The cation-exchange capacities (CEC) of a previously well-characterized beidellite have been estimated nondestructively from X-ray photoelectron spectroscopy (XPS) data following exchange by various cations. The CEC obtained as an atomic ratio to silicon from Na- and Ca-clays are close to that derived chemically, i.e., 0.10(2), and 0.10(1), respectively, compared with 0.12(1). However, the apparent CEC obtained following K-, Pb-, and Ba-exchange are all about 50% greater. These measurements are complemented by XPS studies of clay exchanged in a solution containing both Ca and Ba ions where XPS gave a total apparent exchange capacity relative to Si of 0.16, with 0.10 from Ca and 0.06 from Ba. Bulk chemical analysis has, however, shown that the true Ba value is only 0.01. It is concluded that the cation excess detected by XPS—a technique with a total sampling depth of only about 100 Å—is concentrated at the surfaces of the clay particles.

The nature of Cr(NH3)63+ and Cr(en)33+ (en = ethylenediamine) adsorbed on chlorite, illite, and kaolinite has been studied by X-ray photoelectron spectroscopy (XPS). The interaction of the chromium complexes with the clays began at pH 3. During the 7-day interaction time the pH of the complex-clay suspension increased to 8 for illite and chlorite. For kaolinite the pH increased to about 3.6 with Cr(NH3)63+ and to 6.4 with Cr(en)33+. These pH changes appear to be associated with a clay-catalyzed hydrolysis of the chromium-amine complexes. XPS binding-energy data for adsorbed chromium indicate that the dominant species are chromium aqua complexes. Nitrogen/chromium atom ratios, calculated from the XPS photopeak intensities, are less than 6:1 for complexes adsorbed on the clays, suggesting that chromium complexes are initially adsorbed but subsequently hydrolyze to produce aqua-chromium surface species.

The safe disposal of 60Co, 63Ni, and 59Ni has required considerable information on the interactions of Co2+ and Ni2+ with clay minerals in the geosphere. X-ray photoelectron spectroscopy (XPS) has been used to probe the sorption sites for Co2+ and Ni2+ on hectorite and montmorillonite. The spectra were measured for Co-hectorite, Ni-hectorite, and Ni-montmorillonite immediately following ion exchange and after washing the clay two and five times with distilled water. The spectra, recorded following etching of the surface with an argon ion beam, differentiate two sorption sites; a labile (to washing) fraction sorbed as ion pairs, and a non-labile fraction sorbed by ion exchange at broken bond and interlamellar sites. The data were consistent with the sorption of metal ions (Co2+, Ni2+) in a common “MO6” ligand environment.

Co2+ had a greater affinity for exchange on hectorite than did Ni2+; but Ni2+ had a greater affinity for the surface of montmorillonite than for hectorite. The argon ion etching of Ni-montmorillonite gave rise to a new photopeak of 853 eV, which was probably due to elemental Ni formed consequent to the chemical violation of the surface by ion etching.

Cementing materials in the Arahama sand dune, Japan, were studied mineralogically and biogeochemically to gain a better understanding of the cause of hardening. The cementing material is a clay-organic complex composed of noncrystalline gels and a matrix of small, poorly crystalline particles showing 14–16-Å spacings. The gel materials appear to have transformed into the poorly crystalline particles, which have a high carbon content and Al/Si ratios of 2.2 to 2.0. These particles are slightly richer in Si and poorer in Fe than the gel materials themselves. The organic portion of the complex can be removed by H2O2 treatment, leaving a noncrystalline network-structure containing a dispersed granular component. Scanning auger-depth profiles of individual particles show a high surface concentration of C and O and an increase in the Al/Si ratio with depth. The energy-intensity distribution suggests a mixture of carbon compounds having a major core-line binding energy of a hydrocarbon. The gel-cementing materials in the sand dune may have been formed from biochemical weathering products of organic matter, which subsequently controlled the formation of clay-organic complexes.

When Li-saturated montmorillonite is heated to 200–300 °C, the Li ions migrate from interlayer positions to sites in the layer structure. However, the identity of these sites has not been clearly established. Here we have investigated the migration of Li ions in montmorillonite, after heat treatment at 250 °C, using chemical and instrumental analyses. The latter include X-ray diffractometry (XRD), 7Linuclear magnetic resonance (NMR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Heating causes a large reduction in cation exchange capacity (CEC) and an almost complete loss of interlayer expansion with glycerol as shown by XRD. Static and magic angle spinning (MAS) 7Li-NMR spectroscopy shows that the quadrupole coupling constant of Li increases markedly over the corresponding value for unheated Li-montmorillonite (where Li occupies exchange sites in the interlayer space) and for hectorite (where Li is located in the octahedral sheet). This would indicate that, in heated montmorillonite, Li occupies structural sites of low symmetry which, however, cannot be identified with octahedral vacancies in the layer structure as is commonly assumed. XPS shows that the binding energy (BE) for Li in unheated montmorillonite is comparable to that for other exchangeable cations. Heating broadens the Li 1s band and decreases the BE. The BE for Li in heated montmorillonite is significantly higher than that in either spodumene or lepidolite, where Li is known to occupy octahedral sites. The combined data suggest that heating induces Li to migrate from interlayer sites to ditrigonal cavities in the tetrahedral sheet, rather than into vacancies in the octahedral sheet, of montmorillonite.

Ba3−xSrxTb3−xCexO9 (x = 1 and 1.5) ceramics (BSTC) with a relative density of 93% and a grain size distribution of 0.2–3 µm were prepared by the mixed-oxides reaction route. The crystalline structures, microstructures, valence states, and electrical properties of two ceramics were analyzed using X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and electrical measurements. Rietveld analyses of XRPD patterns show that BSTC1 is indexed as a trigonal structure with the space group R-3c, and BSTC3/2 is indexed as an orthorhombic perovskite structure with the space group Pmcn. The EPR, XPS, and electrical conductivity results confirm that Ce and Tb ions in BSTC exist as Ce4+ and mixed-valence states of Tb4+/Tb3+, respectively. At room temperature, the two BSTC ceramics exhibit a similar semiconducting behavior. The relationships between electrical conductivity and temperature/frequency are provided. The defect chemistry is discussed.

The field of two-dimensional (2D) materials remains a key area of scientific research today, generating continual interest for electronic, sensing, and quantum technology. As the field progresses beyond proof-of-concept devices, experimental and analytical methods and results must be scrutinized to ensure the veracity of scientific claims. Here, some favored synthesis and characterization techniques within the 2D material (2DM) community and certain limitations inherent to these techniques are discussed. The authors highlight select caveats of solid-source and seed-promoted synthesis techniques, such as difficulties in reproducibility and compromised electrical performance of films synthesized with nucleation agents. Furthermore, the importance of careful characterization methodology in determining 2DM layer number, stoichiometry, and dopant effects is discussed. This article is intended to further educate researchers regarding select techniques and claims in the 2DMs field.

The synergetic effects of surface smoothing exhibited during the inductively coupled plasma reactive ion etching (ICP-RIE) of free-standing polycrystalline diamonds (PCDs) were investigated. Changing the assistive gas types generated variable surface oxidation states and chemical environments that resulted in different etching rates and surface morphologies. The main reaction bond mechanism (C–O) during ICP-RIE and the ratio of C–O–C/O–C=O associated with the existence of a uniform smooth surface with root mean square (RMS) roughness of 2.36 nm were observed. An optimal process for PCD smoothing at high etching rate (4.6 μm/min) was achieved as follows: 10% gas additions of CHF3 in O2 plasma at radio frequency power of 400 W. The further etched ultra-smooth surface with RMS roughness <0.5 nm at etching rate of 0.23 μm/min that being produced by transferring this optimum recipe on single crystal diamonds with surface patterns confirmed the effectiveness of the fast smoothing approach and its feasibility for diamond surface patterning.

X-ray photoelectron spectroscopy can be used to measure the ionization energies of electrons in both valence band and core orbitals. As core vacancies are the initial states for X-ray emission, a knowledge of their energies for all atoms in a mineral enables all the X-ray spectra to be placed on a common energy scale. X-ray spectra are atom specific and are governed by the dipole selection rule. Thus the individual bonding roles of the different atoms are revealed by the fine structure of valence X-ray peaks (i.e. peaks which result from electron transitions between valence band orbitals and core vacancies). The juxtaposition of such spectra enables the composition of the molecular orbitals that make up the chemical bonds of a mineral to be determined.

Examples of this approach to the direct determination of electronic structure are given for silica, forsterite, brucite, and pyrite. Multi-electron effects and developments involving anisotropic X-ray emission from single crystals are also discussed.

MoS2(1−x)Te2x thin films were fabricated by high-temperature co-sputtering deposition and post-deposition tellurization annealing using novel Te precursor (i-C3H7)2Te for the first time. As a result, high crystal quality MoS2(1−x)Te2x (6.5 nm) were successfully fabricated with the Te concentration x ranging from 0.48 to 0.61 and band gap value from 0.80 to 0.87 eV. From the obtained band gap values of MoS2(1−x)Te2x , the bowing parameter b was determined to be 1.06 eV. When exploited in device use, if the required band gap value is known, the required composition can be calculated with the bowing parameter. We have also shown the compatibility of co-sputtering to alloy fabrication since the composition ratio can be easily controlled just by adjusting the radio frequency (RF) sputter power on different targets. The fabrication method can be applied to different transition metal dichalcogenide materials as well.

X-ray photoemission spectroscopy using synchrotron radiation from 100 to 1486.6 eV was used to investigate polarity-dependent differences between the Zn-polar (0001) and the O-polar () faces of ultrahigh vacuum cleaved hydrothermally grown ZnO single crystals. The cleaved polar surfaces showed a characteristic polarity effect in that the intensity of emission from the lowest binding energy O 2p related valence band states was significantly stronger on the Zn-polar face, even when the cleaved surfaces were imperfect with irregular nonatomically flat features. A residual submonolayer hydroxyl termination of approximately 0.5 ML was observed on both the Zn-polar and O-polar surfaces immediately after cleaving. The near-surface downward band bending on the O-polar face was removed by the cleaving process leaving almost flat bands, while on the cleaved Zn-polar face, emission from states above the valence band edge was observed.

We have demonstrated resistance switching using polycrystalline HfO2 film with a Cu top electrode for nonvolatile memory applications and revealed the Cu diffusion into the HfO2 layer during the filament formation process. Resistive switching was clearly observed in the Cu/HfO2/Pt structure by performing a current–voltage measurement. The current step from a high-resistive state to a low-resistive state was of the order of 103–104 Ω, which provided a sufficient on/off ratio for use as a switching device. The filament formation process was investigated by employing hard x-ray photoelectron spectroscopy under bias operation. The application of a bias to the structure reduced the Cu2O state at the interface and the intensity ratio of Cu 2p3/2/Hf 3d5/2, providing evidence of Cu2O reduction and Cu diffusion into the HfO2 layer. These results also provide evidence that the resistance switching of the Cu/HfO2/Pt structure originates in a solid electrolyte (nanoionics model) containing Cu ions.

Graphene oxide nanoplatelets (GONPs) were obtained by unraveling helical-ribbon carbon nanofibers (HR-CNF) using a modified Hummers and Offeman method in conjunction with ultrasonication. In this account, we carry out a complete evaluation of the effect of different oxidative agent concentrations on the resulting platelet materials. Transmission electron microscopy, atomic force microscopy, Fourier transform infrared, x-ray diffraction, x-ray photoelectron spectroscopy, and thermogravimetric analysis were performed to carefully characterize GONPs resulting from the oxidative process. Comparative experiments using multiwall carbon nanotubes (MWCNTs) and graphite were also carried out. Our studies suggest that the oxidation treatment is more effective in HR-CNFs than in MWCNTs. Furthermore, the unraveling of HR-CNFs results in GONPs consisting of less stacked layers when compared to other starting materials such as graphite. Therefore, HR-CNFs appear to be excellent precursors to produce few-layered GONPs.

There are a large number of natural fibers that have the potential to replace synthetic fibers made from glass, carbon, and polymers as the reinforcing phase in composites. Interest in these fibers has increased, as they offer a sustainable, readily available, high specific modulus option. The high modulus of cellulose crystals makes them attractive as a reinforcing phase in composites. These cellulose crystals are the key structural component in natural fibers, but the complex microstructure of the fiber means that the full value of the cellulose crystal modulus cannot be utilized. Moreover, the surface of natural fibers can have varying chemistry depending on the pretreatment of the fiber and the degree to which lignin and other hydrophobic materials are removed from the fiber. In addition, cellulose swells in contact with water, and this can degrade the properties of the fiber and composite. A better understanding of the surface properties and techniques to control the composite interface are required if natural fibers are to fulfill their potential.

The catalytic influence of Ni, Zr2Ni5, and LaNi5 on the dehydrogenation properties of milled MgH2 was investigated. MgH2 milled in the presence of Ni (5 wt%) and Zr2Ni5 (5 wt%) catalysts for 2 h showed apparent activation energies, EA, of 81 and 79 kJ/mol, respectively, corresponding to ∼50% decrease in EA and a moderate decrease (∼100 °C) in the decomposition temperature (Tdec). A further 27 °C decrease in Tdec was observed after milling with 10 wt%Ni. Based on the EA values, the catalytic activity decreased in the following order: Ni ≈ Zr2Ni5 > LaNi5. X-ray photoelectron spectroscopy analysis of the milled and dehydrogenated states of the hydrides modified with Ni catalyst revealed that the observed reduction in EA may be due to the ability of Ni catalyst to decrease the amount of oxygen atoms in defective positions that are capable of blocking catalytically active sites thereby enhancing the dehydrogenation kinetics. In particular, our results reveal a strong correlation between the type of oxygen species adsorbed on Ni-modified MgH2 and the EA of the dehydrogenation reaction.

The depth profile of thin film layers on bulk substrate, avoiding the cross-sectioning of samples, is commonly performed by techniques such as X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and secondary ion mass spectroscopy (SIMS). Techniques based on X-ray emission intensity measurements by energy dispersive spectroscopy (EDS), with conventional matrix or ZAF correction, are normally applied to cross-sectioned samples. This article compares XPS with surface X-ray intensity measurements by EDS, carried out with a more realistic X-ray generation and absorption model, known as the ϕ(ρ Z) model. The ϕ(ρ Z) approach has been adopted together with Monte Carlo simulation for the proper selection of SEM accelerating voltages, in conjunction with the analysis of SEM morphological images for thin film density correction. The method discussed hereafter and compared with the XPS technique, has advantages of higher lateral resolution, non-destructive elemental analyses, morphological visualization, low cost, and faster performance. This methodology has been followed to verify the layered structure of SnO2/metal-based gas sensors. X-ray intensities were measured using an EDS ultra-thin window detector. Two different porous layers, 25-nm thick of SnO2 and 10-nm thick of Cu, were detected, showing better agreement with their nominal thickness compared to results obtained using XPS measurements where porosity affects XPS data. If confirmed to be reliable and as effective as XPS depth profiling, this technique may be adopted for process quality control purposes.