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Diamond is one of the fascinating films appropriate for optoelectronic applications due to its wide bandgap (5.45 eV), high thermal conductivity (3320 W m−1·K−1), and strong chemical stability. In this report, we synthesized a type of diamond film called nanocrystalline diamond (NCD) by employing a physical vapor deposition method. The synthesis process was performed in different ratios of nitrogen and hydrogen mixed gas atmospheres to form nitrogen-doped (n-type) NCD films. A high-resolution scanning electron microscope confirmed the nature of the deposited films to contain diamond nanograins embedded into the amorphous carbon matrix. Sensitive spectroscopic investigations, including X-ray photoemission (XPS) and near-edge X-ray absorption fine structure (NEXAFS), were performed using a synchrotron beam. XPS spectra indicated that the nitrogen content in the film increased with the inflow ratio of nitrogen and hydrogen gas (IN/H). NEXAFS spectra revealed that the σ*C–C peak weakened, accompanied by a π*C=N peak strengthened with nitrogen doping. This structural modification after nitrogen doping was found to generate unpaired electrons with the formation of C–N and C=N bonding in grain boundaries (GBs). The measured electrical conductivity increased with nitrogen content, which confirms the suggestion of structural investigations that nitrogen-doping generated free electrons at the GBs of the NCD films.

This study investigates the spatial distribution of organic carbon (C) in free stable microaggregates (20-250 μm; not encapsulated within macroaggregates) from one Inceptisol and two Oxisols in relation to current theories of the mechanisms of their formation. Two-dimensional micro- and nano-scale observations using synchrotron-based Fourier-transform infrared (FTIR) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy yielded maps of the distribution of C amounts and chemical forms. Carbon deposits were unevenly distributed within microaggregates and did not show any discernable gradients between interior and exterior of aggregates. Rather, C deposits appeared to be patchy within the microaggregates. In contrast to the random location of C, there were micron-scale patterns in the spatial distribution of aliphatic C-H (2922 cm-¹), aromatic C=C and N-H (1589 cm-¹) and polysaccharide C-O (1035 cm-¹). Aliphatic C forms and the ratio of aliphatic C/aromatic C were positively correlated (r ² of 0.66-0.75 and 0.27-0.59, respectively) to the amount of O-H on kaolinite surfaces (3695 cm-¹), pointing at a strong role for organo-mineral interactions in C stabilization within microaggregates and at a possible role for molecules containing aliphatic C-H groups in such interactions. This empirical relationship was supported by nanometer-scale observations using NEXAFS which showed that the organic matter in coatings on mineral surfaces had more aliphatic and carboxylic C with spectral characteristics resembling microbial metabolites than the organic matter of the entire microaggregate. Our observations thus support models of C stabilization in which the initially dominant process is adsorption of organics on mineral surfaces rather than occlusion of organic debris by adhering clay particles.

Hydrothermal vents release significant quantities of dissolved iron into the oceans. Spectromicroscopic examination of a hydrothermal plume suggests that carbon-rich matrices protect this iron from oxidation and precipitation. Hydrothermal venting associated with mid-ocean ridge volcanism is globally widespread 1 . This venting is responsible for a dissolved iron flux to the ocean that is approximately equal to that associated with continental riverine runoff 2 . For hydrothermal fluxes, it has long been assumed that most of the iron entering the oceans is precipitated in inorganic forms. However, the possibility of globally significant fluxes of iron escaping these mass precipitation events and entering open-ocean cycles is now being debated 3 , and two recent studies suggest that dissolved organic ligands might influence the fate of hydrothermally vented metals 4 , 5 . Here we present spectromicroscopic measurements of iron and carbon in hydrothermal plume particles at the East Pacific Rise mid-ocean ridge. We show that organic carbon-rich matrices, containing evenly dispersed iron( II )-rich materials, are pervasive in hydrothermal plume particles. The absence of discrete iron( II ) particles suggests that the carbon and iron associate through sorption or complexation. We suggest that these carbon matrices stabilize iron( II ) released from hydrothermal vents in the region, preventing its oxidation and/or precipitation as insoluble minerals. Our findings have implications for deep-sea biogeochemical cycling of iron, a widely recognized limiting nutrient in the oceans.

Microbialites are sedimentary deposits associated with microbial mat communities and are thought to be evidence of some of the oldest life on Earth. Despite extensive studies of such deposits, little is known about the role of microorganisms in their formation. In addition, unambiguous criteria proving their biogenicity have yet to be established. In this study, we characterize modern calcareous microbialites from the alkaline Lake Van, Turkey, at the nanometer scale by combining x-ray and electron microscopies. We describe a simple way to locate microorganisms entombed in calcium carbonate precipitates by probing aromatic carbon functional groups and peptide bonds. Near-edge x-ray absorption fine structure spectra at the C and N K-edges provide unique signatures for microbes. Aragonite crystals, which range in size from 30 to 100 nm, comprise the largest part of the microbialites. These crystals are surrounded by a 10-nm-thick amorphous calcium carbonate layer containing organic molecules and are embedded in an organic matrix, likely consisting of polysaccharides, which helps explain the unusual sizes and shapes of these crystals. These results provide biosignatures for these deposits and suggest that microbial organisms significantly impacted the mineralogy of Lake Van carbonates.

X-ray absorption spectroscopy is applied to investigate relationships between hierarchical organization of the skeleton and nanostructure of femoral bone in knee compartments and to understand the osteoarthritis (OA) related changes at the subcellular level. Our focus is on local electronic and atomic and molecular architectonics of the medial and lateral condyles of the femur resected during total knee arthroplasty in patients with medial compartmental knee OA. The element-specific and site-dependent peculiarities in spectral distributions of oscillator strength for core-to-valence transitions are revealed. The near Ca 2p and O 1s edges x-ray absorption fine structure (Ca 2p and O 1s NEXAFS) spectra of the saw cuts demonstrate substantial redistributions in intact and OA damaged areas on the proximal side, and on the proximal and distal sides of the samples. Examining the O 1s NEXAFS spectra new chemical bonds are revealed on the proximal surface in the OA areas. Strong intra-atomic intershell Ca 2+ 2 p 3 / 2 , 1 / 2 5 3 d 1 interaction specifies the great similarity of the Ca 2p NEXAFS spectra. Their analysis performed in combination with the x-ray photoelectron data has demonstrated the formation of non-apatite calcium in the OA areas of the samples. It is shown that NEXAFS spectroscopy is a powerful tool for deeper understanding relationship between hierarchical skeletal organization and nanostructure of native bone. Perspectives for development of novel methods for medical imaging and diagnosis of subchondral bone at the nanolevel are discussed.

A number of freshly abraded surfaces of pentlandite have been characterised by X-ray photoelectron spectroscopy to establish whether the initial intensity of the S 2p component near 161.4 eV, previously assigned to the 25% of S atoms in fourfold coordination by metal atoms in pentlandite, was always at least 25% of the total S 2p intensity. It was found that the intensity of this S 2p component could be lower than 20% for surfaces that were not significantly oxidised. To assess whether the proposed 0.75–0.8 eV 2p binding energy difference for the two sulfur environments in pentlandite was justified, ab initio calculations of the difference in core electron binding energies and of the densities of unfilled states have been carried out. The corresponding simulated S K near-edge X-ray absorption fine structure (NEXAFS) spectra have been compared with experimental spectra. The calculated S 2p and S 1s binding energy differences were 0.45 and 0.5 eV at most, in agreement with the experimental NEXAFS spectra. It was concluded that the S 2p component near 161.4 eV arises entirely from violarite present at the pentlandite surface rather than from 4-coordinate S in pentlandite itself. Ab initio calculations of the difference in S 2p binding energies for the 2- and 3-coordinate S in stibnite have also been carried out and found to be quite small, in agreement with previously reported experimental values. Nevertheless, for both pentlandite and stibnite, calculations have confirmed that an increase in coordination number is associated with an increase in sulfur core electron binding energies, even although that increase is barely measurable for the latter sulfide.

Below we review methods for the quantitative analysis of NEXAFS spectra. Theoretical expressions are given for the lineshapes of features, such as steps and peaks, that are commonly encountered in NEXAFS spectra. Also, we discuss general guidelines for the positions and shapes of characteristic features.

Here we show how the K-shell excitation spectra of simple free molecules, discussed in Chap. 4, evolve under the influence of extramolecular interactions in the form of van-der-Waals or chemical bonds at surfaces, and develop a molecular-orbital-based understanding of the systematic changes of the spectra with increasing molecular size.

In this chapter a basic question is addressed: How can the X-ray absorption signal from a single molecular layer on the surface of a bulk material be measured? In particular, electron yield and fluorescence yield detectors and experimental techniques are discussed and specific attention is given to the problems of normalization and background correction of experimental data.

With the availability of dedicated (second generation) synchrotron radiation sources around the world and suitable soft X-ray monochromators, such as the SX-700 plane grating [11.1, 2] or Dragon spherical grating [11.3, 4] instruments, conventional NEXAFS studies in the 1990s are limited neither by flux nor by resolution. Although many improvements in instrumentation are possible, to conclude this book we want to ask whether there are any truly novel and exciting opportunities on the horizon. In the following let us therefore do some brainstorming about possible future applications of NEXAFS spectroscopy. We shall restrict ourselves to novel ideas not mentioned in previous chapters. Most of these ideas are centered around new instrumentation in the form of new synchrotron radiation sources, novel monochromators or simply end-of-line equipment.