Low Energy Photoelectron Spectroscopy Research Articles

Synthesis of the composites of carbon quantum dots and metal organic framework and their application in hydrogen evolution

The Ti-MIL-125 metal-organic framework (MOF) functions as a nanoreactor, producing carbon quantum dots (CQDs) within its structure and forming CQD/MOF composites. Similarly, a Pt-CQD/MOF three-component composite is synthesized. Their properties, along with those of CQDs and MOF-free-CQDs (mf-CQDs) enclosed within the MOF, undergo assessment and comparison. Integrating CQDs and Pt minimally alters the MOF structure but reduces specific surface areas due to incorporation. The emitted wavelength of CQD/MOF (570 nm) differs from pristine CQDs (450 nm) and mf-CQDs (496 nm), indicating MOF influence on CQDs' growth and photoluminescence. HOMO and LUMO levels of CQDs/MOF, measured via ultraviolet photoelectron spectroscopy and low-energy inverse photoelectron spectroscopy, are more positive than those of the MOF, suggesting heterogeneous junction formation, aiding electron separation. CQD/MOF exhibits a modest photocatalytic hydrogen evolution rate of 20.4 μmol/g/h. Conversely, Pt-CQD/MOF significantly boosts the rate to 2213 μmol/g/h, underscoring Pt's pivotal catalytic role.

Dependence of Exciton Binding Energy on Bandgap of Organic Semiconductors.

Strongly bound excitons crucially affect the operation of organic optoelectronic devices. Nevertheless, precise experimental data on the exciton binding energy of organic semiconductors are lacking. In this study, we determine the exciton binding energy as the difference between the optical and transport bandgaps with a precision of 0.1 eV. In particular, electron affinities with a precision higher than 0.05 eV determined by low-energy inverse photoelectron spectroscopy allow us to determine the transport gap and the exciton binding energies with such high precision. Through a systematic comparison of a wide range of organic semiconductors, including 42 organic solar cell materials (15 nonfullerene acceptors, 4 fullerene acceptors, 13 low-bandgap polymers, 7 organic light-emitting diode materials, and 3 crystalline materials), we found that the exciton binding energy is one-quarter of the transport gap regardless of the materials. We interpret this unexpected relation from a hydrogen atom-like model, i.e., the quantized energy levels in a Coulomb potential between the positive and the negative charges.

Improving the Stability of Li Metal Anode/Solid Electrolyte Interfaces via an Li3PO4 Intermediate Layer: An Investigation of Surface Chemistry and Electronic Band Structure

Recently, researchers are extensively developing next-generation batteries, including all-solid-state batteries (ASSBs), to meet the increasing demand for electric vehicles (EVs) and renewable energy storage. Li metal has been considered an ideal anode material due to its high theoretical capacity and low redox potential. However, it is highly reactive and severe side reactions occur at the interface between Li metal anode and solid electrolytes (SEs), significantly affecting battery performance. Therefore, Li metal anodes have not yet been commercialized. To obtain a chemically stable Li metal anode, the authors examined the side reactions at the interface between the Li metal anode and oxide-type SE using surface analysis techniques such as time-of-flight secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and low-energy inverse photoelectron spectroscopy (LEIPS). In this paper, we present the results of interface analysis between Li metal anode/SE and discuss how to obtain a stable Li metal anode.

Thermal Instability of Gold Thin Films

The disintegration of a continuous metallic thin film leads to the formation of isolated islands, which can be used for the preparation of plasmonic structures. The transformation mechanism is driven by a thermally accelerated diffusion that leads to the minimalization of surface free energy in the system. In this paper, we report the results of our study on the disintegration of gold thin film and the formation of nanoislands on silicon substrates, both pure and with native silicon dioxide film. To study the processes leading to the formation of gold nanostructures and to investigate the effect of the oxide layer on silicon diffusion, metallic film with a thickness of 3 nm was deposited by molecular beam epitaxy (MBE) technique on both pure and oxidized silicon substrates. Transformation of the thin film was observed by low-energy electron microscopy (LEEM) and a scanning electron microscope (SEM), while the nanostructures formed were observed by atomic force microscope (AFM) method. Structural investigations were performed by low-energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS) methods. Our experiments confirmed a strong correlation between the formation of nanoislands and the presence of native oxide on silicon substrates.

High-energy-resolution angle-resolved inverse-photoelectron spectroscopy apparatus for damage-free measurements of conduction band structures of functional materials.

The energy band structure of the conduction band (energy-momentum relation of electrons) is crucial to understanding the electron transport of crystalline materials. In this paper, we describe an angle-resolved low-energy inverse photoelectron spectroscopy (AR-LEIPS) apparatus that examines the conduction band structures of materials sensitive to the electron beam, such as organic semiconductors and organic-inorganic hybrid perovskites. The principle of this apparatus is based on AR inverse photoelectron spectroscopy. To minimize radiation damage and improve energy resolution, we employed our previous approach used in LEIPS [H. Yoshida, Chem. Phys. Lett. 539-540, 180 (2012)]. We obtained an overall energy resolution of 0.23eV with a momentum resolution of 0.9nm-1 at the electron kinetic energy of 2eV or higher.

Electron affinities of small-molecule organic semiconductors: Comparison among cyclic voltammetry, conventional inverse photoelectron spectroscopy, and low-energy inverse photoelectron spectroscopy

The electron affinity ( A ) of an organic semiconductor is an energy parameter representing the electron transport level. The precise value of A in a solid is indispensable for examining and designing organic semiconductor devices. In principle, A in a solid can be determined by inverse photoelectron spectroscopy (IPES). However, because IPES is normally available only for specialists of IPES, A is often estimated from the reduction potential E red measured in solution using a more easily available method, cyclic voltammetry (CV). Thus, the conversion relation from E red into A is practically important in the research of organic semiconductors. On the other hand, previous IPES data may have errors of about 0.3–0.5 eV owing to sample damage and low energy resolution. In 2012, one of the authors developed low-energy inverse photoelectron spectroscopy (LEIPS), which enables the determination of A with the precision of 0.1 eV. In this work, we establish the correlation between CV data E red and solid-state A based on LEIPS data and suggest the relation A = (1.24 ± 0.07) × e E red + (5.06 ± 0.15) eV. We also discuss the reliability of the A values determined by the previous IPES and the present LEIPS in terms of the LUMO spectral onset and the vacuum level. • Electron affinities of 30 small-molecule organic semiconductors. • Correlation between electron affinity and reduction potential. • Electron affinities determined by low-energy inverse photoelectron spectroscopy. • Comparison between conventional and low-energy inverse photoelectron spectroscopies.

Sample-shape dependent energy levels in organic semiconductors

Energy levels in an organic semiconductor are mainly determined by the molecular orbital energies of the constituent molecules. Recent studies, however, have revealed that the energy levels can be altered as much as 1 eV by the molecular orientation in the film or the molecular mixing ratio in the binary film, owing to the intermolecular electrostatic interaction. Because of the long-range nature of Coulomb interaction, theory predicts that the electrostatic energy should depend on the sample shape. In this article, we examine the coverage-dependent energy levels of zinc phthalocyanine and per-fluorinated zinc phthalocyanine in the submonolayer region with ultraviolet photoelectron spectroscopy (UPS) and low-energy inverse photoelectron spectroscopy (LEIPS). Using the procedure we reported previously, we separately evaluated the electronic polarization energy and electrostatic energy as a function of coverage. Unlike the electronic polarization, which contributes only as much as 10 meV, the electrostatic energy contributes as much as 120 meV to the coverage-dependent energy shift. We conclude that the shift in energy levels by changing the coverage is attributed to the sample shape-dependent energy level, owing to the long-range nature of the charge--permanent quadrupole interaction.

The Energy Level Conundrum of Organic Semiconductors in Solar Cells.

The frontier molecular energy levels of organic semiconductors are decisive for their fundamental function and efficiency in optoelectronics. However, the precise determination of these energy levels and their variation when using different techniques makes it hard to compare and establish design rules. In this work, the energy levels of 33 organic semiconductors via cyclic voltammetry (CV), density functional theory, ultraviolet photoelectron spectroscopy, and low-energy inverse photoelectron spectroscopy are determined. Solar cells are fabricated to obtain key device parameters and relate them to the significant differences in the energy levels and offsets obtained from different methods. In contrast to CV, the photovoltaic gap measured using photoelectron spectroscopy (PES) correlates well with the experimental device VOC . It is demonstrated that high-performing systems such as PM6:Y6 and WF3F:Y6, which are previously reported to have negligible ionization energy (IE) offsets (ΔIE), possess sizable ΔIE of ≈0.5eV, determined by PES. Using various D-A blends, it is demonstrated that ΔIE plays a key role in charge generation. In contrast to earlier reports, it is shown that a vanishing ΔIE is detrimental to device performance. Overall, these findings establish a solid base for reliably evaluating material energetics and interpreting property-performance relationships in organic solar cells.

Conduction band structure of high-mobility organic semiconductors and partially dressed polaron formation.

The energy band structure provides crucial information on charge transport behaviour in organic semiconductors, such as effective mass, transfer integrals and electron-phonon coupling. Despite the discovery of the valence (the highest occupied molecular orbital (HOMO)) band structure in the 1990s, the conduction band (the lowest unoccupied molecular orbital (LUMO)) has not been experimentally observed. Here we employ angle-resolved low-energy inverse photoelectron spectroscopy to reveal the LUMO band structure of pentacene, a prototypical high-mobility organic semiconductor. The derived transfer integrals and bandwidths from the LUMO are substantially smaller than those predicted by density functional theory calculations. To reproduce this bandwidth reduction, we propose an improved (partially dressed) polaron model that accounts for the electron-intramolecular vibrational interaction with frequency-dependent coupling constants based on Debye relaxation. This model quantitatively reproduces not only the transfer integrals, but also the temperature-dependent HOMO and LUMO bandwidths, and the hole and electron mobilities. The present results demonstrate that electron mobility in high-mobility organic semiconductors is indeed limited by polaron formation.

Oxygen-rich tetrahedral surface phase on high-temperature rutile VO2(110)T single crystals

Vanadium dioxide undergoes a metal-insulator transition (MIT) from an insulating (monoclinic) to a metallic (tetragonal) phase close to room temperature, which makes it a promising functional material for many applications, e.g. as chemical sensors. Not much is known about its surface and interface properties, although these are critical in many of its applications. This work presents an atomic-scale investigation of the tetragonal rutile VO$_2$(110)$_\text{T}$ single-crystal surface and reports results obtained with scanning tunneling microscopy (STM), low-energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS), supported by density-functional theory-based (DFT) calculations. The surface reconstructs into an oxygen-rich (2$\times$2) superstructure that coexists with small patches of the underlying, unreconstructed (110)-(1$\times$1) surface. The best structural model for the (2$\times$2) surface termination, conceptually derived from a vanadium pentoxide (001) monolayer, consists of rings of corner-shared tetrahedra. Over a wide range of oxygen chemical potentials this reconstruction is more stable than the unreconstructed (110) surface as well as models proposed in the literature.

Effect of graphene oxide on the energy level alignment and photocatalytic performance of Engelhard Titanosilicate-10

A smaller band gap with lower electron-hole recombination is required to ensure good photocatalytic performance of a photocatalyst. This study reveals that the incorporation of graphene oxide (GO) into Engelhard Titanosilicate-10 (ETS-10) forms GO/ETS-10 material with reduced optical band gap of about 2.9 eV, thereby making the GO/ETS-10 material a functional photocatalyst under regions of visible and ultraviolet radiations. Moreover, the results of ultraviolet photoelectron and low-energy inverse photoelectron spectroscopy (UPS-LEIPS) show that GO is a good platform for ETS-10, which significantly lowers the electronic band gap (Eg = 4.005 eV) between the highest occupied (HOMO) and lowest unoccupied molecular orbitals (LUMO) to ease electron transport, significantly reduces the work function (WF = 4.357 eV) to facilitate excitation of electron, and significantly increases the electron affinity (EA = 4.179 eV) to slow down the electron-hole recombination. The results are in good agreement with the empirical photocatalytic degradation of aqueous methylene blue (MB) by the GO/ETS-10 material. Under ultraviolet light irradiation, photocatalytic degradation of MB by the GO/ETS-10 material (as GO/ETS-10/UV-A) shows a similar degradation rate (k1 = 1.6 × 10−3 min−1) in comparison to that under visible light irradiation (as GO/ETS-10/Vis) (k1 = 1.6 × 10−3 min−1), and double the degradation rate in comparison to that in the ETS-10/UV-A system (k1 = 0.7 × 10−3 min−1). Furthermore, the addition of 10 mM of hydrogen peroxide (H2O2) into the photocatalytic system significantly increases the rate of MB degradation with k1 = 4.8 × 10−3 min−1 for the GO/ETS-10/H2O2/UV-A system and k1 = 2.9 × 10−3 min−1 for the GO/ETS-10/H2O2/Vis system. This study illustrates that UPS-LEIPS can be a good technique to predict the performance of a solid photocatalyst, and the GO/ETS-10 material is a good photocatalyst for the degradation of organic pollutants in water.

Metal screening effect on energy levels at metal/organic interface: Precise determination of screening energy using photoelectron and inverse-photoelectron spectroscopies

The energy level alignment at the metal/organic interface greatly affects the charge injection/extraction efficiency of electrodes in organic semiconductor devices. The charge carrier in the vicinity of the metal surface should be stabilized by the screening effect of the metal surface, thereby resulting in the narrowing of the energy gap (highest occupied molecular orbital (HOMO)--lowest unoccupied molecular orbital (LUMO) gap) and modifying the energy level alignment at the metal/organic interface. However, this metal screening effect has not been fully clarified because there has been no precise way to quantitatively evaluate the experimental values. In this study, we employed ultraviolet photoelectron spectroscopy (UPS), metastable atom electron spectroscopy (MAES), and low-energy inverse photoelectron spectroscopy (LEIPS) to examine the quasi--layer-by-layer grown film of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) on the atomically flat metal surface of Ag(111) and Au(111). By applying a procedure we established recently, we precisely evaluated the energy of the metal screening effect. The results demonstrate that the screening effect of the metal surface modifies the charge injection/collection barrier at the metal/organic interface by as much as 0.25 eV. We found that the PTCDA thickness dependent screening effect is precisely reproduced by the image charge model.

Characterization of cathode-electrolyte interface in all-solid-state batteries using TOF-SIMS, XPS, and UPS/LEIPS

In recent years, all-solid-state batteries (ASSBs) have been attracting attention as the next generation batteries for electric vehicles, energy storage systems, etc. Despite the growing interest, there are still many challenges faced in the commercial use of ASSBs. One of the biggest issues is the internal resistance, especially generated at the interface between solid electrolyte and electrode. The internal resistance at the interface limits the charge-discharge cycling performances. In order to solve this issue, it is necessary to examine the chemical and physical interactions at the interface. In this study, we have performed a detailed characterization of a LiPON/LiCoO2 interface using time-of-flight secondary ion mass spectrometry, x-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and low-energy inverse photoelectron spectroscopy to obtain information on chemical species, chemical compositions, chemical states, and energy band diagrams. These powerful techniques have revealed that an interlayer between LiPON and LiCoO2 was formed due to the temperature rise during the manufacturing process. The temperature rise caused a change of the LiPON network structure and stimulated Co reduction in the LiCoO2 layer near the interface. Energy band diagram analysis suggests that the electron diffusion from LiPON to LiCoO2 may have triggered the reduction of Co. We concluded that the chemical changes that occur at the interface caused an increase in interfacial impedance. Preventing the chemical reduction of Co would be a key to minimize the internal resistance. In this article, the detailed chemical interactions between the LiPON and LiCoO2 layers will be discussed.

Accessing the Conduction Band Dispersion in CH3NH3PbI3 Single Crystals.

The conduction band dispersion in methylammonium lead iodide (CH3NH3PbI3) was studied by both angle-resolved two-photon photoelectron spectroscopy (AR-2PPE) with low photon intensity (∼0.0125 nJ/pulse) and angle-resolved low-energy inverse photoelectron spectroscopy (AR-LEIPS). Clear energy dispersion of the conduction band along the Γ-M direction was first observed by these independent methods under different temperatures, and the dispersion was found to be consistent with band calculation under the cubic phase. The effective mass of the electrons at the Γ point was estimated to be (0.20 ± 0.05)m0 at the temperature of 90 K. The observed conduction band energy was different between the AR-LEIPS and AR-2PPE, which was ascribed to the electronic-correlation-dependent difference of initial and final states probing processes. The present results also indicate that the surface structure in CH3NH3PbI3 provides the cubic-dominated electronic property even at lower temperatures.

Formation of Iron Silicides Under Graphene Grown on the Silicon Carbide Surface

The formation of iron silicide thin films under graphene grown on the silicon carbide surface is investigated. The thin films are synthesized by consecutive intercalation of iron and silicon atoms into the graphene. Experiments are carried out in situ in ultrahigh vacuum. The elemental composition and chemical state of the surface of prepared samples and their atomic structure are determined by low-energy electron diffraction and high-resolution X-ray photoelectron spectroscopy using synchrotron radiation. The thickness of deposited iron and silicon layers varies in the range of 0.1–2 nm, and the sample annealing temperature is varied from room temperature to 600°C. We show that intercalation of silicon into the graphene/Fe/SiC system leads to the formation of a layer of Fe–Si solid solution coated with the surface silicide Fe3Si. The films are effectively protected by graphene from exposure to ambient environment, which opens possibilities for their practical application.

A new approach for synthesis of epitaxial nano-thin [formula omitted] alloy via intercalation underneath a graphene

In the present study we synthesized nano-thin epitaxial PtxGd alloys on Pt(111) single crystal surface covered with well-oriented graphene and investigated their electronic and atomic structure at different stages of synthesis. Low-energy electron diffraction, photoelectron spectroscopy and scanning tunneling microscopy data suggest that deposition of Gd on the graphene/Pt(111) system and its further intercalation at 1080 °C lead to formation of nano-thin Pt5Gd alloy covered with a quasi-freestanding graphene. We demonstrate that atomically flat alloy surface is terminated by Pt atomic layer with “kagome” structure. Control of graphene doping through variation of the alloy stoichiometry may open up new opportunities in developing advanced electronics. Owing to a well-known catalytic activity of Pt5Gd alloy, our thin-film system is promising for low-cost production of catalysts in the near future.

Crystalline versus Amorphous Donor-Acceptor Blends: Influence of Layer Morphology on the Charge-Transfer Density of States

Organic small molecule solar cells are used as a test bed to investigate the influence of film morphology on the density of charge-transfer (CT) states. CT states are considered as precursors for charge generation and their energy as the upper limit for the open-circuit voltage in organic donor-acceptor solar cells. In this study the influence of morphology for two perylene donors [crystalline diindenoperylene (DIP) versus amorphous tetraphenyldibenzoperiflanthene (DBP)] with almost identical ionization energy is investigated. As acceptor material, the fullerene ${\mathrm{C}}_{60}$ is used. By combining device measurements with optical and low-energy ultraviolet photoelectron spectroscopy, a comprehensive picture is obtained that describes how morphology and the connected density of states (DOS) affect device performance and the spectroscopic signature of CT states. Especially for the crystalline donor material DIP, strong exponential tail states reaching far into the gap are observed, which can be related to the presence of grain boundaries. A voltage-dependent filling of these states is identified as the origin of a blue shift of electroluminescence spectra with increasing applied voltage. Different approaches are compared to study the influence of static and dynamic disorder in the description of CT emission and absorption spectra of organic solar cells. Despite the fact that both donors yield almost identical CT energy (and, thus, the same open-circuit voltage) the Stokes shift between photocurrent and electroluminescence spectra and, concomitantly, the width of the CT DOS varies by more than a factor of 2. We discuss this observation in terms of the donor-acceptor reorganization energy as well as an additional line broadening by static disorder. Remarkably, the more crystalline donor DIP shows a significant deviation from a Marcus-type description, while this is not the case for the amorphous DBP. This highlights the importance of film morphology in organic solar cells.

Growth and characterization of nickel oxide ultra-thin films

The oxidation of the Ni(111) surface under ultrahigh-vacuum conditions is studied experimentally with low-energy electron diffraction and high-resolution X-ray photoelectron spectroscopy. Exposure of the clean Ni(111) surface to molecular oxygen at room temperature followed by annealing at 400 K leads to the formation of two different structures (2×2) and (33×33)R30∘, prior to the formation of the NiO(111) monolayer. The O 1s core levels indicate that the obtained oxide is terminated by oxygen atoms while the valence band measurements clearly reveal the band gap of NiO. The energy difference between the Fermi level and the maximum of the valance band is extracted and is found to be 0.47 eV.

2D Antimony-Arsenic Alloys.

Alloying in group V 2D materials and heterostructures is an effective degree of freedom to tailor and enhance their physical properties. Up to date, black arsenic-phosphorus is the only 2D group V alloy that has been experimentally achieved by exfoliation, leaving all other possible alloys in the realm of theoretical predictions. Herein, the existence of an additional alloy consisting of 2D antimony arsenide (2D-Asx Sb1- x ) grown by molecular beam epitaxy on group IV semiconductor substrates and graphene is demonstrated. The atomic mixing of As and Sb in the lattice of the grown 2D layers is confirmed by low-energy electron diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. The As content in 2D-Asx Sb1- x is shown to depend linearly on the As4 /Sb4 deposition rate ratio and As concentrations up to 15 at% are reached. The grown 2D alloys are found to be stable in ambient conditions in a timescale of weeks but to oxidize after longer exposure to air. This study lays the groundwork for a better control of the growth and alloying of group V 2D materials, which is critical to study their basic physical properties and integrate them in novel applications.

Growth of thin Sn films on Ag(111) studied with low-energy electron diffraction and X-ray photoelectron spectroscopy

Thin Sn films on Ag(111) grown at different Sn coverage and substrate temperature were characterized with low-energy electron diffraction and x-ray photoelectron spectra. The results show that surface alloying of Sn atoms on Ag(111) occurs at a temperature as low as 96 K, indicating a strong tendency to form a surface alloy between Sn and Ag. During the alloying, Sn atoms substitute Ag atoms in random locations, resulting in a disordered Sn/Ag(111) surface. The alloy surface becomes completely ordered with a (√3 × √3) R30° reconstruction (the √3 phase) only when it is annealed above 453 K, but annealing at 403 K converts all Sn atoms on Ag(111) into the alloy state; the surface coverage of Sn is no more than 1/3 monolayer with excess Sn diffusing into the Ag(111) substrate. These observations indicate that the √3 phase with the Sn-Ag surface alloy is the only ordered phase obtainable on Sn/Ag(111) once the Sn-Ag surface alloy is formed. It is consequently impracticable to grow non-alloy ordered phases, such as stanene, on Ag(111) epitaxially at a temperature above 96 K, showing evident discrepancies with the conclusions of the previous computational study.