Research on natural minerals and their chemical bonding to economically critical raw materials is a viable industrially relevant research area due to its increasing demand. Meeting demands requires fast, robust, and efficient techniques to explore new ore deposits and continuous operation of active mines as well as recycling. One of the most critical metals is gold which occurs in three main types of ore deposits: i) hydrothermal quartz veins and related deposits in metamorphic and igneous rocks; ii) volcanic-exhalative sulfide deposits, and iii) consolidated to unconsolidated placer deposits. Gold is commonly found as disseminated grains in quartz veins in pyrite and other sulfides or as rounded grains, flakes or nuggets in deposits in riverbanks, in contact with metamorphic or hypothermal deposits (e.g., skarns) or epithermal deposits such as volcanic fumaroles. Pathfinder elements and indicator minerals provide means to explore large areas for their potential mineral commodities such as gold, diamond, base metals, platinum group of elements, and rare earth elements by narrowing the search area to reduce exploration costs. The recent technological advancement in obtaining rapid geochemical results using field portable analytical devices as alternatives to the old approach where collected field samples are carried to the laboratory calls for further investigation to explore other techniques in mineral and metal exploration.

In this Thesis, I investigate the properties of artisanal small-scale gold mining concentrate, outcrop, bulk Au, and drill hole samples from the Kubi Gold Project of the Asante Gold Corporation near Dunkwa-on-Offin in the Central Region of Ghana with a materials science perspective. X-ray diffraction (XRD) is used to identify SiO₂ (quartz), Fe₃O₄ (magnetite), garnet, pyrite (FeS₂), periclase (MgO), arsenopyrites, pyrrhotite, biotite, titanium oxide, and Fe₂O₃ (hematite) as the main indicator minerals in the mining site with less significant contributions from chalcopyrite, iridosmine, scheelite, tetradymite, gypsum, and a few other sulfates. X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX) indicate that Fe, Ag, Al, N, O, Si, Hg, C, Ba, P, Ca, Mg, Na, Mn, Cl, S, K, and Ti are important host elements that form alloys with Au or are inherent in the sediment at the concession site. The results also indicate that Si and Ag are in strong co-occurrence with Au due to their eutectic qualities, while N, C, and O occur due to their attraction to Si. Also, the XPS results indicate that the relationship between Au and pathfinder elements or indicator minerals depends on the d-orbital of Au and other elements that possess octahedral or tetrahedral geometry to split into two states, e_g and t_2g that can acquire either higher or lower energy depending on the geometry and are responsible for the covalent, metallic, and ionic states of Au with other ligands. From the air anneal furnace (AAF) and differential scanning calorimetry (DSC), I investigated the transformations in quartz and pyrite minerals that alter to hematite minerals. The quartz samples are observed to transform from α-quartz to β-quartz and finally to cristobalite while the pyrite transforms to magnetite and later to hematite. These findings suggest that during the hydrothermal flow regime impurity materials are trapped by voids and faults and can be altered at different depositional stages by oxidation and reduction processes. Results from the scanning electron microscopy (SEM) revealed the presence of carbonates in fracture zones in the quartz, pyrite, and almandine-type garnet mineral in gabbroic rocks.

The findings indicate that, from the top of the oxide zone, grains within sediments are seen to be controlled by quartz, and hematite, the bedrock consists of pyrite and pyrrhotite, and the orebody contains garnet, arsenopyrite, periclase, and biotite as pathfinder minerals within the concession area. Therefore, the Au mineralogy of the alluvial environment that is mined by artisanal small-scale miners is traced from the chemical weathering reaction of garnet minerals from the orebody that produces fractions of other indicator minerals as by-products in the Kubi mining area. These findings also indicate that primary geochemical dispersion evolving from the crystallization of magma and hydrothermal liquids are the main attributes and constitute the identification of indicator minerals and pathfinding elements in this mineralogical study area.Furthermore, the findings suggest that XRD, XPS, TEM, and EDX could be combined in other mineralogical laboratories to aid in identifying indicator minerals of Au and the location of ore bodies, to increase the knowledge in this field, and reduce environmental and exploration costs.

We arc deposit Cr-rich Cr-N coatings and show that these coatings are a promising alternative to electrodeposited hard chrome. We find that the substrate bias is of importance for controlling the N content in the grown coatings as it determines the degree of preferential resputtering of N. The substrate bias also affects the substrate temperature and film growth rate. Higher bias results in higher temperatures due to higher energy transfer to the substrate, while the growth rate decreases due to an increased re-sputtering. The N content affects the morphology, microstructure, hardness, and resistivity of the coatings. The hardness increases from 10 GPa with 0.5 at. % N to 17 GPa with 7.5 at. % N, after which no further increase in hardness is seen. At the same time, the grain structure changes from columnar to more featureless and the resistivity rises from 15 to 45 mu omega cm.

We report conformal chemical vapor deposition (CVD) of boron carbide (BxC) thin films on silicon substrates with 8:1 aspect-ratio morphologies, using triethylboron [B(C2H5)(3)] as a single source CVD precursor. Step coverage (SC) calculated from the cross-sectional scanning electron microscopy measurements shows that films deposited at & LE;450 & DEG;C were highly conformal (SC = 1). We attribute this to the low reaction probability at low substrate temperatures enabling more gas phase diffusion into the features. The chemical state of the material, determined by x-ray photoelectron spectroscopy, shows as a carbide with B-B, B-C, C-B, and C-C chemical bonds. Quantitative analysis by time-of-flight elastic recoil detection analysis reveals that films deposited at 450 & DEG;C are boron-rich with around 82.5 at. % B, 15.6 at. % C, 1.3 at. % O, and 0.6 at. % H, i.e., about B5C. The film density as measured by x-ray reflectometry varies from 1.9 to 2.28 g/cm(3) depending on deposition temperature. (C) 2022 Author(s).All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY)license (http://creativecommons.org/licenses/by/4.0/).

Correction for Discovering atomistic pathways for supply of metal atoms from methyl-based precursors to graphene surface by Davide G. Sangiovanni et al., Phys. Chem. Chem. Phys., 2023, 25, 829-837, https://doi.org/10.1039/D2CP04091C.

Group 4 transition metal diboride films were deposited epitaxially onto different substrates, typically at 900 °C, using direct-current magnetron sputtering from compound targets of ZrB₂, TiB₂, and HfB₂. Epitaxial ZrB₂ has been deposited on Al₂O₃(0001), 4H-SiC(0001), and Si(100) describing the epitaxial relationships on Si(100) for the first time, where two relationships were observed from pole-figure analysis, namely A) in-plane: ZrB₂[001] ∥ Si[110] and ZrB₂[110] ∥ Si[110], out-of-plane: ZrB2(100) ∥ Si(100), and B) in-plane: ZrB₂[11] ∥ Si[110] and the same rotated 90° around the 102 axis, out-of- plane: ZrB₂(102) ∥ Si(100). Composition analysis by time-of-flight elastic recoil detection analysis revealed typically B-rich ZrB₂ and TiB₂, and stoichiometric to Hf-rich HfB₂. For ZrB₂, the application of an additional external magnetic field during growth influenced the B-to-Zr ratio towards being stoichiometric. Rocking curve measurements of ZrB₂ deposited onto Si(100) reveal a higher crystal order in the 100-oriented domains, compared to the 102-oriented domains. In ZrB₂ films annealed to temperatures in the range of 1100-1500 °C, rocking curve measurements of the symmetric 001 reflection as well as the asymmetric 101 reflection reveal increased order with increased temperature. This phenomenon occurred at lower temperature when the annealing was performed in H₂ compared to Ar.

The morphology in plan-view transmission electron microscopy reflects the composition of the film: TiB_2.5 has B-rich areas around the grain boundaries, forming an almost continuous network around the grains. ZrB_x films with x between 2.0 and 2.3 also contain B-rich regions, though to a smaller extent and mostly in areas where more than two grains adjoin each other. In Hf-rich HfB_1.8, no B-rich areas were observed. Scanning transmission electron micrographs and a combination of B electron energy loss spectroscopy and energy dispersive X-ray analysis Hf distribution maps revealed Hf-rich areas in a close-to single crystalline matrix. The hardness of epitaxial HfB₂ films is reported to 33 and 36 GPa for films deposited onto Al₂O₃ and SiC, respectively. These values are slightly higher than reported for bulk HfB₂. ZrB₂ films on SiC decrease in hardness to 38, 37, and 30 GPa, upon annealing in Ar up to 1100, 1300, and 1500 °C, respectively. In summary, the knowledge is expanded about epitaxially grown group 4 transition metal diborides in terms of their Chemical composition, crystallographic orientations, microstructure, electrical and mechanical properties, as well as their response to heat treatment.

Zinc aluminogallate, Zn(AlxGa1−x)2O4 (ZAGO), a single-phase spinel structure, offers considerable potential for high-performance electronic devices due to its expansive compositional miscibility range between aluminum (Al) and gallium (Ga). Direct growth of high-quality ZAGO epilayers however remains problematic due to the high volatility of zinc (Zn). This work highlights a novel synthesis process for high-quality epitaxial quaternary ZAGO thin films on sapphire substrates, achieved through thermal annealing of a ZnGa2O4 (ZGO) epilayer on sapphire in an ambient air setting. In-situ annealing x-ray diffraction measurements show that the incorporation of Al in the ZGO epilayer commenced at 850 °C. The Al content (x) in ZAGO epilayer gradually increased up to around 0.45 as the annealing temperature was raised to 1100 °C, which was confirmed by transmission electron microscopy (TEM) and energy dispersive x-ray spectroscopy. X-ray rocking curve measurement revealed a small full width at half maximum value of 0.72 °, indicating the crystal quality preservation of the ZAGO epilayer with a high Al content. However, an epitaxial intermediate �–(AlxGa1−x)2O3 layer (� - AGO) was formed between the ZAGO and sapphire substrate. This is believed to be a consequence of the interdiffusion of Al and Ga between the ZGO thin film and sapphire substrate. Using density functional theory, the substitution cost of Ga in sapphire was determined to be about 0.5 eV lower than substitution cost of Al in ZGO. Motivated by this energetically favorable substitution, a formation mechanism of the ZAGO and AGO layers was proposed. Spectroscopic ellipsometry studies revealed an increase in total thickness of the film from 105.07 nm (ZGO) to 147.97 nm (ZAGO/AGO) after annealing to 1100 °C, which were corroborated using TEM. Furthermore, an observed increase in the direct (indirect) optical bandgap from 5.06 eV (4.7 eV) to 5.72 eV (5.45 eV) with an increasing Al content in the ZAGO layer further underpins the formation of a quaternary ZAGO alloy with a tunable composition.

Thin films of BaZr1-xScxO3-x/2, (0 ≤ x ≤ 0.64), well known as proton conducting solid electrolytes for intermediatetemperature solid oxide fuel cell, were deposited by magnetron sputtering. X-ray diffraction analysis of theas deposited films reveals the presence of single-phase perovskite structure. The films were deposited on fourdifferent substrates (c-Al2O3, LaAlO3〈100〉, LaAlO3〈110〉, LaAlO3〈111〉) yielding random, (110)- or (100)-orientedfilms. The stability of the as-deposited films was assessed by annealing in air at 600 ◦C for 2 h. Theannealing treatment revealed instabilities of the perovskite structure for the (110) and randomly oriented films,but not for (100) oriented film. The instability of the coating under heat treatment was attributed to the lowoxygen content in the film (understoichiometry) prior annealing combined with the surface energy and atomiclayers stacking along the growth direction. An understoichiometric (100) oriented perovskite films showedhigher stability of the structure under an annealing in air at 600 ◦C.

The Au mineralization in the Kubi Gold Mining Area in the Birimian of Ghana is associated with garnet (about 85 vol.%), magnetite, pyrrhotite, arsenopyrite, and sulfide minerals, as well as quartz with gold and calcite. These minerals and the included elements can act as indicator minerals or pathfinder elements. For the present work, we collected samples from drill holes at different depths, from the alluvial zone (0–45 m) to the ore zone (75–100 m). The distributions of minerals and elements in the rocks that act as indicator minerals and pathfinder elements in the concession area were investigated along the drill hole cross sections. X-ray diffraction shows that the samples contain garnet, pyrite, periclase, and quartz as the main indicator minerals. By energy-dispersive X-ray spectroscopy, Fe, Mg, Al, S, O, Mn, Na, Cu, Si, and K are identified as corresponding pathfinder elements. The results indicate that the Au mineralization in the Kubi Mine area correlates mostly with the occurrence of garnet, pyrite, goethite, and kaolinite in the host rocks, which show towards the surface increasingly hematitic and limonitic alteration in form of Fe(oxy-)hydroxides.

Lead-free halide double perovskites (HDPs) have emerged as a new generation of thermochromic materials. However, further materials development and mechanistic understanding are required. Here, a highly stable HDP Cs2NaFeCl6 single crystal is synthesized, and its remarkable and fully reversible thermochromism with a wide color variation from light-yellow to black over a temperature range of 10 to 423 K is investigated. First-principles, density functional theory (DFT)-based calculations indicate that the thermochromism in Cs2NaFeCl6 is an effect of electron–phonon coupling. The temperature sensitivity of the bandgap in Cs2NaFeCl6 is up to 2.52 meVK−1 based on the Varshni equation, which is significantly higher than that of lead halide perovskites and many conventional group-IV, III–V semiconductors. Meanwhile, this material shows excellent environmental, thermal, and thermochromic cycle stability. This work provides valuable insights into HDPs' thermochromism and sheds new light on developing efficient thermochromic materials.

By addressing precursor prevalence and energetics using the DFT-based synthetic growth concept (SGC), the formation mechanism of self-induced InAlN core–shell nanorods (NRs) synthesized by reactive magnetron sputter epitaxy (MSE) is explored. The characteristics of In- and Al-containing precursor species are evaluated considering the thermal conditions at a typical NR growth temperature of around 700 °C. The cohesive and dissociation energies of In-containing precursors are consistently lower than those of their Al-containing counterparts, indicating that In-containing precursors are more weakly bonded and more prone to dissociation. Therefore, In-containing species are expected to exhibit lower abundance in the NR growth environment. At increased growth temperatures, the depletion of In-based precursors is even more pronounced. A distinctive imbalance in the incorporation of Al- and In-containing precursor species (namely, AlN/AlN+, AlN2/AlN2+, Al2N2/Al2N2+, and Al2/Al2+ vs InN/InN+, InN2/InN2+, In2N2/In2N2+, and In2/In2+) is found at the growing edge of the NR side surfaces, which correlates well with the experimentally obtained core–shell structure as well as with the distinctive In-rich core and vice versa for the Al-rich shell. The performed modeling indicates that the formation of the core–shell structure is substantially driven by the precursors’ abundance and their preferential bonding onto the growing edge of the nanoclusters/islands initiated by phase separation from the beginning of the NR growth. The cohesive energies and the band gaps of the NRs show decreasing trends with an increment in the In concentration of the NRs’ core and with an increment in the overall thickness (diameter) of the NRs. These results reveal the energy and electronic reasons behind the limited growth (up to ∼25% of In atoms of all metal atoms, i.e., InxAl1–xN, x ∼ 0.25) in the NR core and may be qualitatively perceived as a limiting factor for the thickness of the grown NRs (typically <50 nm).

Structural changes in Ti_1-xAl_xN coated tool inserts used for turning in 316L stainless steel were investigated by XANES, EXAFS, EDS, and STEM. For coarse-grained fcc-structured Ti_1-xAl_xN coatings, with 0 ≤ x ≤ 0.62, the XANES spectrum changes with Al-content. XANES Ti 1s line-scans across the rake face of the worn samples reveals that TiN-enriched domains have formed during turning in Ti_0.47Al_0.53N and Ti_0.38Al_0.62N samples as a result of spinodal decomposition. The XANES spectra reveal the locations on the tool in which the most TiN-rich domains have formed, indicating which part of the tool-chip contact area that experienced the highest temperature during turning. Changes in the pre-edge features in the XANES spectra reveal that structural changes occur also in the w-TiAlN phase in fine-grained Ti_0.38Al_0.62N during turning. EDS shows that Cr and Fe from the steel adhere to the tool rake face during machining. Cr 1s and Fe 1s XANES show that Cr is oxidized in the end of the contact length while the adhered Fe retains in the same fcc-structure as that of the 316L stainless steel.

A potential application of two-dimensional (2D) MXenes, such as Ti2CTx and Ti3C2Tx, is energy storage devices, such as supercapacitors, batteries, and hydride electrochemical cells, where intercalation of ions between the 2D layers is considered as a charge carrier. Electrochemical cycling investigations in combination with Ti 1s x-ray absorption spectroscopy have therefore been performed with the objective to study oxidation state changes during potential variations. In some of these studies Ti3C2Tx has shown main edge shifts in the Ti 1s x-ray absorption near-edge structure. Here we show that these main edge shifts originate from the Ti 4p orbital involvement in the bonding between the surface Ti and the termination species at the fcc-sites. The study further shows that the t2g–eg crystal field splitting (10Dq) observed in the pre-edge absorption region indicate weaker Ti–C bonds in Ti2CTx and Ti3C2Tx compared to TiC and the corresponding MAX phases. The results from this study provide information necessary for improved electronic modeling and subsequently a better description of the materials properties of the MXenes. In general, potential applications, where surface interactions with intercalation elements are important processes, will benefit from the new knowledge presented.

Silica glass is a high-performance material used in many applications such as lenses, glassware, and fibers. However, modern additive manufacturing of micro-scale silica glass structures requires sintering of 3D-printed silica-nanoparticle-loaded composites at similar to 1200 degrees C, which causes substantial structural shrinkage and limits the choice of substrate materials. Here, 3D printing of solid silica glass with sub-micrometer resolution is demonstrated without the need of a sintering step. This is achieved by locally crosslinking hydrogen silsesquioxane to silica glass using nonlinear absorption of sub-picosecond laser pulses. The as-printed glass is optically transparent but shows a high ratio of 4-membered silicon-oxygen rings and photoluminescence. Optional annealing at 900 degrees C makes the glass indistinguishable from fused silica. The utility of the approach is demonstrated by 3D printing an optical microtoroid resonator, a luminescence source, and a suspended plate on an optical-fiber tip. This approach enables promising applications in fields such as photonics, medicine, and quantum-optics.

Identification and synthesis of 2D topological insulators is particularly elusive. According to previous ab initio predictions 2D InBi (Indium Bismide) is a material exhibiting topological properties which are combined with a band gap suitable for practical applications. We employ ab initio molecular dynamics (AIMD) simulations to assess the thermal stability as well as the mechanical properties such as elastic modulus and stress-strain curves of 2D InBi. The obtained new knowledge adds further characteristics appealing to the feasibility of its synthesis and its potential applications. We find that pristine 2D InBi, H-InBi (hydrogenated 2D InBi) as well as 2D InBi heterostructures with graphene are all stable well above room temperature, being the calculated thermal stability for pristine 2D InBi 850 K and for H-InBi in the range above 500 K. The heterostructures of 2D InBi with graphene exhibit thermal stability exceeding 1000 K. In terms of mechanical properties, pristine 2D InBi exhibits similarities with another 2D material, stanene. The fracture stress for 2D InBi is estimated to be similar to 3.3 GPa (similar to 3.6 GPa for stanene) while elastic modulus of 2D InBi reads similar to 34 GPa (to compare with similar to 23 GPa for stanene). Overall, the thermal stability, elastic, and fracture resistant properties of 2D InBi and its heterostructures with graphene appear as high enough to motivate future attempts directed to its synthesis and characterization.

Thin films of boron nitride in its sp(2)-hybridized form (sp(2)-BN) have potential uses in UV devices and dielectrics. Here, we explore chemical vapor deposition (CVD) of sp(2)-BN on various cuts of sapphire: Al2O3 ( 11 2 over bar 0 ), Al2O3 ( 1 1 over bar 02 ), Al2O3 ( 10 1 over bar 0 ), and Al2O3 (0001) using two CVD processes with two different boron precursors triethylborane and trimethylborane. Fourier transform infrared spectroscopy shows that sp(2)-BN grows on all the sapphire substrates; using x-ray diffraction, 2 theta/omega diffractogram shows that only Al2O3 ( 11 2 over bar 0 ) and Al2O3 (0001) rendered crystalline films: and using phi(phi)-scans, growth of the rhombohedral polytype (r-BN) films on these substrates is confirmed. These films were found to be epitaxially grown on an AlN interlayer with comparatively higher crystalline quality for the films grown on the Al2O3 ( 11 2 over bar 0 ) substrate, which is determined using omega(omega)-scans. Our study suggests that Al2O3 ( 11 2 over bar 0 ) is the most favorable sapphire substrate to realize the envisioned applications of r-BN films.

Conceptual 2D group III nitrides and oxides (e.g., 2D InN and 2D InO) in heterostructures with graphene have been realized by metal-organic chemical vapor deposition (MOCVD). MOCVD is expected to bring forth the same impact in the advancement of 2D semiconductor materials as in the fabrication of established semiconductor materials and device heterostructures. MOCVD employs metal-organic precursors such as trimethyl-indium, -gallium, and -aluminum, with (strong) metal-carbon bonds. Mechanisms that regulate MOCVD processes at the atomic scale are largely unknown. Here, we employ density-functional molecular dynamics - accounting for van der Waals interactions - to identify the reaction pathways responsible for dissociation of the trimethylindium (TMIn) precursor in the gas phase as well as on top-layer and zero-layer graphene. The simulations reveal how collisions with hydrogen molecules, intramolecular or surface-mediated proton transfer, and direct TMIn/graphene reactions assist TMIn transformations, which ultimately enables delivery of In monomers or InH and CH3In admolecules, on graphene. This work provides knowledge for understanding the nucleation and intercalation mechanisms at the atomic scale and for carrying out epitaxial growth of 2D materials and graphene heterostructures.

Tritantalum pentanitride (Ta₃N₅) semiconductor is a promising material for photoelectrolysis of water with high efficiency. Ta₃N₅ is a metastable phase in the complex system of TaN binary compounds. Growing stabilized single-crystal Ta₃N₅ films is correspondingly challenging. Here, we demonstrate the growth of a nearly single-crystal Ta₃N₅ film with epitaxial domains on c-plane sapphire substrate, Al₂O₃(0001), by magnetron sputter epitaxy. Introduction of a small amount ~2% of O₂ into the reactive sputtering gas mixed with N₂ and Ar facilitates the formation of a Ta₃N₅ phase in the film dominated by metallic TaN. In addition, we indicate that a single-phase polycrystalline Ta₃N₅ film can be obtained with the assistance of a Ta₂O₅ seed layer. With controlling thickness of the seed layer smaller than 10 nm and annealing at 1000 °C, a crystalline β phase Ta₂O₅ was formed, which promotes the domain epitaxial growth of Ta₃N₅ films on Al₂O₃(0001). The mechanism behind the stabilization of the orthorhombic Ta₃N₅ structure resides in its stacking with the ultrathin seed layer of orthorhombic β-Ta₂O₅, which is energetically beneficial and reduces the lattice mismatch with the substrate.

Zirconium diboride (ZrB2) films have been deposited by direct current magnetron sputtering (DCMS) from a ZrB2 compound target on Al2O3 (0001) substrates held at 600, 700, 800, and 900 degrees C, and with two different axial magnetic field strengths, 34 and 104 G, generated using a coil surrounding the substrate. Plasma probe measurements show an increase of the ion fluxes on floating-potential substrates of the two different configurations by a factor of 2.8 for 104 G compared to 34 G, while the ion energy remained relatively constant at approximate to 12 eV. Time-of-flight elastic recoil detection analysis (ToF-ERDA) show that films deposited with a magnetic field of 34 G are highly overstoichiometric with B/Zr ratios approximate to 2.4, while films deposited with 104 G exhibit a B/Zr ratios approximate to 2.1. The levels of oxygen and carbon in the films are below 1 at. % irrespective of growth conditions. X-ray diffraction (XRD) 0/20 scans, complemented by pole figure measurements, reveal that all deposited films are 0001-oriented. XRD 0/20 scans of the 000t peak intensities and co (rocking-curve) widths show increased ZrB2 crystal quality with increasing temperature for both magnetic field strengths. Minimum electrical resistivity of approximate to 100 p omega cm is achieved for an axial magnetic field of 104 G, independent of temperature.

Epitaxial growth of ZrB2 films on Si(100) substrates at 900 degrees C is demonstrated using direct-current magnetron sputter deposition from sintered ZrB2 targets. This case of epitaxial growth is structurally more challenging than on Si(111), 4 H-SiC(001), and Al2O3(001). From pole figure measurements, two epitaxial relationships are determined: A) in-plane: ZrB 2 [ 001 ] parallel to Si [ 110 ] and ZrB 2 [ 110 ] parallel to Si [ 110 ] , out-of-plane: ZrB 2 ( 100 ) parallel to Si ( 100 ) , and B) in-plane: ZrB 2 [ 1 2 over bar 1 ] parallel to Si [ 110 ] and the same multiply rotated 90 degrees around the 102 axis, out of plane: ZrB 2 ( 102 ) parallel to Si ( 100 ) . From full width at half maximum (FWHM) values from rocking curve measurements (omega-scans) of the 100 and 102 peaks, a measure of epitaxial quality for these two preferred orientations is obtained. Both omega-scans and theta/2 theta diffractograms show higher quality for the A-type with a FWHM value of 2.00 degrees compared with 4.97 degrees for the B-type. The film composition is found to be ZrB2.3 from time-of-flight elastic recoil detection analysis. The B-type crystallographic relationship ZrB 2 ( 102 ) parallel to Si ( 100 ) and ZrB 2 [ 1 2 over bar 0 ] parallel to Si [ 110 ] has not been previously reported.

We review the thin film growth, chemistry, and physical properties of Group 4-6 transition-metal diboride (TMB2) thin films with AlB2-type crystal structure (Strukturbericht designation C32). Industrial applications are growing rapidly as TMB2 begin competing with conventional refractory ceramics like carbides and nitrides, including pseudo-binaries such as Ti1-xAlxN. The TMB2 crystal structure comprises graphite-like honeycombed atomic sheets of B interleaved by hexagonal close-packed TM layers. From the C32 crystal structure stems unique properties including high melting point, hardness, and corrosion resistance, yet limited oxidation resistance, combined with high electrical conductivity. We correlate the underlying chemical bonding, orbital overlap, and electronic structure to the mechanical properties, resistivity, and high-temperature properties unique to this class of materials. The review highlights the importance of avoiding contamination elements (like oxygen) and boron segregation on both the target and substrate sides during sputter deposition, for better-defined properties, regardless of the boride system investigated. This is a consequence of the strong tendency for B to segregate to TMB2 grain boundaries for boron-rich compositions of the growth flux. It is judged that sputter deposition of TMB2 films is at a tipping point towards a multitude of applications for TMB2 not solely as bulk materials, but also as protective coatings and electrically conducting high-temperature stable thin films.

The electronic structure of rhombohedral sp2-hybridized boron nitride (r-BN) is characterized by X-ray absorption near-edge structure spectroscopy. Measurements are performed at the boron and nitrogen K-edges (1s) and interpreted with first-principles density functional theory calculations, including final state effects by applying a core hole. We show that it is possible to distinguish between different 2D planar polytypes such as rhombohedral, twinned rhombohedral, hexagonal, and turbostratic BN by the difference in chemical shifts. In particular, the chemical shift at the B 1s-edge is shown to be significant for the turbostratic polytype. This implies that the band gap can be tuned by a superposition of different polytypes and stacking of lattice planes.

Boron carbide in its rhombohedral form (r-BxC), commonly denoted B4C or B13C2, is a well-known hard material, but it is also a potential semiconductor material. We deposited r-BxC by chemical vapor deposition between 1100 degrees C and 1500 degrees C from triethylboron in H-2 on 4H-SiC(0001) and 4H-SiC(0001). We show, using ToF-ERDA, that pure B4C was grown at 1300 degrees C, furthermore, using XRD that graphite forms above 1400 degrees C. The films deposited above 1300 degrees C on 4H-SiC(0001) were found to be epitaxial, with the epitaxial relationships B4C(0001)[1010]||4H-SiC(0001)[1010] obtained from pole figure measurements. In contrast, the films deposited on 4H-SiC(0001) were polycrystalline. We suggest that the difference in growth mode is explained by the difference in the ability of the different surfaces of 4H-SiC to act as carbon sources in the initial stages of the film growth.

The influence of the choice of process parameters in an industrial high-power impulse magnetron sputtering (HiPIMS) system on the surface roughness and crystallinity of Ti coatings is presented in this work. A current density of 1 A/cm(2) was kept constant by varying the pulse frequency to control the average power. The films were characterised by scanning electron microscopy, atomic force microscopy, X-ray diffraction and transmission electron microscopy. The surface roughness, residual stress and grain size are discussed as a function of the HiPIMS target average power in the 1.45-7.90 kW range. The surface roughness, ranging from 14 to 24 nm, is lower than that of the SnO2 glass substrate, and has a non-linear dependence on the HiPIMS power. X-ray 20 diffraction shows (100), (001) and (101) orientation of the film crystallites. The peak shifts reveal a gradual reduction in residual stress as target power increases. Further, the effect of target power on crystal grain length and geometric orientation is also determined.

Gold-associated pathfinder minerals have been investigated by identifying host minerals of Au for samples collected from an artisanal mining site near a potential gold mine (Kubi Gold Project) in Dunkwa-On-Offin in the central region of Ghana. We find that for each composition of Au powder (impure) and the residual black hematite/magnetite sand that remains after gold panning, there is a unique set of associated diverse indicator minerals. These indicator minerals are identified as SiO2 (quartz), Fe3O4 (magnetite), and Fe2O3 (hematite), while contributions from pyrite, arsenopyrites, iridosmine, scheelite, tetradymite, garnet, gypsum, and other sulfate materials are insignificant. This constitutes a confirmative identification of Au pathfinding minerals in this particular mineralogical area. The findings suggest that X-ray diffraction could also be applied in other mineralogical sites to aid in identifying indicator minerals of Au and the location of ore bodies at reduced environmental and exploration costs.

MXenes are technologically interesting 2D materials that show potential in numerous applications. The properties of the MXenes depend at large extent on the selection of elements that build the 2D MX-layer. Another key parameter for tuning the attractive material properties is the species that terminate the surfaces of the MX-layers. Although being an important parameter, experimental studies on the bonding between the MX-layers and the termination species are few and thus an interesting subject of investigation. Here we show that the termination species fluorine (F) bonds to the T3C2-surface mainly through Ti 3p – F 2p hybridization and that oxygen (O) bonds through Ti 3p – O 2p hybridization with a significant contribution of Ti 3d and Ti 4p. The study further shows that the T3C2-surface is not only terminated by F and O on the threefold hollow face-centered-cubic (fcc) site. A significant amount of O sits on a bridge site bonded to two Ti surface atoms on the T3C2-surface. In addition, the results provide no support for hydroxide (OH) termination on the T3C2-surface. On the contrary, the comparison of the valence band intensity distribution obtained through ultraviolet- and x-ray photoelectron spectroscopy with computed spectra by density of states, weighed by matrix elements and sensitivity factors, reveals that OH cannot be considered as a inherent termination species in Ti3C2Tx. The results from this study have implications for correct modeling of the structure of MXenes and the corresponding materials properties. Especially in applications where surface composition and charge are important, such as supercapacitors, Li-ion batteries, electrocatalysis, and fuel- and solar cells, where intercalation processes are essential.

X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX) are applied to investigate the properties of fine-grained concentrates on artisanal, small-scale gold mining samples from the Kubi Gold Project of the Asante Gold Corporation near Dunwka-on-Offinin the Central Region of Ghana. Both techniques show that the Au-containing residual sediments are dominated by the host elements Fe, Ag, Al, N, O, Si, Hg, and Ti that either form alloys with gold or with inherent elements in the sediments. For comparison, a bulk nugget sample mainly consisting of Au forms an electrum, i.e., a solid solution with Ag. Untreated (impure) sediments, fine-grained Au concentrate, coarse-grained Au concentrate, and processed ore (Au bulk/nugget)samples were found to contain clusters of O, C, N, and Ag, with Au concentrations significantly lower than that of the related elements. This finding can be attributed to primary geochemical dispersion, which evolved from the crystallization of magma and hydrothermal liquids as well as the migration of metasomatic elements and the rapid rate of chemical weathering of lateralization in secondary processes. The results indicate that Si and Ag are strongly concomitant with Au because of their eutectic characteristics, while N, C, and O follow alongside because of their affinity to Si. These non-noble elements thus act as pathfinders for Au ores in the exploration area. This paper further discusses relationships between gold and sediments of auriferous lodes as key to determining indicator minerals of gold in mining sites.

The emergence of specific and outstanding 2D-structure-related material performance has motivated a search for 2D atomic structures that can even be described as non-van-der-Waals-type materials. This has been exemplified with materials from group IV and group III-V which naturally crystallize in diamond, zincblende or wurtzite crystal structures. Here, we give insight into various atomic structures of indium oxide at the 2D limit featuring different stoichiometry, including 2D InO and 2D In2O3. We find that 2D InO with an InSe-type structure and its characteristic In-In distances compare closely with available first-time experimental results. An as yet unexplored 2D structure of indium oxide is found to be a planar hexagonal monolayer of h-In2O3.

Multicomponent or high-entropy ceramics show unique combinations of mechanical, electrical, and chemical properties of importance in coating applications. However, generalizing controllable thin-film processes for these complex materials remains a challenge. Here, understoichiometric (TiZrTaMe)N1–x (Me = Hf, Nb, Mo, or Cr, 0.12 ≤ x ≤ 0.30) films were deposited on Si(100) substrates at 400 °C by reactive magnetron sputtering using single elemental targets. The influence of ion energy during film growth was investigated by varying the negative substrate bias voltage from ∼10 V (floating potential) to 130 V. The nitrogen content for the samples determined by elastic recoil detection analysis varied from 34.9 to 43.8 at. % (0.12 ≤ x ≤ 0.30), and the metal components were near-equimolar and not affected by the bias voltage. On increasing the substrate bias, the phase structures of (TiZrTaMe)N1–x (Me = Hf, Nb, or Mo) films evolved from a polycrystalline fcc phase to a (002) preferred orientation along with a change in surface morphology from faceted triangular features to a dense and smooth structure with nodular mounds. All the four series of (TiZrTaMe)N1–x (Me = Hf, Nb, Mo, or Cr) films exhibited increasing intrinsic stress with increasing negative bias. The maximum compressive stress reached ∼3.1 GPa in Hf- and Cr-containing films deposited at −130 V. The hardness reached a maximum value of 28.0 ± 1.0 GPa at a negative bias ≥100 V for all the four series of films. The effect of bias on the mechanical properties of (TiNbZrMe)N1–x films can thus guide the design of protective high-entropy nitride films.

The hydrogen evolution reaction (HER) is a key process in electrochemical water splitting. To lower the cost and environmental impact of this process, it is highly motivated to develop electrocatalysts with low or no content of noble metals. Here, we report on an ingenious synthesis of hybrid PtxNi1-x electrocatalysts in the form of a nanoparticle-nanonetwork structure with very low noble metal content. The structure possesses important features such as good electrical conductivity, high surface area, strong interlinking, and substrate adhesion, which render an excellent HER activity. Specifically, the best performing Pt0.05Ni0.95 sample demonstrates a Tafel slope of 30 mV dec-1 in 0.5 M H2SO4 and an overpotential of 20 mV at a current density of 10 mA cm-2 with high stability. The impressive catalytic performance is further rationalized in a theoretical study, which provides insight into the mechanism on how such small platinum content can allow for close-to-optimal adsorption energies for hydrogen.

Realization of semiconductor materials at the two-dimensional (2D) limit can elicit exceptional and diversified performance exercising transformative influence on modern technology. We report experimental evidence for the formation of conceptually new 2D indium oxide (InO) and its material characteristics. The formation of 2D InO was harvested through targeted intercalation of indium (In) atoms and deposition kinetics at graphene/SiC interface using a robust metal organic chemical vapor deposition (MOCVD) process. A distinct structural configuration of two sub-layers of In atoms in "atop" positions was imaged by scanning transmission electron microscopy (STEM). The bonding of oxygen atoms to indium atoms was indicated using electron energy loss spectroscopy (EELS). A wide bandgap energy measuring a value of 4.1 eV was estimated by conductive atomic force microscopy measurements (C-AFM) for the 2D InO.

The initial stages of metal organic chemical vapor deposition (MOCVD) of AlN on epitaxial graphene at temperatures in excess of 1200 degrees C have been rationalized. The use of epitaxial graphene, in conjunction with high deposition temperatures, can deliver on the realization of nanometer thin AlN whose material quality is characterized by the appearance of luminescent centers with narrow spectral emission at room temperature. It has been elaborated, based on our previous comprehensive ab initio molecular dynamics simulations, that the impact of graphene on AlN growth consists in the way it promotes dissociation of the trimethylaluminum, (CH3)(3)Al, precursor with subsequent formation of Al adatoms during the initial stages of the deposition process. The high deposition temperatures ensure adequate surface diffusion of the Al adatoms which is an essential factor in material quality enhancement. The role of graphene in intervening with the dissociation of another precursor, trimethylgallium, (CH3)(3)Ga, has accordingly been speculated by presenting a case of propagation of ultrathin GaN of semiconductor quality. A lower deposition temperature of 1100 degrees C in this case has better preserved the structural integrity of epitaxial graphene. Breakage and decomposition of the graphene layers has been deduced in the case of AlN deposition at temperatures in excess of 1200 degrees C.

We investigate theoretically the electronic and optical absorption properties of two sub-classes of oligosilanes: (i) Si(CH3)(4), Si-4(CH3)(8), and Si-8(CH3)(8) that contain Si dot, ring and cage, respectively, and exhibit typical Si-C and Si-Si bonds; and (ii) persilastaffanes Si7H6(CH3)(6) and Si12H6(CH3)(12), which contain extended delocalized s-electrons in Si-Si bonds over three-dimensional Si frameworks. Our modeling is performed within the GW approach up to the partially self-consistent GW(0) approximation, which is more adequate for reliably predicting the optical band gaps of materials. We examine how the optical properties of these organosilicon compounds depend on their size, geometric features, and Si/C composition. Our results indicate that the present methodology offers a viable way of describing the optical excitations of tailored functional Si-C-based clusters and molecular optical tags with potential use as efficient light absorbers/emitters in molecular optical devices. (C) 2020 The Author(s). Published by Elsevier B.V.

Boron nitride (BN) layers with sp(2) bonding have been grown by metal organic chemical vapor deposition on AlN underlayers, which are deposited on c-plane sapphire substrates. Two different boron precursors were employed-trimethylboron and triethylboron-while ammonia was used as the nitrogen precursor. The BN obtained epitaxial BN films contain ordered rhombohedral (rBN) and partially ordered turbostratic (tBN) stackings as evidenced by x-ray diffraction analysis. We discriminatively identify the PL signatures of the rBN and tBN from those typical of the hexagonal (hBN) and Bernal stackings (bBN). The optical signature of tBN appears at 5.45eV, and it intercalates between the two recombination bands typical of rBN at 5.35eV (strong intensity) and 5.55eV(weaker intensity). The analogs of the high intensity band at 5.35eV in rBN sit at 5.47eV for hBN and at 5.54eV for bBN.

Epitaxial rhombohedral boron nitride (r-BN) films were deposited on ZrB2(0001)/4H-SiC(0001) by chemical vapor deposition at 1485 degrees C from the reaction of triethylboron and ammonia and with a minute amount of silane (SiH4). X-ray diffraction (XRD) w-scans yield the epitaxial relationships of r-BN(0001) k ZrB2(0001) out-of-plane and r-BN[11-20] k ZrB2[11-20] in-plane. Cross-sectional transmission electron microscopy (TEM) micrographs showed that epitaxial growth of r-BN films prevails to similar to 10 nm. Both XRD and TEM demonstrate the formation of carbon- and nitrogen-containing cubic inclusions at the ZrB2 surface. Quantitative analysis from x-ray photoelectron spectroscopy of the r-BN films shows B/N ratios between 1.30 and 1.20 and an O content of 3-4 at. %. Plan-view scanning electron microscopy images reveal a surface morphology where an amorphous material comprising B, C, and N is surrounding the epitaxial twinned r-BN crystals.

Thin films of the sp(2)-hybridized polytypes of boron nitride (BN) are interesting materials for several electronic applications such as UV devices. Deposition of epitaxial sp(2)-BN films has been demonstrated on several technologically important semiconductor substrates such as SiC and Al2O3 and where controlled thin film growth on Si would be beneficial for integration of sp(2)-BN in many electronic device systems. The authors investigate the growth of BN films on Si(111) by chemical vapor deposition from triethylboron [B(C2H5)(3)] and ammonia (NH3) at 1300 degrees C with focus on treatments of the Si(111) surface by nitridation, carbidization, or nitridation followed by carbidization prior to BN growth. Fourier transform infrared spectroscopy shows that the BN films deposited exhibit sp(2) bonding. X-ray diffraction reveals that the sp(2)-BN films predominantly grow amorphous on untreated and pretreated Si(111), but with diffraction data showing that turbostratic BN can be deposited on Si(111) when the formation of Si3N4 is avoided. The authors accomplish this condition by combining the nitridation procedure with reactions from the walls on which BxC had previously been deposited.

The electronic structure, chemical bonding, and interface component in ZrN-AlN nanocomposites formed byphase separation during thin film deposition of metastable Zr1−xAlxN (x = 0.0, 0.12, 0.26, 0.40) are investigatedby resonant inelastic x-ray scattering, x-ray emission, and x-ray absorption spectroscopy and compared to firstprinciples calculations including transitions between orbital angular momentum final states. The experimentalspectra are compared with different interface-slab model systems using first principles all-electron full-potentialcalculations where the core states are treated fully relativistically. As shown in this work, the bulk sensitivity andelement selectivity of x-ray spectroscopy enables one to probe the symmetry and orbital directions at interfacesbetween cubic and hexagonal crystals. We show how the electronic structure develops from local octahedralbond symmetry of cubic ZrN that distorts for increasing Al content into more complex bonding. This results inthree different kinds of bonding originating from semicoherent interfaces with segregated ZrN and lamellar AlNnanocrystalline precipitates. An increasing chemical shift and charge transfer between the elements takes placewith increasing Al content and affects the bond strength and increases resistivity.

The chemical bonding within the transition-metal carbide materials MAX phase Ti₃AlC₂ and MXene Ti₃C₂T_xis investigated by x-ray absorption near-edge structure (XANES) and extended x-ray absorption fine-structure(EXAFS) spectroscopies. MAX phases are inherently nanolaminated materials that consist of alternating layersof M_n+1X_n and monolayers of an A-element from the IIIA or IVA group in the Periodic Table, where M is atransition metal and X is either carbon or nitrogen. Replacing the A-element with surface termination speciesT_x will separate the M_n+1X_n-layers forming two-dimensional (2D) flakes of M_n+1X_nT_x. For Ti₃C₂T_x the T_x corresponds to fluorine (F) and oxygen (O) covering both sides of every single 2D M_n+1X_n-flake. The Ti K-edge(1s) XANES of both Ti₃AlC₂ and Ti₃C₂T_x exhibit characteristic preedge absorption regions of C 2p-Ti 3dhybridization with clear crystal-field splitting while the main-edge absorption features originate from the Ti1s → 4p excitation, where only the latter shows sensitivity toward the fcc-site occupation of the terminationspecies. The coordination numbers obtained from EXAFS show that Ti₃AlC₂ and Ti₃C₂T_x are highly anisotropicwith a strong in-plane contribution for Ti and with a dynamic out-of-plane contribution from the Al monolayersand termination species, respectively. As shown in the temperature-dependent measurements, the O contributionshifts to shorter bond length while the F diminishes as the temperature is raised from room temperature up to 750 °C.

The magnetism in the inherently nanolaminated ternary MAX-phase Cr₂GeC is investigated by element-selective, polarization and temperature-dependent, soft X-ray absorption spectroscopy and X-ray magnetic circular dichroism. The measurements indicate an antiferro-magnetic Cr-Cr coupling along the c-axis of the hexagonal structure modulated by a ferromagnetic ordering in the nanolaminated ab-basal planes. The weak chromium magnetic moments are an order of magnitude stronger in the nanolaminated planes than along the vertical axis. Theoretically, a small but notable, non-spin-collinear component explains the existence of a non-perfect spin compensation along the c-axis. As shown in this work, this spin distortion generates an overall residual spin moment inside the unit cell resembling that of a ferri-magnet. Due to the different competing magnetic interactions, electron correlations and temperature effects both need to be considered to achieve a correct theoretical description of the Cr₂GeC magnetic properties.

The possibility for kinetic stabilization of prospective 2D AlN was explored by rationalizing metal organic chemical vapor deposition (MOCVD) processes of AlN on epitaxial graphene. From the wide range of temperatures which can be covered in the same MOCVD reactor, the deposition was performed at the selected temperatures of 700, 900, and 1240 degrees C. The characterization of the structures by atomic force microscopy, electron microscopy and Raman spectroscopy revealed a broad range of surface nucleation and intercalation phenomena. These phenomena included the abundant formation of nucleation sites on graphene, the fragmentation of the graphene layers which accelerated with the deposition temperature, the delivery of excess precursor-derived carbon adatoms to the surface, as well as intercalation of sub-layers of aluminum atoms at the graphene/SiC interface. The conceptual understanding of these nanoscale phenomena was supported by our previous comprehensiveab initiomolecular dynamics (AIMD) simulations of the surface reaction of trimethylaluminum, (CH3)(3)Al, precursor with graphene. A case of applying trimethylindium, (CH3)(3)In, precursor to epitaxial graphene was considered in a comparative way.

Amorphous boron-carbon-nitrogen (B-C-N) films with low density are potentially interesting as alternative low-dielectric-constant (low-kappa) materials for future electronic devices. Such applications require deposition at temperatures below 300 degrees C, making plasma chemical vapor deposition (plasma CVD) a preferred deposition method. Plasma CVD of B-C-N films is today typically done with separate precursors for B, C and N or with precursors containing B-N bonds and an additional carbon precursor. We present an approach to plasma CVD of B-C-N films based on triethylboron (B(C2H5)(3)), a precursor with B-C bonds, in an argon-nitrogen plasma. From quantitative analysis with time-of-flight elastic recoil detection analysis (ToF-ERDA), we find that the deposition process can afford B-C-N films with a B/N ratio between 0.9-1.3 and B/C ratios between 3.4-8.6 and where the films contain from 3.6 to 7.8 at% H and from 6.6 to 20 at% O. The films have low density, from 0.32 to 1.6 g cm(-3) as determined from cross-section scanning electron micrographs and ToF-ERDA with morphologies ranging from smooth films to separated nanowalls. Scanning transmission electron microscopy shows that C and BN do not phase-separate in the film. The static dielectric constant kappa, measured by capacitance-voltage measurements, varies with the Ar concentration in the range from 3.3 to 35 for low and high Ar concentrations, respectively. We suggest that this dependence is caused by the energetic bombardment of plasma species during film deposition.

We deposit CSx thin solid films by reactive direct current magnetron sputtering of a C target in an argon plasma, using carbon disulfide (CS2) as a precursor to film growth. We investigate the influence of the partial pressure of the CS2 vapor introduced into the plasma on the composition, the chemical bonding structure, the structural, and the mechanical properties as determined by x-ray photoelectron spectroscopy (XPS), Raman spectroscopy, scanning electron microscopy (SEM), and nanoindentation for films deposited at 150 and 300 degrees C. The Raman and the XPS results indicate that S atoms are incorporated in mostly sp(2) bonded C network. These results agree with previous ab-initio theoretical findings obtained by modeling of the CSx compound by the Synthetic Growth Concept. The microstructure of the films as well as the results of their Raman characterization and the nano mechanical testing results all point out that with the increasing S content some spa bonding is admixed in the predominantly sp(2) bonded CSx network, leading to typical amorphous structure with short and interlocked graphene-like planes for S contents between 2% and 8%. We conclude that CSx thin solid films deposited by using CS2 as a precursor would be CSx films deposited at low temperature of similar to 150 degrees C and with an S content in the region of 6 at.% may be interesting candidates for applications as hard/elastic protective coatings.