Core-level Spectroscopy Research Articles

Reference binding energies of transition metal carbides by core-level x-ray photoelectron spectroscopy free from Ar+ etching artefacts

We report x-ray photoelectron spectroscopy (XPS) core level binding energies (BE’s) for the widely-applicable groups IVb-VIb transition metal carbides (TMCs) TiC, VC, CrC, ZrC, NbC, MoC, HfC, TaC, and WC. Thin film samples are grown in the same deposition system, by dc magnetron co-sputtering from graphite and respective elemental metal targets in Ar atmosphere. To remove surface contaminations resulting from exposure to air during sample transfer from the growth chamber into the XPS system, layers are either (i) Ar+ ion-etched or (ii) UHV-annealed in situ prior to XPS analyses. High resolution XPS spectra reveal that even gentle etching affects the shape of core level signals, as well as BE values, which are systematically offset by 0.2–0.5 eV towards lower BE. These destructive effects of Ar+ ion etch become more pronounced with increasing the metal atom mass due to an increasing carbon-to-metal sputter yield ratio. Systematic analysis reveals that for each row in the periodic table (3d, 4d, and 5d) C 1s BE increases from left to right indicative of a decreased charge transfer from TM to C atoms, hence bond weakening. Moreover, C 1s BE decreases linearly with increasing carbide/metal melting point ratio. Spectra reported here, acquired from a consistent set of samples in the same instrument, should serve as a reference for true deconvolution of complex XPS cases, including multinary carbides, nitrides, and carbonitrides.

Amorphous carbon nanocomposite films doped by titanium: Surface and sub-surface composition and bonding

Hydrogen free Ti-doped amorphous carbon layers were prepared by dual beam pulsed laser deposition using two excimer lasers. The air-exposed surfaces were analyzed by high-energy resolved and angular-resolved core-level photoelectron spectroscopy, and were then step-by-step sputtered with an argon gas cluster ion beam (ArGCIB), which is known to be a very gentle technique with respect to changes in surface chemistry. The results show that the top surface of the sample and its sub-surface region differ in composition and in bonding. The top surface is enriched by oxygen-bearing species. Carbon-bearing species located on the surface are mostly in sp3 hybridization. Titanium carbide clusters, TiC, are not directly exposed at the surface. They are embedded in a carbon network with dominating C sp2 hybridization. Their interface is formed by a distinct carbon-rich titanium carbide with stoichiometry close to TiC3. The surface damage induced by ArGCIB was found to be minimal, verifiably affecting carbon atoms in the carbon network.

How Indium Nitride Senses Water

The unique electronic band structure of indium nitride InN, part of the industrially significant III-N class of semiconductors, offers charge transport properties with great application potential due to its robust n-type conductivity. Here, we explore the water sensing mechanism of InN thin films. Using angle-resolved photoemission spectroscopy, core level spectroscopy, and theory, we derive the charge carrier density and electrical potential of a two-dimensional electron gas, 2DEG, at the InN surface and monitor its electronic properties upon in situ modulation of adsorbed water. An electric dipole layer formed by water molecules raises the surface potential and accumulates charge in the 2DEG, enhancing surface conductivity. Our intuitive model provides a novel route toward understanding the water sensing mechanism in InN and, more generally, for understanding sensing material systems beyond InN.

Ultrafast Intersystem Crossing in Acetylacetone via Femtosecond X-ray Transient Absorption at the Carbon K-Edge

Molecular triplet states constitute a crucial gateway in the photochemical reactions of organic molecules by serving as a reservoir for the excess electronic energy. Here, we report the remarkable sensitivity of soft X-ray transient absorption spectroscopy for following the intricate electronic structure changes accompanying the non-adiabatic transition of an excited molecule from the singlet to the triplet manifold. Core-level X-ray spectroscopy at the carbon-1s K-edge (284 eV) is applied to identify the role of the triplet state (T1, 3ππ*) in the ultraviolet-induced photochemistry of pentane-2,4-dione (acetylacetone, AcAc). The excited-state dynamics initiated at 266 nm (1ππ*, S2) is investigated with element- and site-specificity using broadband soft X-ray pulses produced by high harmonic generation, in combination with time-dependent density functional theory calculations of the X-ray spectra for the excited electronic singlet and triplet states. The evolution of the core-to-valence resonances at the carbon K-edge establishes an ultrafast population of the T1 state (3ππ*) in AcAc via intersystem crossing on a 1.5 ± 0.2 ps time scale.

Multi-Stage Structural Transformations in Zero-Strain Lithium Titanate Unveiled by in Situ X-ray Absorption Fingerprints.

Zero-strain electrodes, such as spinel lithium titanate (Li4/3Ti5/3O4), are appealing for application in batteries due to their negligible volume change and extraordinary stability upon repeated charge/discharge cycles. On the other hand, this same property makes it challenging to probe their structural changes during the electrochemical reaction. Herein, we report in situ studies of lithiation-driven structural transformations in Li4/3Ti5/3O4 via a combination of X-ray absorption spectroscopy and ab initio calculations. Based on excellent agreement between computational and experimental spectra of Ti K-edge, we identified key spectral features as fingerprints for quantitative assessment of structural evolution at different length scales. Results from this study indicate that, despite the small variation in the crystal lattice during lithiation, pronounced structural transformations occur in Li4/3Ti5/3O4, both locally and globally, giving rise to a multi-stage kinetic process involving mixed quasi-solid solution/macroscopic two-phase transformations over a wide range of Li concentrations. This work highlights the unique capability of combining in situ core-level spectroscopy and first-principles calculations for probing Li-ion intercalation in zero-strain electrodes, which is crucial to designing high-performance electrode materials for long-life batteries.

Electronic properties and bonding in ZrHx thin films investigated by valence-band x-ray photoelectron spectroscopy

The electronic structure and chemical bonding in reactively magnetron sputtered ZrHx (x=0.15, 0.30, 1.16) thin films with oxygen content as low as 0.2 at% are investigated by 4d valence band, shallow 4p core-level and 3d core-level X-ray photoelectron spectroscopy. With increasing hydrogen content, we observe significant reduction of the 4d valence states close to the Fermi level as a result of redistribution of intensity towards the H 1s - Zr 4d hybridization region at about 6 eV below the Fermi level. For low hydrogen content (x=0.15, 0.30), the films consist of a superposition of hexagonal closest packed metal (alpha-phase)and understoichiometric delta-ZrHx (CaF2-type structure) phases, while for x=1.16, the film form single phase ZrHx that largely resembles that of stoichiometric delta-ZrH2 phase. We show that the cubic delta-ZrHx phase is metastable as thin film up to x=1.16 while for higher H-contents, the structure is predicted to be tetragonally distorted. For the investigated ZrH1.16 film, we find chemical shifts of 0.68 and 0.51 eV towards higher binding energies for the Zr 4p3/2 and 3d5/2 peak positions, respectively. Compared to the Zr metal binding energies of 27.26 and 178.87 eV, this signifies a charge-transfer from Zr to H atoms. The change in the electronic structure, spectral line shapes, and chemical shifts as function of hydrogen content is discussed in relation to the charge-transfer from Zr to H that affects the conductivity by charge redistribution in the valence band.

Density Functional Theory Modeling the Interfacial Chemistry of the LiNO3 Additive for Lithium–Sulfur Batteries by Means of Simulated Photoelectron Spectroscopy

Lithium–sulfur (Li–S) batteries are considered candidates for next-generation energy storage systems due to their high theoretical specific energy. There exist, however, some shortcomings of these batteries, not least the solubility of intermediate polysulfides into the electrolyte generating a so-called “redox shuttle”, which gives rise to self-discharge. LiNO3 is therefore frequently used as an electrolyte additive to help suppress this mechanism, but the exact nature of the LiNO3 functionality is still unclear. Here, density functional theory calculations are used to investigate the electronic structure of LiNO3 and a number of likely species (N2, N2O, LiNO2, Li3N, and Li2N2O2) resulting from the reduction of this additive on the surface of Li metal anode. The N 1s X-ray photoelectron spectroscopy core level binding energies of these molecules on the surface are calculated in order to compare the results with experimentally reported values. The core level shifts (CLS) of the binding energies are studie...

Partially Reversible Photoinduced Chemical Changes in a Mixed-Ion Perovskite Material for Solar Cells.

Metal halide perovskites have emerged as materials of high interest for solar energy-to-electricity conversion, and in particular, the use of mixed-ion structures has led to high power conversion efficiencies and improved stability. For this reason, it is important to develop means to obtain atomic level understanding of the photoinduced behavior of these materials including processes such as photoinduced phase separation and ion migration. In this paper, we implement a new methodology combining visible laser illumination of a mixed-ion perovskite ((FAPbI3)0.85(MAPbBr3)0.15) with the element specificity and chemical sensitivity of core-level photoelectron spectroscopy. By carrying out measurements at a synchrotron beamline optimized for low X-ray fluxes, we are able to avoid sample changes due to X-ray illumination and are therefore able to monitor what sample changes are induced by visible illumination only. We find that laser illumination causes partially reversible chemistry in the surface region, including enrichment of bromide at the surface, which could be related to a phase separation into bromide- and iodide-rich phases. We also observe a partially reversible formation of metallic lead in the perovskite structure. These processes occur on the time scale of minutes during illumination. The presented methodology has a large potential for understanding light-induced chemistry in photoactive materials and could specifically be extended to systematically study the impact of morphology and composition on the photostability of metal halide perovskites.

Magnetic Circular Dichroism in X-Ray Emission from Ferromagnets.

The existence of novel magnetic circular dichroism in core-level x-ray emission is reported. By means of circular polarization analysis, the dichroic effect of the Fe Kα_{1} emission spectrum is measured on an Fe single crystal. The observed dichroic effect (12%) is remarkably large, if one takes into account the small dichroic effect (about 0.5%) in the conventional K-edge absorption spectroscopy of 3d transition metal elements. The mechanism is ascribed to exchange splitting of the 2p level possessing large spin-orbit coupling. This new magnetooptical effect enables us to explore a variety of new research subjects in the magnetism of 3d transition metals and their compounds by fully utilizing its large dichroic effect, the true bulk sensitivity of hard x rays, and the element selectivity of core-level spectroscopy.

Selenidation of epitaxial silicene on ZrB2

Abstract The deposition of elemental Se on epitaxial silicene on ZrB 2 thin films was investigated with synchrotron-based core-level photoelectron spectroscopy and low-energy electron diffraction. The deposition of Se at room temperature caused the appearance of Si 2 p peaks with chemical shifts of n × 0.51 ± 0.04 eV (n = 1-4), suggesting the formation of SiSe 2 . This shows that capping the silicene monolayer, without affecting its structural and electronic properties, is not possible with Se. The annealing treatments that followed caused the desorption of Se and Si, resulting in the etching of the Si atoms formerly part of the silicene layer, and the formation of bare ZrB 2 (0001) surface area. In addition, a ZrB 2 (0001)-(√7 × 3)R40.9° surface reconstruction was observed, attributed to a Se-termination of the surface of the transition metal diboride thin film.

Coexistence of strongly buckled germanene phases on Al(111).

We report a study of structural and electronic properties of a germanium layer on Al(111) using scanning tunneling microscopy (STM), low energy electron diffraction and core-level photoelectron spectroscopy. Experimental results show that a germanium layer can be formed at a relatively high substrate temperature showing either (3×3) or (√7×√7)R±19.1° reconstructions. First-principles calculations based on density functional theory suggest an atomic model consisting of a strongly buckled (2×2) germanene layer, which is stable in two different orientations on Al(111). Simulated STM of both orientations fit nicely with experimental STM images and the Ge 3d core-level data decomposed into four components is consistent with the suggested model.

Sensitivity of core-level spectroscopy to electrostatic environments of nitrile groups: An ab initio study.

Ab initio quantum chemistry calculations have been performed to probe the influence of hydrogen bonding on the electronic structure of hydrogen cyanide (HCN). Our calculations determine the origin of nitrogen-specific Raman spectral features from resonant inelastic X-ray scattering occurring in the presence of a water molecule and an electric dipole field. The similarity of the two interactions in altering the electronic structure of the nitrogen atom differs only in the covalent contributions from the water molecule. The CN stretching mode as a structural probe was also investigated to study the electronic origin of the anomalous frequency shift of the nitrile group when subjected to hydrogen bonding and an electrostatic dipole field. The major changes in the electronic structure of HCN are electrostatic in nature and originate from dipole-dipole interactions. The relative shifts of the CN stretching frequency are in good agreement with those experimentally observed.

Adsorption and charge transfer interactions of bi-isonicotinic acid on Ag(111).

The adsorption and charge transfer dynamics of the organic molecule bi-isonicotinic acid (4,4-dicarboxy-2,2-bipyridine) on single crystal Ag(111) has been studied using synchrotron radiation-based photoemission, x-ray absorption, and resonant core spectroscopies. Measurements for multilayer and monolayer coverage are used to determine the nature of the molecule-surface interactions and the molecular orientation. An experimental density of states for the monolayer with respect to the underlying metal surface is obtained by combining x-ray absorption spectroscopy at the N 1s edge and valence photoemission to measure the unoccupied and occupied valence states, respectively. This shows that the lowest unoccupied molecular orbital in the core-excited state lies energetically below the Fermi level of the surface allowing charge transfer from the metal into this orbital. Resonant photoelectron spectroscopy was used to probe this charge transfer in the context of super-spectator and super-Auger electron transitions. The results presented provide a novel interpretation of resonant core-level spectroscopy to explore ultra-fast charge transfer between an adsorbed organic molecule and a metal surface through the observation of electrons from the metal surface playing a direct role in the core-hole decay of the core-excited molecule.

Study of structural, dielectric, optical properties and electronic structure of Cr-doped LaInO3 perovskite nanoparticles

This work reports the change in the structural, dielectric and optical behaviour of Cr-doped LaInO3 nanoparticles synthesized via sol-gel method. X-ray diffraction patterns confirm that systems crystallize in orthorhombic Pnma space group. Raman spectroscopy measurements exhibit blue-shift in Raman modes with Cr-doping due to the compressive stress introduced by smaller Cr3+ cations. Trivalent oxidation state of Cr was confirmed from Cr(2p) core-level X-ray photoemission spectroscopy measurements, while valence band spectra suggest the absence of electronic states near Fermi level. High-resolution Ultraviolet photoemission spectra near Fermi level shows the electronic density of states arises sharply near Fermi level. Room temperature dielectric constant decreases with increasing Cr-concentration, which shows that conductivity has been increased after Cr-doping. Ultraviolet–visible spectroscopy measurements provide band gap of 4.8eV for LaInO3 and Cr-doped LaInO3nanoparticles.Moreover, Cr-doped LaInO3systems exhibit an intermediate band gap of 3eV, which might have been created from Cr(3d) states.

Low-Dimensional Carbon Allotropes: Ground- and Excited-State Charge Transfer with NIR-Absorbing Heptamethine Cyanine

Summary At the focal point of our studies are mutual interactions between an anionic heptamethine cyanine and individualized single-walled carbon nanotubes (SWCNTs) or exfoliated nanographene (NG). Here, we report the distinct near-infrared absorption of the heptamethine cyanine, which assists in visualizing the electronic interactions in the ground state with ease and precision. In statistical Raman assays, we conclude from downshifted 2D- and G-modes for SWCNTs, as well as upshifted 2D- and downshifted G-modes for NG, that these electronic interactions result in stable n-doping of SWCNTs and NG. Key to this shift of charge density is the electron-donating character of the heptamethine cyanine. In the excited state, a complete but metastable transfer of charges is accompanied by a radical-ion-pair state that lives for several nanoseconds. Such a time domain has not yet been realized, for example, in NG to date.

Communication: Direct evidence for sequential dissociation of gas-phase Fe(CO)5 via a singlet pathway upon excitation at 266 nm.

We prove the hitherto hypothesized sequential dissociation of Fe(CO)5 in the gas phase upon photoexcitation at 266 nm via a singlet pathway with time-resolved valence and core-level photoelectron spectroscopy with an x-ray free-electron laser. Valence photoelectron spectra are used to identify free CO molecules and to determine the time constants of stepwise dissociation to Fe(CO)4 within the temporal resolution of the experiment and further to Fe(CO)3 within 3 ps. Fe 3p core-level photoelectron spectra directly reflect the singlet spin state of the Fe center in Fe(CO)5, Fe(CO)4, and Fe(CO)3 showing that the dissociation exclusively occurs along a singlet pathway without triplet-state contribution. Our results are important for assessing intra- and intermolecular relaxation processes in the photodissociation dynamics of the prototypical Fe(CO)5 complex in the gas phase and in solution, and they establish time-resolved core-level photoelectron spectroscopy as a powerful tool for determining the multiplicity of transition metals in photochemical reactions of coordination complexes.

Key role of rotated domains in oxygen intercalation at graphene on Ni(1 1 1)

Herein, we provide a complete description of the intercalation of oxygen at the strongly interacting graphene on Ni(1 1 1), highlighting the role of rotated graphene domains in triggering the intercalation. High-resolution core-level photoelectron spectroscopy provided a full characterization of the interface at each stage of the intercalation, revealing the formation of an oxide layer between graphene and the metal substrate. Angle-resolved photoemission spectroscopy measurements showed that the oxide decouples efficiently graphene from the substrate, restoring the Dirac cone and providing a slight n-doping. Photoelectron diffraction experiments revealed that graphene domains not aligned with the Ni substrate are the first to be intercalated with oxygen and are preferential regions under which the oxygen is retained during the deintercalation.

Initial stages of Lutetium growth on Si (111)-7 × 7 probed by STM and core-level photoelectron spectroscopy

The interaction of small amounts of Lutetium with the Si (111)-7 × 7 reconstructed surface was investigated in detail using a combination of Scanning Tunneling Microscopy (STM) and Photoelectron Spectroscopy (XPS and UPS). Various immobile and also fastly moving atoms and nanocluster were found in the initial growth of the Lu/Si interface. Density functional theory calculations and photoelectron spectroscopy results suggest that the most attractive adsorption sites for the Lu atoms are basins around Si rest-atoms and there is no strong interaction between Lu and Si at the initial steps of film growth. However Lu nanocluster could also be found on other adsorption sites which results in a different voltage dependence in STM. Coverage-dependent STM images reveal the growth of a closed Lu metal overlayer by joining of the clusters. The existence of a stoichiometric Lu silicide compound was not detected on the surface in the initial growth for deposition at room temperature.

Lead-silicate glass surface sputtered by an argon cluster ion beam investigated by XPS

The conventional ion beam sputter-cleaning technique is frequently used for removing surface adsorbates and carbon contamination from air-exposed glass surfaces. Due to the ion-surface interaction, however, an altered near-surface layer is formed with a modified composition and modified bonding. In the present work, we first examine changes in surface composition and bonding due to X-ray and electron irradiation for both air-exposed and sputter-cleaned surfaces. Then we apply argon cluster ion beam sputtering, known as a very gentle technique with respect to the changes in surface chemistry, to air-exposed lead-silicate glass surfaces analyzed by high-energy resolved core-level photoelectron spectroscopy. It was found that (i) the surface contamination present on air-exposed lead-silicate glass surfaces has a qualitative influence on the results of an XPS analysis, and (ii) Ar cluster ion beam sputter-cleaning with mean energy per Ar atom in clusters of a few eV was successfully used to remove surface contamination from air-exposed lead-silicate glass with no substantial violation of the glass surface structure. This made it easier to reveal their intrinsic surface properties.

Structural and Chemical Evolution of Li-Excess Li2IrO3 during Electrochemical Cycling

The family of Li-excess layered Li2TMO3 (TM=Mn, Ru, Ir, etc.) compounds has recently drawn considerable attention in the pursuit of improved capacity of Li-ion batteries. Many studies have unambiguously demonstrated the extra capacity of Li2TMO3 associated with oxygen redox behavior.1,2 Unlike Li2MnO3, which suffers from severe structural degradation and capacity fading upon cycling, Li2IrO3 shows negligible structural change and much improved reversibility,3 and thus serves as a model system to understand the structural response of Li-excess cathodes to Li extraction, as well the exact role of oxygen in compensating Li+ loss. In this study, we employed various experimental techniques as well as first-principles density functional theory (DFT) to investigate the structural and electronic evolution of Li2IrO3 upon electrochemical cycling. It is found that Li2IrO3 undergoes phase transition and slight capacity fading at each cycle. All the thermodynamically stable phases of Li2-xIrO3 (0≤x<2) are identified through a complete structural screening based on electrostatic energy and DFT calculations, and compared with Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD) experiments. Core Level Spectroscopy is adopted to probe the changes in the oxygen electronic structure at various (de)lithiation stages, and corresponding oxygen K-edge spectra are simulated based on first-principles calculations. The cationic/anionic charge compensation mechanism of Li2IrO3 upon delithiation, as well as its resistance to O2 loss are discussed based on the spectroscopic observations. Reference: 1. D. Seo, J. Lee, A. Urban, and R. Malik, Nat. Chem., 8, 692–697 (2016) 2. M. Saubanere, E. McCalla, J.M. Tarascon, and M.L. Doublet, Energy Environ. Sci., 984–991 (2016) 3. E. McCalla et al., Science, 350, 1516–1521 (2015)