Analysis Of X-ray Photoelectron Spectroscopy Data Research Articles

Large Language Model-Informed X-ray Photoelectron Spectroscopy Data Analysis

X-ray photoelectron spectroscopy (XPS) remains a fundamental technique in materials science, offering invaluable insights into the chemical states and electronic structure of a material. However, the interpretation of XPS spectra can be complex, requiring deep expertise and often sophisticated curve-fitting methods. In this study, we present a novel approach to the analysis of XPS data, integrating the utilization of large language models (LLMs), specifically OpenAI’s GPT-3.5/4 Turbo to provide insightful guidance during the data analysis process. Working in the framework of the CIRCE-NAPP beamline at the CELLS ALBA Synchrotron facility where data are obtained using ambient pressure X-ray photoelectron spectroscopy (APXPS), we implement robust curve-fitting techniques on APXPS spectra, highlighting complex cases including overlapping peaks, diverse chemical states, and noise presence. Post curve fitting, we engage the LLM to facilitate the interpretation of the fitted parameters, leaning on its extensive training data to simulate an interaction corresponding to expert consultation. The manuscript presents also a real use case utilizing GPT-4 and Meta’s LLaMA-2 and describes the integration of the functionality into the TANGO control system. Our methodology not only offers a fresh perspective on XPS data analysis, but also introduces a new dimension of artificial intelligence (AI) integration into scientific research. It showcases the power of LLMs in enhancing the interpretative process, particularly in scenarios wherein expert knowledge may not be immediately available. Despite the inherent limitations of LLMs, their potential in the realm of materials science research is promising, opening doors to a future wherein AI assists in the transformation of raw data into meaningful scientific knowledge.

Insight note: X‐ray photoelectron spectroscopy (XPS) peak fitting of the Al 2p peak from electrically isolated aluminum foil with an oxide layer

X‐ray photoelectron spectroscopy (XPS) is the most widely used and important method for chemically analyzing and speciating surfaces. XPS has surface sensitivity (5–10 nm), is quantitative, and is able to probe the oxidation states of the elements at surfaces. However, during the past few years, a great deal of incorrect XPS data analysis has entered the scientific literature. Accordingly, efforts, including this Insight Note, are being made to provide tutorial information to the scientific community. Aluminum is a scientifically and technologically important element. Here we discuss approaches for fitting the Al 2p peak envelope from a sample of aluminum foil with a thin layer of oxide on it. Signals from the metal and oxide are present. We discuss methods for electrically isolating (or not isolating) the sample during data acquisition, the choice of the baseline, fitting the oxide peak with one or two synthetic peaks, and fitting the metal signal with two symmetric or two asymmetric peaks. The thickness of the oxide is calculated based on the areas of the oxide and metal signals.

Insufficient reporting of x-ray photoelectron spectroscopy instrumental and peak fitting parameters (metadata) in the scientific literature

This study was motivated by earlier observations. It is a systematic examination of the adequacy of reporting of information (metadata) necessary to understand x-ray photoelectron spectroscopy (XPS) data collection and data analysis in the scientific literature. The information for this study was obtained from papers published in three high-quality journals over a six-month period in 2019 and throughout 2021. Each paper was evaluated to determine whether the authors had reported (percentages of the papers properly providing the information are given in parentheses) the spectrometer (66%), fitting software (15%), x-ray source (40%), pass energy (10%), spot size (5%), synthetic peak shapes in fits (10%), backgrounds in fits (10%), whether the XPS data are shown in the main body of the paper or in the supporting information (or both), and whether fitted or unfitted spectra were shown (80% of published spectra are fit). The Shirley background is the most widely used background in XPS peak fitting. The Al Kα source is the most widely used x-ray source for XPS data collection. casaxps is the most widely used fitting program for XPS data analysis. There is good agreement between the results gathered during the two years of our survey. There are some hints the situation may be improving. This study also provides a list of the information/parameters that should be reported when XPS is performed.

Perspective on improving the quality of surface and material data analysis in the scientific literature with a focus on x-ray photoelectron spectroscopy (XPS)

Due to significant advances in instrumentation, many previously specialized techniques have become “routine” in user facilities. However, detailed knowledge held by experts has often not been relayed to general users, so they often rely on entry-level information, basic principles, and comparison with literature results for data analysis. As a result, major errors in the data analysis of multiple surface and material analysis techniques, including in x-ray photoelectron spectroscopy (XPS), have been appearing in the scientific literature. Representative examples of serious errors in XPS data analysis are shown in this work. We suggest that surface and material analysis, and perhaps even science in general, are in a state of “pre-crisis.” We use two (logistic) models from population biology to suggest that bad analyses self-correct if they remain below a critical number. However, beyond a threshold, the literature can become useless because of the perpetuation of faulty analyses and concomitant loss of its self-correcting ability. XPS is used by scientists in many communities because of the power of the technique and high-quality instrumentation that is commercially available. Those who make new surfaces and materials face unique challenges because of the large number of surface and material analytical techniques that are often needed to characterize their materials. Graduate students and post-docs are often provided with only minimal instruction on using surface and material characterization methods. High fees for instruments may affect both the quality and the quantity of the data people collect. The Prisoner's Dilemma is a model from game theory that describes situations with reward structures that encourage uncooperative behavior and lead to suboptimal outcomes. However, the outcomes of Prisoner's Dilemma are not inevitable—their consequences change if their reward structures change. The current system does not appear to incentivize detailed learning of surface and material characterization techniques and careful material characterization. Prisoner's dilemmas appear to lead to other undesirable consequences in science. The concerns raised in this work suggest that many manuscripts are incompletely reviewed at present. The different stakeholders in this problem, including authors, research advisers, subject matter experts, reviewers, scientists who notice examples of faulty data analysis, editors, journals and publishers, funding agencies, scientific societies, leaders at universities and research centers, and instrument vendors, can improve the current situation. This work provides specific recommendations for each of these stakeholders. For example, we believe that authors are primarily responsible for the correctness of their work, not reviewers or editors; we question the wisdom of listing the names of the editor and reviewers on a paper; we are grateful for the significant contributions that have been made by subject matter experts to produce standards and tutorial information; the high cost of instrument time at some institutions may limit student access and result in suboptimal analyses; staff scientists often need to be better recognized for their intellectual contributions to studies; publishers may wish to allow selective reviewing of specific sections of papers related to material characterization; the reviewing at some open access journals may be inadequate; while it had its shortcomings, the pre-open access model of publishing incentivized the production and publication of high-quality work; audits of the products (scientific papers) of funding agencies may be necessary; collaboration needs to be encouraged to a greater extent at some institutions; and instrument vendors should not suggest to potential customers that surface characterization, e.g., by XPS, is trivial or simple.

Modification of conventional peak shapes to accurately represent spectral asymmetry: High-Resolution X-ray photoelectron spectra of [C4C1Pyrr][NTf2] and [C8C1Im][NTf2] ionic liquids

X-ray photoelectron spectroscopy (XPS) is one of the most widely used techniques for surface characterization. Analysis of XPS data is challenging and requires the analyst to fit the data with synthetic line shapes to reach physically meaningful interpretations. Experimental spectral envelopes, however, are complex and display asymmetric features that are often ignored or attributed to additional chemical components. The high-resolution XPS spectra of [C4C1Pyrr][NTf2] and [C8C1Im][NTf2] all exhibit a degree of asymmetry which is systematically observed at the higher binding energy side of photoemission envelopes. We present the development of a refined fitting procedure for XPS spectra of these ionic liquid-based systems which include (a) Shirley background offset necessary to account for the insulator-like region and (b) spectral asymmetry in C 1s and N 1s regions. Further, Shirley and trapezoid components are applied to compensate for inelastic scattering taking place during electron transitions as high as 7.8 eV above the start of the fitting region in C 1s high-resolution spectrum. To demonstrate the fitness of this model, we present an analysis of a 2:1 mixture of [C4C1Pyrr][NTf2]: [C8C1Im][NTf2].

Guide to XPS data analysis: Applying appropriate constraints to synthetic peaks in XPS peak fitting

Peak fitting of x-ray photoelectron spectroscopy (XPS) data is the primary method for identifying and quantifying the chemical states of the atoms near the surface of a sample. Peak fitting is typically based on the minimization of a figure-of-merit, such as the residual standard deviation (RSD). Here, we show that optimal XPS peak fitting is obtained when the peak shape (the synthetic mathematical function that represents the chemical states of the material) best matches the physics and chemistry of the underlying data. However, because this ideal peak shape is often unknown, constraints on the components of a fit are usually necessary to obtain good fits to data. These constraints may include fixing the relative full width at half maxima (peak widths), area ratios, and/or the relative positions of fit components. As shown in multiple examples, while unconstrained, less-than-optimal peak shapes may produce lower RSDs, they often lead to incorrect results. Thus, the “suboptimal” results (somewhat higher RSDs) that are obtained when constraints are applied to less-than-perfect peak shapes are often preferable because they prevent a fit from yielding unphysical or unchemical results. XPS peak fitting is best performed when all the information available about a sample is used, including its expected chemical and physical composition, information from other XPS narrow and survey scans from the same material, and information from other analytical techniques.

A study of in situ reduction of MoO3 to MoO2 by X-ray Photoelectron Spectroscopy

Results from X-ray Photoelectron Spectroscopy (XPS) of molybdenum oxide samples are presented to elucidate how Mo (VI) oxide evolves to Mo (IV) oxide upon heating of a MoO3 sample. XPS data analysis techniques based on manipulation of spectra treated as vectors are shown and allow insights into intermediate phases of Mo oxide which suggest how the original oxide changes under the influence of heat but also supports an interpretation of as-received tetravalent Mo powders as multivalent materials. In particular, several new spectral components were observed and assigned to the Magnéli phase as well as MoO3 domains that have been modified by the presence of X-rays or temperature. These assignments comprise a new method of data processing where sample modification is used to inform XPS data interpretation and differ from previous work where the linear relationship of the binding energy of molybdenum oxides has been used.

Systematic and collaborative approach to problem solving using X-ray photoelectron spectroscopy

The methodology presented within this work is a result of years of interactions between many junior and senior X-ray Photoelectron Spectroscopy (XPS) users operating within the CasaXPS spectral processing and interpretation program framework. In particular, discussions arising from a series of workshops have been a significant source for developing the overall XPS data processing concept and are the motivation for creating this work. These workshops organized by the Institut des Matériaux Jean Rouxel (IMN), Nantes gather both experienced and novice users of XPS for a week of discourse in conceptual experiment design and the resulting data processing. However, the framework constructed and utilized within these workshops encouraged the dissemination of knowledge beyond XPS data analysis and emphasized the importance of a multi-disciplinary collaborative approach to surface analysis problem-solving. The material presented here embodies data treatment originating from data made available to the first CNRS Thematic Workshop presented at Roscoff 2013. The methodology described here has evolved over the subsequent workshops in 2016 and 2019 and currently represents the philosophy used in CasaXPS spectral data processing paradigm.

Study of Electronic States in LaNiO3/SrRuO3 Bilayers: Interface‐Induced Magnetism and Charge Transfer

The results of a study on the electronic states and valence band offset (VBO) in heterostructures of the transition metal oxide LaNiO3 (LNO)/SrRuO3 (SRO) grown on (001) SrTiO3 (STO) substrates are reported. X‐ray photoelectron spectroscopy (XPS) data reveal the presence of Ni2+ states in LNO layer that can develop a reduced bandwidth of O‐2p and Ni‐3d. Further analysis of XPS data confirms the presence of a VBO, and the value of VBO is found to be +0.02 eV and –0.38 eV for the bilayers of STO/LaNiO3/SrRuO3 (BL‐1) and STO/SrRuO3/LaNiO3 (BL‐2), respectively. Distinct signs of VBO are noticed between the bilayers due to the relative shift of the valence band of the top layer with respect to the bottom layer. Such band shifts can lead to the charge transfer across the (3d−4d) interface, which significantly modifies the global electronic transport and magnetic properties of the bilayers. A detailed discussion on the underlying physical phenomena of electrical transport and magnetic responses triggered by the interface is also incorporated herein.

CVD growth of the nanostructured Ni3S2 thin films as efficient electrocatalyst for hydrogen evolution reaction

The development of low cost and earth abundant electrocatalyst with high performance and desirable stability for hydrogen evolution reaction (HER) is an important issue in energy applications. Nickel sulfide thin films (NiSx) are formed on conductive nickel foam substrates via chemical vapor deposition (CVD) at 300 °C under low pressure condition. A single phase of Ni3S2 was produced by controlling the ratio of precursors. X-ray diffraction (XRD), field emission scanning electron spectroscopy (FESEM), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements were conducted to characterize and compare properties of the samples. According to XRD and XPS data analysis, the growth of single phase and surface chemical composition of the Ni3S2 was confirmed on the substrate. The results showed that by changing the molar ratio of S/Ni, nickel sulfides are crystalized in different phases including Ni3S4, NiS and Ni3S2. Electrochemical measurements conducted for HER activity showed that the Ni3S2 phase has the lowest overpotential, 116 mV vs. RHE, in comparison with two other phases (NiS and Ni3S4). Ni3S2 possesses many accessible active sites with a relative electrochemical surface area of about 83. Finally, the Tafel slopes for Ni3S2, NiS and Ni3S4 were obtained to be 96, 154 and 197 mV/dec, respectively.

Intrinsic catalase-mimicking MOFzyme for sensitive detection of hydrogen peroxide and ferric ions

Lanthanide metal-organic frameworks (Ln-MOFs) exhibit outstanding properties, including high chemical and thermal stability, as well as their promising enzyme-mimic activity (MOFzyme). A new cerium MOFs (Ce-MOF) was synthesized via a solvothermal method using organic linker 4,4′,4″-nitrilotribenzoic acid (H3NTB). The crystallinity of the prepared material was confirmed using X-ray diffraction (XRD). The coordination between Ce and H3NTB was approved using Fourier transforms infrared (FT-IR). The chemical and oxidation state of Ce-MOF was characterized using X-ray photoelectron spectroscopy (XPS). The analysis of XPS data suggested the presence of two oxidation states of cerium, i.e., Ce(III) and Ce(IV). According to the imaging using a scanning electron microscope (SEM) and transmission electron microscope (TEM), Ce-MOF exhibits hexagonal rods’ morphology. Ce-MOF offered thermal stability up to 350 °C. It showed a fluorescence emission signal at wavelength 550 nm with a Stock’s shift of 200 nm. Ce-MOF’s application as a probe for sensing hydrogen peroxide (H2O2) and ferric ions (Fe3+) was reported. Ce-MOF exhibited peroxidase MOFzyme activity. Thus, it offered a turn-on emission upon interaction with different concentrations of H2O2. It detects Fe3+ ions with a limit of detection (LOD) and a linear range of 0.016 µM and 0.016–0.133 µM, respectively. The study also investigated the mechanisms of sensing for H2O2 and Fe3+ ions. The changes in the emission signals were due to the intrinsic catalase activity of Ce-MOF. Ce-MOF offered MOFzyme properties providing a promising feature for biocatalysis and biosensing applications.

Atomic Structure and Optical Properties of Plasma Enhanced Chemical Vapor Deposited SiCOH Low-k Dielectric Film-=SUP=-*-=/SUP=-

The SiCOH low-k dielectric film was grown on Si substrate using plasma enhanced chemical vapor deposition method. Atomic structure and optical properties of the film were studied with the use of X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) absorption spectroscopy, Raman spectroscopy and ellipsometry. Analysis of XPS data showed that the low-k dielectric film consists of Si-O4 bonds (83%) and Si-SiO3 bonds (17%). In FTIR spectra some red-shift of Si-O-Si valence (stretching) vibration mode frequency was observed in the low-k dielectric film compared with the frequency of this mode in thermally grown SiO2 film. The peaks related to absorbance by C-H bonds were observed in FTIR spectrum. According to Raman spectroscopy data, the film contained local Si-Si bonds and also C-C bonds in the s-p3 and s-p2 hybridized forms. Scanning laser ellipsometry data show that the film is quite homogeneous, homogeneity of thickness is ~ 2.5%, and homogeneity of refractive index is ~ 2%. According to analysis of spectral ellipsometry data, the film is porous (porosity is about 24%) and contains clusters of amorphous carbon (~ 7%).

Oxygen plasma surface treatment of polymer films—Pellethane 55DE and EPR-g-VTMS

A systematic study using a central composite design of experiments (DoE) was performed on the oxygen plasma surface modifications of two different polymers—Pellethane 2363-55DE, which is a polyurethane, and vinyltrimethoxysilane-grafted ethylene-propylene (EPR-g-VTMS), a cross-linked ethylene-propylene rubber. The impacts of four parameters—gas pressure, generator power, treatment duration, and process temperature—were assessed, with static contact angles and calculated surface free energies (SFEs) as the main responses in the DoE. The plasma effects on the surface roughness and chemistry were determined using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Through the sufficiently accurate DoE model evaluation, oxygen gas pressure was established as the most impactful factor, with the surface energy and polarity rising with falling oxygen pressure. Both polymers, though different in composition, exhibited similar modification trends in surface energy rise in the studied system. The SEM images showed a rougher surface topography after low pressure plasma treatments. XPS and subsequent multivariate data analysis of the spectra established that higher oxidized species were formed with plasma treatments at low oxygen pressures of 0.2 mbar.

Local, electronic and surface structure of multi-component Fe-doped CdTe(S) systems

Local structural and electronic properties around Fe in multi-component Cd0.99Fe0.01Te0.97S0.03 system were studied by means of X-ray absorption fine structure (XAFS). Composition of non-polar (110) surfaces of Cd0.97Fe0.03Te and Cd0.99Fe0.01Te0.97S0.03 systems and mechanism of their oxidation in ambient conditions were studied by Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS). It has been found that Fe preferentially substitutes Cd, but due to much smaller covalent radius and preferences for paring with S, it causes local distortion of the host CdTe lattice. The distortion is confined to the Fe-immediate surrounding and the second and third coordination shell atoms are (inside experimental uncertainties) placed at distances expected in CdTe. Although local structure around Fe is well defined in the bulk of both samples, their near-surface region is completely depleted from Fe, and in case of Cd0.99Fe0.01Te0.97S0.03 somewhat enriched in S. Special attention is, therefore, paid to characterization of the near-surface region and evaluation of its composition and structure. To that end we have introduced a general standard-free algorithm for XPS data analysis of the two-layer surface structure (bulk, oxide layer, and the impurity layer). Results of the in-depth composition analysis revealed that despite different bulk composition and impurity layer thickness, underneath the topmost impurity layer lays approximately one monolayer of CdTeO3 which passivates the surface.

The Gaussian-Lorentzian Sum, Product, and Convolution (Voigt) functions in the context of peak fitting X-ray photoelectron spectroscopy (XPS) narrow scans

X-ray photoelectron spectroscopy (XPS) is arguably the most important vacuum technique for surface chemical analysis, and peak fitting is an indispensable part of XPS data analysis. Functions that have been widely explored and used in XPS peak fitting include the Gaussian, Lorentzian, Gaussian-Lorentzian sum (GLS), Gaussian-Lorentzian product (GLP), and Voigt functions, where the Voigt function is a convolution of a Gaussian and a Lorentzian function. In this article we discuss these functions from a graphical perspective. Arguments based on convolution and the Central Limit Theorem are made to justify the use of functions that are intermediate between pure Gaussians and pure Lorentzians in XPS peak fitting. Mathematical forms for the GLS and GLP functions are presented with a mixing parameter m. Plots are shown for GLS and GLP functions with mixing parameters ranging from 0 to 1. There are fundamental differences between the GLS and GLP functions. The GLS function better follows the ‘wings’ of the Lorentzian, while these ‘wings’ are suppressed in the GLP. That is, these two functions are not interchangeable. The GLS and GLP functions are compared to the Voigt function, where the GLS is shown to be a decent approximation of it. Practically, both the GLS and the GLP functions can be useful for XPS peak fitting. Examples of the uses of these functions are provided herein.

XPSSurfA: An open collaborative XPS data repository using the CMSShub platform

X‐ray photoelectron spectroscopy (XPS) is a widely used surface analysis technique employed in fundamental research, applied research, service laboratories, and industry. Good‐quality analytical outcomes depend critically on spectral references. Many examples of XPS reference databases exist, including print editions, sets of spectral peak positions drawn from the literature, and digital archives and libraries. We report the development of a new digital XPS database comprising survey spectra and region spectra for a range of materials types, collected under a common set of analytical conditions. Each material is described using spectra collected at multiple pass energies with all photoelectron and X‐ray induced Auger transitions represented. Detailed metadata are provided for each material and each spectrum, presented using a schema that incorporates the ISO 16243 and 14976 standards and extensions developed in this work. Spectra are shared under a Creative Commons International (4.0) attribution, non‐commercial licence (CC BY‐NC) in Kratos (.dset), VAMAS (.vms), and XML (.xml) formats. It is intended that reference spectra be imported directly into XPS data analysis software packages for reference and comparison purposes, matching either the peak or transition of interest and the instrument pass energy. The database is flexible and scalable in structure and has the potential to become a core XPS reference resource.

Minimizing Light-Induced Degradation of the Al2O3 Rear Passivation Layer for Highly Efficient PERC Solar Cells

Commercializing a highly efficient passivated-emitter-and-rear-cell solar cell requires high passivation quality and stability of the cell's Al2O3 layer. This paper reports on light-induced degradation (LID) of the Al2O3 layer and the effects of post-annealing temperatures after light soaking on the passivation quality. To understand the LID phenomenon of the Al2O3 passivation layer, we used a Ga-doped Si wafer that prevented boron-oxygen LID effects. The fabrication process was carried out on large-area (156 × 156 mm2), commercially available, (100)-oriented Ga-doped Czochralski(Cz) Si wafers in the pilot line. Before and after light soaking, the effective lifetime was measured using Sinton's quasi-steady-state photoconductance as a function of annealing temperature. Chemical binding structures near the interface of the Al2O3 film and Si wafer were investigated using X-ray photoelectron spectroscopy (XPS). The passivation quality and light-induced degradation showed the best performance at an annealing temperature of 600°C. Analysis of XPS data revealed that the chemical binding structures at the interface of the Al2O3 layer and Si wafer were stabilized by optimizing the annealing condition of the Al2O3 layer. By optimizing an industrially feasible Al2O3 passivation process, an efficiency of 20.1% was achieved on large-area, commercial-grade Cz c-Si wafers.

Fe-doping effects on the structural, vibrational, magnetic, and electronic properties of ceria nanoparticles

In this work, we report on a single-pot synthesis route based on a polymeric precursor method used for successfully producing undoped and iron-doped CeO2 nanoparticles with iron contents up to 10.0 mol. %. The formation of high-crystalline nanoparticles with a cubic fluorite structure is determined for all the studied samples. Meanwhile, the magnetic measurements of the undoped ceria nanoparticles revealed the occurrence of ferromagnetism of bound magnetic polarons of a fraction of Ce3+ at room temperature, and only a paramagnetic behavior of Fe3+ ions was determined for Fe-doped ceria nanoparticles. A monotonous reduction of the effective magnetic moment of the Fe3+ ions was determined. It suggests a change from a high-spin to low-spin state of Fe ions as the Fe content is increased. The 3+ valence state of the iron ions has been confirmed by the Fe K-edge X-ray absorption near-edge structure (XANES) and Mössbauer spectroscopy measurements. X-ray photoelectron spectroscopy data analysis evidenced a coexistence of Ce3+ and Ce4+ ions and a decreasing tendency of the relative fraction of Ce3+ ions in the surface region of the particles as the iron content is increased. Although the coexistence of Ce3+ and Ce4+ is confirmed by results obtained via Ce L3-edge XANES measurements, any clear dependence of the relative relation of Ce3+ ions on the iron content is determined, suggesting a homogeneous distribution of Ce3+ and Ce4+-ions in the whole volume of the particles. Ce L3-edge extended X-ray absorption fine structure revealed that the Ce-O bond distance shows a monotonous decrease as the Fe content is increased, which is in good agreement with the shrinking of the unit cell volume with the iron content determined from XRD data analysis, reinforcing the substitutional solution of Ce and Fe ions in the CeO2 matrix.

Determination of the impact of Bi content on the valence band energy of GaAsBi using x-ray photoelectron spectroscopy

We investigate the change of the valence band energy of GaAs1-xBix (0<x<0.025) as a function of dilute bismuth (Bi) concentration, x, using x-ray photoelectron spectroscopy (XPS). The change in the valence band energy per addition of 1 % Bi is determined for strained and unstrained thin films using a linear approximation applicable to the dilute regime. Spectroscopic ellipsometry (SE) was used as a complementary technique to determine the change in GaAsBi bandgap resulting from Bi addition. Analysis of SE and XPS data together supports the conclusion that ∼75% of the reduction in the bandgap is in the valence band for a compressively strained, dilute GaAsBi thin film at room temperature.

Quantitative determination of ligand densities on nanomaterials by X-ray photoelectron spectroscopy.

X-ray photoelectron spectroscopy (XPS) is a nearly universal method for quantitative characterization of both organic and inorganic layers on surfaces. When applied to nanoparticles, the analysis is complicated by the strong curvature of the surface and by the fact that the electron attenuation length can be comparable to the diameter of the nanoparticles, making it necessary to explicitly include the shape of the nanoparticle to achieve quantitative analysis. We describe a combined experimental and computational analysis of XPS data for molecular ligands on gold nanoparticles. The analysis includes scattering in both Au core and organic shells and is valid even for nanoparticles having diameters comparable to the electron attenuation length (EAL). To test this model, we show experimentally how varying particle diameter from 1.3 to 6.3 nm leads to a change in the measured AC/AAu peak area ratio, changing by a factor of 15. By analyzing the data in a simple computational model, we demonstrate that ligand densities can be obtained, and, moreover, that the actual ligand densities for these nanoparticles are a constant value of 3.9 ± 0.2 molecules nm(-2). This model can be easily extended to a wide range of core-shell nanoparticles, providing a simple pathway to extend XPS quantitative analysis to a broader range of nanomaterials.