Simulation Of Electron Spectra For Surface Analysis Research Articles

Sample structure prediction from measured XPS data using Bayesian estimation and SESSA simulator

We have developed a framework for solving the inverse problem of X-ray photoelectron spectroscopy (XPS) by incorporating an XPS simulator, Simulation of Electron Spectra for Surface Analysis (SESSA), into Bayesian estimation to obtain an overall picture of the distribution of plausible sample structures from the measured XPS data. The Bayesian estimation framework automated the very tedious task of adjusting the sample structure parameters manually in the simulator. As an example, we performed virtual experiments of angle-resolved XPS on a four-layered sample, and we estimated the sample structures based on the XPS intensity data obtained from experiments. We succeeded in not only obtaining an optimal solution, but also visualizing the distribution of the solution through the Bayesian posterior probability distribution.

Quantification of the Shell Thickness of Tin Oxide/Gold Core–Shell Nanoparticles by X-ray Photoelectron Spectroscopy

Encapsulation of nanoparticles (NP) by a shell material provides characteristics and properties not achievable by the individual materials of the core and the shell. Therefore, the characterization of morphology parameters of core–shell nanoparticles (CSNP) is critical to determine their performance. In this work, an analysis to determine the shell thickness of CSNP has been conducted using a simple and noniterative procedure known as Shard’s methodology, where the conversion of XPS peak intensities into shell thickness can be performed. Implementing the Simulation of Electron Spectra for Surface Analysis (SESSA), we acquired an insight into the morphology and composition of the CSNP by simulating the spectra from XPS to extract the parameters (Shard’s methodology) and confirm the core–shell ratio with experimental spectra to quantify the shell thickness. The CSNPs were synthesized with reverse micelle templating using diblock copolymer micellar templates, using various ratios of tin and gold precursors to form SnO2@Au core–shell nanoparticles. Considering elastic-scattering effects, a good agreement was found in the quantification of the shell thicknesses with a variation inside the ±10% regime of the effective attenuation length (EAL). This work demonstrates the use of simulation software as a complementary tool to a multitechnique analysis for a detailed understanding of CSNP.

A theoretical characterization method for non-spherical core-shell nanoparticles by XPS.

Core-shell nanoparticles (NPs) are active research areas for their unique properties and wide applications. By changing the elemental composition in the core and shell, a series of core-shell NPs with specific functions can be obtained, where the sizes of the core and shell also influence the properties. X-ray photoelectron spectroscopy (XPS) is useful in this context as a means of quantitatively analyzing such NPs. The empirical formula proposed by Shard [J. Phys. Chem. C, 2012, 116(31), 16806-16813] for calculating the shell thickness of the spherical core-shell NPs has been verified by Powell et al. [J. Phys. Chem. C, 2016, 120(39), 22730-22738] through a simulation of XPS with Simulation of Electron Spectra for Surface Analysis (SESSA) software. However, real core-shell NPs are not necessarily ideal spheres; such NPs can have rich shapes and uneven thicknesses. This work aims to extend the Shard formula to non-ideal core-shell NPs. We have used a Monte Carlo simulation method to study the XPS signal variation with the shell thickness for several modeled non-spherical shapes of core-shell NPs including some complex geometric structures which are numerically constructed with finite-element triangular meshes. Five types of non-spherical shapes, i.e. egg, ellipsoid, rod, rough-surface, and star shapes, are considered, while the size parameters are varied over a wide range. The equivalent radius and equivalent thickness are defined to characterize the average size of the nanoparticles for the use of the Shard formula. We have thus derived an extended Shard formula for the specific core-shell NPs, with which the relative error between the predicted shell thickness and the real thickness can be reduced to less than 10%.

Chemical bonding of copper and epoxy through a thiol-based layer for post 5G/6G semiconductors

With the development of post 5G/6G high-speed communication, the current frequency in the substrate is increasing. A flat copper substrate surface is wanted to reduce the signal loss caused by the skin effect. However, a flat surface harms the bonding strength between copper and epoxy, resulting in poor reliability for printed circuit boards (PCBs). This work tried to improve the bonding strength between a flat copper surface and an epoxy by bonding copper and epoxy chemically via 4-aminothiophenol (4-ATP). We investigated the influence of the treatment time of copper in a 2 mM 4-ATP ethanol solution. The treated surfaces were characterized by SEM, IRRAS, Raman, AFM, and XPS. In addition, we compared the experimental XPS results with the simulated XPS spectrum obtained via Simulation of Electron Spectra for Surface Analysis (SESSA) software, enabling us to understand the treated surface quantitatively. The interaction between treated cooper surface and epoxy was analyzed via Density Function Theory (DFT). The best treatment time is 1 h. Under this condition, the shear strength between copper and epoxy improved from 8.2 MPa to 24.1 MPa. The processing and bonding mechanisms were discussed. The results are expected to contribute significantly to fabricating of high-speed communication PCBs.

Inferring layer-by-layer composition in Au-Ag nanoparticles using a combination of X-ray Photoelectron Spectroscopy and Monte Carlo simulations

A strategy to estimate the composition profile in the top few atom layers of a binary metal alloy nanoparticle is presented. The method is based on a combination of the X-ray Photoelectron Spectroscopy (XPS) and Monte Carlo (MC) simulations. Au-Ag NPs were synthesized via solution-phase co-reduction followed by reduction in gas phase at 400 °C. The average composition at the NP surface was measured using XPS. The number of surface atomic layers whose compositions differ from bulk was identified using MC. XPS intensities were calculated using the number of independent layers as an input to the NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA). Upon analyzing the simulated XPS intensity we conclude that not one but several layer-by-layer Au/Ag composition profiles at the surface are consistent with the measured (experimental) XPS intensities. Finally, a procedure to identify the layer-by-layer composition profile consistent with both XPS analysis and MC simulations is proposed. The segregation free energy is calculated from the layer-by-layer composition profile identified. The resulting atomic scale information can guide first-principles prediction of catalyst activity where the elemental distribution at the surface is crucial.

Effective attenuation length dependence on photoelectron kinetic energy for gold from 1 keV to 10 keV: Role of island growth in overlayer experiments

We analyzed the experiments of Rubio-Zuazo and Castro [J. Electron Spectrosc. Relat. Phenom. 184 (2011) 384] who reported measurements of effective attenuation lengths (EALs) of gold for electron energies between 1 keV and 15 keV. They deposited thin films of gold on a copper substrate and measured the intensities of various Cu and Au photoelectron lines excited by synchrotron X-rays. Their derived EALs were based on the assumption that their films were of uniform thickness (i.e., layer-by-layer film growth). We considered two other forms of film growth: island formation (Volmer-Weber film growth) and island growth on a continuous monatomic wetting layer (Stranski-Krastanov film growth). We utilized the National Institute of Standards and Technology Database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to determine the fractional Au island areas for each Au film thickness that would give the same intensity changes of Cu and Au photoelectron lines that were observed in the experiments. These results showed that growth of the Au film as islands provided a better description of the experimental results than uniform film growth. We could also distinguish Stranski-Krastanov film growth from Volmer-Weber growth and believe that the former is more likely.

Correction to Impact of Nonideal Nanoparticles on X-ray Photoelectron Spectroscopic Quantitation: An Investigation Using Simulation and Modeling of Gold Nanoparticles.

Quantitative X-ray photoelectron spectroscopic (XPS) analysis combined with spectral modeling of photoelectrons can be valuable while investigating the surface chemistry of nanoparticles (NPs) with different morphologies. Herein, with the use of NIST Simulation of Electron Spectra for Surface Analysis (SESSA), a comparative analysis of experimental and simulated photoelectron peak intensities in gold nanoparticles (AuNPs) of different morphologies is presented. Three sets of supported AuNPs with different morphologies were selected from a series of as synthesized Au-TiO2 catalyst samples. Using transmission electron microscopy (TEM) analyzed morphological information on the AuNPs as input model parameters in SESSA, XPS spectra were generated from the respective input NP morphologies. A degree of greater mismatch between SESSA simulated and experimental XPS spectra was observed while using the TEM obtained average diameter of the nanoparticles. The degree of mismatch lowered when the true nonspherical shap...

Impact of Nonideal Nanoparticles on X-ray Photoelectron Spectroscopic Quantitation: An Investigation Using Simulation and Modeling of Gold Nanoparticles.

Quantitative X-ray photoelectron spectroscopic (XPS) analysis combined with spectral modeling of photoelectrons can be valuable while investigating the surface chemistry of nanoparticles (NPs) with different morphologies. Herein, with the use of NIST Simulation of Electron Spectra for Surface Analysis (SESSA), a comparative analysis of experimental and simulated photoelectron peak intensities in gold nanoparticles (AuNPs) of different morphologies is presented. Three sets of supported AuNPs with different morphologies were selected from a series of as synthesized Au-TiO2 catalyst samples. Using transmission electron microscopy (TEM) analyzed morphological information on the AuNPs as input model parameters in SESSA, XPS spectra were generated from the respective input NP morphologies. A degree of greater mismatch between SESSA simulated and experimental XPS spectra was observed while using the TEM obtained average diameter of the nanoparticles. The degree of mismatch lowered when the true nonspherical shape of the nanoparticles as obtained from TEM images was taken into account for the simulation. This demonstrates the impact of surface morphology on the XPS peak intensities which needs to be incorporated to obtain precise quantified information from the supported nanoparticles. This work demonstrates the applicability of SESSA in combination with experimental XPS and TEM measurements for precise quantification of XPS spectra from complex, nonideal shaped nanoparticles. This study can be extended to include a broad range of nanoparticles with ideal or nonideal geometries, thus providing a simple method to utilize quantitative XPS analysis to a wide range of nanomaterials.

Quantitative analysis of trace levels of surface contamination by X‐ray photoelectron spectroscopy. Part II: Systematic uncertainties and absolute quantification

We discuss analyses of trace levels of surface contamination using X‐ray photoelectron spectroscopy (XPS). The problem of quantifying common sources of statistical and systematic uncertainties for these measurements is formulated in terms of the needs of extreme ultraviolet lithography, but the results and conclusions are applicable to a broad range of XPS applications. We quantify the systematic uncertainties introduced by particular cases of overlapping peaks on different substrate structures by simulating measured spectra with the National Institute of Standards and Technology Database for the Simulation of Electron Spectra for Surface Analysis (SESSA). One example demonstrates that the relative atomic concentrations of trace elements such as S, P, and halogens on a Ru surface could be dramatically overestimated if the fitting of the overlapping Ru 3d and C 1s peaks excludes the contribution from carbon. We also show how spectra generated by SESSA can be compared with measured spectra to determine absolute amounts of surface impurities on layered samples of the type used for extreme ultraviolet lithography. We provide estimates of the total uncertainty for such measurements by considering the systematic limitations of SESSA and the statistical uncertainties of the measurements. The same procedure can be employed for other multilayered materials. Finally, we describe two approaches for converting XPS detection limits for an elemental impurity in an elemental matrix to the corresponding detection limits for the impurity as a thin film on the surface of the matrix material.

Experimental determination of the effective attenuation length of palladium 3d 5/2 photoelectrons in a magnetron sputtered Pd nanolayer

An electron effective attenuation length (EAL) of 1.68 nm for Al Kα excited Pd 3d 5/2 photoelectrons with a kinetic energy of 1.152 keV has been determined experimentally using a sputtered Pd film deposited on an ultra flat fused quartz substrate. The film thickness was reduced by Ar ion sputtering several times in order to obtain different Pd film thicknesses which are used to determine experimental EAL values. These results are compared to data generated by using a Simulation of Electron Spectra for Surface Analysis (SESSA) simulation using an inelastic mean free path (IMFP) calculated with the Tanuma–Powell–Penn (TPP)‐2M formula and with ‘elastic scattering on and off’. Contributions to the uncertainty budget related to the experimental approach are discussed in detail. Proposals on how to further improve the approach are suggested. Copyright © 2016 John Wiley & Sons, Ltd.

Gold/silver core-shell 20 nm nanoparticles extracted from citrate solution examined by XPS

Silver nanoparticles of many types are widely used in consumer and medical products. The surface chemistry of particles and the coatings that form during synthesis or use in many types of media can significantly impact the behaviors of particles including dissolution, transformation and biological or environmental impact. Consequently it is useful to be able to extract information about the thickness of surface coatings and other attributes of nanoparticles produced in a variety of ways. It has been demonstrated that X-ray Photoelectron Spectroscopy (XPS) can be reliably used to determine the thickness of coatings and shells. However, care is required to produce reliable and consistent information. Here we report XPS spectra from gold/silver core-shell nanoparticles of nominal size 20 nm removed from a citrate saturated solution after one washing cycle. The Simulation of Electron Spectra for Surface Analysis (SESSA) program has been used to model peak amplitudes to obtain information on citrate coatings that remain after washing and demonstrate the presence of the gold core. This data is provided in digital form so that others can compare use of SESSA or other modeling approaches to quantify the nature of coatings to those already published and to explore the impacts particle non-uniformities on XPS signals from core-shell nanoparticles.

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.

Evaluating the Internal Structure of Core-Shell Nanoparticles Using X-ray Photoelectron Intensities and Simulated Spectra.

The functionality of a new version of the National Institute of Standards and Technology database Simulation of Electron Spectra for Surface Analysis (SESSA) has been extended by implementing a new geometry engine. The engine enables users to simulate Auger-electron spectra and X-ray photoelectron spectra for different predefined morphologies (planar, islands, spheres, multi-layer core-shell particles). We compared shell thicknesses of core-shell nanoparticles derived from core-shell XPS peak intensities using Shard's method, which allows one to estimate shell thicknesses of core-shell nanoparticles, and a series of SESSA simulations for a wide range of nanoparticle dimensions. We obtained very good agreement of the shell thicknesses for cases where elastic scattering within the shell can be neglected, a result that is in accordance with the underlying assumptions of the Shard model. If elastic-scattering effects are important, there can be thickness uncertainties of up to 25 %. Experimental spectra of functionalized gold nanoparticles obtained by Techane et al. were analyzed with SESSA 2.0 both with respect to the relevant peak intensities as well as the spectral shape. Good agreement between experiment and theory was found for both cases. These results show that the single-sphere model for core-shell nanoparticles is valid when just using peak intensities, but more detailed modeling is needed to describe the inelastic background.

Sample-morphology effects on x-ray photoelectron peak intensities. II. Estimation of detection limits for thin-film materials

The authors show that the National Institute of Standards and Technology database for the simulation of electron spectra for surface analysis (SESSA) can be used to determine detection limits for thin-film materials such as a thin film on a substrate or buried at varying depths in another material for common x-ray photoelectron spectroscopy (XPS) measurement conditions. Illustrative simulations were made for a W film on or in a Ru matrix and for a Ru film on or in a W matrix. In the former case, the thickness of a W film at a given depth in the Ru matrix was varied so that the intensity of the W 4d5/2 peak was essentially the same as that for a homogeneous RuW0.001 alloy. Similarly, the thickness of a Ru film at a selected depth in the W matrix was varied so that the intensity of the Ru 3p3/2 peak matched that from a homogeneous WRu0.01 alloy. These film thicknesses correspond to the detection limits of each minor component for measurement conditions where the detection limits for a homogeneous sample varied between 0.1 at. % (for the RuW0.001 alloy) and 1 at. % (for the WRu0.01 alloy). SESSA can be similarly used to convert estimates of XPS detection limits for a minor species in a homogeneous solid to the corresponding XPS detection limits for that species as a thin film on or buried in the chosen solid.

Modeling of X‐ray photoelectron spectra: surface and core hole effects

The shape and intensity of photoelectron peaks are strongly affected by extrinsic excitations due to electron transport out of the surface and by intrinsic excitations induced by the sudden creation of the static core hole. Besides, elastic electron scattering may also be important. These effects should be included in the theoretical description of the emitted photoelectron peaks. To investigate the importance of surface and core hole effects relative to elastic scattering effect, we have calculated full XPS spectra for the Cu 2p emissions of Cu and CuO with the simulation of electron spectra for surface analysis (SESSA) software and with a convolution procedure using the differential inelastic electron scattering cross‐section obtained with the quantitative analysis of electron energy loss in XPS (QUEELS‐XPS) software. Surface and core hole effects are included in QUEELS‐XPS but absent in SESSA while elastic electron scattering effects are included in SESSA but absent in QUEELS‐XPS. Our results show that the shape of the XPS spectra are strongly modified because of surface and core hole effects, especially for energy losses smaller than about 20 eV. Copyright © 2014 John Wiley &amp; Sons, Ltd.

Simulation of Electron Spectra for Surface Analysis (SESSA)for quantitative interpretation of (hard) X-ray photoelectron spectra(HAXPES)

For the interpretation of photoelectron spectra and in order to obtain quantitative information on the chemical structure of surfaces, one commonly makes a number of simplifying assumptions concerning the generation of the signal electrons, such as the neglect of photoelectron elastic scattering, and the anisotropy of photoelectron emission. While the effects of these assumptions for planar surfaces and for conventional X-ray sources has been investigated in detail in the past, the combined influence of the nanomorphology, the polarisation of the incoming beam and other processes playing a role in the photoelectron escape on the angular- and energy-distribution of emitted photoelectrons has not been clarified to date. The National Institute of Standards and Technology (NIST) Database for the Simulation of Electron Spectra for Surface Analysis (SESSA) is a unique tool for interpretation of experimental data for nanostructured surfaces as well as for experimental design with photoelectron energies between 50eV and 30keV. SESSA has recently been modified to allow a user to simulate X-ray photoelectron spectroscopy (XPS) spectra of nanostructured surfaces, such as surfaces covered with rectangular islands, nanowires, pyramids, spheres, and layered spheres. The effect of the nanomorphology on the emitted angular and energy distribution of photoelectrons is investigated and comparison is made of simulated data with experimental results. Finally, the full potential of XPS for characterising nanostructures by a consistent analysis of the angular distribution of both the photoelectron peaks and their associated inelastic loss features is explored.

Effective attenuation lengths for photoelectrons in thin films of silicon oxynitride and hafnium oxynitride on silicon

AbstractWe have used the National Institute of Standards and Technology Database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to simulate photoelectron intensities for thin films of SiO1.6N0.4 and HfO1.9N0.1 on silicon with excitation by Al Kα X‐rays. We considered Si 2p3/2 photoelectrons from SiO1.6N0.4 and the substrate and Hf 4f7/2 photoelectrons from HfO1.9N0.1. The simulations were performed for ranges of film thicknesses and photoelectron emission angles and for two common configurations for X‐ray photoelectron spectroscopy (XPS), the sample‐tilting configuration and the Theta Probe configuration. We determined photoelectron effective attenuation lengths (EALs) by two methods, one by analyzing photoelectron intensities as a function of film thickness for each emission angle (Method 1) and the other by analyzing photoelectron intensities as a function of emission angle for each film thickness (Method 2). Our analyses were made with simple expressions that had been derived with the assumption that elastic‐scattering effects were negligible. We found that EALs from both methods were systematically larger for the Theta Probe configuration, by amounts varying between 1% and 5%, than those for the sample‐tilting configuration. These differences were attributed to anisotropy effects in the photoionization cross section that are expected to occur in the former configuration. Generally, similar EALs were found by each method for each film material although larger EALs were found from Method 2 for film thicknesses less than 1.5 nm. SESSA is a useful tool for showing how elastic scattering of photoelectrons modifies EALs for particular materials, film thicknesses, and XPS configurations. Copyright © 2012 John Wiley &amp; Sons, Ltd.

Simulation and Modeling of Self-Assembled Monolayers of Carboxylic Acid Thiols on Flat and Nanoparticle Gold Surfaces

Quantitative analysis of the 16-mercaptohexadecanoic acid self-assembled monolayer (C16 COOH-SAM) layer thickness on gold nanoparticles (AuNPs) was performed using simulation of electron spectra for surface analysis (SESSA) software and X-ray photoelectron spectroscopy (XPS) experimental measurements. XPS measurements of C16 COOH-SAMs on flat gold surfaces were made at nine different photoelectron emission angles (5-85° in 10° increments), corrected using geometric weighting factors and then summed together to approximate spherical AuNPs. The SAM thickness and relative surface roughness (RSA) in SESSA were optimized to determine the best agreement between simulated and experimental surface composition. On the basis of the glancing-angle results, it was found that inclusion of a hydrocarbon-contamination layer on top the C16 COOH-SAM was necessary to improve the agreement between the SESSA and XPS results. For the 16 COOH-SAMs on flat Au surfaces, using a SAM thickness of 1.1 Å/CH(2) group, an RSA of 1.05, and a 1.5 Å CH(2)-contamination overlayer (total film thickness = 21.5 Å) for the SESSA calculations provided the best agreement with the experimental XPS data. After applying the appropriate geometric corrections and summing the SESSA flat-surface compositions, the best fit results for the 16 COOH-SAM thickness and surface roughness on the AuNPs indicated a slightly thinner overlayer with parameters of 0.9 Å/CH(2) group in the SAM, an RSA of 1.06 RSA, and a 1.5 Å CH(2)-contamination overlayer (total film thickness = 18.5 Å). The 3 Å difference in SAM thickness between the flat Au and AuNP surfaces suggests that the alkyl chains of the SAM are slightly more tilted or disordered on the AuNP surfaces.

Photoelectron angular distributions of Cu, Ag, Pt and Au samples: experiments and simulations

AbstractAngular distributions of photoelectrons emitted from semi‐infinite Cu, Ag, Pt and Au specimens have been measured for off‐normal emission angles in the range between 20 and 70° with a Thermo Theta Probe electron spectrometer. Experimental peak intensities for peaks of atomic subshells observable in the spectra were compared with results of simulations using the NIST Database for the Simulation of Electron Spectra for Surface Analysis (SESSA) that takes into account the effects of (i) anisotropy of the photoelectric cross‐section; (ii) elastic scattering of the photoelectrons; and (iii) the finite solid angle of the detector. In addition, a separate correction was made to the simulated intensities for the effects of surface excitations. The combined influence of these effects was found to significantly affect the angular distributions. Furthermore, it was found that ratios of the calculated peak intensities of the observed subshells for a particular material to the measured intensities deviate from unity by typically less than 1% after corrections for multiple inelastic scattering and surface excitations. Copyright © 2010 John Wiley &amp; Sons, Ltd.

Effects of elastic scattering and analyzer‐acceptance angle on the analysis of angle‐resolved X‐ray photoelectron spectroscopy data

AbstractWe have made calculations of N 1s, O 1s, Si(oxide) 2p, Hf 4f, and Si(substrate) 2p photoelectron intensities at selected emission angles for films of SiO1.6N0.4 and HfO1.9N0.1 of various thicknesses on silicon. These calculations were made with the National Institute of Standards and Technology (NIST) Database for Simulation of Electron Spectra for Surface Analysis (SESSA) to investigate effects of elastic scattering and analyzer‐acceptance angle that could be relevant in the analysis of angle‐resolved X‐ray photoelectron spectroscopy (ARXPS) experiments. The simulations were made for an XPS configuration with a fixed angle between the X‐ray source (i.e. for the sample‐tilting mode of ARXPS) and with Al and Cu Kα X‐ray sources. The no‐loss intensities changed appreciably as elastic scattering was switched ‘on’ and ‘off’, but changing the analyzer‐acceptance angle had a smaller effect. Ratios of intensities for each line from the overlayer film for the least realistic model condition (elastic scattering switched ‘off’, small analyzer‐acceptance angle) to those from the most realistic model condition (elastic scattering switched ‘on’, finite analyzer‐acceptance angle) changed relatively slowly with emission angle, but the corresponding intensity ratio for the Si(substrate) 2p line changed appreciably with emission angle. The latter changes, in particular, indicate that neglect of elastic‐scattering effects can lead to erroneous results in the analysis of measured ARXPS data. The elastic‐scattering effects were larger in HfO1.9N0.1 than in SiO1.6N0.4 (due to the larger average atomic number in the former compound) and were larger with the Al Kα X‐ray source than with the Cu Kα source because of the larger cross sections for elastic scattering at the lower photoelectron energies. Copyright © 2010 John Wiley &amp; Sons, Ltd.