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The Ambient-Pressure X-ray Photoelectron Spectroscopy (APXPS) endstation at the SPECIES beamline at MAX IV Laboratory has been improved. The latest upgrades help in performing photo-assisted experiments under operando conditions in the mbar pressure range using gas and vapour mixtures whilst also reducing beam damage to the sample caused by X-ray irradiation. This article reports on endstation upgrades for APXPS and examples of scientific cases of in situ photocatalysis, photoreduction and photo-assisted atomic layer deposition (photo-ALD).

Welcome to ICESS 15th Welcome to the 15th ICESS conference! Finally, after five years of waiting it is our pleasure to welcome you - the whole international community – to Oulu, Finland. The scientific program built in collaboration with international advisory board (IAB) covers widely the areas of research and surely engages plenty of discussions and ideas for future collaborations. Great thanks for participating and making the event possible! Let us all make the event pleasant respecting the diversity and committing to strengthening the international community of ICESS. Welcome to Oulu! ICESS local committee: Marko Huttula, chair Minna Patanen, program committee Samuli Urpelainen, Satu Ojala, local organization

An ambient pressure cell is described for conducting synchrotron-based x-ray photoelectron spectroscopy (XPS) measurements during atomic layer deposition (ALD) processes. The instrument is capable of true in situ and operando experiments in which it is possible to directly obtain elemental and chemical information from the sample surface using XPS as the deposition process is ongoing. The setup is based on the ambient pressure XPS technique, in which sample environments with high pressure (several mbar) can be created without compromising the ultrahigh vacuum requirements needed for the operation of the spectrometer and the synchrotron beamline. The setup is intended for chemical characterization of the surface intermediates during the initial stages of the deposition processes. The SPECIES beamline and the ALD cell provide a unique experimental platform for obtaining new information on the surface chemistry during ALD half-cycles at high temporal resolution. Such information is valuable for understanding the ALD reaction mechanisms and crucial in further developing and improving ALD processes. We demonstrate the capabilities of the setup by studying the deposition of TiO₂ on a SiO₂ surface by using titanium(IV) tetraisopropoxide and water as precursors. Multiple core levels and the valence band of the substrate surface were followed during the film deposition using ambient pressure XPS.

FinEstBeAMS (Finnish–Estonian Beamline for Atmospheric and Materials Sciences) is a multidisciplinary beamline constructed at the 1.5 GeV storage ring of the MAX IV synchrotron facility in Lund, Sweden. The beamline covers an extremely wide photon energy range, 4.5–1300 eV, by utilizing a single elliptically polarizing undulator as a radiation source and a single grazing-incidence plane grating monochromator to disperse the radiation. At photon energies below 70 eV the beamline operation relies on the use of optical and thin-film filters to remove higher-order components from the monochromated radiation. This paper discusses the performance of the beamline, examining such characteristics as the quality of the gratings, photon energy calibration, photon energy resolution, available photon flux, polarization quality and focal spot size.

An experimental approach is described in which well-defined perturbations of the gas feed into an Ambient Pressure X-ray Photoelectron Spectroscopy (APXPS) cell are fully synchronized with the time-resolved x-ray photoelectron spectroscopy data acquisition. These experiments unlock new possibilities for investigating the properties of materials and chemical reactions mediated by their surfaces, such as those in heterogeneous catalysis, surface science, and coating/deposition applications. Implementation of this approach, which is termed perturbation-enhanced APXPS, at the SPECIES beamline of MAX IV Laboratory is discussed along with several experimental examples including individual pulses of N₂ gas over a Au foil, a multi-pulse titration of oxygen vacancies in a pre-reduced TiO₂ single crystal with O₂ gas, and a sequence of alternating precursor pulses for atomic layer deposition of TiO₂ on a silicon wafer substrate.

The SPECIES beamline has been transferred to the new 1.5 GeV storage ring at the MAX IV Laboratory. Several improvements have been made to the beamline and its endstations during the transfer. Together the Ambient Pressure X-ray Photoelectron Spectroscopy and Resonant Inelastic X-ray Scattering endstations are capable of conducting photoelectron spectroscopy in elevated pressure regimes with enhanced time-resolution and flux and X-ray scattering experiments with improved resolution and flux. Both endstations offer a unique capability for experiments at low photon energies in the vacuum ultraviolet and soft X-ray range. In this paper, the upgrades on the endstations and current performance of the beamline are reported.

MAX IV is a fourth-generation, or diffraction-limited, synchrotron light source with a number of state-of-the-art beamlines. The performance of a beamline is, to a high degree, set by the energy resolution it can achieve, which in turn is governed to a large extent by the monochromator. During the design phase of a monochromator, the mechanical requirements must be fully understood and met with margin. During commissioning, the performance must be verified and optimized. In this paper, six soft X-ray monochromators at MAX IV beamlines (Bloch, Veritas, HIPPIE, SPECIES, FinEstBeAMS and SoftiMAX) are examined with a focus on their resolving power, energy range and the time required to change measurement range, as those parameters are dependent on each other. The monochromators have a modern commercial design, planned and developed in close collaboration with the vendors. This paper aims to present the current status of the commissioning at MAX IV with emphasis on elucidating the mechanical limitations on the performance of the monochromators. It contains analysis of the outcome and our approach to achieve fast and high-resolution monochromators.

Free bare gold clusters in the size range from few tens to few hundred atoms (<= 1 nm dimensions) have been produced in a beam, and the size-dependent development of their full valence band including the 5d and 6s parts has been mapped 'on the fly' by synchrotron-based photoelectron spectroscopy. The Au 4f core level has been also probed, and the cluster-specific Au 4f ionization energies have been used to estimate the cluster size. The recorded in the present work valence spectra of the small clusters are compared with the spectra of the large clusters (N similar to 10(3)) created by us using a magnetron-based gas aggregation source. The comparison shows a substantially narrower 5d valence band and the decrease in its splitting for gold clusters in the size range of few hundred atoms and below. Our DFT calculations involving the pseudopotential method show that the 5d band width of the ground state increases with the cluster size and by the size N = 20 becomes comparable with the experimental width of the valence photoelectron spectrum. Similar to the earlier observations on supported clusters we interpret our experimental and theoretical results as due to the undercoordination of a large fraction of atoms in the clusters with N similar to 10(2) and below. The consequences of such electronic structure of small gold clusters are discussed in connection with their specific physical and chemical properties related to nanoplasmonics and nanocatalysis.

Neutral Pb clusters in the size range from a few tens of atoms up to similar to 100 atoms are studied using synchrotron-based photoelectron spectroscopy. The electronic structure is seen to differ increasingly from that of the solid when the cluster size decreases. The valence band narrows gradually - down to about one fifth of the solid-state band width at the smallest size of few tens of atoms. Simultaneously the Fermi-edge energy shifts further away from the solid value by more than 2 eV. The Pb 5d core level binding energy also increases and the spectral features broaden and change in shape. The changes observed for the valence and for the 5d response energies and shapes are discussed in the context of the metal-to-insulator transition observed earlier in Pb clusters below the critical size of 20-30 atoms/cluster. (C) 2014 Elsevier B.V. All rights reserved.

The evolution of electronic properties in free antimony (Sb) nanoclusters as a function of the cluster size has been studied experimentally using synchrotron radiation. Antimony 4d core-level and valence-band regions have been probed, and the 4d binding energies and valence ionization potentials of clusters of various mean sizes have been determined. The binding-energy shifts with respect to polycrystalline solid have been used for deriving the electronic properties of the clusters. The observed results suggest that even large Sb clusters are not metallic.

Evolution of metallic properties of free and initially neutral nanoscale Bi clusters has been studied using synchrotron radiation excited photoelectron spectroscopy. The 4f and 5d core as well as the valence levels have been probed. The cross-level analysis indicates metallic properties in Bi clusters in the observed size range from 0.5 nm to 1.4 nm. The behavior of the core-level and valence binding energies as a function of cluster size has been observed to be smooth and relatively consistent. Valence responses for the largest clusters have their shape and width similar to those of the polycrystalline solid Bi.

Auger decay following C 1s core ionization leads to dissociating doubly ionized molecular states of CO2 and CS2. Detailed dynamics of these three- and two-body processes is investigated using electron-ion multicoincidence spectroscopy and Monte-Carlo simulations of various dissociation scenarios., QC 20130115

The angular distribution of photoelectrons and linear magnetic dichroism in the angular distribution for the 4p photoemission from Rb atoms in the ground state, oriented by laser pumping, were measured in the photon energy range from 50 to 100 eV. The experimental results are compared with the multiconfiguration Dirac-Fock (MCDF) calculations. We show that the zero-crossing of the dichroism as a function of energy is connected with the Cooper minimum in the cross section. This fact can be used for an accurate determination of the position of the Cooper minimum., QC 20110210

This paper reports a study of valence photoionization of the LiCl monomer and dimer. The behavior of the photoionization partial cross section for molecular valence orbitals was measured as a function of photon energy between 15 and 35 eV. A square-integrable-function method was used to model the ionization partial cross section in both the LiCl monomer and dimer., QC 20110103

The valence photoelectron spectrum of Sb-4 clusters and the following fragmentation patterns have been studied using synchrotron radiation and electron-ion coincidence technique. An experimental photoelectron spectrum of the 5t(2) ionization of Sb-4 is presented. Theoretical molecular calculations, together with the existing data on the noble gas xenon, were used to describe the experimental results. The bonding properties of the molecular orbitals involved are used to qualitatively describe the dissociation process., QC 20110427

The 3d(-1) photoionization and subsequent M4,5N2,3N2,3 Auger electron spectra of free initially laser-excited rubidium atoms have been investigated. The rubidium atoms were excited from the ground state [Kr]5s(1/2) to the [Kr]5p(1/2) and [Kr]5p(3/2) states. Emphasis was put on the changes in coupling and electron correlation between the three different initial states. The ground state 3d photoelecton spectrum of free Rb atoms was interpreted in detail. The binding energies for 3d(3/2,5/2) orbitals of initially ground-state and laser-excited Rb atoms were obtained. Extensive multiconfiguration Dirac-Fock calculations performed in the relativistic jj coupled basis were compared to the experimental photoelectron and Auger electron spectra.