Angle-resolved X-ray Photoelectron Spectroscopy Research Articles

Angle-resolved X-ray photoelectron spectroscopy intensity modeling of SiNx ultrathin layer grown on Si (100) and Si (111) substrates by N2 plasma treatment

In this work, we investigate the silicon nitridation process using a N2 plasma Glow Discharge Source (GDS) in an ultra-high vacuum chamber. In situ Angle Resolved X-ray Photoelectron Spectroscopy (ARXPS) measurements were performed to determine various chemical environments of the surface species. The main goals of this study are determination of the film chemical composition, to estimate its thickness and identify various phenomena taking place during the nitridation process under different experimental conditions. To achieve these objectives, we developed an ARXPS intensity model for an ultrathin SiNx overlayer. Based on the ARXPS results, which indicate that the silicon nitride film is not homogenous, we adopted a bi-layer model composed of two SixNyOz layers with varying thickness and chemical composition. The model is built from analysis of photoelectron intensities, considering a comparison between experimental and theoretical data. This bi-layer model revealed that the silicon nitride layer consists of a surface layer composed of approximately equal amounts of silicon and nitrogen (50% each), and an interfacial layer containing varying amounts of oxygen depending on experimental parameters. The presence of oxygen is due to residual air contamination in the vacuum chamber and/or to Si native oxide. The estimated thickness of silicon nitride film is less than 9 nm, depending on the nitridation time and temperature.The model developed in this work enabled us to study the effects of initial surface state (as received or chemically cleaned), Si substrate crystallographic orientation (such as (100) and (111)), and the nitridation temperature (room temperature and 500°C). The diffusing species (N+, N2+, O+), which play a crucial role during nitridation, were found to be influenced by temperature, treatment time, and substrate orientation. The diffusion phenomenon competed with other processes such as NO desorption, leading to a significant impact on formation of the SiNx film. Furthermore, we compared the thickness obtained from the ARXPS model using cross-sectional High-Resolution Transmission Electron Microscopy (HR-TEM) images. Additional Low-Energy Electron Diffraction (LEED) measurements indicated that the SiNx film was amorphous.

Investigations towards nanoscale precise polishing of Nb3Sn thin films for SRF applications

The superconducting radio frequency performance of Nb3Sn is significantly impacted by its near-surface composition and nanostructure. In this study, an innovative polishing technique for Nb3Sn thin films with nanoscale precision is proposed. Systematic angle-resolved X-ray photoelectron spectroscopy (ARXPS) analysis reveal that the mechanism of this polishing process involves the formation of a few nanometer-thick oxide layer on the film's surface, followed by the uniform removal of the oxide layers with HF rinse. It is approximated that the polishing depth achieved in a single cycle can reach several nanometers. Advanced material characterization demonstrates that optimized polishing process effectively eliminates compulsive tin droplets and potential tin-rich phases with poor superconductivity generated on the surface during the preparation of Nb3Sn thin films. Simultaneously, no additional impurity phase will be formed on the surface, and the surface roughness will remain undamaged. Meanwhile, the results of magnetic and electrical analysis show that the superconducting properties of the polished films are not affected. This polishing technique is anticipated to ease the stringent coating conditions for the preparation of high-performance Nb3Sn thin film superconducting cavity, and will be a valuable addition to the post-treatment process of Nb3Sn thin films.

Unlocking the Fluorine-Free Buoy Effect: Surface-Enriched Ruthenium Polypyridine Complexes in Ionic Liquids.

Controlling the local concentration of metal complexes at the surface of ionic liquids (ILs) is a highly sought-after objective due to its pivotal implications in supported ionic liquid phase (SILP) catalysis. Equally important is to avoid per- and polyfluorinated substances due to environmental concerns. Herein, we investigate the surface enrichment of Ru polypyridyl complexes with fluorine-free alkylic side groups of varying lengths and shapes, using the hydrophilic IL [C2C1Im][OAc] as solvent. Additional charged carboxylate groups are included into the polypyridyl ligands to increase the solubility of the complex in the IL. When the ligand system is functionalized with long and hydrophobic alkyl side chains, the complex predominantly localizes at the IL/vacuum interface, as deduced from angle-resolved X-ray photoelectron spectroscopy. Conversely, in the presence of short or more bulky substituents, no surface enrichment is observed. This buoy-like behaviour with fluorine-free side groups is explored for 0.05 %mol to 1 %mol solutions. Intriguingly, surface saturation occurs at approximately 0.5 %mol, which is beneficial to the efficient operation of catalytic systems featuring high surface areas, such as SILP catalysts.

Structure-Related Electronic and Magnetic Properties in Ultrathin Epitaxial NixFe3-xO4 Films on MgO(001).

Off-stoichiometric NixFe3-xO4 ultrathin films (x < 2.1) with varying Ni content x and thickness 16 (±2) nm were grown on MgO(001) by reactive molecular beam epitaxy. Synchrotron-based high-resolution X-ray diffraction measurements reveal vertical compressive strain for all films, resulting from a lateral pseudomorphic adaption of the film to the substrate lattice without any strain relaxation. Complete crystallinity with smooth interfaces and surfaces is obtained independent of the Ni content x. For x < 1 an expected successive conversion from Fe3O4 to NiFe2O4 is observed, whereas local transformation into NiO structures is observed for films with Ni content x > 1. However, angle-resolved hard X-ray photoelectron spectroscopy measurements indicate homogeneous cationic distributions without strictly separated phases independent of the Ni content, while X-ray absorption spectroscopy shows that also for x > 1, not all Fe2+ cations are substituted by Ni2+ cations. The ferrimagnetic behavior, as observed by superconducting quantum interference device magnetometry, is characterized by decreasing saturation magnetization due to the formation of antiferromagnetic NiO parts.

An interpretation for the components of 2p 3/2 core level x-ray photoelectron spectra of the cations in some inverse spinel oxides

In an effort to reconcile the various interpretations for the cation components of the 2p 3/2 observed in x-ray photoelectron spectroscopy (XPS) of several spinel oxide materials, the XPS spectra of both spinel alloy nanoparticles and crystalline thin films are compared. We observed that different components of the 2p 3/2 core level XPS spectra, of these inverse spinel thin films, are distinctly surface and bulk weighted, indicating surface-to-bulk core level shifts in the binding energies. Surface-to-bulk core level shifts in binding energies of Ni and Fe 2p 3/2 core levels of NiFe2O4 thin film are observed in angle-resolved XPS. The ratio between surface-weighted components and bulk-weighted components of the Ni and Fe core levels shows appreciable dependency on photoemission angle, with respect to surface normal. XPS showed that the ferrite nanoparticles Ni x Co1−x Fe2O4 (x = 0.2, 0.5, 0.8, 1) resemble the surface of the NiFe2O4 thin film. Surface-to-bulk core level shifts are also observed in CoFe2O4 and NiCo2O4 thin films but not as significantly as in NiFe2O4 thin film. Estimates of surface stoichiometry of some spinel oxide nanoparticles and thin films suggested that the apportionment between cationic species present could be farther from expectations for thin films as compared to what is seen with nanoparticles.

Effects of plasma oxidation and plasma nitridation on chemical bonding state of AlScN evaluated by AR-HAXPES

The effect of plasma treatment on AlScN films is investigated using angle-resolved hard X-ray photoelectron spectroscopy (HAXPES). As a result, it was observed that the ratio of the oxide component to the nitride component in the AlScN film increased with oxygen plasma treatment. It was also observed that AlScN was less susceptible to oxidation after 1 min of pre-nitridation. Furthermore, the inhibition of oxidation was more pronounced for Sc atoms than for Al atoms. These suggest that the nitridation treatment reduced the number of nitrogen vacancies around Sc atoms. These facts mean that the increase in the on/off ratio of the current in the MIM capacitor can be attributed to the decrease in the number of nitrogen vacancies in the AlScN.

XPS and ARXPS for Characterizing Multilayers of Silanes on Gold Surfaces

X-ray photoelectron spectroscopy (XPS) and angle-resolved XPS (ARXPS) characterization of surface layers resulting from the functionalization of polymers such as polyvinylchloride (PVC) modified with 3(mercaptopropyl)-trimethoxysilane (MPTMS) and (3-aminopropyl) triethoxysilane (APTES) is challenging due to the overlap in signals, deriving both from the substrate and the functionalized layers. In this work, a freshly cleaved, ideally flat gold surface was used as carbon-free model substrate functionalized with MPTMS and subsequently grafted with APTES. Avoiding the overlap of signals from carbon atoms present in the substrate, the signals in the C1s, O1s, Si2p, S2p and N1s high-resolution spectra could be assigned to the MPTMS/APTES functionalized layer only and the curve-fitting parameters could be determined. Quantitative analysis was in very good agreement with the expected stoichiometry of the functionalized layer, confirming the adopted curve-fitting procedure. In addition, it was found that one molecule of APTES grafted two MPTMS via silane groups. ARXPS allowed for determining the thickness of the functionalized layers: MPTMS thickness was found to be 0.5 (0.2) nm, whereas MPTMS + APTES thickness 1.0 (0.2) nm was in good agreement with Avogadro model calculations. This approach can be considered a powerful tool for characterizing functionalized surfaces of more complex systems by XPS.

Surface modification of food-grade PVC monitored by angle-resolved XPS

In this work the covalent functionalization of polyvinyl chloride (PVC) with (3-mercaptopropyl)trimethoxysilane (MPTMS) by nucleophilic substitution was investigated by X-ray photoelectron spectroscopy (XPS). The surface of food-grade PVC was characterized before and after treatment with ethanol and with 5% and 10% MPTMS solutions in ethanol. Special attention was paid to the determination of the chemistry, composition and thickness of the functionalized polymer surface by angle-resolved XPS (ARXPS). XPS analysis in standard mode and ARXPS spectra showed the presence of sulphur, silicon and oxygen from the MPTMS molecule. The quantitative analysis was in good agreement with the stoichiometry of the molecule. A small amount of chlorine, detected also at grazing angles, supported the formation of a layer, which resulted to be 2.2(0.2) nm thick including the hydrocarbon contamination usually detected by XPS on samples in contact with solutions. It is here demonstrated that XPS and ARXPS allow monitoring the surface functionalization and tune the conditions for achieving a good reproducibility during the functionalization of food-grade PVC by MPTMS. This is the starting point for further functionalization to obtain active food packaging with antimicrobial properties.

Oxide-Free SiC-SiC Direct Wafer Bonding and Its Characterization

There are different requirements for the production process and the final product of SiC-SiC wafer bonding. The manufacturing of devices that are sensitive to high temperature processing – due to broadened doping profiles and induced thermal stresses – requires room temperature bonding with high bond strength, while for electrical devices, it is mandatory that the bonding interface with a thin amorphous layer is oxide-free.[1] Reduced complexity of processes is also an important point for the final production. Hence, the goal of this work was to perform and characterize direct bonding of SiC-SiC without any added/deposited bonding layer. This type of bonded SiC wafers can be used for power electronics such as for the fabrication of traction inverter for automotive applications, DC/DC converter, on board charger or charging station.[2]For the wafer bonding processes standard 100 mm 4H SiC wafers were bonded with their Si-terminated faces in order to fabricate oxide-free bonds. The wafer bonding process was performed using the EVG ComBond® system: first the native oxides from both wafer surfaces were removed using an ion beam sputtering process, followed by the transfer of both wafers to the bonding process station operated in ultra-high vacuum (UHV) to significantly retard the oxidation process. Finally, the bonding process was performed at room temperature (RT).The goal of this study was to demonstrate the feasibility of the bonding process and to gain insight on the surface chemistry after activation. The investigations covered three areas: incoming inspection of the original wafer, characterization of activated single wafer and analysis of bonded wafer pairs. The focus was on compositional, chemical, mechanical and morphological analysis of the surfaces and of the bonded interfaces. In the case of single wafers, the focus of the incoming inspection was on whether the wafers fulfill the requirements of wafer bonding, and on the characterization of activated wafers to measure the surface modifications. Atomic force microscopy (AFM), white light interferometry (WLI) and spectroscopic ellipsometry (SE) were used to determine the surface roughness, the wafer topography and the surface layer structure, respectively. All three parameters are essential for successful RT SiC-SiC wafer bonding. The change of the surface chemistry was investigated by angle resolved x-ray photoelectron spectroscopy (AR-XPS). The quality of the bonded wafers and the bonding energy were verified using scanning acoustic microscopy (SAM) measurements (Fig. 1) as well as the Maszara blade test. Furthermore, cross-section transmission electron microscopy (X-TEM) showed a bonding interface with a thin amorphous layer and no noticeable additional oxygen containing layer (Fig. 2). In order to gain quantitative elemental distributions of oxygen and argon, energy dispersive x-ray spectroscopy (EDXS) was applied.The work reported is a demonstration of the capability of the different characterization methods regarding SiC-SiC wafer bonding. Future work will focus on the investigation of the bonded interface characteristics in the function of the bonding process parameters and the annealing conditions.[1] F. Mu, M. Fujino, T. Suga, Y. Takahashi, H. Nakazawa and K. Iguchi, "Wafer bonding of SiC-SiC and SiC-Si by modified surface activated bonding method" 2015 International Conference on Electronics Packaging and iMAPS All Asia Conference (ICEP-IAAC), Kyoto, Japan, 2015, pp. 542-545, doi: 10.1109/ICEP-IAAC.2015.7111073.[2] Tsunenobu Kimoto, "Material science and device physics in SiC technology for high-voltage power devices" Jpn. J. Appl. Phys. 54 040103 (2015), doi: 10.7567/JJAP.54.040103. Figure 1

(Invited) Proton Surface Exchange Kinetics and Stability of Thin-Film Triple Conducting Oxides for Protonic Ceramic Electrolysis Cells

Protonic ceramic electrolysis cells (PCECs) have been attracting attention due to their ability to operate in the intermediate temperature (300 - 500 ˚C) sweet-spot. These temperatures enable fast kinetics, inexpensive materials (no precious metals; stainless interconnects), and lower operating voltage for producing green hydrogen, without the accelerated degradation that may be observed at higher temperatures. The steam electrodes often support triple conduction and thereby host the proton exchange / oxygen evolution process at the surface, where steam is split. Steam electrode materials development is at a relatively early stage, with open questions around the relationships among bulk composition, evolving surface chemistry, kinetic quantities, and degradation mechanisms. We are investigating the proton exchange surface coefficient (k) and its evolution over time on model thin film electrodes in order to ultimately develop highly active and long-term stable steam electrodes for PCECs.ABO3 perovskites with Ba on the A-site and nominally multivalent ions on the B-site are candidates for steam electrodes given the varied compositions in this class that can transport oxide ions, protons, and electronic species, and the lowering of hydration enthalpies by the basicity introduced by Ba. However, very few measurements of k exist for these materials, and the evolution of surface chemistry and thus k is poorly understood.In this work, we fabricated and compared two perovskite triple conducting oxides by growing geometrically well-defined films of Ba(Pr,Y)O3-x (BPY) and Ba(Co,Fe,Zr,Y)O3-x (BCFZY) with pulsed laser deposition. We examined the proton surface exchange coefficients (k-values) using simultaneous in-situ optical transmission relaxation and electrical conductivity relaxation measurements upon switching pH2O at a temperature of 400 ˚C, and continued these switches as a function of time to assess stability. To our knowledge, this is the first use of an optical transmission method to probe elevated temperature steam splitting kinetics, and we interpret the optical (and electrical) changes as indicative of redox during the hydrogenation process. The k-values of BPY thin films were approximately ten times higher than those of the BCFZY thin films, and BPY also retained higher k-values over time. The bulk and surface chemical compositions of BPY and BCFZY thin films before and after relaxation measurements were compared using Rutherford backscattering spectrometry, angle-resolved X-ray photoelectron spectroscopy, and scanning transmission electron microscopy with spectroscopy. Pronounced Ba enrichment and Si contamination (from the quartz tube) were evident at the surface of BPY by both S/TEM-EDS and XPS, whereas for BCFZY these surface chemical features were only detectable by XPS and absent in S/TEM-EDS. Implications for materials design of steam electrodes will be discussed, considering efficiency and lifetime.

Functionalizing self-assembled monolayers to reduce interface scattering in ruthenium/dielectric for next-generation microelectronic interconnects

As the number of transistor increases in modern devices, the resistivity of metal lines increases with the downscaling of the vias dimension due to the increased in surface scattering of electrons. Herein, we evaluated the electrical performance and the adhesion strength of the Ru/SiO2 substrate upon functionalizing with benzyliminetriethoxysilane (BITES) and aminoproyltriethoxysilane (APTES) self-assembled monolayers (SAMs)s at the Ru/SiO2 interface. The covalent bonding and retention of the SAM film on the SiO2 surface were characterized via angle-resolved X-ray Photoelectron Spectroscopy (AR-XPS) and Time-of-Flight Secondary Ion Mass Spectrometry (Tof-SIMS), respectively. According to the Fuchs–Sondheimer (FS) model and scratch test, the specularity parameter and the adhesion strength of the Ru/BITES/SiO2 simultaneously improved after thermal annealing compared to the non-functionalized Ru/SiO2 substrate. The effect of different SAM’s terminal groups (amine and benzylimine) on the electron scattering behavior was investigated based on the formation of an interface dipole upon chemisorption of organic molecules on the metal film. Our results indicate that SAM with the benzylimine terminal group formed a larger positive dipole at the SAM layer of the Ru/BITES/SiO2 interface compared to the Ru/APTES/SiO2, leading to an increased in specular electron scattering events and, thus an enhanced electrical performance of the Ru/BITES/SiO2.

Understanding the Buoy Effect of Surface-Enriched Pt Complexes in Ionic Liquids: A combined ARXPS and Pendant Drop Study.

Recently, we demonstrated that Pt catalyst complexes dissolved in the ionic liquid (IL) [C4C1Im][PF6] can be deliberately enriched at the IL surface by introducing perfluorinated substituents, which act like buoys dragging the metal complex towards the surface. Herein, we extend our angle-resolved X-ray photoelectron spectroscopy (ARXPS) studies at complex concentrations between 30 and 5%mol down to 1%mol and present complementary surface tension pendant drop (PD) measurements under ultra clean vacuum conditions. This combination allows for connec-ting the microscopic information on the IL/gas interface from ARXPS with the macroscopic property surface tension. The surface enrichment of the Pt complexes is found to be most pronounced at 1%mol. It also displays a strong temperature dependence, which was not observed for 5%mol and above, where the surface is already saturated with the complex. The surface enrichment deduced from ARXPS is also reflected by the pronounced decrease in surface tension with increasing concentration of the catalyst. We furthermore observe by ARXPS and PD a much stronger surface affinity of the buoy-complex as compared to the free ligands in solution. Our results are highly interesting for an optimum design of ionic catalyst solutions contact areas with a surrounding reactant/product phase, such as in SILP catalysis.

Calcite Surfaces Modified with Carboxylic Acids (C2 to C18): Layer Organization, Wettability, Stability, and Molecular Structural Properties.

A fundamental understanding of the interactions between mineral surfaces and amphiphilic surface modification agents is needed for better control over the production and uses of mineral fillers. Here, we controlled the carboxylic acid layer formation conditions on calcite surfaces with high precision via vapor deposition. The properties of the resulting carboxylic acid layers were analyzed using surface-sensitive techniques, such as atomic force microscopy (AFM), contact angle measurements, angle resolved X-ray photoelectron spectroscopy (XPS), and vibrational sum-frequency spectroscopy. A low wettability was achieved with long hydrocarbon chain carboxylic acids such as stearic acid. The stearic acid layer formed by vapor deposition is initially patchy, but with increasing vapor exposure time, the patches grow and condense into a homogeneous layer with a thickness close to that expected for a monolayer as evaluated by AFM and XPS. The build-up process of the layer occurs more rapidly at higher temperatures due to the higher vapor pressure. The stability of the deposited fatty acid layer in the presence of a water droplet increases with the chain length and packing density in the adsorbed layer. Vibrational sum frequency spectroscopy data demonstrate that the stearic acid monolayers on calcite have their alkyl chains in an all-trans conformation and are anisotropically distributed on the plane of the surface, forming epitaxial monolayers. Vibrational spectra also show that the stearic acid molecules interact with the calcite surface through the carboxylic acid headgroup in both its protonated and deprotonated forms. The results presented provide new molecular insights into the properties of adsorbed carboxylic acid layers on calcite.

Angle resolved x-ray photoelectron spectroscopy assessment of the structure and composition of nanofilms—including uncertainties—through the multilayer model

The multilayer model (MLM) for assessing the structural and composition parameters of multilayered nanofilms from angle-resolved x-ray photoelectric spectroscopy is described in detail. It is compared with regularized back-transform (RBT) approaches such as the maximum entropy method (MEM) with Tikhonov-type regularizations. The advantages of MLM over MEM, such as the possibility of assessing confidence ranges, modeling structures beyond conformal multilayered nanofilms, and modeling abrupt interfaces, are discussed and exemplified. In contrast with MLM, the RBT methods have shortcomings such as the violation of the conservation of information and the inability to adequately address the dependence of the effective attenuation length on the material. Examples of the application of MLM to conformal films and systems with protrusions are shown. The covariance matrix method (CMM) is described and applied to assess uncertainties in structural parameters and composition under the MLM. The CMM constitutes the canonical method for assessing confidence ranges and adequately accounts for the covariance among structural (e.g., layer thicknesses) and composition parameters.

Investigation of Oxide Thickness on Technical Aluminium Alloys—A Comparison of Characterization Methods

In this study the oxide layer of technical 6xxx aluminium surfaces, pickled as well as passivated, were comparatively investigated by means of transmission electron microscopy (TEM), Auger electron and X-ray photoelectron spectroscopy (AES, XPS), the latter in two different operating modes, standard and angle resolved mode. In addition, confocal microscopy and focused ion beam cutting were used for structural studies of the surfaces and for specimen preparation. The results illustrate in detail the strengths and weaknesses of each measurement technique. TEM offers a direct way to reliably quantify the thickness of the oxide layer, which is in the range of 5 nm, however, on a laterally restricted area of the surface. In comparison, for AES, the destructiveness of the electron beam did not allow to achieve comparable results for the thickness determination. XPS was proven to be the most reliable method to reproducibly quantify the average oxide thickness. By evaluating the angle resolved XPS data, additional information on the average depth distribution of the individual elements on the surface could be obtained. The findings obtained in this study were then successfully used for the investigation of the increase in the aluminium oxide thickness on technical samples during an aging test of 12 months under standard storage conditions.

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.

Atomistic Understanding of the Formation, Structure, and Decomposition of an Fe4C Iron Carbide Phase on a Copper Substrate

Having an atomistic understanding of the formation and structural characteristics of bulk and surface iron carbide phases plays a crucial role in comprehending the mechanisms of phase transformation, microstructure formation, and surface reconstructions in the development of advanced materials with improved magnetic, mechanical, and catalytic properties. This study uses synchrotron (SR) and angle-resolved (AR) XPS, STM, LEED, and theoretical calculations (DFT) with the aim to provide a detailed experimental and theoretical discussion on the formation, stabilization, structure, and decomposition of Fe4C iron carbide. FCC(100) Fe4C iron carbide multilayer films were prepared on Cu(100) by evaporating iron in the presence of an ethylene atmosphere. Angle-resolved XPS measurements reveal that surface and interior carbon can be distinguished due to their appearance at different binding energies and reveal that the surface consists of Fe2C while the bulk has Fe4C stoichiometry. LEED and STM measurements show that the surface exhibits the p4g(2 × 2) clock reconstruction. Theory simulations show that the bulk Fe4C iron carbide has a constrained crystal lattice with alternating Fe and Fe4C2 layers, which grow in a pseudomorphic way on the copper. The carbide phase is stable up to 700 K. Above this temperature, iron diffuses into the copper while carbon remains on the surface, where it forms graphite.

Surface analysis insight note: Straightforward concentration depth profiling by angle‐resolved X‐ray photoelectron spectroscopy using a Tikhonov regularization algorithm

Angle‐resolved X‐ray photoelectron spectroscopy (ARXPS) is a technique used for depth‐dependent analysis in the near‐surface region of samples. Calculation of a concentration depth profile using ARXPS requires an inverse Laplace transform, which adds considerable complexity to the analysis. In this insight note, the Tikhonov regularization algorithm for depth profile reconstruction from ARXPS data is examined. The steps required to produce a concentration depth profile are provided. The discussion includes strategies that deal with elastic scattering, electron attenuation, choice of regularization terms and optimization of the regularization parameters. The method is implemented in a Microsoft Excel spreadsheet that allows users to calculate a depth profile for data collected at up to five angles for five different peak components.

Structure and Surface Behavior of Rh Complexes in Ionic Liquids Studied Using Angle-Resolved X-ray Photoelectron Spectroscopy

We present an ARXPS study on the surface composition and interfacial behavior of commercial [Rh(COD)2][TfO] in [C2C1Im][TfO], [C4C1Im][TfO], [C8C1Im][TfO], and [C2C1Im][EtOSO3]. The complex was found to be non-intact in a solution of these ILs through the loss of COD ligands, accompanied by the depletion of the metal center from the IL/vacuum interface. Increasing the chain length of the aliphatic substituent on the imidazolium cation of the [TfO]−-based ILs led to a more pronounced depletion from the interface, due to the higher surface affinity of the solvent cations with the longer alkyl chains. The loss of COD ligands offered facile in situ ligand substitution with surface-active TPPTS to afford a moderate increase in the surface concentration of Rh. We propose the formation of a Schrock−Osborn-type catalyst [Rh(COD)(TPPTS)2][TfO]. Information on the surface composition and targeted design of the gas/IL interface is highly relevant for applications in IL-based catalytic systems, such as in supported ionic liquid phase (SILP) catalysis.

Surface Passivation of FAPbI3-Rich Perovskite with Cesium Iodide Outperforms Bulk Incorporation

Metal halide perovskites (MHPs) have shown an incredible increase in efficiency, reaching as high as 25.7%, which now competes with traditional photovoltaic technologies. Herein, we excluded CsX and RbX (X = I–, Br–, Cl–), the most commonly used cations to stabilize α-FAPbI3, from the bulk of perovskite thin films and applied them on the surface as passivation agents. Extensive device optimization led to a power conversion efficiency (PCE) of 24.1% with a high fill factor (FF) of 82.2% upon passivation with CsI. We investigated in depth the effect of CsI passivation on structural and optoelectronic properties using X-ray diffraction (XRD), angle-resolved X-ray photoelectron spectroscopy (ARXPS), Kelvin probe force microscopy (KPFM), time-resolved photoluminescence (TRPL), photoluminescence quantum yield (PLQY), and electroabsorption spectroscopy (TREAS). Furthermore, passivated devices exhibit enhanced operational stability, with optimized passivation with CsI leading to a retention of ∼90% of the initial PCE under 1 sun illumination with maximum power point tracking for 600 h.