Unoccupied Band Structure Research Articles

Nonlinear Optical Properties of the Topological Material Bi2Se3 Family for the Application of an Ultrafast Pulse Laser Based on the Occupied and Unoccupied Band Structures.

The Bi2Se3 family can exhibit many intriguing topological insulator properties, including a narrow bandgap and strong surface states, which show excellent nonlinear optical properties. Thinning bulk Bi2Se3 family materials to create a low-cost photoelectric modulation device and explaining the mechanisms of nonlinear optical differences in different types of materials remain challenges. Based on liquid-phase exfoliation technology and tapered fiber, this work prepared optoelectronic modulation devices for various samples within the Bi2Se3 family, quantitatively compared their nonlinear optical properties, and analyzed the sources of differentiation using the occupied and unoccupied multiband structure theory. The results correspond well to the phenomena observed in the ultrafast laser, which will provide strong support for the design of higher performance photoelectric devices based on topological insulators.

Electron transmission and mean free path in molybdenum disulfide at electron-volt energies

In van der Waals (vdW) materials, the electron mean free path (MFP) is largely influenced by the discrete states in the unoccupied band structure. So far, the influence of these states has only been measured in graphene, while all measurements on other vdW materials lack energy resolution. Here, we present reflection and transmission spectra of freestanding, few-layered molybdenum disulfide $(\mathrm{Mo}{\mathrm{S}}_{2})$ samples in the $0--55$ eV electron range. Our measurements reveal states of enhanced electron transmissivity above the vacuum level, that correspond to the (unoccupied) density of states. We also show a full quantum-mechanical calculation that confirms a good understanding of the elastic scattering in $\mathrm{Mo}{\mathrm{S}}_{2}$. A model is developed to extract the inelastic MFP spectrum, which is a measure of the inelastic scattering cross section. As $\mathrm{Mo}{\mathrm{S}}_{2}$ is a complicated system of different atomic planes, we expect that our methods generalize well to other van der Waals materials and heterostacks thereof.

Mapping the dispersion of the occupied and unoccupied band structure in photoexcited 1T-TiSe2

Charge density waves (CDW) are states of broken symmetry with a periodic modulation of charge and lattice typically leading to the opening of a gap in the band structure. In the model CDW system 1T-TiSe2 such a gap opens up between its Se4p valence and Ti3d conduction band, accompanied by a change of dispersion. These changes are crucial in understanding the CDW phase, as they provide a measure of the Se4p-Ti3d hybridization strength and characteristic mechanistic features. Using time- and angle-resolved photoelectron spectroscopy (trARPES), the unoccupied band structure is populated with near-infrared (NIR) pump pulses which allows to directly visualize the parabolically-shaped Ti3d conduction band. Furthermore, we observe a transient change of effective mass in the Se4p valence band following photoexcitation. This occurs alongside an overall reduction due to weakening of the CDW phase and is accompanied by an oscillating component with the frequency of the characteristic A1g phonon. These observations, enabled by trAPRES, highlight the importance of the lattice contributions in establishing the CDW order in 1T-TiSe2.

Low-Energy Electron Irradiation Damage in Few-Monolayer Pentacene Films.

Crystalline films of pentacene molecules, two to four monolayers in thickness, are grown via in situ sublimation on silicon substrates in the ultrahigh vacuum chamber of a low-energy electron microscope. It is observed that the diffraction pattern of the pentacene layers fades upon irradiation with low-energy electrons. The damage cross section is found to increase by more than an order of magnitude for electron energies from 0 to 10 eV and by another order of magnitude from 10 to 40 eV. Close to 0 eV, damage is virtually nil. Creation of chemically reactive atomic centers after electron attachment or impact ionization is thought to trigger chemical reactions between neighboring molecules that gradually transform the layer into a disordered carbon nanomembrane. Additionally, diminishing spectroscopic features related to the unoccupied band structure of the layers, accompanied by loss of definition in real-space images, and an increase in the background intensity of diffraction images during irradiation point to chemical changes and formation of a disordered layer.

Plasmon localization by adatoms in gold atomic wires on Si(775)

Self-organized gold chains on vicinal Si(111) surfaces represent prototype examples of quasi-one-dimensional objects that are stabilized by hybridization with Si surface states. Their plasmons contain important information about the unoccupied bandstructure close to the Fermi level. Using Si(775)–Au as an example, we report here the modifications of the plasmon dispersion by the simple atomic adatom species H and O. Using a combination of low energy electron diffraction and high-resolution electron energy loss spectroscopy, we study the interconnection between plasmonic excitation and the corresponding local surface structure. Both adsorbates do not destroy metallicity, but, similar to Si(553)–Au, atomic hydrogen enhances dimerization of the Au chains, which at small concentrations counteracts the disorder introduced by random adsorption. This effect, most likely caused by electron donation of H to the surface states, is missing in case of adsorbed oxygen, so that only the effect of disorder is observed. For both adsorbates increasing disorder as a function of adsorbate concentration finally results in plasmon localization and opening of a band gap.

Secondary Electron Emission by Plasmon-Induced Symmetry Breaking in Highly Oriented Pyrolytic Graphite.

Two-particle spectroscopy with correlated electron pairs is used to establish the causal link between the secondary electron spectrum, the (π+σ) plasmon peak, and the unoccupied band structure of highly oriented pyrolytic graphite. The plasmon spectrum is resolved with respect to the involved interband transitions and clearly exhibits final state effects, in particular due to the energy gap between the interlayer resonances along the ΓA direction. The corresponding final state effects can also be identified in the secondary electron spectrum. Interpretation of the results is performed on the basis of density-functional theory and tight-binding calculations. Excitation of the plasmon perturbs the symmetry of the system and leads to hybridization of the interlayer resonances with atomlike σ^{*} bands along the ΓA direction. These hybrid states have a high density of states as well as sufficient mobility along the graphite c axis leading to the sharp ∼3 eV resonance in the spectrum of emitted secondary electrons reported throughout the literature.

Empty‐State Band Mapping Using Momentum‐Resolved Secondary Electron Emission

AbstractMaterial band structures of occupied electronic states are obtainable using conventional angle‐resolved photoemission experiments, leaving the unoccupied states far less explored. Here, an alternative approach is built on and expanded to investigate thermalized photoelectrons emitted from crystal surfaces. A model for electron emission is constructed and reveals the material unoccupied state band structure. Potentially applicable to any material and independent from the secondary electron generation mechanism, it is demonstrated on diamond and copper using different light sources. Moreover, the diamond indirect band gap is directly observed and the transverse effective mass at the conduction band minimum can be experimentally obtained, mt = (0.21 ± 0.015) me. This offers a convenient path for angle‐resolved photoemission data interpretation and empty‐state information extraction.

View on Si(111)−(5×2)−Au with plasmon spectroscopy

$\mathrm{Si}(111)\text{\ensuremath{-}}(5\ifmmode\times\else\texttimes\fi{}2)\text{\ensuremath{-}}\mathrm{Au}$ represents a prototype system for an adsorbate-induced spontaneous symmetry break by formation of quasi-one-dimensional atomic chains that are metallic. Surprisingly, the geometric structure of these chains is still under debate. In this paper, we show that examination of the unoccupied band structure by plasmon spectroscopy in combination with low energy electron diffraction contains sufficient information to discriminate between suggested models, favoring an optimal concentration of 6 atoms per $(5\ifmmode\times\else\texttimes\fi{}2)$ unit cell. Furthermore, we tested the stability of this structure and found that higher concentrations of Au tend to destabilize the single-domain structure on the slightly misoriented Si(111) surface, favoring formation of $(\sqrt{3}\ifmmode\times\else\texttimes\fi{}\sqrt{3})R{30}^{\ensuremath{\circ}}\text{\ensuremath{-}}\mathrm{ordered}$ islands with a local concentration of 1 ML already at a surplus of 0.08 ML. The precise role of Au atoms at concentrations exceeding 0.60 ML that seem to stabilize formation of three domains, however, must remain open.

Band-Resolved Imaging of Photocurrent in a Topological Insulator.

We study the microscopic origins of photocurrent generation in the topological insulator Bi_{2}Se_{3} via time- and angle-resolved photoemission spectroscopy. We image the unoccupied band structure as it evolves following a circularly polarized optical excitation and observe an asymmetric electron population in momentum space, which is the spectroscopic signature of a photocurrent. By analyzing the rise times of the population we identify which occupied and unoccupied electronic states are coupled by the optical excitation. We conclude that photocurrents can only be excited via resonant optical transitions coupling to spin-orbital textured states. Our work provides a microscopic understanding of how to control photocurrents in systems with spin-orbit coupling and broken inversion symmetry.

Modification of Pb quantum well states by the adsorption of organic molecules

The successful implementation of nanoscale materials in next generation optoelectronic devices crucially depends on our ability to functionalize and design low dimensional materials according to the desired field of application. Recently, organic adsorbates have revealed an enormous potential to alter the occupied surface band structure of tunable materials by the formation of tailored molecule-surface bonds. Here, we extend this concept of adsorption-induced surface band structure engineering to the unoccupied part of the surface band structure. This is achieved by our comprehensive investigation of the unoccupied band structure of a lead (Pb) monolayer film on the Ag(1 1 1) surface prior and after the adsorption of one monolayer of the aromatic molecule 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA). Using two-photon momentum microscopy, we show that the unoccupied states of the Pb/Ag(1 1 1) bilayer system are dominated by a parabolic quantum well state (QWS) in the center of the surface Brillouin zone with Pb p orbital character and a side band with almost linear dispersion showing Pb p orbital character. After the adsorption of PTCDA, the Pb side band remains completely unaffected while the signal of the Pb QWS is fully suppressed. This adsorption induced change in the unoccupied Pb band structure coincides with an interfacial charge transfer from the Pb layer into the PTCDA molecule. We propose that this charge transfer and the correspondingly vertical (partially chemical) interaction across the PTCDA/Pb interface suppresses the existence of the QWS in the Pb layer. Our results hence unveil a new possibility to orbital selectively tune and control the entire surface band structure of low dimensional systems by the adsorption of organic molecules.

Unoccupied electronic band structure of pentagonal Si nanoribbons on Ag(110).

Silicon nanoribbons - one dimensional silicon structures with a pentagonal atomic structure and mixed sp2- and sp3-hybridisation - grow on Ag(110) upon deposition of silicon. These nanostructures are viewed as promising candidates for modern day electronics as they are comprised of the same element as today's semiconductor devices. Even though they have been studied extensively over the last decade, only little is known about their unoccupied band structure which is important for possible future optoelectronics, semiconductor, and spintronics applications. In order to elucidate the unoccupied band structure of the nanoribbons, k-resolved inverse photoemission spectroscopy (KRIPES) studies were performed on both nanoribbon structures reported in the literature as well as on the bare Ag(110) substrate within the energy range of E-EF = 0-6.5 eV. The obtained experimental results are compared to density functional theory (DFT) calculated band structures to assign individual spectral features to specific bands. Since even small changes in the structural model of the nanoribbons lead to a change in the calculated band structure, this comparison allows us to assess the validity of the proposed structural models.

Development of angle-resolved spectroscopy system of electrons emitted from a surface with negative electron affinity state.

We developed an angle-resolved photoemission spectroscopy system for the analysis of conduction-band electrons. By forming a negative electron affinity surface on a semiconductor surface, electrons in conduction bands are emitted into a vacuum and measured by using an analyzer. This method enables us to determine the energy and momentum of the conduction electrons. Furthermore, it can be used to determine unoccupied conduction band structures. The main challenges of this method are that the energies of the emitted electrons are extremely low and the trajectories of the electrons change due to various influences. We overcame these problems by placing the shielding mesh close to the sample and parallel to the sample surface. The entire chambers, including the shielding mesh, were grounded, and a negative bias voltage was applied only to the sample. This configuration realizes the acceleration of electrons while preserving the momentum component parallel to the sample surface. Another problem is the establishment of a method for converting a detected angle into the corresponding wavevector. We focused on the emission angle of electrons emitted from a sample and their minimum energy and then established an analytical method for converting detected angles into corresponding wavevectors on the basis of the minimum energy.

Plasmon spectroscopy: Robust metallicity of Au wires on Si(557) upon oxidation

We investigated initial steps of oxidation of the Si(557)-Au system by plasmon spectroscopy and first-principles calculations. The measurements, performed using an electron energy loss instrument with simultaneous high resolution in energy and momentum, reveal that metallicity is preserved under all oxidation conditions that are experimentally accessible in UHV. Corresponding simulations, performed within density functional theory, confirm this finding: Only the oxidation of the Si environment of the Au chains turned out to be strongly exothermic, with similar binding energy for adsorption on different structural elements. While large and site specific changes of the band structure were observed, the upper edge of the excitation spectrum of electron-hole pairs, to which plasmon dispersion is most sensitive, remains almost unchanged during the various steps of oxidation, due to the opposite and largely compensating contributions of different adsorption configurations. This investigation not only proves the robustness of metallicity of the gold chains upon oxidation of the surrounding environment of Si atoms, but also demonstrates the usefulness of plasmon spectroscopy in characterizing the electronic excitation spectrum of quasi-one-dimensional systems and unoccupied band structure.

Alkali-metal induced band structure deformation investigated by angle-resolved photoemission spectroscopy and first-principles calculations

Alkali-metal adsorption on the surface of materials is widely used for in situ surface electron doping, particularly for observing unoccupied band structures by angle-resolved photoemission spectroscopy (ARPES). However, the effects of alkali-metal atoms on the resulting band structures have yet to be fully investigated, owing to difficulties in both experiments and calculations. Here, we combine ARPES measurements on cesium-adsorbed ultrathin bismuth films with first-principles calculations of the electronic charge densities and demonstrate a simple method to evaluate alkali-metal induced band deformation. We reveal that deformation of bismuth surface bands is directly correlated with vertical charge-density profiles at each electronic state of bismuth. In contrast, a change in the quantized bulk bands is well described by a conventional rigid-band-shift picture. We discuss these two aspects of the band deformation holistically, considering spatial distributions of the electronic states and cesium-bismuth hybridization, and provide a prescription for applying alkali-metal adsorption to a wide range of materials.

Dynamics of out-of-equilibrium electron and hole pockets in the type-II Weyl semimetal candidate WTe2

We present a time- and angular-resolved photoemission (TR-ARPES) study of the transition- metal dichalcogenide WTe2, a candidate type II Weyl semimetal exhibiting extremely large magne- toresistence. Using femtosecond light pulses, we characterize the unoccupied states of the electron pockets above the Fermi level. We track the relaxation dynamics of photoexcited electrons along the unoccupied band structure and into a bulk hole pocket. Following the ultrafast carrier relaxation, we report remarkably similar decay dynamics for electrons and holes. Our results corroborate the hypothesis that carrier compensation is a key factor in the exceptional magnetotransport properties of WTe2.

Femtosecond Dynamics of Spin-Polarized Electrons in Topological Insulators

A fast control of spins is a major quest in spintronic systems. Ultrashort light pulses have been utilized to trigger and detect the spin dynamics of electrons in magnetic materials and multilayers. Recently, three-dimensional topological insulators have received attention due to the existence, within the insulating band gap of bulk states, of spin-polarized surface states that are protected from backscattering by time-reversal symmetry. We studied sub-picosecond dynamics in the spin-polarized unoccupied electronic structure of Bi2Te3, employing circular-polarized light in time- and angle-resolved photoemission spectroscopy. Noncollinear optical parametric amplification and several nonlinear optical processes result in tunable, ultrashort visible pump pulses with a duration of 30 fs and 1.8 eV energy and ultraviolet probe pulses with about 60 fs duraction and about 6 eV energy. The stable optical setup and the high repetition rate of an Yb-laser source gives a high signal-to-noise ratio in our photoemission process. The 65 fs time resolution, along with 30 meV energy resolution of the time-of-flight energy analyzer, provides the opportunity to explore the ultrafast electronic dynamics in the unoccupied band structures. Furthermore, circular dichroism allows access to the spin state of the photoemitted electrons. A signature of femtosecond unpolarized bulk bands dynamics appears in the presence of spin-polarized electrons of the surface states. This helps distinguish the bulk and surface contributions in the spin-electronic current.

Enhanced ultrafast relaxation rate in the Weyl semimetal phase of MoTe2 measured by time- and angle-resolved photoelectron spectroscopy

$\mathrm{MoTe_2}$ has recently been shown to realize in its low-temperature phase the type-II Weyl semimetal (WSM). We investigated by time- and angle- resolved photoelectron spectroscopy (tr-ARPES) the possible influence of the Weyl points in the electron dynamics above the Fermi level $\mathrm{E_F}$, by comparing the ultrafast response of $\mathrm{MoTe_2}$ in the trivial and topological phases. In the low-temperature WSM phase, we report an enhanced relaxation rate of electrons optically excited to the conduction band, which we interpret as a fingerprint of the local gap closure when Weyl points form. By contrast, we find that the electron dynamics of the related compound $\mathrm{WTe_2}$ is slower and temperature-independent, consistent with a topologically trivial nature of this material. Our results shows that tr-ARPES is sensitive to the small modifications of the unoccupied band structure accompanying the structural and topological phase transition of $\mathrm{MoTe_2}$.

Energy- and k -resolved mapping of the magnetic circular dichroism in threshold photoemission from Co films on Pt(111)

The magnetic circular dichroism in threshold photoemission (TPMCD) for perpendicularly magnetized fcc Co films on Pt(111) has been revisited. A complete mapping of the spectral function $I({E}_{B},{k}_{x},{k}_{y})$ (binding energy ${E}_{B}$, momentum parallel to surface ${k}_{x}$, ${k}_{y}$) and the corresponding TPMCD asymmetry distribution ${A}_{\mathrm{MCD}}({E}_{B},{k}_{x},{k}_{y})$ has been performed for one-photon and two-photon photoemission using time-of-flight momentum microscopy. The experimental results allow distinguishing direct from indirect transitions. The measurements reveal clear band features of direct transitions from bulk bands that show a nontrivial asymmetry pattern. A significant homogeneous background with substantial asymmetry stemming from indirect transitions superposes direct transitions. Two-photon photoemission reveals enhanced emission intensity via an image potential state, acting as intermediate state. The image potential state enhances not only intensity but also asymmetry. The present results demonstrate that two-photon photoemission is a powerful method for mapping the spin-polarized unoccupied band structures and points out pathways for applying TPMCD as a contrast mechanism for various classes of magnetic materials.

Quantifying electronic band interactions in van der Waals materials using angle-resolved reflected-electron spectroscopy.

High electron mobility is one of graphene's key properties, exploited for applications and fundamental research alike. Highest mobility values are found in heterostructures of graphene and hexagonal boron nitride, which consequently are widely used. However, surprisingly little is known about the interaction between the electronic states of these layered systems. Rather pragmatically, it is assumed that these do not couple significantly. Here we study the unoccupied band structure of graphite, boron nitride and their heterostructures using angle-resolved reflected-electron spectroscopy. We demonstrate that graphene and boron nitride bands do not interact over a wide energy range, despite their very similar dispersions. The method we use can be generally applied to study interactions in van der Waals systems, that is, artificial stacks of layered materials. With this we can quantitatively understand the ‘chemistry of layers' by which novel materials are created via electronic coupling between the layers they are composed of.

Imaging pulsed laser deposition growth of homo-epitaxial SrTiO3 by low-energy electron microscopy

By combining low-energy electron microscopy with in situ pulsed laser deposition we have developed a new technique for film growth analysis, making use of both diffraction and real-space information. Working at the growth temperature, we can use: the intensity and profile variations of the specular beam to follow the coverage in a layer-by-layer fashion; real-space microscopy to follow e.g. atomic steps at the surface; and electron reflectivity to probe the unoccupied band structure of the grown material. Here, we demonstrate our methodology for homo-epitaxial growth of SrTiO3. Interestingly, the same combination of techniques will also be applicable to hetero-epitaxial oxide growth, largely extending the scope of research possibilities.