Core-level Binding Energies Research Articles

Band alignment of B0.14Al0.86N/Al0.7Ga0.3N heterojunction

Owing to large bandgaps of BAlN and AlGaN alloys, their heterojunctions have the potential to be used in deep ultraviolet and power electronic device applications. However, the band alignment of such junctions has not been identified. In this work, we investigated the band-offset parameters of a B0.14Al0.86 N/Al0.7Ga0.3N heterojunction grown by metalorganic vapor phase epitaxy. These specific compositions were chosen to ensure a sufficiently large band offset for deep ultraviolet and power electronic applications. High resolution transmission electron microscopy confirmed the high structural quality of the heterojunction with an abrupt interface and uniform element distribution. We employed high resolution X-ray photoemission spectroscopy to measure the core level binding energies of B 1s and Ga 2p3/2 with respect to the valence band maximum of B0.14Al0.86N and Al0.7Ga0.3N layers, respectively. Then, we measured the energy separation between the B 1s and Ga 2p3/2 core levels at the interface of the heterojunction. The valence band offset was determined to be 0.40 ± 0.05 eV. As a consequence, we identified a staggered-gap (type-II) heterojunction with the conduction band offset of 1.10 ± 0.05 eV. The determination of the band alignment of the B0.14Al0.86N/Al0.7Ga0.3N heterojunction facilitates the design of optical and electronic devices based on such junctions.

Determination of band offsets between p-NiO gate electrode and unintentionally doped GaN for normally-off GaN power device

Combining the p-NiO gate electrode and the stack barrier structure with unintentionally doped GaN insertion layer (serves as etching termination layer) is promising for achieving normally-off GaN power device. The band alignment and band offsets at the interface of NiO and GaN insertion layer play a crucial role in determining the performance of GaN device. In this letter, the p-NiO thin film/unintentionally doped GaN heterojunction was fabricated through a simple thermal oxidation method. The p-NiO thin film presents face-centered cubic crystalline structure with a band gap of approximately 3.69 eV. The interfacial band alignment of the heterojunction is characterized by X-ray photoelectron spectroscopy. Based on core-level binding energies and valence band maximum values, the valence and the conduction band offsets were determined to be 1.16 eV and 1.45 eV, respectively. The NiO/GaN heterojunction is concluded to be type-II staggered band configuration.

Effects of rhenium on graphene grown on SiC(0001)

We study the effects of Rhenium (Re) deposited on epitaxial monolayer graphene grown on SiC(0001) and after subsequent annealing at different temperatures, by performing high resolution photoelectron spectroscopy (PES) and angle resolved photoelectron spectroscopy (ARPES). The graphene-Re system is found to be thermally stable. While no intercalation or chemical reaction of the Re is detected after deposition and subsequent annealing up to 1200°C, a gradual decrease in the binding energy of the Re 4f doublet is observed. We propose that a larger mobility of the Re atoms with increasing annealing temperature and hopping of Re atoms between different defective sites on the graphene sample could induce this decrease of Re 4f binding energy. This is corroborated by first principles density functional theory (DFT) calculations of the Re core-level binding energy shift. No change in the doping or splitting of the initial monolayer graphene electronic band structure is observed after Re deposition and annealing up to 1200°C, only a broadening of the bands.

Energy level offsets and space charge layer formation at electrode-electrolyte interfaces: X-ray photoelectron spectroscopy analysis of Li-ion model electrodes

Energy level offsets and related space charge layer formation are crucial for the kinetic properties of functional electric interfaces. In this contribution, we give a concise overview of our results on model Li-ion cathode interfaces with different overlayer phases obtained by surface science methodology using X-ray photoelectron spectroscopy. In particular, we present electronic energy level alignment, space charge layer formation, and Li1s core level binding energy differences at thin film LiCoO2 surfaces covered by thin layers of solid state electrolyte, other ionic compounds and organic solvents. The data suggest a correlation between the binding energy of the Li1s emission and the extent of the space charge layer formation, which can be rationalized using the concept of ionic energy levels. The data also indicate that interface dipole potentials might be relevant for the formation of some of the investigated interfaces, and suggest that large electronic bulk energy level offsets are insufficient indicators for interface stability, as is usually assumed for electrode-electrolyte interfaces.

Electron band bending and surface sensitivity: X-ray photoelectron spectroscopy of polar GaN surfaces

The role of electron band bending and surface sensitivity in determining the core level binding energies by X-ray photoelectron spectroscopy is investigated. A dominating contribution of surface atomic layers to photoemission intensity is confirmed for normal photoemission. The energy of the photoelectron core level peak does not deviate from core level peak energies of electrons photoemitted from the surface atomic layers of the crystal. The higher surface sensitivity regime, achieved e.g. at off-normal photoelectron detection angle, can be used to study the surface potential barrier in just a few topmost atomic layers. In addition, it is demonstrated that core level binding energy measured by angle-resolved X-ray photoelectron spectroscopy reflect the electron attenuation anisotropy. In particular, core level binding energy changes with emission angle and correlates with the forward focusing directions in a crystal. This effect is demonstrated by measuring the polar angle dependence of Ga 3d core levels on clean GaN(0001) and GaN(0001¯) surfaces with a higher and a lower band bending, respectively. The effect is explained by variation of emission depth in a crystal for normal and off-normal photoelectron emission angles.

Assessing the ability of DFT methods to describe static electron correlation effects: CO core level binding energies as a representative case.

We use a total energy difference approach to explore the ability of various density functional theory based methods in accounting for the differential effect of static electron correlation on the C(1s) and O(1s) core level binding energies (BEs) of the CO molecule. In particular, we focus on the magnitude of the errors of the computed C(1s) and O(1s) BEs and on their relative difference as compared to experiment and to previous results from explicitly correlated wave functions. Results show that the different exchange-correlation functionals studied here behave rather erratically and a considerable number of them lead to large errors in the BEs and/or the BE shifts. Nevertheless, the TPSS functional, its TPSSm and RevTPSS derivations, and its corresponding hybrid counterpart, TPSSh, perform better than average and provide BEs and BE shifts in good agreement with experiment.

Computational insights and the observation of SiC nanograin assembly: towards 2D silicon carbide

While an increasing number of two-dimensional (2D) materials, including graphene and silicene, have already been realized, others have only been predicted. An interesting example is the two-dimensional form of silicon carbide (2D-SiC). Here, we present an observation of atomically thin and hexagonally bonded nanosized grains of SiC assembling temporarily in graphene oxide pores during an atomic resolution scanning transmission electron microscopy experiment. Even though these small grains do not fully represent the bulk crystal, simulations indicate that their electronic structure already approaches that of 2D-SiC. This is predicted to be flat, but some doubts have remained regarding the preference of Si for sp3 hybridization. Exploring a number of corrugated morphologies, we find completely flat 2D-SiC to have the lowest energy. We further compute its phonon dispersion, with a Raman-active transverse optical mode, and estimate the core level binding energies. Finally, we study the chemical reactivity of 2D-SiC, suggesting it is like silicene unstable against molecular absorption or interlayer linking. Nonetheless, it can form stable van der Waals-bonded bilayers with either graphene or hexagonal boron nitride, promising to further enrich the family of two-dimensional materials once bulk synthesis is achieved.

Origin of the core-level binding energy shifts in Au nanoclusters

We investigate the shifts of the core-level binding energies in small gold nanoclusters by using {\it ab initio} density functional theory calculations. The shift of the 4$f$ states is calculated for magic number nanoclusters in a wide range of sizes and morphologies. We find a non-monotonous behavior of the core-level shift in nanoclusters depending on the size. We demonstrate that there are three main contributions to the Au 4$f$ shifts, which depend sensitively on the interatomic distances, coordination and quantum confinement. They are identified and explained by the change of the on-site electrostatic potential.

Core-level binding energy shifts as a tool to study surface processes on LaAlO3/SrTiO3

X-ray photoelectron spectroscopy (XPS) is used to study the adsorbed species on LalAlO3/SrTiO3 surfaces combined with computational modeling. Core level binding energy shifts are calculated from first-principles for various terminations of LaAlO3 (LAO) surfaces with adsorbed H and OH in different concentrations and with or without the presence of oxygen vacancies on the surface. Final state relaxation effects in the presence of the core hole are included. Energies of formation and adsorption for the various species and relevant reaction energies are calculated. These are used to interpret the changes in XPS spectra of an LAO film under different growth and annealing treatments. We find a peak with 2eV binding energy shift toward higher binding energy in the O1s spectrum cannot be associated with OH as is commonly assumed. Instead it is assigned to carbonaceous species by studying the corresponding changes in the C1s spectrum. The OH and H species are found to be too strongly bound to be removed at 500°C.

In-situ growth of HfO2 on clean 2H-MoS2 surface: Growth mode, interface reactions and energy band alignment

Room temperature growth of HfO2 thin film on clean 2H-MoS2 via plasma-sputtering of Hf-metal target in an argon/oxygen environment was studied in-situ using x-ray photoelectron spectroscopy (XPS). The deposited film was observed to grow akin to a layer-by-layer growth mode. At the onset of growth, a mixture of sulfate- and sulfite-like species (SOx2− where x=3, 4), and molybdenum trioxide (MoO3), are formed at the HfO2/MoS2 interface. An initial decrease in binding energies for both Mo 3d and S 2p core-levels of the MoS2 substrate by 0.4eV was also observed. Their binding energies, however, did not change further with increasing HfO2 thickness. There was no observable change in the Hf4f core-level binding energy throughout the deposition process. With increasing HfO2 deposition, MoO3 becomes buried at the interface while SOx2− was observed to be present in the film. The shift of 0.4eV for both Mo 3d and S 2p core-levels of the MoS2 substrate can be attributed to a charge transfer from the substrate to the MoO3/SOx2−-like interface layer. Consequently, the Type I heterojunction valence band offset (conduction band offset) becomes 1.7eV (2.9eV) instead of 1.3eV (3.3eV) expected from considering the bulk HfO2 and MoS2 valence band offset (conduction band offset). The formation of these states and its influence on band offsets will need to be considered in their device applications.

(Invited) Determining Solid/Liquid Junction Energetics By Operando Ambient-Pressure X-Ray Photoelectron Spectroscopy

The performance of a photoelectrochemical solar cell (PEC) depends strongly on the electrochemical nature of the semiconductor/electrolyte junction. Operando ambient pressure X-ray photoelectron spectroscopy (OAP-XPS) investigation of solid/liquid junctions provides quantitative understanding of the energetic relations in PECs [1-3]. We demonstrate that OAP-XPS can be used to determine these relationships for solid/liquid systems. The OAP-XPS data can be analyzed to determine the relationship between the energy bands in a semiconductor electrode and the redox levels in the solution as well as directly analyze the energetics of the double layer at a metal-aqueous solution interface. From the response of the core level binding energy shifts and the broadening to variations in applied potential, we obtain the energetics of the solid/electrolyte interface. All major conditions for semiconductor-electrolyte contacts including accumulation, depletion, and Fermi-level pinning were observed, and the flat-band potential was determined. The data are compared to theoretical evaluations of the potential in the solid and electrolyte near the interface. 1. H.J. Lewerenz et al., Electrochimica Acta, 211, 711–719 2016 2. M. F. Lichterman et al., Journal of the Electrochemical Society, 163(2), H139–H146, 2016 3. M. F. Lichterman et al., Energy & Environmental Science, 8(8), 2409–2416, 2015

Adsorptive Removal of Carbamazepine and Diatrizoate in Iron Oxide Nanoparticles Amended Sand Column Mimicing Managed Aquifer Recharge

The sorption–desorption of recalcitrant pharmaceuticals in sand/soil columns can be used to infer performance of managed aquifer recharge. Removal of carbamazepine (CBZ) and diatrizoate (DTZ) from synthetic wastewater, containing 100 µg·L−1 of each pharmaceuticals, was studied in recirculating sand columns amended with uncoated or methacrylic acid (MAA) coated magnetite nanoparticles. Removal of CBZ and DTZ in MAA-magnetite column (68.34% and 61.91%, respectively) was much higher than that with uncoated magnetite (53.47% and 50.26%, respectively). Rapid decrease of dissolved organic carbon concentrations across nanoparticle amended columns (between 42.28% and 50.08% on Day 1), followed by slow recuperation suggests adsorption–desorption dynamics and competition of dissolved organic matter for sorption sites. Core-level binding energy and charge analysis for Fe(2s) and O(1s) in X-ray photoelectron spectroscopy suggests involvement of physisorption process on the NP surfaces.

Single-particle excitation of core states in epitaxial silicene

Recent studies of core-level x-ray photoelectron spectroscopy (XPS) spectra of silicene on ${\mathrm{ZrB}}_{2}(0001)$ were found to be inconsistent with the density of states (DOS) of a planar-like structure that has been proposed as the ground state by density functional theory (DFT). To resolve the discrepancy, a reexamination of the XPS spectra and direct theoretical access of accurate single-particle excitation energies are desired. By analyzing the XPS data using symmetric Voigt functions, different binding energies and their sequence of Si $2p$ orbitals can be assigned from previously reported ones where asymmetric pseudo-Voigt functions are adopted. Theoretically, we have adopted an approach developed very recently, which follows the sophisticated $\mathrm{\ensuremath{\Delta}}$ self-consistent field $(\mathrm{\ensuremath{\Delta}}\mathrm{SCF})$ methods, to study the single-particle excitation of core states. In the calculations, each single-particle energy and the renormalized core-hole charge density are calculated straightforwardly via two SCF calculations. By comparing the results, the theoretical core-level absolute binding energies including the splitting due to spin-orbit coupling are in good agreement with the observed high-resolution XPS spectra. The good agreement not only resolves the puzzling discrepancy between experiment and theory (DOS) but also advocates the success of DFT in describing many-body interactions of electrons at the surface.

In Situ X-ray Photoelectron Spectroscopy Study of Lithium Interaction with Graphene and Nitrogen-Doped Graphene Films Produced by Chemical Vapor Deposition

It is commonly accepted that the presence of nitrogen atoms in a graphene lattice improves many properties of carbon materials and particularly enhances their electrochemical capacity in Li ion batteries. Here, we present model experiments for revealing the difference in interaction of lithium with N-doped and N-free graphene samples by monitoring the changes in their electronic states after the deposition of Li vapors. Graphene and N-doped graphene films have been grown by chemical vapor deposition on copper substrates using methane and acetonitrile as precursors. The electronic structure of the films transferred onto SiO2/Si substrates was examined by X-ray photoelectron spectroscopy (XPS) before and after deposition of lithium from a Li evaporation source under vacuum conditions. A comparison between two graphene samples using in situ XPS measurements has detected a higher accumulation of lithium on the N-doped graphene, which implies its high prospects in energy storage applications. Analysis of the XPS core-level binding energy shifts showed that charge density donated by lithium is localized near the nitrogen defects, especially around the nitrogen atoms directly substituting for carbon atoms.

Observation of surface oxidation resistant Shubnikov-de Haas oscillations in Sb2SeTe2 topological insulator

The robustness of Sb2SeTe2 topological insulators against surface oxidation has been comparatively investigated through their magneto-transport and X-ray photoelectron spectroscopic properties with samples freshly cleaved or exposed to air over various timeframes. The magnetoresistance data exhibit Shubnikov-de Haas oscillations with the same period of oscillations for all samples regardless of surface oxidation, whereas the core-level electron binding energies of the constituent elements vary. That there is no shift in Fermi levels and no smearing-out in the amplitude of oscillations suggests that the surface states of the studied topological insulators are impervious to surface oxidation.

Absolute Binding Energies of Core Levels in Solids from First Principles.

A general method is presented to calculate absolute binding energies of core levels in metals and insulators, based on a penalty functional and an exact Coulomb cutoff method in the framework of density functional theory. The spurious interaction of core holes between supercells is avoided by the exact Coulomb cutoff method, while the variational penalty functional enables us to treat multiple splittings due to chemical shift, spin-orbit coupling, and exchange interaction on equal footing, both of which are not accessible by previous methods. It is demonstrated that the absolute binding energies of core levels for both metals and insulators are calculated by the proposed method in a mean absolute (relative) error of 0.4eV (0.16%) for eight cases compared to experimental values measured with x-ray photoemission spectroscopy within a generalized gradient approximation to the exchange-correlation functional.

Predicting core level binding energies shifts: Suitability of the projector augmented wave approach as implemented in VASP.

Here, we assess the accuracy of various approaches implemented in Vienna ab initio simulation package code to estimate core-level binding energy shifts (ΔBEs) using a projector augmented wave method to treat core electrons. The performance of the Perdew-Burke-Ernzerhof (PBE) and the Tao-Perdew-Staroverov-Scuseria (TPSS) exchange-correlation density functionals is examined on a dataset of 68 molecules containing B→F atoms in diverse chemical environments, accounting for 185 different 1s core level binding energy shifts, for which both experimental gas-phase X-ray photoemission (XPS) data and accurate all electron ΔBEs are available. Four procedures to calculate core-level shifts are investigated. Janak-Slater transition state approach yields mean absolute errors of 0.37 (0.21) eV at PBE (TPSS) level, similar to highly accurate all electron ΔSCF approaches using same functionals, and close to XPS experimental accuracy of 0.1 eV. The study supports the use of these procedures to assign ΔBEs of molecular moieties on material surfaces of interest in surface science, nanotechnology, and heterogeneous catalysis. © 2017 Wiley Periodicals, Inc.

Band alignment of atomic layer deposited TiO2/multilayer MoS2 interface determined by x-ray photoelectron spectroscopy

High-resolution x-ray photoelectron spectroscopy (XPS) was employed to characterize the energy band alignment between TiO2/multilayer (ML)-MoS2. The TiO2 film and ML-MoS2 film was grown by an atomic layer deposition (ALD) and chemical vapor deposition (CVD), respectively. The effect of CHF3 plasma treatment on the band alignment between TiO2/ML-MoS2 was evaluated. It was found that the valence band offset (VBO) and a conduction band offset (CBO) of TiO2/ML-MoS2 interface was changed from 2.28 eV to 2.51 eV, and from 0.28 eV to 0.51 eV, respectively for the sample with CHF3 plasma treatment. With the CHF3 plasma treatment, the down-shift of Mo 3d core level binding energy results in a bend-up of energy potential on the MoS2 side, leading to 0.23 eV ΔEC difference between the control and the sample with CHF3 plasma treatment, which is caused by the interfacial layer in rich of F element. The physics details of the band alignment at TiO2/ML-MoS2 interface will provide a guide for the MoS2 based electronic device design.

Band alignment of MAPb(I1–xBrx)3 thin films by vacuum deposition

In this work, the mixed bromide iodide lead perovskites CH3NH3Pb(I1–xBrx)3 (0 ≤ x ≤ 0.67) thin films were prepared by co-evaporation of CH3NH3I, PbI2, and PbBr2. The electronic properties of CH3NH3Pb(I1–xBrx)3 thin films were investigated by X-ray and ultraviolet photoelectron spectroscopy in-situ. The results of core level binding energy show that there is no chemical shift of the C1s, N1s, Br3d5, and I3d5 when the Br composition changes, while there is an approximately linear chemical shift of Pb4f7 to higher binding energy as the Br composition increases. The density functional theory calculation reveals that there is more charge transfer from Pb to Br than I, which results in the chemical shift of Pb4f states. On the other hand, the valence band maximum increases as the Br composition increases, while the work function shows no obvious change, because the conduction band is dominated by Pb 6p orbitals while the valence band is dominated by halide p orbitals. Our work demonstrates the adjustability of the energy level alignment of MAPb(I1–xBrx)3 by the Br composition.

Core-level spectra and binding energies of transition metal nitrides by non-destructive x-ray photoelectron spectroscopy through capping layers

We present the first measurements of x-ray photoelectron spectroscopy (XPS) core level binding energies (BE:s) for the widely-applicable group IVb-VIb polycrystalline transition metal nitrides (TMN’s) TiN, VN, CrN, ZrN, NbN, MoN, HfN, TaN, and WN as well as AlN and SiN, which are common components in the TMN-based alloy systems. Nitride thin film samples were grown at 400°C by reactive dc magnetron sputtering from elemental targets in Ar/N2 atmosphere. For XPS measurements, layers are either (i) Ar+ ion-etched to remove surface oxides resulting from the air exposure during sample transfer from the growth chamber into the XPS system, or (ii) in situ capped with a few nm thick Cr or W overlayers in the deposition system prior to air-exposure and loading into the XPS instrument. Film elemental composition and phase content is thoroughly characterized with time-of-flight elastic recoil detection analysis (ToF-E ERDA), Rutherford backscattering spectrometry (RBS), and x-ray diffraction. High energy resolution core level XPS spectra acquired with monochromatic Al Kα radiation on the ISO-calibrated instrument reveal that even mild etching conditions result in the formation of a nitrogen-deficient surface layer that substantially affects the extracted binding energy values. These spectra-modifying effects of Ar+ ion bombardment increase with increasing the metal atom mass due to an increasing nitrogen-to-metal sputter yield ratio.The superior quality of the XPS spectra obtained in a non-destructive way from capped TMN films is evident from that numerous metal peaks, including Ti 2p, V 2p, Zr 3d, and Hf 4f, exhibit pronounced satellite features, in agreement with previously published spectra from layers grown and analyzed in situ. In addition, the N/metal concentration ratios are found to be 25–90% higher than those obtained from the corresponding ion-etched surfaces, and in most cases agree very well with the RBS and ToF-E ERDA values. The N 1s BE:s extracted from capped TMN films, thus characteristic of a native surface, show a systematic trend, which contrasts with the large BE spread of literature “reference” values.Hence, non-destructive core level XPS employing capping layers provides an opportunity to obtain high-quality spectra, characteristic of virgin in situ grown and analyzed TMN films, although with larger versatility, and allows for extracting core level BE values that are more reliable than those obtained from sputter-cleaned N-deficient surfaces. Results presented here, recorded from a consistent set of binary TMN’s grown under the same conditions and analyzed in the same instrument, provide a useful reference for future XPS studies of multinary materials systems allowing for true deconvolution of complex core level spectra.