Low-energy Photoemission Research Articles

High- and Low-Energy Photoemission Study of Strongly Correlated Au–Ga–Ce Quasicrystal Approximants: Localized 4f Nature and Disorder Effects

High- and Low-Energy Photoemission Study of Strongly Correlated Au–Ga–Ce Quasicrystal Approximants: Localized 4<i>f</i> Nature and Disorder Effects

Cesium Modulation in Cu(In, Ga)(S, Se)2 Solar Cells: Comprehensive Analysis on Interface, Surface, and Grain Boundary.

Cesium (Cs) incorporation and sulfurization on copper indium gallium selenide solar cells are the keys to improving the device quality. In this study, we explore the impact of Cs modulation on sulfur-containing Cu(In, Ga)(S, Se)2 (CIGSSe) absorbers, resulting in a performance increase of over 2%, reaching 18.11%. The improvement stems from a widened surface bandgap, grain boundary (GB) passivation, and a moderate injection blocking layer. The surface bandgap widens from 1.44 to 2.63 eV after Cs incorporation, confirmed by ultraviolet photoelectron spectroscopy (UPS) and low-energy inverse photoemission spectroscopy (LEIPS) analysis. Cs presence and S depletion in GBs suggest a new phase that might mitigate carrier recombination. Heightened Cs incorporation introduces interface issues, including an augmented injection blocking layer and interface defects. Our study offers insights into interface challenges and GB engineering strategies in Cs-treated CIGSSe solar cells, illuminating the multifaceted impact of heavy alkali metal ion Cs in CIGS-based photovoltaics.

The influence of ligands passivation on strength of Fermi level pinning in the quantum dots interface

PbS quantum dots capped by ethanedithiol (PbS QD-EDT) and tetrabutylammonium iodide (PbS QD-TBAI) and supported by different substrates were examined in terms of Fermi level pinning (FLP), gap states, and electron and hole barriers (Φe and Φh, respectively) using ultraviolet and low-energy inverse photoemission spectroscopy. The former analysis showed that TBAI and EDT differed in their ability to induce gap-state passivation, with the corresponding energy difference determined as 4.0 eV. Two FLP regimes were identified: at substrate work function (Фsub) < 4.0 eV, both ligands showed perfect FLP (S ≈ 0 for holes and electrons), whereas at Фsub > 4.0 eV, the pinning strength of PbS QD-EDT (S of Фb,h and Фb,e = 0.19 and 0.24, respectively) exceeded that of PbS QD-TBAI (S of Фb,h and Фb,e = 0.53 and 0.57, respectively). Thus, the gap states were more effectively passivated in the case of PbS QD-TBAI. Our results indicate the importance of considering FLP strength when working with high-work-function substrates for the design of optimized QD-based devices.

The fate of graphene on copper: Intercalation / de-intercalation processes and the role of silicon

Intercalation and de-intercalation processes below graphene (g) grown by chemical vapor deposition (CVD) on Cu foils (g/Cu) were investigated in a combined low-energy electron microscopy and X-ray photoemission electron microscopy study. Exposure of g/Cu to air induces oxygen and water intercalation which can be removed by annealing in vacuum leading to clean and well-ordered graphene on Cu. However, prolonged air exposure leads to intercalation of large amounts of oxygen, most likely inducing the formation of copper oxides. If sufficient intercalated oxygen remains at the interface when exceeding 320 °C, graphene is oxidized and burned off. Cu foils can be loaded with silicon on purpose during foil pre-treatment or accidently during long growth time when applying high temperatures at elevated H2 pressure inducing the reactive removal of Si species from the quartz reactor wall. Due to the dissolution of Si in the Cu bulk, the Si surface concentration remains below detection limit and graphene of equal crystalline quality is grown as if the Cu foil was silicon-free. However, oxygen intercalation underneath graphene on Si-containing Cu foils can induce Si segregation towards the surface and formation of intercalated silica without attacking the covering graphene. Even at high temperatures, segregating Si acts as oxygen scavenger so that graphene resists oxidation. The observed effect explains the usefulness of certain synthesis protocols and paves the way towards large-scale fabrication of electronically decoupled graphene. The effect can be used to immobilize adsorbing oxygen at the interface and image the initial steps of intercalation below graphene in-situ.

Spectral Signatures of a Negative Polaron in a Doped Polymer Semiconductor: Energy Levels and Hubbard U Interactions.

The modern picture of negative charge carriers on conjugated polymers invokes the formation of a singly occupied (spin-up/spin-down) level within the polymer gap and a corresponding unoccupied level above the polymer conduction band edge. The energy splitting between these sublevels is related to on-site Coulomb interactions between electrons, commonly termed Hubbard U. However, spectral evidence for both sublevels and experimental access to the U value is still missing. Here, we provide evidence by n-doping the polymer P(NDI2OD-T2) with [RhCp*Cp]2, [N-DMBI]2, and cesium. Changes in the electronic structure after doping are studied with ultraviolet photoelectron and low-energy inverse photoemission spectroscopies (UPS, LEIPES). UPS data show an additional density of states (DOS) in the former empty polymer gap while LEIPES data show an additional DOS above the conduction band edge. These DOS are assigned to the singly occupied and unoccupied sublevels, allowing determination of a U value of ∼1 eV.

Exploring the range of applicability of anisotropic optical detection in axially coordinated supramolecular structures

Ensuring the highest accuracy in determining the molecular assembling and the preservation of the chemical and physical properties of the molecules during the growth of organic layers requires a real-time monitoring of film formation. In this respect, optical techniques are preferred since they result in minimum organic film damage. Among these techniques, Reflectance Anisotropy Spectroscopy (RAS) proved to be the one with the highest sensitivity due to the development of intrinsic anisotropies in the optical response of molecular films, where molecular packing is driven by Van der Waals interactions. Recently, we proposed an original strategy to enable the growth of organic films via molecular self-assembly through highly directional coordination bonds. Herein, we consider a straightforward supramolecular structure employing axial bonds, based on the 1:1 assembly of a CoII porphyrin (CoTPP) and a linear ligand (DPNDI). This system is characterized by a rather isotropic structure that might, in principle, result in a weak RAS signal. Therefore, in the present work, we critically assess the range of applicability of such a spectroscopy. A number of other surface science techniques, including Low Energy Electron Diffraction (LEED), photoemission spectroscopies (PES and IPES) and Atomic Force Microscopy (AFM) is employed to fully characterize the axially coordinated molecular film.

Observation of electronic structure replicas in photoemission spectra of graphite upon adsorption of tin phthalocyanine

Cone-type bands near the center of the surface Brillouin zone were observed in low-energy angle-resolved photoemission spectra of tin phthalocyanine adsorbed on graphite. Simulations in comparison with the experimental data show that the spectral features represent replicas of the electronic structure of graphite near resulting from high-order momentum transfer processes up to the fourth order owing to the interaction of substrate electrons with the long-range structural order of the adsorbate overlayer. The analysis of time-resolved photoemission data from one of the replicas yields a quantitative and very good agreement with previous studies on the excited carrier dynamics in the Dirac cones of graphite and graphene.

Direct Observation of Increased Free Carrier Generation Owing to Reduced Exciton Binding Energies in Polymerized Small-Molecule Acceptors.

Energy loss caused by exciton binding energy (Eb) has become a key factor that restricts further advancement of organic solar cells (OSCs). Herein, we used transient mid-IR spectroscopy to study direct photogeneration of free charge carriers in small-molecule acceptors (SMAs) Y6 and IDIC as well as polymerized SMAs (PSMAs) PYFT and PZ1. We found that free carrier concentration is higher in PSMAs than in their corresponding SMAs, indicating reduced exciton Eb, which is then confirmed by ultraviolet photoelectron spectroscopy, low-energy inverse photoemission spectroscopy, and film absorption spectra measurements. The measured Eb values of PYFT and PZ1 are 0.24 and 0.37 eV, respectively, smaller than those of Y6 (0.32 eV) and IDIC (0.47 eV). This work not only provides a method to directly monitor the photogenerated free carriers in OSC materials but also demonstrates that polymerization is an effective strategy to reduce the Eb, which is crucial to decrease the energy losses in high-performance OSCs.

Multilateral surface analysis of the CeB6 electron-gun cathode used at SACLA XFEL.

The CeB6(001) single crystal used as a cathode in a low-emittance electron gun and operated at the free-electron laser facility SACLA was investigated using cathode lens electron microscopy combined with X-ray spectroscopy at SPring-8 synchrotron radiation facility. Multilateral analysis using thermionic emission electron microscopy, low-energy electron microscopy, ultraviolet and X-ray photoemission electron microscopy and hard X-ray photoemission spectroscopy revealed that the thermionic electrons are emitted strongly and evenly from the CeB6 surface after pre-activation treatment (annealing at 1500°C for >1 h) and that the thermionic emission intensity as well as elemental composition vary between the central area and the edge of the old CeB6 surface.

The Transition From MoS2 Single-Layer to Bilayer Growth on the Au(111) Surface

The transition from single-layer to bilayer growth of molybdenum disulfide on the Au(111) surface is investigated by in situ low-energy electron and photoemission microscopy. By mapping the film morphology with nanometer resolution, we show that a MoS2 bilayer forms at the boundaries of single-layer single-domain MoS2 islands and next to merging islands whereas bilayer nucleation at the island centers is found to be suppressed, which may be related to the usage of dimethyl disulfide as sulfur precursor in the growth process. This approach, which may open up the possibility of growing continuous films over large areas while delaying bilayer formation, is likely transferable to other transition metal dichalcogenide model systems.

Role of Surface Termination in the Metal–Insulator Transition of V2O3(0001) Ultrathin Films

Surface termination is known to play an important role in determining the physical properties of materials. It is crucial to know how surface termination affects the metal-insulator transition (MIT) of V2O3 films for both fundamental understanding and its applications. By changing growth parameters, we achieved a variety of surface terminations in V2O3 films that are characterized by low-energy electron diffraction (LEED) and photoemission spectroscopy techniques. Depending upon the terminations, our results show that MIT can be partially or fully suppressed near the surface region due to the different fillings of the electrons at the surface and subsurface layers and the change of screening length compared to the bulk. Across MIT, a strong redistribution of spectral weight and its transfer from a high-to-low-binding energy regime is observed in a wide energy scale. Our results show that the total spectral weight in the low-energy regime is not conserved across MIT, indicating a breakdown of the "sum rules of spectral weight", signature of a strongly correlated system. Such a change in spectral weight is possibly linked to the change in hybridization, lattice volume (i.e., effective carrier density), and the spin degree of freedom in the system that occurs across MIT. We find that MIT in this system is strongly correlation-driven, where the electron-electron interactions play a pivotal role. Moreover, our results provide better insight into the understanding of the electronic structure of strongly correlated systems and highlight the importance of accounting for surface effects during interpretation of the physical property data mainly using surface-sensitive probes, such as surface resistivity.

Tuning graphene doping by carbon monoxide intercalation at the Ni(111) interface

Under near-ambient pressure conditions, carbon monoxide molecules intercalate underneath an epitaxial graphene monolayer grown on Ni(111), getting trapped into the confined region at the interface. On the basis of ab-initio density functional theory calculations, we provide here a full investigation of the intercalated CO pattern, highlighting the modifications induced on the graphene electronic structure. For a CO coverage as low as 0.14 monolayer (ML), the graphene layer is spatially decoupled from the metallic substrate, with a significant C 1s core level shift towards lower binding energies. The most relevant signature of the CO intercalation is a clear switching of the graphene doping state, which changes from n-type, when strongly interacting with the metal surface, to p-type. The shift of the Dirac cone linearly depends on the CO coverage, reaching about 0.9 eV for the saturation value of 0.57 ML. Theoretical predictions are compared with the results of scanning tunnelling microscopy, low-energy electron diffraction and photoemission spectroscopy experiments, which confirm the proposed scenario for the nearly saturated intercalated CO system.This result opens the way to the application of the graphene/Ni(111) interface as gas sensor to easily detect and quantify the presence of carbon monoxide.

Micro-spectroscopy of Buried Short-Range Surface Plasmon Polaritons Supported by Thin Polycrystalline Gold Films

The dispersive properties of short-range surface plasmon polaritons are investigated at the buried interfaces in vacuum/Au/fused silica and vacuum/Au/SiO2/Si multilayer systems for different gold film thicknesses of up to 50 nm using two-photon photoemission electron microscopy. The experimental data agrees excellently with results of transfer matrix method simulations, emphasizing the sensitivity of the plasmonic wave vector to the thickness of the gold film and an ultrathin native substrate oxide layer. The results furthermore illustrate the exceptional qualification of low-energy electron photoemission techniques in studying electronic excitations at buried interfaces.

Adsorption of Se on Cu(1 0 0) and formation of two-dimensional copper selenide layer

In order to understand the adsorption process of selenium (Se) and Se-based molecules on noble metal surfaces, we report here on the properties of a thin film of Se on Cu(1 0 0) substrate. The deposition was carried out by incubating of a clean Cu(1 0 0) surface into Na 2 Se solution under controlled conditions. The film properties were analysed as a function of the annealing temperature of the sample, using Low Energy Electron Diffraction (LEED) and photoemission techniques. A progressive structural transition from disordered thick layer to a two-dimensional Copper Selenide CuSe thin layer is obtained upon the thermal treatment. Our study proves that a large scale, well-ordered, and highly-stabilized metal chalcogenide layer can be produced for promising use in potential applications.

Quantitative analysis of the electrostatic and electronic polarization energies in molecularly mixed films of organic semiconductors

The energy levels of organic semiconductors are primarily determined by the molecular orbital energies of constituent molecules. Recent studies have, however, shown that the energy levels can be changed by the mixing ratio of two molecules which have different permanent quadrupole moments. From the good correlation between the magnitude of the mixed film's energy shift and the constituent molecules' permanent quadrupole moment, it was noted that the molecular quadrupole plays an important role in the energy shift. In this study, ultraviolet photoelectron spectroscopy (UPS) and low-energy inverse photoemission spectroscopy (LEIPS) are applied to the mixed films of zinc phthalocyanine (ZnPc) and perfluorinated ZnPc (${\mathrm{F}}_{16}\mathrm{ZnPc}$), which have permanent quadrupole moments with opposite directions. From the precisely determined ionization energies and electron affinities, we directly determine the electronic polarization energy $D$ and electrostatic energy $S$ as a function of mixing ratio. Furthermore, we examined the molecular orientation dependence of $S$ and $D$ values. $D$ is almost independent of the mixing ratio (the difference is less than 0.2 eV over the range of mixing ratio) whereas $S$ differs by as much as 1.6 eV. The result clearly shows that the energy levels' continuous shift by the mixing ratio originates in the electrostatic interaction, whose leading term is the charge-permanent quadrupole interaction.

Low energy photoemission from (100) Ba1−xLaxSnO3 thin films for photocathode applications

Recent research on photocathodes for photoinjectors has focused on the understanding of the photoemission process at low energy (i.e. at photon energy close to the material’s work function) as well as on the study of ordered and innovative photocathode materials, with the aim of minimizing the emittance at the cathode. We here present a preliminary study on low energy photoemission from (100) oriented Ba1−xLaxSnO3 thin films, characterizing their quantum efficiency and the mean transverse energy of the photoelectrons. The aim of the study is to pave the way for future experiments on innovative photocathodes based on perovkite oxides.

Growth of Germanene on Al(111) Hindered by Surface Alloy Formation

Obtaining pure group IV 2D films on well-behaved substrates is at present a major goal in materials science and of great interest for the associated industries. This goal still represents a challenge in surface science because often these materials tend to form alloys. As a consequence, some of the proposed 2D films resulted in topics of controversy regarding the top-layer elemental composition and interpretation of the honeycomb patterns measured by STM. Very recently, germanene on Al(111) was proposed to be a system having a larger gap than silicene and a quantum-spin Hall effect. This system was studied by several techniques including scanning tunnel microscopy, low-energy electron diffraction, photoemission, and density functional theory. None of the techniques used until now have the capability to detect unambiguously the presence of substrate atoms within the ultrathin film (i.e., separated from the corresponding substrate), thus leaving open the question of the composition or purity of the layer. Here we follow previous guidelines to grow a Ge film on Al(111) with the expected 3 × 3 arrangement that was assumed to be characteristic of germanene, and then we study in situ the properties of the films with ion scattering and recoiling spectrometry, a technique particularly suited for determining the elemental composition of the last surface layer. Our results unambiguously show the formation of a mixture of well-ordered Ge and Al atoms for all of the temperatures and conditions tested, in clear disagreement with the pure single germanene layer proposed in previous works. These conclusions led us to investigate by DFT calculations other possible structures compatible with our present results and the previously reported ones. The most favorable alloyed structures obtained by DFT were then compared with new I–V low-energy electron diffraction curves, and from this comparison, a top surface model composed of five Ge atoms and three Al atoms is proposed to replace the germanene model.

In-situ study of microstructural evolution during thermal treatment of 6063 aluminum alloy

The present study reports microstructural observation during thermal treatment of 6063 aluminum alloy. Microscopic investigation employing low-energy electron and X-ray photoemission electron techniques was conducted. Work function pertaining thereto such techniques was analyzed. During the thermal treatment representing homogenization of the alloy, as-cast intermetallics transform morphologically from initial β-AlFeSi to α-Al(FeMn)Si. The transformation is governed by elemental diffusion between the as-cast intermetallics and the aluminum matrix and by reversible wetting of grain boundaries. These lead to formation of discrete and globular particles of α-Al(FeMn)Si all over the aluminum matrix. This in-situ study reveals that the phase transformation is not taken place by nucleation of α-Al(FeMn)Si onto surfaces of β-AlFeSi.

Structural, chemical, and magnetic properties of cobalt intercalated graphene on silicon carbide

We report on a study of the Co intercalation process underneath the R30° reconstructed 6H-SiC(0001) surface for Co film-thicknesses in a range of 0.4–12 nm using a combination of surface sensitive imaging, diffractive, and spectroscopic methods. In situ photoemission electron microscopy reveals a dependence of the intercalation temperature on the Co film-thickness. Using low energy electron diffraction and photoemission spectroscopy (XPS), we find that the SiC surface reconstruction is partially lifted and transformed. We show that the R30° reconstruction does not prevent silicide formation for Co film-thicknesses ≥0.4 nm according to XPS and x-ray absorption spectra. Our results indicate that the silicide formation is self-limited to a thin interface region and is followed by Co intercalation between graphene and silicide. Furthermore, we analyze the magnetic properties using x-ray magnetic circular dichroism at the Co L-edge. In-plane magnetization is observed for all analyzed film-thicknesses. For ultra-thin Co films, self-assembled magnetic wires with a width of the order of 100 nm form at the step-edges.

Localized segregation of gold in ultrathin Fe films on Au(001)

The growth of up to 10 monolayer-thick Fe films on a Au(001) surface was investigated during deposition at room temperature and during annealing using low-energy electron diffraction and x-ray photoemission spectroscopy as well as locally with low-energy electron microscopy and photoemission electron microscopy. The growth proceeds with a submonolayer of Au segregating to the surface of Fe, which is in agreement with previous studies. Annealing was found to be critical for the presence of Au on the Fe surface. Our findings show that Au segregation proceeds by the formation of cracks in the Fe film, starting at the annealing temperature of 190 {\deg}C, through which Au diffuses towards the surface. We explain the localized Au segregation with a shadowing effect due to the oblique deposition geometry. As a result, an Fe film with significantly improved roughness, but covered with a Au overlayer, is obtained. This study shows the necessity to employ spatially-resolved techniques to fully understand the growth modes of the layered epitaxial systems.