X-ray Photoemission Spectroscopy Research Articles

2D Vanadium Sulfides: Synthesis, Atomic Structure Engineering, and Charge Density Waves.

Two ultimately thin vanadium-rich 2D materials based on VS2 are created via molecular beam epitaxy and investigated using scanning tunneling microscopy, X-ray photoemission spectroscopy, and density functional theory (DFT) calculations. The controlled synthesis of stoichiometric single-layer VS2 or either of the two vanadium-rich materials is achieved by varying the sample coverage and sulfur pressure during annealing. Through annealing of small stoichiometric single-layer VS2 islands without S pressure, S-vacancies spontaneously order in 1D arrays, giving rise to patterned adsorption. Via the comparison of DFT calculations with scanning tunneling microscopy data, the atomic structure of the S-depleted phase, with a stoichiometry of V4S7, is determined. By depositing larger amounts of vanadium and sulfur, which are subsequently annealed in a S-rich atmosphere, self-intercalated ultimately thin V5S8-derived layers are obtained, which host 2 × 2 V-layers between sheets of VS2. We provide atomic models for the thinnest V5S8-derived structures. Finally, we use scanning tunneling spectroscopy to investigate the charge density wave observed in the 2D V5S8-derived islands.

Spectroscopic investigations on trivalent ruthenium ions in ruthenium perovskite oxide thin films

The d5 electron configurations under the crystal field, spin–orbit coupling, and Coulomb interaction give rise to a plethora of profound ground states. Ruthenium perovskite oxides exhibit a number of unconventional properties yet the Ru4+ state (4d4) is usually stable in these materials. In this regard, Ru3+ ions in perovskite materials are expected to be a mesmerizing playground of 4d5 electron configurations. Here, we report measurements of x-ray photoemission spectroscopy on recently synthesized perovskite ruthenium oxide thin films, LaRuO3 and NdRuO3, whose valence state of the ruthenium ions is trivalent. We discuss correlation and spin–orbit effects from the valence band spectra, in particular an additional peak structure around 3–5 eV, reminiscent of the so-called 3 eV peak observed in Sr2RuO4. Moreover, we find that the core-level spectra of these materials are quantitatively different from those in other ruthenates, which possess Ru4+ ions, e.g., SrRuO3. We therefore argue that the core level spectra of LaRuO3 and NdRuO3 are peculiar to the Ru3+ states.

Reliable unencapsulated Ag/Ag2S micro-reference electrodes for battery research and other applications in organic media

Reliable electrochemical measurements depend on the availability of robust reference electrodes (RE) with well-defined potentials. While many reliable REs are known, they are not applicable in certain demanding media such as ionic liquids, nor in small confined spaces. Here, we describe the fabrication of a simple yet robust Ag/Ag2S micro-reference electrode (μ-RE) where a micron-thick Ag2S layer is formed by isothermal reaction with sulfur vapor. Scanning electron microscopy, X-ray photoemission spectroscopy, and spectroscopic ellipsometry characterization reveals that the optimal morphology corresponds to a slightly porous Ag2S film. We demonstrate that the Ag/Ag2S μ-RE can be operated in and cycled through a wide variety of polar organic solvents, including common protic solvents (EtOH), aprotic solvents (ACN, DMSO, NMP, DMF) and ionic liquids (EMIM-TFSI, BMP-TFSI), with short equilibration time (tens of seconds) and little drift (<20 mV), without requiring encapsulation, protective liquid junctions, nor special conditioning. A redox potential of 0.54 ± 0.02 V was obtained for ferrocene in acetonitrile, which places this RE at 0.08 V vs Ag/AgCl. We have also successfully embedded the electrode inside the CR2032 coin cell to perform cyclic voltammetry of battery materials. These results underpin the suitability of this simple micro-reference electrode for a wide variety of electrochemical measurements in demanding and/or miniaturized environments.

Direct Work Function Measurement Using In-situ APXPS and Its Application on Copper Oxidation Process.

The work function (WF) measurement plays a critical role in engineering energy materials and energy devices. However, the ultra-high vacuum (UHV) environments of photoemission method limit the practical application for absolute work function measurements of materials, especially under complex working conditions. To understand the energy level of materials under complex chemical environments, the in-situ measurements of work function is necessary in complex metal/semiconductor system for various application. In this paper, we describe the utilization of ambient pressure X-ray photoemission spectroscopy (APXPS) with utilization of low photon energy X-ray for absolute WF measurements at BL02B of the Shanghai Synchrotron Radiation Facility. We herein present the WF measurement during oxygen adsorption on Pt(111) and oxidation of Cu(111) in ambient oxygen environment as demonstration of the APXPS capability for WF measurement. After oxygen chemisorption on Pt and formation of Cu2O, the WF will increase. This is due to charge transfer from metal to chemisorbed oxygen atoms. After the formation of bulk Cu2O and CuO, the WF value almost remain at ~5.5 eV. We believe the direct measurement of absolute work function via APXPS could help bridge the gap between the physical properties and the surface chemical species for metal/semiconductor materials.

Exploring the Mineral Composition, Structure, and Function of a Freshwater Bivalve Adhesive

AbstractEtheria elliptica is a freshwater oyster that produces an adhesive that hardens underwater, allowing them to attach to other oysters, rocks, wood, and other natural substrates, producing complex oyster bed communities. Despite the importance of the adhesive in oyster bed formation, little is known about its chemical composition, structure, or mechanical properties. Through a combination of scanning electron microscopy (SEM), x‐ray photoemission electron microscopy (X‐PEEM), infrared (IR) spectroscopy, microhardness testing, and nanoindentation, it is found that the oyster adhesive consists entirely of aragonite nanoparticles that clump together into crystallites of varied shape, size, and orientation. The crystallite clumping density varies from the exterior of the adhesive to the interior, with the adhesive closest to the prismatic layer generally being denser. With this variation in density comes a variation in material properties with the exterior adhesive layer being softer and more flexible and the interior adhesive layer being harder and less elastic, or more similar to the prismatic and nacre shell structures produced by the E. elliptica. The resultant material exhibits varied materials properties, despite similar mineral composition.

Overcoming poisoning issues in hydrogen fuel cells with face-centered tetragonal FePt bimetallic catalysts

Hydrogen fuel cells are expected to play a central role in the next-generation energy paradigm. However, owing to practical limitations, hydrogen is supplied in the form of refined hydrocarbons or alcohols in industrial applications. Among them, methanol is widely used as a hydrogen source, and CO is inevitably generated during its oxidation process. Even a small amount of CO (∼20 ppm) strongly binds to Pt used as a catalyst, and deactivates it. In addition to CO, surface adsorption of organic cations by binder or ionomer use in alkaline fuel cells is also one of the poisoning issues to be overcome. Herein, we propose FePt bimetallic catalysts that can resist unavoidable CO and organic cation poisoning. Our synthetic strategy, including annealing and acid treatment, allows the catalysts to possess different alloying degrees and surface structures, which in turn induce different levels of resistance to CO and organic-cation poisonings. The correlation between the surface and bulk structures of the catalysts and poisoning resistance was elucidated through X-ray photoemission spectroscopy and electrochemical analysis. The results revealed that an FePt catalyst having an ordered atomic arrangement displayed a better poisoning resistance than that having a disordered arrangement.

Palladium enhanced electrochemical supercapacitive performance of Chromium oxide thin films synthesized by sputtering process

Recently, the use of transition metal oxide electrodes for supercapacitor applications has increased due to the possibility of variable mixed valence states. The present study has established the use of Pd-Cr2O3 composite thin films as a working electrode for high-performance supercapacitors. The reactive dc magnetron co-sputtering method has been used for the fabrication of thin film of Cr2O3 and Pd-Cr2O3 on SS-304 substrate. X-ray diffraction and X-ray photoemission spectroscopy techniques were used to examine the surface chemistry and phase purity of chromium oxide and Pd-Cr2O3 composite thin films. The incorporation of Pd in Cr2O3 delivers a drastic change in the surface morphology. Due to the modified morphology and electronic properties, a noticeable improvement in the electrochemical properties of Pd-Cr2O3 electrode is observed. The obtained value of specific capacitance for this electrode is 401 Fg−1 at 0.1 mAcm−2 scan rate and within the potential window range 0 to +1.2 V. This value of specific capacitance is almost twice in comparison to the Cr2O3 based electrode. The Pd-Cr2O3 composite thin film shows a good cycle retention capability of 8000 cycles with 87.5% retention. The obtained value of energy density and power density for Pd-Cr2O3 electrode was 80.2 Whkg−1 and 3.23 kWkg−1, respectively at 0.1 mAcm−2. Consequently, this composite material electrode can be seen as a promising advancement for electrodes in supercapacitor devices.

Impact of annealing on the resistance of Li3PO4 electrolyte–LiNi0.5Mn1.5O4 electrode interfaces

The operation of solid-state Li batteries, which are promising power supplies for portable electronic devices and electric vehicles, is accompanied by heating. Therefore, investigating the thermal stability of battery systems is essential. In this study, we report the impact of annealing on the interface of a Li3PO4 electrolyte and LiNi0.5Mn1.5O4 electrode in thin-film batteries. The batteries with the interface annealed at 200 °C show low Li3PO4–LiNi0.5Mn1.5O4 interface resistance of 7.2 Ω cm2. Furthermore, the batteries exhibit stable charge–discharge characteristics with high current density up to 1170 μA cm−2, similar to those of batteries with the non-annealing interface. The batteries with the interface annealed at 450 °C show high Li3PO4–LiNi0.5Mn1.5O4 interface resistance of 490 Ω cm2, resulting in low battery performance. X-ray photoemission spectroscopy indicates that the P in Li3PO4 is reduced by high-temperature annealing, possibly causing the performance degradation of batteries. This study provides an in-depth understanding of the interfaces of solid-state batteries and is expected to facilitate the development of thermally stable batteries.

Multiple magnetic transition and magnetocaloric properties in the mixed valence Eu8CuNi2.5Si42.5 type I clathrate compound

We investigated the magnetocaloric and electrical transport properties of the Eu8CuNi2.5Si42.5 clathrate compound, synthesized by an arc melting and annealing method. X-ray photoemission spectroscopy revealed a mixed valence state of Eu2+ and Eu3+. The low-field and low-temperature magnetic measurements indicated a multiple magnetic transition, from ferromagnetic near 35 K to antiferromagnetic at 25 K. Increasing the magnetic field led to the broadening of antiferromagnetic peaks and a final ferromagnetic state under high magnetic fields, indicative of spin reorientation. The transition from a ferromagnetic to an antiferromagnetic state was further corroborated by specific heat measurements. We noted spontaneous magnetization at low temperatures via magnetic hysteresis and Arrott plot analysis. The coexistence of an antiferromagnetic ground state (attributed to the Eu2+ ions) and ferromagnetic clusters (associated with the Ni2+ ions) was supported by spontaneous magnetization at low temperatures in the antiferromagnetic state. The magnetocaloric analyses revealed a high spin entropy change over a broad temperature range for Eu8CuNi2.5Si42.5, which implies its potential as a robust low-temperature magnetocaloric material, distinguished by its high refrigerant capacity.

Electronic structures of skyrmionic polycrystalline MnSi thin film studied by resonance photoemission and x-ray near edge spectroscopy

Magnetic nanometric skyrmions are small complex vortex-like topological defects, mainly found in non-centrosymmetric crystals such as MnSi. They have potential applications for future spintronic devices. In this article, the structural, electronic, and magnetic states of the Mn atoms in a polycrystalline MnSi thin film facing a c-sapphire substrate were studied using x-ray diffraction, x-ray photo-emission spectroscopy, resonance photoemission spectroscopy (RPES), and extended x-ray absorption fine structure (EXAFS). The valence band spectra indicate the metallic nature of the film. The RPES study reveals the presence of major itinerant Mn 3d states near EF and also the mixed Mn 3d and Si 3s–3p states from 5.3 to 11.3 eV. The EXAFS spectrum does not show the existence of oxygen vacancies in the system, and the obtained magnetic moment in the non-stoichiometric MnSi thin film is a combination of the partially itinerant and partially localized Mn 3d states.

Pristine and UV-Weathered PET Microplastics as Water Contaminants: Appraising the Potential of the Fenton Process for Effective Remediation

Polyethylene terephthalate (PET) microplastics constitute a significant portion of plastic pollution in the environment and pose substantial environmental challenges. In this study, the effectiveness of the Fenton process and post-oxidation coagulation for the removal of non-weathered and UV-weathered PET microplastics (PET MPs) were investigated. A response surface methodology was used to investigate the interplay between PET concentration and ferrous ion (Fe2+) concentration. The models revealed an intricate interplay between these variables, highlighting the need for a balanced system for optimal PET MP removal. For non-weathered PET, the simultaneous increase in the concentrations of both PET microplastics and Fe2+ was found to enhance the removal efficiency. However, this synergistic effect was not observed in UV-weathered PET, which also demonstrated a more pronounced effect from the Fe2+ concentration. The statistical analysis provided a strong basis for the validity of the models. X-ray photoemission spectroscopy (XPS) further elucidated the mechanisms behind these findings, revealing that UV weathering results in surface changes, which facilitate hydroxyl radical oxidation. These findings underline the complexity of the Fenton process in PET microplastic removal and the different behavior of non-weathered and UV-weathered microplastics. This has significant implications for tailoring remediation strategies and underscores the importance of considering environmental weathering in these strategies.

The fate of graphene on copper: Intercalation / de-intercalation processes and the role of silicon

Intercalation and de-intercalation processes below graphene (g) grown by chemical vapor deposition (CVD) on Cu foils (g/Cu) were investigated in a combined low-energy electron microscopy and X-ray photoemission electron microscopy study. Exposure of g/Cu to air induces oxygen and water intercalation which can be removed by annealing in vacuum leading to clean and well-ordered graphene on Cu. However, prolonged air exposure leads to intercalation of large amounts of oxygen, most likely inducing the formation of copper oxides. If sufficient intercalated oxygen remains at the interface when exceeding 320 °C, graphene is oxidized and burned off. Cu foils can be loaded with silicon on purpose during foil pre-treatment or accidently during long growth time when applying high temperatures at elevated H2 pressure inducing the reactive removal of Si species from the quartz reactor wall. Due to the dissolution of Si in the Cu bulk, the Si surface concentration remains below detection limit and graphene of equal crystalline quality is grown as if the Cu foil was silicon-free. However, oxygen intercalation underneath graphene on Si-containing Cu foils can induce Si segregation towards the surface and formation of intercalated silica without attacking the covering graphene. Even at high temperatures, segregating Si acts as oxygen scavenger so that graphene resists oxidation. The observed effect explains the usefulness of certain synthesis protocols and paves the way towards large-scale fabrication of electronically decoupled graphene. The effect can be used to immobilize adsorbing oxygen at the interface and image the initial steps of intercalation below graphene in-situ.

Enhanced Hemocompatibility and Cytocompatibility of Stainless Steel.

The present study introduces an advanced surface modification approach combining electrochemical anodization and non-thermal plasma treatment, tailored for biomedical applications on stainless steel grade 316L (SS316L) surfaces. Nanopores with various diameters (100-300 nm) were synthesized with electrochemical anodization, and samples were further modified with non-thermal oxygen plasma. The surface properties of SS316L surfaces were examined by scanning electron microscopy, atomic force microscopy, X-ray photoemission spectroscopy, and Water contact angle measurements. It has been shown that a combination of electrochemical anodization and plasma treatment significantly alters the surface properties of SS316L and affects its interactions with blood platelets and human coronary cells. Optimal performance is attained on the anodized specimen featuring pores within the 150-300 nm diameter range, subjected to subsequent oxygen plasma treatment; the absence of platelet adhesion was observed. At the same time, the sample demonstrated good endothelialization and a reduction in smooth muscle cell adhesion compared to the untreated SS316L and the sample with smaller pores (100-150 nm). This novel surface modification strategy has significant implications for improving biocompatibility and performance of SS316L in biomedical applications.

Valence band spectra and doping based alterations in band gap and electric modulus of Nd2NiMnO6

Here in this paper, extending our earlier study, we have investigated the electrical properties of Sr doped Nd2NiMnO6 through the study of electric modulus. Nd2NiMnO6 has been doped with Sr by replacing Nd and the doping has not induced any new phase as all the samples of Nd2-xSrxNiMnO6 (x = 0.0, 0.1, 0.3) show monoclinic phase. Valence band spectra have been determined through x-ray photoemission spectroscopy and the absence of spectral density at Fermi energy EF for all the three samples indicates the insulating behavior with the sample having doping concentration x = 0.1 being the highly insulating of all the samples. Modulus study has been carried out in order to investigate more about the electrical properties by studying the dependence of real and imaginary part of modulus on frequency and temperature. The variation of real and imaginary part of electric modulus with the concentration of dopant has also been observed. The modulus study reveals the relaxation phenomenon in all the three samples. Further, we have determined the band gap of three samples through UV-Visible spectroscopy and the variation in the value of band gap with changing concentration of dopant Sr is in accordance with the conductivity plots already discussed in our earlier studies.

Light-Induced Increase of the Local Molecular Coverage on a Surface.

Light is a versatile tool to remotely activate molecules adsorbed on a surface, for example, to trigger their polymerization. Here, we explore the spatial distribution of light-induced chemical reactions on a Au(111) surface. Specifically, the covalent on-surface polymerization of an anthracene derivative in the submonolayer coverage range is studied. Using scanning tunneling microscopy and X-ray photoemission spectroscopy, we observe a substantial increase of the local molecular coverage with the sample illumination time at the center of the laser spot. We find that the interplay between thermally induced diffusion and the reduced mobility of reaction products steers the accumulation of material. Moreover, the debromination of the adsorbed species never progresses to completion within the experiment time, despite a long irradiation of many hours.

Unveiling nano-scale chemical inhomogeneity in surface oxide films formed on V- and N-containing martensite stainless steel by synchrotron X-ray photoelectron emission spectroscopy/microscopy and microscopic X-ray absorption spectroscopy

Nano-scale chemical inhomogeneity in surface oxide films formed on a V- and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron- based hard X-ray Photoelectron emission spectroscopy (HAXPES) and microscopy (HAXPEEM) as well as microscopic X-ray absorption spectroscopy (m-XAS) techniques. The results reveal the inhomogeneity in the oxide films on the micron-sized Cr2N- and VN-type particles, while the inhomogeneity on the martensite matrix phase exists due to localised formation of nano-sized tempering nitride particles at 600 °C. The oxide film formed on Cr2N-type particles is rich in Cr2O3 compared with that on the martensite matrix and VN-type particles. With the increase of tempering temperature, Cr2O3 formation is faster for the oxidation of Cr in the martensite matrix than the oxidation of Cr nitride-rich particles.

Accelerating X-ray photoemission spectroscopy measurements using Bayesian super-resolution

This study applies Bayesian super-resolution to X-ray photoelectron spectroscopy (XPS), achieving up to a 20-fold reduction in measurement time while preserving data quality. Traditional XPS, crucial for surface analysis, typically requires extensive measurement durations. Our methodology significantly accelerates the process, as demonstrated with glass and Polytetrafluoroethylene samples, where we reduced measurement times by up to 1/20th without compromising spectral accuracy. This approach decreases noise levels and retains spectral integrity, offering a highly efficient solution for XPS. This innovation is particularly valuable in material science, enabling rapid, reliable surface analysis.

Magnetoelastic Coupling Evidence by Anisotropic Crossed Thermal Expansion in Magnetocaloric RSrCoFeO6 (R = Sm, Eu) Double Perovskites.

Double perovskite oxides, characterized by their tunable magnetic properties and robust interconnection between the lattice and magnetic degrees of freedom, present an enticing foundation for advanced magnetic refrigeration materials. Herein, we delve into the influence of rare-earth elements on RSrCoFeO6 (R = Sm, Eu) disordered double perovskites by examining their structural, electronic, magnetic, and magnetocaloric properties. Temperature-dependent synchrotron X-ray diffraction analysis confirmed the stability of the orthorhombic phase (Pnma) across a wide temperature range. X-ray photoemission spectroscopy revealed that both Sm and Eu are in the 3+ state, whereas multiple states for Co2+/3+ and Fe3+/4+ are identified. The magnetic investigation and magnetocaloric effect (MCE) analysis brought to light the presence of a long-range antiferromagnetic (AFM) order with a second-order phase transition (SOPT) in both samples. The maximum magnetic entropy change ΔSMmax was approximately 0.9 J/kg K for both samples at applied field 0-7 T, manifesting prominently above Neel temperatures TN ≈ 93 K (Sm) and 84 K (Eu). Nevertheless, different relative cooling powers (RCP) of 112.6 J/kg (Sm) and 95.5 J/kg (Eu) were observed. A detailed analysis of the temperature-dependent lattice parameters shed light on a distinct magnetocaloric effect across the magnetic transition temperature, unveiling an anisotropic thermal expansion [αV = 1.41 × 10-5 K-1 (Sm) and αV = 1.54 × 10-5 K-1 (Eu)] wherein the thermal expansion axial ratio αbSm/αbEu = 0.61 became lower with increasing temperature, which suggests that the Eu sample experiences a greater thermal expansion in the b-axis direction. At the atomic bonding level, the evidence for magnetoelastic coupling around the magnetic transition temperatures TN was found through the anomalies along the average Co/Fe-O bond distance, formal valence, octahedral distortion, as well as an anisotropic lattice expansion.

Efficient prediction of attosecond two-colour pulses from an X-ray free-electron laser with machine learning

X-ray free-electron lasers are sources of coherent, high-intensity X-rays with numerous applications in ultra-fast measurements and dynamic structural imaging. Due to the stochastic nature of the self-amplified spontaneous emission process and the difficulty in controlling injection of electrons, output pulses exhibit significant noise and limited temporal coherence. Standard measurement techniques used for characterizing two-coloured X-ray pulses are challenging, as they are either invasive or diagnostically expensive. In this work, we employ machine learning methods such as neural networks and decision trees to predict the central photon energies of pairs of attosecond fundamental and second harmonic pulses using parameters that are easily recorded at the high-repetition rate of a single shot. Using real experimental data, we apply a detailed feature analysis on the input parameters while optimizing the training time of the machine learning methods. Our predictive models are able to make predictions of central photon energy for one of the pulses without measuring the other pulse, thereby leveraging the use of the spectrometer without having to extend its detection window. We anticipate applications in X-ray spectroscopy using XFELs, such as in time-resolved X-ray absorption and photoemission spectroscopy, where improved measurement of input spectra will lead to better experimental outcomes.

The Effect of Sputtering Target Density on the Crystal and Electronic Structure of Epitaxial BaTiO3 Thin Films

Barium titanate (BaTiO3) is a promising material for silicon-integrated photonics due to its large electro-optical coefficients, low loss, high refractive index, and fast response speed. Several deposition methods have been employed to synthesize BaTiO3 films. Magnetron sputtering is one of these methods, which offers specific advantages for growing large-scale films. However, there is a scarcity of studies investigating the effect of sputtering target density on the quality of BaTiO3 films. Therefore, this study aims to uncover the effect of sputtering targets on the crystal and electronic structures of epitaxial BaTiO3 thin films. Two BaTiO3 ceramic targets were sintered at different densities by altering the sintering temperatures. The crystal structure and chemical composition of the targets were then characterized using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy with energy-dispersive X-ray spectroscopy. Subsequently, BaTiO3 epitaxial films were grown by magnetron sputtering using these two targets. The crystal and electronic structures of the BaTiO3 films were analyzed using high-resolution X-ray diffraction, X-ray photoemission spectroscopy, atomic force microscopy, and spectroscopic ellipsometry. Notably, the BaTiO3 films grown with high-density targets show superior quality but contain oxygen vacancies, whereas those films synthesized with low-density targets display high surface roughness. These findings provide insights into the effect of sputtering target density on the crystal and electronic structures of epitaxial BaTiO3 thin films.