Phase composition and transformations in magnetron-sputtered (Al,V)2O3 coatings

Coatings of (Al1-xVx)2O3, with x ranging from 0 to 1, were deposited by pulsed DC reactive sputter deposition on Si(100) at a temperature of 550 {\deg}C. XRD showed three different crystal structures depending on V-metal fraction in the coating: {\alpha}-V2O3 rhombohedral structure for 100 at.% V, a defect spinel structure for the intermediate region, 63 - 42 at.% V. At lower V-content, 18 and 7 at.%, a gamma-alumina-like solid solution was observed, shifted to larger d-spacing compared to pure {\gamma}-Al2O3. The microstructure changes from large columnar faceted grains for {\alpha}-V2O3 to smaller equiaxed grains when lowering the vanadium content toward pure {\gamma}-Al2O3. Annealing in air resulted in formation of V2O5 crystals on the surface of the coating after annealing to 500 {\deg}C for 42 at.% V and 700 {\deg}C for 18 at.% V metal fraction respectively. The highest thermal stability was shown for pure {\gamma}-Al2O3-coating, which transformed to {\alpha}-Al2O3 after annealing to 1100{\deg} C. Highest hardness was observed for the Al-rich oxides, ~24 GPa. The latter decreased with increasing V-content, larger than 7 at.% V metal fraction. The measured hardness after annealing in air decreased in conjunction with the onset of further oxidation of the coatings

Electronic structure and chemical bonding of nc-TiC/a-C nanocomposites

The electronic structure of nanocrystalline (nc-) TiC/amorphous C nanocomposites has been investigated by soft x-ray absorption and emission spectroscopy. The measured spectra at the Ti 2p and C 1s thresholds of the nanocomposites are compared to those of Ti metal and amorphous C. The corresponding intensities of the electronic states for the valence and conduction bands in the nanocomposites are shown to strongly depend on the TiC carbide grain size. An increased charge-transfer between the Ti 3d-eg states and the C 2p states has been identified as the grain size decreases, causing an increased ionicity of the TiC nanocrystallites. It is suggested that the charge-transfer occurs at the interface between the nanocrystalline TiC and the amorphous C matrix and represents an interface bonding which may be essential for the understanding of the properties of nc-TiC/amorphous C and similar nanocomposites.Comment: 13 pages, 6 figures, 1 table; http://link.aps.org/doi/10.1103/PhysRevB.80.23510

A 10B-based neutron detector with stacked Multiwire Proportional Counters and macrostructured cathodes

We present the results of the measurements of the detection efficiency for a 4.7 \r{A} neutron beam incident upon a detector incorporating a stack of up to five MultiWire Proportional Counters (MWPC) with Boron-coated cathodes. The cathodes were made of Aluminum and had a surface exhibiting millimeter-deep V-shaped grooves of 45{\deg}, upon which the thin Boron film was deposited by DC magnetron sputtering. The incident neutrons interacting with the converter layer deposited on the sidewalls of the grooves have a higher capture probability, owing to the larger effective absorption film thickness. This leads to a higher overall detection efficiency for the grooved cathode when compared to a cathode with a flat surface. Both the experimental results and the predictions of the GEANT4 model suggests that a 5-counter detector stack with coated grooved cathodes has the same efficiency as a 7-counter stack with flat cathodes. The reduction in the number of counters in the stack without altering the detection efficiency will prove highly beneficial for large-area position-sensitive detectors for neutron scattering applications, for which the cost-effective manufacturing of the detector and associated readout electronics is an important objective. The proposed detector concept could be a technological option for one of the new chopper spectrometers and other instruments planned to be built at the future European Spallation Source in Sweden. These results with macrostructured cathodes generally apply not just to MWPCs but to other gaseous detectors as well.Comment: 14 pages, 9 figure

Self-organized nanostructuring in Zr0.69Al0.31N thin films studied by atom probe tomography

We have applied atom probe tomography (APT) to analyze self-organizing structures of wear-resistant Zr0.69Al0.31N thin films grown by magnetron sputtering. Transmission electron microscopy shows that these films grow as a three-dimensional nanocomposite, consisting of interleaved lamellae in a labyrinthine structure, with an in-plane size scale of ~ 5 nm. The structure was recovered in the Al APT signal, while the Zr and N data lacked structural information. The onset of the self-organized labyrinthine growth was observed to occur by surface nucleation, 5–8 nm above the MgO substrate, due to increasing Zr–Al compositional fluctuations during elemental segregation. At a final stage, the labyrinthine growth mode was observed to be interrupted by the formation of larger ZrN grains

Bonding mechanism in the nitrides Ti2AlN and TiN: an experimental and theoretical investigation

The electronic structure of nanolaminate Ti2AlN and TiN thin films has been investigated by bulk-sensitive soft x-ray emission spectroscopy. The measured Ti L, N K, Al L1 and Al L2,3 emission spectra are compared with calculated spectra using ab initio density-functional theory including dipole transition matrix elements. Three different types of bond regions are identified; a relatively weak Ti 3d - Al 3p bonding between -1 and -2 eV below the Fermi level, and Ti 3d - N 2p and Ti 3d - N 2s bonding which are deeper in energy observed at -4.8 eV and -15 eV below the Fermi level, respectively. A strongly modified spectral shape of 3s states of Al L2,3 emission from Ti2AlN in comparison to pure Al metal is found, which reflects the Ti 3d - Al 3p hybridization observed in the Al L1 emission. The differences between the electronic and crystal structures of Ti2AlN and TiN are discussed in relation to the intercalated Al layers of the former compound and the change of the materials properties in comparison to the isostructural carbides.Comment: 18 pages, 7 figures; http://link.aps.org/doi/10.1103/PhysRevB.76.19512

Electronic structure and chemical bonding in Ti4SiC3 investigated by soft x-ray emission spectroscopy and first principle theory

The electronic structure in the new transition metal carbide Ti4SiC3 has been investigated by bulk-sensitive soft x-ray emission spectroscopy and compared to the well-studied Ti3SiC2 and TiC systems. The measured high-resolution Ti L, C K and Si L x-ray emission spectra are discussed with ab initio calculations based on density-functional theory including core-to-valence dipole matrix elements. The detailed investigations of the Ti-C and Ti-Si chemical bonds provide increased understanding of the physical properties of these nanolaminates. A strongly modified spectral shape is detected for the buried Si monolayers due to Si 3p hybridization with the Ti 3d orbitals. As a result of relaxation of the crystal structure and the charge-transfer from Ti (and Si) to C, the strength of the Ti-C covalent bond is increased. The differences between the electronic and crystal structures of Ti4SiC3 and Ti3SiC2 are discussed in relation to the number of Si layers per Ti layer in the two systems and the corresponding change of materials properties.Comment: 12 pages, 7 figures, 1 tabl

Electronic structure investigation of Ti3AlC2, Ti3SiC2, and Ti3GeC2 by soft-X-ray emission spectroscopy

The electronic structures of epitaxially grown films of Ti3AlC2, Ti3SiC2 and Ti3GeC2 have been investigated by bulk-sensitive soft X-ray emission spectroscopy. The measured high-resolution Ti L, C K, Al L, Si L and Ge M emission spectra are compared with ab initio density-functional theory including core-to-valence dipole matrix elements. A qualitative agreement between experiment and theory is obtained. A weak covalent Ti-Al bond is manifested by a pronounced shoulder in the Ti L-emission of Ti3AlC2. As Al is replaced with Si or Ge, the shoulder disappears. For the buried Al and Si-layers, strongly hybridized spectral shapes are detected in Ti3AlC2 and Ti3SiC2, respectively. As a result of relaxation of the crystal structure and the increased charge-transfer from Ti to C, the Ti-C bonding is strengthened. The differences between the electronic structures are discussed in relation to the bonding in the nanolaminates and the corresponding change of materials properties.Comment: 15 pages, 8 figure