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19,477 result(s) for "X ray photoelectron spectroscopy"
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Influence of the Morphology on the Functionalization of Graphene Nanoplatelets Analyzed by Comparative Photoelectron Spectroscopy with Soft and Hard X‐Rays
Since its isolation, graphene has received growing attention from academia and industry due to its unique properties. However, the “what is my material” barrier hinders further commercialization. X‐ray photoelectron spectroscopy (XPS) is considered as a method of choice for the determination of the elemental and chemical composition. In this work the influence of the morphology of graphene particles on the XPS results is studied and investigated as a function of X‐ray energy, using conventional XPS with Al Kα radiation and hard X‐ray photoemission spectroscopy (HAXPES) using Cr Kα radiation. Thereby, the information depth is varied between 10 and 30 nm. For this purpose, two commercial powders containing graphene nanoplatelets with lateral dimensions of either ≈100 nm or in the micrometer range are compared. These larger ones exist as stack of graphene layers which is inspected with scanning electron microscopy. Both kinds of particles are then functionalized with either oxygen or fluorine. The size of the graphene particles is found to influence the degree of functionalization. Only the combination of XPS and HAXPES allows to detect the functionalization at the outermost surface of the particles or even of the stacks and to provide new insights into the functionalization process. Functionalization is a crucial process for the application of graphene in composites or as sensors. Comparative hard and conventional X‐ray photoelectron spectra with different information depths provide new possibilities for quantifying and localizing the functional elements like oxygen or fluorine in graphitic particles which consists of small, rounded particles, or stack of flakes.
Pump-Probe X-ray Photoemission Spectroscopy of Free-Standing Graphane
Free-standing nanoporous graphene was hydrogenated at about 60 at.% H uptake, as determined by the emerging of the sp3 bonding component in the C 1s core level investigated by high-resolution X-ray photoelectron spectroscopy (XPS). Fully unsupported graphane was investigated by XPS under optical excitation at 2.4 eV. At a laser fluence of 1.6 mJ/cm2, a partial irreversible dehydrogenation of the graphane was observed, which could be attributed either to the local temperature increase or to a photo-induced softening of the H-to-C stretching mode. The sub-ns dynamics of the energy shift and peak broadening of the C 1s core level revealed two different decay constants: 210 ps and 130 ps, respectively, the former associated with photovoltage dynamics and the latter with thermal heating on a time scale comparable with the synchrotron temporal resolution.
Momentum‐Space Imaging of Ultra‐Thin Electron Liquids in δ‐Doped Silicon
Two‐dimensional dopant layers (δ‐layers) in semiconductors provide the high‐mobility electron liquids (2DELs) needed for nanoscale quantum‐electronic devices. Key parameters such as carrier densities, effective masses, and confinement thicknesses for 2DELs have traditionally been extracted from quantum magnetotransport. In principle, the parameters are immediately readable from the one‐electron spectral function that can be measured by angle‐resolved photoemission spectroscopy (ARPES). Here, buried 2DEL δ‐layers in silicon are measured with soft X‐ray (SX) ARPES to obtain detailed information about their filled conduction bands and extract device‐relevant properties. This study takes advantage of the larger probing depth and photon energy range of SX‐ARPES relative to vacuum ultraviolet (VUV) ARPES to accurately measure the δ‐layer electronic confinement. The measurements are made on ambient‐exposed samples and yield extremely thin (< 1 nm) and dense (≈10 14  cm −2 ) 2DELs. Critically, this method is used to show that δ‐layers of arsenic exhibit better electronic confinement than δ‐layers of phosphorus fabricated under identical conditions.
NiO as Hole Transporting Layer for Inverted Perovskite Solar Cells: A Study of X‐Ray Photoelectron Spectroscopy
Hygroscopic and acidic nature of organic hole transport layers (HTLs) insisted to replace it with metal oxide semiconductors due to their favorable charge carrier transport with long chemical stability. Apart from large direct bandgap and high optical transmittance, ionization energy in the range of −5.0 to −5.4 eV leads to use NiO as HTL due to good energetic matching with lead halide perovskites. Analyzing X‐ray photoelectron spectroscopic (XPS) data of NiO, it is speculated that p‐type conductivity is related to the NiOOH or Ni2O3 states in the structure and the electrical conductivity can be modified by altering the concentration of nickel or oxygen vacancies. However, it is difficult to separate the contribution from nonlocal screening, surface effect and the presence of vacancy induced Ni3+ ion due to very strong satellite structure in the Ni 2p XPS spectrum of NiO. Thus, an effective approach to analyze the NiO XPS spectrum is presented and the way to correlate the presence of Ni3+ with the conductivity results which will help to avoid overestimation in finding the oxygen‐rich/deficient conditions in NiO. The shoulder peak of Ni2p XPS spectrum is important to understand p‐type semiconducting behavior. Both the Ni 2p and O 1s XPS spectra shall be carefully recorded with fixed take‐off angle (and/or depending on take‐off angle) and compare results with transport measurements.
Beamline commissioning for microscopic measurements with ultraviolet and soft X‐ray beam at the upgraded beamline BL‐13B of the Photon Factory
Beamline 13 of the Photon Factory has been in operation since 2010 as a vacuum ultraviolet and soft X‐ray undulator beamline for X‐ray photoelectron spectroscopy (XPS), X‐ray absorption spectroscopy (XAS), and angle‐resolved photoelectron spectroscopy (ARPES) experiments. The beamline and the end‐station at branch B have been recently upgraded, enabling microscopic XPS, XAS, and ARPES measurements to be performed. In 2015, a planar undulator insertion device was replaced with an APPLE‐II (advanced planar polarized light emitter II) undulator. This replacement allows use of linear, circular, and elliptical polarized light between 48 and 2000 eV with photon intensities of 109–1013 photons s−1. For microscopic measurements, a toroidal post‐mirror was renewed to have more focused beam with profile sizes of 78 µm (horizontal) × 15 µm (vertical) and 84 µm × 11 µm at photon energies of 100 and 400 eV, respectively. A high‐precision sample manipulator composed of an XYZ translator, a rotary feedthrough, and a newly developed goniometer, which is essential for microscopic measurements, has been used to control a sample specimen in six degrees of freedom, i.e. translation in the X, Y, and Z directions and rotation in the polar, azimuthal, and tilt directions. To demonstrate the performance of the focused beams, one‐ and two‐dimensional XPS and XAS scan measurements of a copper grid have been performed. It was indicated from analysis of XPS and XAS intensity maps that the actual spatial resolution can be determined by the beam size. Beamline BL‐13B of the Photon Factory and the end‐station have been upgraded, enabling microscopic XPS, XAS, and ARPES measurements with a spatial resolution that is comparable with the size of the focused beam. Beam profile evaluation and experimental demonstration of microscopic measurements are presented.
Quantitative alignment parameter estimation for analyzing X‐ray photoelectron spectra
The interpretation of X‐ray photoelectron spectroscopy (XPS) data relies on measurement models that depend on several parameters, including the photoelectron attenuation length and X‐ray photon flux. However, some of these parameters are not known, because they are not or cannot be measured. The unknown geometrical parameters can be lumped together in a multiplicative factor, the alignment parameter. This parameter characterizes the ability of the exciting light to interact with the sample. Unfortunately, the absolute value of the alignment parameter cannot be measured directly, in part because it depends on the measurement model. Instead, a proxy for the experimental alignment is often estimated, which is closely related to the alignment parameter. Here, a method for estimating the absolute value of the alignment parameter based on the raw XPS spectra (i.e. non‐processed photoelectron counts), the geometry of the sample and the photoelectron attenuation length is presented. The proposed parameter estimation method enables the quantitative analysis of XPS spectra using a simplified measurement model. All computations can be executed within the open and free Julia language framework PROPHESY. To demonstrate feasibility, the alignment parameter estimation method is first tested on simulated data with known acquisition parameters. The method is then applied to experimental XPS data and a strong correlation between the estimated alignment parameter and the typically used alignment proxy is shown. A model of an X‐ray photoelectron spectroscopy experiment accounting for photon beam asperities, sample geometry and kinetic energy analyzer is introduced. This model is related via the alignment parameter to a simple model commonly used for data interpretation. An alignment parameter estimation method is introduced and tested with simulated and experimental data.
Characterization of Archaeological European White Elm (Ulmus laevis P.) and Black Poplar (Populus nigra L.)
The present study aims at characterization of freshly-cut and archaeological European white elm and poplar. The archaeological elm sample was buried at a depth of 8–10 m inside of soil with age approximation of ~1800–2000 years old, and the archaeological poplar sample was a part of a boat in a freshwater lake or river with age estimation of ~1000–1200 years. Alteration in the chemical structure of the elm and poplar samples due to the ageing process were confirmed by X-ray photoelectron spectroscopy (XPS). Both archaeological wood (AW) samples illustrated considerably lower cellulose crystallinity than the fresh samples as determined by X-ray diffraction. The sorption behavior of AW and fresh wood (FW) samples were evaluated by means of dynamic vapor sorption (DVS) analysis. Results exhibited a higher equilibrium moisture content (EMC) and sorption hysteresis values in archaeological elm and poplar as compared with the fresh samples. Higher hydrophilicity of the AW samples than the FW ones is attributed to their higher amorphous structure. The extensive degradation of AW samples were also confirmed by scanning electron microscopy (SEM) micrographs.
Bond Formation at Polycarbonate | X Interfaces (X = Al2O3, TiO2, TiAlO2) Studied by Theory and Experiments
Interfacial bond formation during sputter deposition of metal‐oxide thin films onto polycarbonate (PC) is investigated by ab initio molecular dynamics simulations and X‐ray photoelectron spectroscopy (XPS) analysis of PC|X interfaces (X = Al2O3, TiO2, TiAlO2). Generally, the predicted bond formation is consistent with the experimental data. For all three interfaces, the majority of bonds identified by XPS are (C─O)─metal bonds, whereas C─metal bonds are the minority. Compared to the PC|Al2O3 interface, the PC|TiO2 and PC|TiAlO2 interfaces exhibit a reduction in the measured interfacial bond density by 75 and ∼65%, respectively. Multiplying the predicted bond strength with the corresponding experimentally determined interfacial bond density shows that Al2O3 exhibits the strongest interface with PC, while TiO2 and TiAlO2 exhibit ∼70 and ∼60% weaker interfaces, respectively. This can be understood by considering the complex interplay between the metal‐oxide composition, the bond strength, and the population of bonds formed across the interface. To study the interfacial bond formation for Al2O3, TiO2, and TiAlO2 sputter depositions onto polycarbonate, ab initio molecular dynamics simulations, and X‐ray photoelectron spectroscopy analysis are carried out. Simulated and experimental data align, revealing predominantly (C─O)─metal bonds at the interfaces and the strongest bond formation at the PC | Al2O3 interface.
Prism-like integrated Bi2WO6 with Ag-CuBi2O4 on carbon nanotubes (CNTs) as an efficient and robust S-scheme interfacial charge transfer photocatalyst for the removal of organic pollutants from wastewater
Photocatalytic hybrid carbon nanotubes (CNTs)–mediated Ag-CuBi 2 O 4 /Bi 2 WO 6 photocatalyst was fabricated using a hydrothermal technique to effectively eliminate organic pollutants from wastewater. The as-prepared samples were characterized via Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction patterns (XRD), high-resolution transmission electron microscope (HR-TEM), UV–vis Diffuse Reflectance spectrum (UV–Vis DRS), and photoluminescence (PL) studies. The photocatalytic performance of fabricated pristine and hybrid composites was examined by photo-degradation of toxic dye viz. Rhodamine B (RhB) under visible light. Photo-degradation results revealed that the fabricated Ag-CuBi 2 O 4 /CNTs/Bi 2 WO 6 semiconductor photocatalyst followed pseudo-first-order kinetics and displayed a higher photocatalytic rate, which was found to be approximately 3.33 and 2.35 times higher than the pristine CuBi 2 O 4 and Bi 2 WO 6 semiconductor photocatalyst, respectively. Re-cyclic results demonstrated that the formed composite owns excellent stability, even after five consecutive cycles. As per the matched Fermi level of CNTs in between Ag-CuBi 2 O 4 and Bi 2 WO 6 , carbon nanotubes severed as electron transfer-bridge, Ag doping on CuBi 2 O 4 surface successfully increased photon absorption all across CuBi 2 O 4 surface. Also, it hindered the assimilation of photoinduced electron–hole pairs. The increased photocatalytic efficiency is contributed to the uniform dispersion of photo-generated electron–hole pairs via the construction of an S-scheme system. ROS trapping and ESR experiments suggested that (∙OH) and (O 2 − ∙) were the main radical species for enhanced photo-degradation of RhB dye. The current investigation, from our perspective, highlights the new insights for the fabrication of practical CNTs-mediated S-scheme–based semiconductor photocatalyst for the resolution of environmental issues based on practical considerations.
Origins of peaks of graphitic and pyrrolic nitrogen in N1s X-ray photoelectron spectra of carbon materials: quaternary nitrogen, tertiary amine, or secondary amine?
X-ray photoelectron spectroscopy (XPS) is among the most powerful techniques to analyse structures of nitrogen-doped carbon materials. However, reported assignments of (1) graphitic nitrogen (N)/substitutional N, quaternary N (Q–N), or tertiary amine (T–N) and (2) pyrrolic N/secondary amine or T–N are questionable. Most reports assign peaks at ca. 401 eV as Q–N or graphitic N, whereas raw materials in most of those works contain neither counter anion nor halogen. Besides, the peak at ca. 400 eV has been assigned as pyrrolic N, but the presence of N–H is generally not confirmed. In this work, it was clarified that one of the reasons for the prevailing ambiguous assignments is the presence of N in heptagonal and pentagonal rings. The peaks at 400.1–401.2 eV were determined to be T–N, but not Q–N by analyzing graphitized polyimide (with the oxygen content of 0.01 at% or lower and the hydrogen content of 0 at%) using Raman spectroscopy, XPS, X-ray diffraction, total neutron scattering, elemental analysis, and molecular dynamics simulation. Besides, it was revealed that the peak at 400.1 eV originated from T–N on 5-membered rings or 7- and 5-membered rings, but not pyrrolic N because graphite including no hydrogen was used for analysis.