A high intensity discharge lamp for monochromatized UV angle-resolved photoemission spectroscopy

A differentially pumped rare gas discharge lamp is described which, when used with a curved grating monochromator, yields sufficiently high intensities so that even the weaker Ne(II) discharge lines can be used in angle-resolved photoemission experiments employing an electron velocity analyzer with single-channel detection.     

A microcomputer-controlled modulation technique for the detection of transient species in UV photoelectron spectroscopy

A microcomputer-controlled modulation method is described to measure UV photoelectron spectra of transient species generated in a microwave discharge. Spectra at low and high microwave power levels are simultaneously recorded and afterwards linearly combined in order to remove parent compound signals. The method is applied to discharged oxygen where the transition O₂⁺ (²Φ_u) ← O₂ (¹Δ_g) becomes visible without interference from the parent molecule O₂ (³Σ_g^?), and to discharged sulphur dioxide where SO (³Σ^?) and S (³P) photoelectron spectra are obtained free from SO₂ bands. Finally the build-up of transient bands as a function of time is recorded.     

A study of LaCoO3 by UV photoelectron spectroscopy

He(II) photoelectron spectra of LaCoO₃ and La_0.7Sr_0.3CoO₃ have been recorded. Spectra of LaCoO₃ were recorded at various temperatures in the range 77 K ? T ? 873 K and changes in the spectra were observed corresponding to the variation of the Co spin state in the lattice.     

Angle-resolved UV photoelectron spectroscopy of ethylene and benzene on nickel

A review of results obtained by Angle-Resolved UV-Photoelectron Spectroscopy (ARUPS) using linearly polarized synchrotron radiation is presented for two model systems, ethylene/Ni and benzene/Ni. It is shown that for these systems detailed conclusions concerning adsorbate/substrate and adsorbate/adsorbate interactions can be derived from ARUPS spectra using symmetry selection rules, and in combination with model calculations. In particular, electronic structure, bonding, orientation and symmetry of the adsorbates in dilute and saturated layers will be discussed. It is shown that at high adsorbate coverages lateral interactions in the adsorbate layer play a dominant role. Steric effects in densely packed layers can lead to a reorientation of the molecules as compared to the orientation of the single molecules. The ARUPS spectra of well ordered, densely packed layers exhibit significant (up to 2 eV) dispersion of the various adsorbate bands and allow detailed conclusions on two-dimensional adsorbate band structures.     

Oxidation of nickel studied by UV and X-ray photoelectron spectroscopy

The nature of argon-ion bombarded nickel surfaces (polycrystalline, and (111), (110) and (100) single crystals) and their subsequent interaction with oxygen at ordinary temperatures have been studied using X-ray and UV photoelectron spectroscopy, including angular variation measurements and the determination of work function changes, in combination in the same apparatus. Variations between the HeI spectra of the four clean substrates were taken to confirm the presence of substantial order within the depth sampled by UPS. The four surfaces exhibited similar but not identical behaviour during oxidation, resembling that reported by other workers from studies of both annealed single crystals and evaporated polycrystalline films. The initial process was deduced to be essentially dissociative chemisorption: no evidence supporting a previous suggestion of associative adsorption at low coverages was found. Oxygen commenced to penetrate below the surface of all samples before oxygen equivalent to a monolayer had been taken up (~10 L exposure) and further substantial uptake followed resulting in the formation of a stable film (~18 Å) of nickel oxide by ~100 L exposure. This oxide layer was not stoichiometric nickel(II) oxide: it was characterized by the presence of two distinct O 1s signals, the relative intensities of which depended on the crystallographic nature of the surface. It is tentatively suggested that the oxygen signal with the higher BE be associated with Ni^III. Comparison of the X-ray and UV spectra suggests that the oxide film is very non-uniform in thickness, some Ni metal remaining very close to the surface.     

Experimental evaluation of a simple model for quantitative analysis in X-ray photoelectron spectroscopy

A simple model is described for calculating the relative intensities of photoelectron peaks for the different elements in a homogeneous solid sample. U     

The use of X-ray photoelectron spectroscopy in corrosion science

Most metals in commercial use are protected from reaction with an environment at ambient temperature by an oxide layer of ~5 nm in thickness. This layer may increase in thickness, by solid state diffusion, at high (>300°C) temperature or may dissolve and be replaced by soluble species by electrochemical reactions in aqueous environments. These are the twin processes of corrosion and the problem of preventing such destructive transformations had led to a longstanding interest by corrosion scientists in the thin film: and indeed in sub-monolayers. Prior to the introduction of the techniques of surface derived ion and electron spectroscopy the chemical analyses of films, which had known physical and electronic characteristics, were unavailable. This review attempts to specify the requirements of an analytical technique for thin films and examines the present role of XPS in this context. The areas covered will include elemental analysis, evaluation of valence state, non-destructive information, elemental distribution and finally the use of ion-etch depth profiling. Examples are drawn from corrosion problems in both aqueous and gaseous environments.     

A UV photoelectron spectrometer featuring rapid analysis

An improved sensitivity electron spectrometer for use in UV photoelectron spectrometry has been developed for rapid analysis. High sensitivity is achieved by the use of a focal-plane position-sensitive multidetector consisting of a linear array of photosensitive diodes (a CCD imaging device) allowing parallel detection and rapid data-acquisition. In the measurement of the He (I) 58.4 nm photoelectron spectrum of Ar, the gain in acquisition time is estimated to be by a factor of ～12.     

A helium 30.4 nm photon source for photoelectron spectroscopy

A new type of photon source of helium 30.4 nm (HeII) radiation is described. The cold cathode discharge is operated at pressures ～10^?4-torr of     

On the use of yttrium and sodium anodes in photoelectron spectroscopy

Low-cost anodes of the active metals yttrium and sodium were constructed and used under modest vacuum conditions. The yttrium Mζ line (132.3 eV) was used to determine np/ns cross-section ratios in the valence shells of three rare gases. The NaKα_{1 2} line and its satellites were characterized with a neon converter. It yielded a linewidth of 0.58(1) eV on the neon 1s line, from which an upper limit of 0.42 eV was set for the NaKα_{1 2} X-ray linewidth. On several “test cases” the NaKα _{1 2} X-ray fell between other characteristic X-rays (e.g., MgKα _{1 2}) and monochromatized sources in its ability to resolve fine structure. The methane C 1s peak was asymmetric and the correct vibrational spacing was obtained by fitting with three components of the correct intensity ratios. Similarly, relative chemical shifts of the unsubstituted carbons in m-difluorobenzene were determined almost completely by fitting the asymmetric peak. In the PF₅ (F 1s) and O₂ (O 1s) cases some new information was obtained.     

A new charge-correction method in X-ray photoelectron spectroscopy

The 2p_{$\text{3}\text{2}$} binding energy (242.3 eV) of Ar implanted in insulating materials is available to correct for charging shifts. Argon ions hav materials SiO₂ and soda glass. In each case the charging shift for Ar 2p_{$\text{3}\text{2}$} electrons agrees exactly with those for core-level elec The charge-corrected binding energies of the insulating materials permit the identification of atomic chemical states. Ion-induced reduction of the ins investigations.     

Interpretative methods in photoelectron spectroscopy

Experimental carbon and nitrogen core electron binding energies measured by high energy photoelectron spectroscopy are reported together with ab initio and semi-empirical molecular orbital studies for a series of organic pseudohalides. The derived wavefunctions are used in a discussion of molecular potential models which are employed in the interpretation of core photoelectron spectra. The application of localized wavefunctions in this context is described.     

Deconvolution in X-ray photoelectron spectroscopy

Published Mg and Al Kα X-ray lineshapes have been used to study the removal of the effects of X-ray broadening in XPS spectra by deconvolution. These results are compared with spectra obtained for the same specimens in the same instrument using a monochromatic X-ray source. The use of deconvolution to remove analyzer broadening from spectra has also been examined, and it has been verified experimentally that the maximum improvement in the full width at half-maximum of a peak that can be achieved is 30%. Deconvolution has also been examined as a means to remove backgrounds from XPS spectra over wide energy ranges, up to 100 eV.     

New method for photoelectron spectroscopy of solutions

A new method of rather general scope is reported for the determination of the photoionization (PI) spectra of solutions. Spectra thus obtained correspond to PI for ejection of quasi-free electrons into the liquid phase. The method is based upon photoelectron emission (PEE) into vacuum by the solution upon irradiation with adjustable photon energy. A new instrument is described which features irradiation (up to 10 eV) of a film of the solution on the rim of a rotating disk target (72 r.p.m.). Two types of data are obtained: PEE quantum yield per incident photon as a function of photon energy; energy distribution curve (EDC) of electrons emitted into vacuum at given photon energies. The PI cross-section is obtained as a function of photon energy by the previously developed method of EDC superposition. The method is applicable even when the contribution by the solvent to total PEE is dominant. Application is made to PI by 0.4 M indole in glycol for irradiation from 6.5 to 10 eV. Experimental results include: the effect of equilibrium vapor pressure (3.5 × 10^?3 ? 4.6 × 10^?2 torr) on EDC's; PEE spectral response of solvent and solution; EDC's from 6.5 to 10 eV. Interpretation covers these results and also includes: attenuation of the photon flux in the gas phase; PI in the gas phase; changes of temperature and solute concentration caused by evaporation. The PI spectrum of indole in glycol at ?7 °C exhibits a band for bound-continuum transitions (rising segment up to ≈ 7.0 eV) and a superimposed band (maximum at ≈ 7.6 eV) for PI via autoionization of excited bound states. Systematic development of the photoionization spectroscopy of solutions up to 10 eV is made possible by this approach. Application of the rotating disk methodology to higher photon energies (HeI, ESCA) may be of interest.     

Vacuum UV photoelectron intensity of gaseous compounds: I. HeI spectra of simple compounds

A new method for determining absolute photoionization cross sections for gaseous compounds is proposed. In this method a mixture of a sample and a standard gas (N₂) is used in photoelectron intensity measurements so that the relative intensity of the component is obtained with respect to N₂ The relative photoelectron band area is converted to the absolute photoionization cross section on the basis of the absolute cross-section data of N₂ recently reported by Samson et al. This method has been applied to various aliphatic compounds to study the effect of alkyl substitution on photoionization cross sections of O- and N-nonbonding electrons for 584-Å radiation.     

Residual benzamide contamination in synthetic oligonucleotides observed using UV resonance Raman spectroscopy

Spectroscopic methods based on Raman scattering have for many years employed synthetic oligonucleotides in a broad range of applications, either as probes or as model analytes for biophysical investigations. Benzamide is commonly used as a protecting group in the phosphoramidite synthesis of oligonucleotides and, while standard desalting used after synthesis yields sufficiently pure reagents for most assay reactions or other routine uses of the oligomer, it does not completely remove benzamide. We show that the 1609 cm⁻¹ band of residual benzamide contamination can interfere with certain nucleic acid bands, particularly when using excitation wavelengths near 244 nm where the benzamide band is strongly enhanced. For example, the 1609 cm⁻¹ band of benzamide could obscure (or be mistaken as) a weak vibration attributed to an  NH₂ scissoring. The extent of benzamide contamination in desalted preparations varies considerably among different commercial sources, and hence caution is advised when making direct comparisons of ultraviolet Raman data of oligonucleotides from different sources. Copyright © 2010 John Wiley & Sons, Ltd.     

Vacuum ultraviolet resonance line radiation source from rare gas atoms and ions for UHV photoelectron spectroscopy

A source and differential pumping system for producing high intensity resonance line radiation from rare gas atoms and ions for ultrahigh vacuum (UHV) photoelectron spectroscopy has been developed. Photoelectron count rates from a gold sample, as measured with a double-pass cylindrical mirror analyzer at pass energy 15 eV and 0.10 eV resolution, are ～ 300,000 c s^?1 for the He(I) (21.22 eV) line and ～30000 c s^?1 for the He(II) (40.81 eV) line. The source design is based on the principle of the electrostatic charged particle oscillator and is capable of sustaining discharges over the pressure range 1 to ～ 10^?6 torr. The discharge segment consists of a cylindrical cold cathode surrounding two tungsten rod anodes which are held at high positive potential. Three stages of differential pumping are employed in order that the vacuum in the main spectrometer chamber can be maintained at 2 × 10^?10 torr during operation. The calculated helium flow reaching the main chamber under these conditions is < 101 s^?1. Details of the construction and operating characteristics of the source are presented.     

A simple quark model for resonance electroproduction

A quark model for resonance electroproduction is developed which is based on the successful photoproduction model of Kubata and Ohta. A detailed comparison is made between the predictions of the model and the results of recent phenomenological analyses of electroproduction data.     

A high intensity U.V. source for photoelectron spectroscopy

A source for the production of high intensity resonance radiation from inert gases has been developed in a form suitable for use with ultrahigh vacuum