Practical Guides for X-Ray Photoelectron Spectroscopy (XPS): First Steps in planning, conducting and reporting XPS measurements.

Over the past three decades, the widespread utility and applicability of X-ray photoelectron spectroscopy (XPS) in research and applications has made it the most popular and widely used method of surface analysis. Associated with this increased use has been an increase in the number of new or inexperienced users which has led to erroneous uses and misapplications of the method. This article is the first in a series of guides assembled by a committee of experienced XPS practitioners that are intended to assist inexperienced users by providing information about good practices in the use of XPS. This first guide outlines steps appropriate for determining whether XPS is capable of obtaining the desired information, identifies issues relevant to planning, conducting and reporting an XPS measurement, and identifies sources of practical information for conducting XPS measurements. Many of the topics and questions addressed in this article also apply to other surface-analysis techniques.

Calculations of electron inelastic mean free paths. XII. Data for 42 inorganic compounds over the 50 eV to 200 keV range with the full Penn algorithm.

We have calculated inelastic mean free paths (IMFPs) for 42 inorganic compounds (AgBr, AgCl, AgI, Al2O3, AlAs, AlN, AlSb, cubic BN, hexagonal BN, CdS, CdSe, CdTe, GaAs, GaN, GaP, GaSb, GaSe, InAs, InP, InSb, KBr, KCl, MgF2, MgO, NaCl, NbC0.712, NbC0.844, NbC0.93, PbS, PbSe, PbTe, SiC, SiO2, SnTe, TiC0.7, TiC0.95, VC0.76, VC0.86, Y3Al5O12, ZnS, ZnSe, and ZnTe) for electron energies from 50 eV to 200 keV. These calculations were made with energy-loss functions (ELFs) obtained from measured optical constants for 15 compounds while calculated ELFs were utilized for the other 27 compounds. Checks based on ELF sum rules showed that the calculated ELFs were superior to the measured ELFs that we had used previously. Our calculated IMFPs could be fitted to a modified form of the relativistic Bethe equation for inelastic scattering of electrons in matter for energies from 50 eV to 200 keV. The average root-mean-square (RMS) deviation in these fits was 0.60 %. The IMFPs were also compared with a relativistic version of our predictive Tanuma-Powell-Penn (TPP-2M) equation. The average RMS deviation in these comparisons was 10.7 % for energies between 50 eV and 200 keV. This average RMS deviation is almost the same as that found in a similar comparison for a group of 41 elemental solids (11.9 %) although relatively large deviations were found for cubic BN (65.6 %) and hexagonal BN (34.3%). If these two compounds are excluded in the comparisons, the average RMS deviation becomes 8.7 %. We found generally satisfactory agreement between our calculated IMFPs and values from other calculations and from experiments.

Simulated photoelectron intensities at the aqueous solution-air interface for flat and cylindrical (microjet) geometries.

Ion spatial distributions at the aqueous-air/vacuum interface are accessible by energy-dependent X-ray photoelectron spectroscopy (XPS). Here we quantify the difference between a flat surface and a cylindrical microjet in terms of the energy-dependent information depth of the XPS experiment and in terms of the simulated photoelectron intensities using solutions of pure water and of 1 mol L-1 NaI as examples.

Quantitative analysis of trace levels of surface contamination by X-ray photoelectron spectroscopy Part I: statistical uncertainty near the detection limit.

We discuss the problem of quantifying common sources of statistical uncertainties for analyses of trace levels of surface contamination using X-ray photoelectron spectroscopy. We examine the propagation of error for peak-area measurements using common forms of linear and polynomial background subtraction including the correlation of points used to determine both background and peak areas. This correlation has been neglected in previous analyses, but we show that it contributes significantly to the peak-area uncertainty near the detection limit. We introduce the concept of relative background subtraction variance (RBSV) which quantifies the uncertainty introduced by the method of background determination relative to the uncertainty of the background area itself. The uncertainties of the peak area and atomic concentration and of the detection limit are expressed using the RBSV, which separates the contributions from the acquisition parameters, the background-determination method, and the properties of the measured spectrum. These results are then combined to find acquisition strategies that minimize the total measurement time needed to achieve a desired detection limit or atomic-percentage uncertainty for a particular trace element. Minimization of data-acquisition time is important for samples that are sensitive to x-ray dose and also for laboratories that need to optimize throughput.

Use of the Bethe Equation for Inner-Shell Ionization by Electron Impact.

We analyzed calculated cross sections for K-, L-, and M-shell ionization by electron impact to determine the energy ranges over which these cross sections are consistent with the Bethe equation for inner-shell ionization. Our analysis was performed with K-shell ionization cross sections for 26 elements, with L-shell ionization cross sections for seven elements, with L3-subshell ionization cross sections for Xe, and with M-shell ionization cross sections for three elements. The validity or otherwise of the Bethe equation could be checked with Fano plots based on a linearized form of the Bethe equation. Our Fano plots, which display theoretical cross sections and available measured cross sections, reveal two linear regions as predicted by de Heer and Inokuti. For each region, we made linear fits and determined values of the two element-specific Bethe parameters. We found systematic variations of these parameters with atomic number for both the low- and the high-energy linear regions of the Fano plots. We also determined the energy ranges over which the Bethe equation can be used.

Quantitative interpretation of molecular dynamics simulations for X-ray photoelectron spectroscopy of aqueous solutions.

Over the past decade, energy-dependent ambient pressure X-ray photoelectron spectroscopy(XPS) has emerged as a powerful analytical probe of the ion spatial distributions at the vapor (vacuum)-aqueous electrolyteinterface. These experiments are often paired with complementary molecular dynamics (MD) simulations in an attempt to provide a complete description of the liquidinterface. There is, however, no systematic protocol that permits a straightforward comparison of the two sets of results. XPS is an integrated technique that averages signals from multiple layers in a solution even at the lowest photoelectron kinetic energies routinely employed, whereas MD simulations provide a microscopic layer-by-layer description of the solution composition near the interface. Here, we use the National Institute of Standards and Technology database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to quantitatively interpret atom-density profiles from MD simulations for XPS signal intensities using sodium and potassium iodide solutions as examples. We show that electron inelastic mean free paths calculated from a semi-empirical formula depend strongly on solution composition, varying by up to 30% between pure water and concentrated NaI. The XPS signal thus arises from different information depths in different solutions for a fixed photoelectron kinetic energy. XPS signal intensities are calculated using SESSA as a function of photoelectron kinetic energy (probe depth) and compared with a widely employed ad hoc method. SESSA simulations illustrate the importance of accounting for elastic-scattering events at low photoelectron kinetic energies (<300 eV) where the ad hoc method systematically underestimates the preferential enhancement of anions over cations. Finally, some technical aspects of applying SESSA to liquidinterfaces are discussed.