Ambient pressure x-ray photoelectron spectroscopy setup for synchrotron-based in situ and operando atomic layer deposition research.

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.

Breakdown of ionic character of molecular alkali bromides in inner-valence photoionization.

The inner-valence region of alkali bromide XBr (X=Li, Na, K, Rb) vapours has been studied experimentally by means of synchrotron radiation excited photoelectron spectroscopy. Experimental spectra were analyzed by comparing them with available theoretical results and previous experiments. Ionic character of alkali bromides is seen to change in the inner-valence region with increasing atomic number of the alkali atom. A mechanism involving mixing between Br 4s and Rb 4p orbitals has been suggested to account for the fine structure observed in inner-valence ionization region of RbBr.

Fragmentation dynamics of doubly charged methionine in the gas phase.

The dependence of the fragmentation of doubly charged gas-phase methionine (C5H11NO2S) on the electronic-state character of the parent ion is studied experimentally by energy-resolved electron ion-ion coincidence spectroscopy. The parent dication electronic states are populated by Auger transitions following site-specific sulfur 2p core ionization. Two fragmentation channels are observed to be strongly dependent on the electronic states with vacancies in weakly bound molecular orbitals. All-electron calculations are applied to assign doubly charged final states of sulfur 2p core ionized methionine. In addition, the Car-Parrinello method is applied to model fragmentation dynamics of doubly charged methionine molecules with various initial temperatures to understand the typical characteristics of the molecular dissociation and partly to support the interpretation of experimental data.

Size selective spectroscopy of Se microclusters.

The electronic structure and photofragmentation in outer and inner valence regions of Se(n) (n ≤ 8) clusters produced by direct vacuum evaporation have been studied with size-selective photoelectron-photoion coincidence technique by using vacuum-ultraviolet synchrotron radiation. The experimental ionization potentials of these clusters were extracted from the partial ion yield measurements. The calculations for the possible geometrical structures of the Se(n) microclusters have been executed. The ionization energies of the clusters have been calculated and compared with the experimental results. In addition, theoretical fragment ion appearance energies were estimated. The dissociation energies of Se(n) clusters were derived from the recurrent relation between the gas phase enthalpies of the formation of corresponding cationic clusters and experimental ionization energies.

Electron-ion coincidence study of photofragmentation of the CdCl(2) molecule.

In this work, the photofragmentation subsequent to valence and Cd4d photoionization of cadmium dichloride (CdCl(2)) were studied using He I and synchrotron excitation. The measurements were performed with a photoelectron-photoion coincidence (PEPICO) setup, and the connection between the singly ionized electronic states and cationic fragments was investigated. The valence-ionized states were found to lead to CdCl(2)(+), Cd(+) and CdCl(+). The Cd4d(- 1) states were found to lead only to Cl(+) ions. The observed charge transfer effect between Cd and Cl was concluded to take place due to internal conversion or fluorescence decay to dissociating valence states either directly or through consecutive fragmentation. The fragmentation energetics were investigated with molecular ab initio calculations, and the calculated energies were found to agree with the detected fragment appearances.