mid-IR pulses for spintronic applications.

Unoccupied electronic structure and momentum-dependent scattering dynamics in Pb/Si(557) nanowire arrays

The unoccupied electronic structure of quasi-one-dimensional reconstructions of Pb atoms on a Si(557) surface is investigated by means of femtosecond time- and angle-resolved two-photon photoemission. Two distinct unoccupied electronic states are observed at $E\ensuremath{-}{E}_{\mathrm{F}}=3.55$ and 3.30 eV, respectively. Density functional theory calculations reveal that these states are spatially located predominantly on the lead wires and that they are energetically degenerated with an energy window of reduced electronic density of states in Si. We further find momentum-averaged lifetimes of 24 and 35 fs of these two states, respectively. The photoemission yield and the population dynamics depend on the electron momentum component perpendicular to the steps of the Si substrate, and the momentum-dependent dynamics cannot be described by means of rate equations. We conclude that momentum- and direction-dependent dephasing of the electronic excitations, likely caused by elastic scattering at the step edges on the vicinal surface, modifies the excited-state population dynamics in this system.

Excitation and Relaxation Dynamics of Two-Dimensional Photoexcited Electrons on Alkanethiolate Self-Assembled Monolayers

The electron dynamics in alkanethiolate self-assembled monolayers (Cn-SAMs; n = 6–18, where n is the number of alkyl carbons) formed on Au(111) surfaces has been investigated by time- and angle-resolved two-photon photoemission spectroscopy. The time evolution of photoexcited electrons flowing down into image potential states (IPSs) formed on standing-up structure of SAMs is resolved two-dimensionally; the electron lifetime in the IPS increases with chain length, from sub-ps to 100 ps. The chain length dependence of the IPS lifetime is particularly marked at shorter chain lengths of n = 6–10, whereas it becomes milder at chain lengths above n = 10, whose alkyl layer thickness is ≈10 A. This thickness dependence can be explained by two competitive channels for the decay of IPS electrons: one is electronic coupling of IPS with unoccupied bulk Au states and an interfacial state localized at the Au–S linkage, and the other is IPS electron decay to the Au substrate through a tunneling barrier of insulating alk...