Core Photoelectron Research Articles

Core and valence photoelectron spectroscopy of a series of substituted disulfides.

The valence and core photoelectron spectra of three substituted disulfide systems, α-lipoic acid, trans-4,5-dihydroxy-1,2-dithiane, and di-Boc-cystamine, are presented alongside detailed theoretical analysis based on equation-of-motion coupled-cluster singles doubles for ionization potentials and the nuclear ensemble approach. A comparison of the linear and five- and six-membered ring cyclic structures reveals that the energetic separation of the non-bonding sulfur orbitals can be used to calculate a reliable estimate of the C-S-S-C dihedral angle, even for substituted disulfides, and that the sulfur 2p, oxygen 1s, and valence band photoelectron spectra are a useful site-specific probe of hydrogen bonding.

Unravelling the complex speciation of halozincate ionic liquids using X-ray spectroscopies and calculations.

Using a combination of liquid-phase X-ray spectroscopy experiments and small-scale calculations we have gained new insights into the speciation of halozincate anions in ionic liquids (ILs). Both core and valence X-ray photoelectron spectroscopy (XPS) experiments were performed directly on the liquid-phase ILs, supplemented by Zn 1s X-ray absorption near edge structure (XANES) spectroscopy. Density functional theory (DFT) calculations were carried out on both 1- and 2- halozincate anions, in both a generalised solvation model SMD (Solvation Model based on Density) and the gas phase, to give XP spectra and total energy differences; time-dependent DFT was used to calculate XANES spectra. Speciation judgements were made using a combination of the shape and width of the experimental spectra, and visual matches to the calculated spectra. For 2- halozincate anions, excellent matches were found between the experimental and calculated XP spectra, clearly showing that only 2- halozincate anions were present at all zinc halide mole fractions, x, studied. At specific values of x (0.33, 0.50, 0.60) only one halozincate anion was present; equilibria of different halozincate anions at those values of x were not observed. All findings show that chlorozincate anion and bromozincate anion speciation matched at the same x. Based on the results, predictions are made of the halozincate anion speciation for all values of x up to 0.67. Caution is advised when using differences in calculated total energies obtained from DFT to judge halozincate anion speciation, even when the SMD was employed, as predictions based on total energy differences did not always match the findings from the experimental and calculated spectra. Our findings clearly establish that the combination of high-quality experimental data from multiple spectroscopies and a wide range of calculated structures are essential to have high confidence in halozincate anion speciation identification.

A photoelectron spectroscopic investigation of aspirin, paracetamol and ibuprofen in the gas phase.

We have investigated the electronic structure of isolated molecules of paracetamol, aspirin and ibuprofen using computational methods and benchmarked the results against valence and core photoelectron spectra. Paracetamol, aspirin and ibuprofen exist as multiple conformers, and we have calculated the free energies and populations of the lowest energy conformers. We find generally good agreement with previous experimental and theoretical structural results. The valence band spectrum of gas phase aspirin has not been reported previously, and we report it and assign the features based on calculations. The effect of acetylation on the frontier orbitals of the parent molecule, salicylic acid, is to increase the ionization potential of the highest occupied molecular orbital (HOMO), and to exchange the energetic ordering of the following two orbitals. The acetyl π bond contributes to the next orbital, which is hybridised with ring π orbitals. The core level spectra of all three molecules are reported and compared with calculations and with the spectra of parent molecules (salicylic acid for aspirin, 4-aminophenol for paracetamol). Observed core ionization energies are in agreement with theory. Although all compounds share a benzene ring, and they also have a number of other chromophores in common, the spectroscopic data indicate chemical diversity, suggesting that their modes of bonding under physiological conditions are likely to be diverse.

Photoemission and photofragmentation of butanoic, hexanoic and octanoic acids in the gas phase

The valence and C 1 s core photoelectron spectra of three carboxylic acids (butanoic, hexanoic and octanoic) as well as the near-edge absorption fine structure spectra and photo-electron photo-ion coincidence spectra have been measured. Changes in the valence spectra are related to the lengthening of the aliphatic chains, and the core spectra have been assigned. Small shifts of the carboxylic carbon 1 s binding energy are related to screening of the core hole by the aliphatic group. The C K edge near-edge absorption fine structure spectra probe the unoccupied density of states and the main changes in the spectra are due to increasing length of the aliphatic chain and related Rydberg states. The coincidence spectra show that soft (near threshold) ionization of all compounds leads to parent ion formation for butanoic and octanoic acids. For hexanoic acid, both parent ions and fragments are produced for near threshold ionization. Fragmentation occurs at the C2C3 bond for all carboxylic acids at the lowest energies, and other channels open for higher internal energy.

Optical and electrical properties of hard (Hf,Nb,Ti,V,Zr)Nx thin films

(Hf,Nb,Ti,V,Zr)Nx coatings with nitrogen content between 0 and 49 at.% were deposited by sputter deposition, and thoroughly characterised. Nitrogen-free coatings were found to have a bcc structure, low hardness (8 GPa), and an electrical resistivity of 144 μΩcm. The nitride coatings (43–49 at.% N) had NaCl-type structure, consistent with a multi-component solid solution phase. Photoelectron core level binding energies indicate that the electronic structure of the multi-component nitride differs from that of the binary nitrides, probably a result of charge transfer between the metal atoms. The nitride coatings exhibited a dense microstructure and a hardness between 29 and 33 GPa, and electrical resistivities of 141–254 μΩcm. They also exhibited a minimum in the optical reflectance, similar to that of TiN, indicating plasmonic properties. The position of this minimum was found to be shifted to smaller wavelengths (272–339 nm) compared to a TiN reference (428 nm) and varied with nitrogen content. The tuneability of the optical properties, in combination with the potential to influence the electronic structure through charge transfer between metal atoms point to new interesting routes to design optical materials, and a new class of optical materials based on the concept of multi-component nitrides.

Polarization dependence of ZnO Schottky barriers revealed by photoelectron spectroscopy

In order to answer the question of whether Schottky barriers on polar ZnO surfaces are different at Zn- and O-terminated surfaces, the interface formation of $n$-type ZnO and different high work function metals and metal oxides (Pt, ${\mathrm{PtO}}_{x}$, and ${\mathrm{RuO}}_{2}$) with Schottky barrier heights of up to 1.5 eV has been studied using photoelectron spectroscopy with in situ sample preparation. The experiments are designed to exclude the effects of substrate reduction and consequent Fermi level pinning by high concentrations of oxygen vacancies. Moreover, by including the Zn LMM Auger emission in the analysis, it is demonstrated that an accurate extraction of barrier heights needs to take into account that the screening of the photoelectron core hole can change in the course of contact formation. The polarization dependence of Schottky barriers, which is important for piezotronic applications, is in most cases dominated by the influence of defects. Reducing the influence of defects, up to $\ensuremath{\sim}240$ meV higher Schottky barriers are revealed on oxygen-terminated surfaces. This is opposite to what has been reported in the literature but agrees with the dependence of barrier heights expected for an incomplete screening of the polarization of ZnO by the electrode as for ferroelectric materials.

Coulomb effect on the dynamics of atoms in a strong elliptical laser field: Unification of the excitation and ionization

We investigate the Coulomb effect on the dynamics of atoms in a strong elliptical laser field by solving the three-dimensional time-dependent Schr\odinger equation with and without the photoelectron core Coulomb interactions and find that the Coulomb effect plays an important role for the excitation and ionization processes, while it is less important for the high-order harmonic generation. Our calculation results can serve as a benchmark for other approximative methods. Looking at the photoelectron momentum distribution, we find that the Coulomb effect is important for the momentum distribution in the polarization plane and less important for the momentum distributions along the normal direction perpendicular to the polarization plane. Similar to the photoabsorption in a weak field, we demonstrate that the excitation and ionization can be treated in a unified way, which implies the low-energy photoelectron distributions can be connected with the populations of highly excited states.

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.

Optimal focusing system of the Fresnel zone plates at the Synchrotron SOLEIL NanoARPES beamline

ANTARES beamline (BL), operating at very low photon energies, is a new soft X-ray scanning microscope recently built at SOLEIL Synchrotron, that offers a spectroscopic non-destructive nano-probe to study advanced materials. It combines a set of Fresnel Zone Plates (FZP) able to focalize the beam spot up to a few tenths of nanometres with a stable and precise sample nanopositioning (<1 nm). High energy-, angular- and spatial- resolution allow accurate electronic and chemical imaging combining angle-resolved photoelectron spectroscopy (NanoARPES or k-nanoscope) and core level detection by using both photoemission and X-ray absorption. Here, we report our latest results related to the optimization of the post-focusing mirrors system as well as its impact on the ultimate spatial resolution of the whole microscope.

Laser induced Bi diffusion in As40S60 thin films and the optical properties change probed by FTIR and XPS

Amorphous chalcogenide semiconducting materials are playing a pivotal role in modern technology. Such type of materials are very sensitive to electromagnetic radiations which is useful for infrared optics. In the present report, Bi doped in As40S60 thin films (As40S60, Bi06As40S54) of 800 nm thickness were prepared by thermal evaporation method. The Bi06As40S54 thin film is subjected to laser irradiation for photo induced study. The X-ray diffraction study reveals no structural change due to laser irradiation. The optical parameters are affected by both Bi addition and laser irradiation which brings a change in the transmitivity and absorption coefficient. The indirect optical band gap is found to be increased by 0.08 eV with laser irradiation with the decrease in disorderness. The Tauc parameter and Urbach energy which measures the degree of disorderness changes with Bi doping and irradiation. The refractive index is modified by the illumination process which is useful for optical applications. The optical property change is well supported by the X-ray photoelectron core level spectra.

Evaluation of Two Methods for Determining Shell Thicknesses of Core-Shell Nanoparticles by X-ray Photoelectron Spectroscopy.

We evaluated two methods for determining shell thicknesses of core-shell nanoparticles (NPs) by X-ray photoelectron spectroscopy (XPS). One of these methods had been developed for determining thicknesses of films on a planar substrate while the other was developed specifically for NPs. Our evaluations were based on simulated Cu 2p3/2 spectra from Cu-core/Cu-shell NPs with a wide range of core diameters and shell thicknesses. Copper was chosen for our tests because elastic-scattering effects for Cu 2p3/2 photoelectrons excited by Al Kα X-rays are known to be strong. Elastic scattering could also be switched off in our simulations so that the two methods could be evaluated in the limit of no elastic scattering. We found that the first method, based on both core and shell photoelectron intensities, was unsatisfactory for all conditions. The second method, based on an empirical equation for NPs developed by Shard, also utilized both core and shell photoelectron intensities and was found to be satisfactory for all conditions. The average deviation between shell thicknesses derived from the Shard equation and the true values was -4.1 % when elastic scattering was switched on and -2.2 % when elastic scattering was switched off. If elastic scattering was switched on, the effective attenuation length for a Cu film on a planar substrate was the appropriate length parameter while the inelastic mean free path was the appropriate parameter when elastic scattering was switched off.

X-ray Photoemission Spectra and Electronic Structure of Coumarin and its Derivatives.

The electronic structures of coumarin and three of its derivatives (7-amino-4-methylcoumarin, 7-amino-4-(trifluoro)methylcoumarin, and 4-hydroxycoumarin) have been studied by theoretical calculations, and compared with experimental valence and core photoelectron spectra to benchmark the predicted spectra. The outer valence band spectra of the first three compounds showed good agreement with theoretical calculations for a single isomer, whereas the spectrum of 4-hydroxycoumarin indicated the presence of more than one tautomer, consistent with published results. Calculations of core level spectra of carbon, nitrogen, oxygen, and fluorine of the first three compounds are also in satisfactory agreement with our measurements. The carbon and oxygen 1s spectra of 4-hydroxycoumarin allow us to identify and quantify the populations of the principle tautomers present. The 4-hydroxy enol form is the most stable isomer at 348 K, followed by the diketo form, with 1.3 kJ·mol(-1) lower energy.

Intermediate pinning states engineering in Bi-doped SnO2 for transparent semi-insulator applications

Bi-doped SnO2 (BTO) thin films were prepared by the magnetron reactive sputtering technique. The BTO thin films were characterized by x-ray photoelectron core level and valence band spectroscopy. Bi was introduced into an SnO2 lattice dominated with Bi5+ states accompanied with Bi3+ minority states. The BTO films exhibited a high optical transparency (>85% @550 nm) in the whole range of solar radiation spectrum without compromising the band gap alignment. The sheet resistance dramatically increased up to 108 Ω/sq after Bi doping. The reduction of electron concentration can be attributed to the electrons pinning to the intermediate state within the band gap. The BTO films have promising applications in high performance optoelectronic and photovoltaic devices.

Electronic and atomic structures of a Sn induced [formula omitted] superstructure on the Ag/Ge(111) [formula omitted] surface

We have investigated sub-monolayer coverages of Sn on the Ag/Ge(111) 3×3 surface. It was found that ≈0.45 monolayer (ML) resulted in a new, well-defined, reconstruction with a 33×33 periodicity. The periodic structure of the surface atoms was verified by low-energy electron diffraction and scanning tunneling microscopy. The electronic structure was studied in detail using angle-resolved photoelectron spectroscopy and core level spectroscopy at a temperature of 100K. Several surface bands were identified and their dispersions are presented along the Γ¯−M¯−Γ¯ and Γ¯−K¯−M¯ high symmetry lines of the 33×33 surface Brillouin zone (SBZ). The 33×33 surface has a metallic character since there is a strong surface band crossing the Fermi level near Γ¯ points coinciding with K¯ points of the 1×1 SBZ. The Fermi contour of the metallic band showed a hexagonal shape in contrast to the circular shaped Fermi contour of the initial 3×3 surface. Both empty and filled state STM images showed a hexagonal arrangement of protrusions with a local 3×3 periodicity and a superimposed modulation of the apparent heights resulting in a 33×33 periodicity.

Trends in adsorbate induced core level shifts

Photoelectron core level spectroscopy is commonly used to monitor atomic and molecular adsorption on metal surfaces. As changes in the electron binding energies are convoluted measures with different origins, calculations are often used to facilitate the decoding of experimental signatures. The interpretation could in this sense benefit from knowledge on trends in surface core level shifts for different metals and adsorbates. Here, density functional theory calculations have been used to systematically evaluate core level shifts for (111) and (100) surfaces of 3d, 4d, and 5d transition metals upon CO, H, O and S adsorption. The results reveal trends and several non-intuitive cases. Moreover, the difficulties correlating core level shifts with charging and d-band shifts are underlined.

Suppression of the molecular ultra-fast dissociation in bromomethane clusters.

We address the influence of clustering on the ultra-fast dissociation of bromomethane. Valence and core photo-electron spectroscopy, partial electron yield absorption, and resonant Auger spectroscopy have been used together with ab initio calculations to investigate the properties of the ultra-fast dissociation. The ratio of ultra-fast dissociation of molecules in clusters as compared to free molecules is determined to be significantly reduced. We propose partial delocalization of the excited electronic state as being responsible for this behavior.

Quantum mechanics/molecular mechanics modeling of photoelectron spectra: the carbon 1s core-electron binding energies of ethanol-water solutions.

Using ethanol-water solutions as illustration, we demonstrate the capability of the hybrid quantum mechanics/molecular mechanics (QM/MM) paradigm to simulate core photoelectron spectroscopy: the binding energies and the chemical shifts. An integrated approach with QM/MM binding energy calculations coupled to preceding molecular dynamics sampling is adopted to generate binding energies averaged over the solute-solvent configurations available at a particular temperature and pressure and thus allowing for a statistical assessment with confidence levels for the final binding energies. The results are analyzed in terms of the contributions in the molecular mechanics model-electrostatic, polarization, and van der Waals-with atom or bond granulation of the corresponding MM charge and polarizability force-fields. The role of extramolecular charge transfer screening of the core-hole and explicit hydrogen bonding is studied by extending the QM core to cover the first solvation shell. The results are compared to those obtained from pure electrostatic and polarizable continuum models. Particularly, the dependence of the carbon 1s binding energies with respect to the ethanol concentration is studied. Our results indicate that QM/MM can be used as an all-encompassing model to study photoelectron binding energies and chemical shifts in solvent environments.

Reliability of Density Functional and Perturbation Theories for Calculating Core-Ionization Spectra of Free Radicals

The C 1s, N 1s, and O 1s ionization energies were calculated for the three stable nitroxide free radicals, viz., tempo and its two analogues, and compared to their most recent high-resolution core photoelectron spectra. We compare the performance of unrestricted and restricted open shell based ΔHF, ΔMP2, and ΔB3LYP methods. A mixed basis set is employed in all cases, which consists of the core-valence correlation-consistent triple-ζ basis set (cc-pCVTZ or cc-pwCVTZ) on the atom whose core-electron binding energy is calculated, model core potentials on the remaining first row atoms, and the cc-pVDZ basis set on the hydrogen atoms. The best overall performance for the three free radicals is offered by the restricted open shell based ΔB3LYP method. Surprisingly, both the restricted open and unrestricted second-order perturbation theories perform relatively poorly and typically do not warrant additional computational effort over the reference ΔHF methods. This is particularly true of the ΔZAPT method, which exhibits a number of grave failures that render it unsuitable for calculating the core-ionization spectra.

Structures of cycloserine and 2-oxazolidinone probed by X-ray photoelectron spectroscopy: theory and experiment.

The electronic structures and properties of 2-oxazolidinone and the related compound cycloserine (CS) have been investigated using theoretical calculations and core and valence photoelectron spectroscopy. Isomerization of the central oxazolidine heterocycle and the addition of an amino group yield cycloserine. Theory correctly predicts the C, N, and O 1s core spectra, and additionally, we report theoretical natural bond orbital (NBO) charges. The valence ionization energies are also in agreement with theory and previous measurements. Although the lowest binding energy part of the spectra of the two compounds shows superficial similarities, further analysis of the charge densities of the frontier orbitals indicates substantial reorganization of the wave functions as a result of isomerization. The highest occupied molecular orbital (HOMO) of CS shows leading carbonyl π character with contributions from other heavy (non-H) atoms in the molecule, while the HOMO of 2-oxazolidinone (OX2) has leading nitrogen, carbon, and oxygen pπ characters. The present study further theoretically predicts bond resonance effects of the compounds, evidence for which is provided by our experimental measurements and published crystallographic data.

Metal nanoparticle size distribution in hybrid organic/inorganic films determined by high resolution X-ray photoelectron spectroscopy

We report on the application of high resolution X-ray photoelectron spectroscopy (HR-XPS) to provide a fast identification of the size distribution of metal nanoparticles (NPs) embedded in a polymer matrix. An accurate spectral analysis was performed on the metal photoelectron core level to determine the specific calibration curve which relates the metal NP core level binding energy shift to its size, which was independently measured by transmission electron microscopy. We have fully characterized the binding energy shifts in the case of silver NPs on a polythiophene based polymer layer. This work shows how this procedure can be applied to characterize multimodal size distributions of metal NPs on a statistical adequate sample area, without having typical experimental limitations of a TEM experiment. Moreover, this technique can give access to chemical analysis and by alternating ion beam sputtering and XPS analysis, the NP diffusion along the growth direction can be revealed.