M. Sky Driver

Surface modification of several dental substrates by non-thermal, atmospheric plasma brush

OBJECTIVE The purpose of this study was to reveal the effectiveness of non-thermal atmospheric plasma brush in surface wettability and modification of four dental substrates. METHODS Specimens of dental substrates including dentin, enamel, and two composites Filtek Z250, Filtek LS Silorane were prepared (∼2mm thick, ∼10mm diameter). The prepared surfaces were treated for 5-45s with a non-thermal atmospheric plasma brush working at temperatures from 36 to 38°C. The plasma-treatment effects on these surfaces were studied with contact-angle measurement, X-ray photoemission spectroscopy (XPS) and scanning electron microscopy (SEM). RESULTS The non-thermal atmospheric argon plasma brush was very efficient in improving the surface hydrophilicity of four substrates studied. The results indicated that water contact angle values decreased considerably after only 5s plasma treatment of all these substrates. After 30s treatment, the values were further reduced to <5°, which was close to a value for super hydrophilic surfaces. XPS analysis indicated that the percent of elements associated with mineral in dentin/enamel or fillers in the composites increased. In addition, the percent of carbon (%C) decreased while %O increased for all four substrates. As a result, the O/C ratio increased dramatically, suggesting that new oxygen-containing polar moieties were formed on the surfaces after plasma treatment. SEM surface images indicated that no significant morphology change was induced on these dental substrates after exposure to plasmas. SIGNIFICANCE Without affecting the bulk properties, a super-hydrophilic surface could be easily achieved by the plasma brush treatment regardless of original hydrophilicity/hydrophobicity of dental substrates tested.

Electronic, magnetic, and physical structure of cobalt deposited on aluminum tris"8-hydroxy quinoline…

X-ray and ultraviolet photoemission of Co deposited onto aluminum tris(8-hydroxyquinoline) (Alq3) is investigated in situ. The initial Co deposited onto Alq3 reacts to form a complex. After 1 nm of Co is deposited core level and valence band spectra show evidence for the formation of metallic cobalt. After 2 nm of Co is deposited onto Alq3 x-ray magnetic circular dichroism spectra reveals the Co is ferromagnetic at 300 K. Transmission electron microscopy images show an abrupt interface between Co and Alq3 with minimal intermixing. These results provide valuable insight into the electronic, magnetic, and physical structure of the Co/Alq3 interface.

Atomic Layer Epitaxy of h-BN(0001) Multilayers on Co(0001) and Molecular Beam Epitaxy Growth of Graphene on h-BN(0001)/Co(0001)

The direct growth of hexagonal boron nitride (h-BN) by industrially scalable methods is of broad interest for spintronic and nanoelectronic device applications. Such applications often require atomically precise control of film thickness and azimuthal registry between layers and substrate. We report the formation, by atomic layer epitaxy (ALE), of multilayer h-BN(0001) films (up to 7 monolayers) on Co(0001). The ALE process employs BCl3/NH3 cycles at 600 K substrate temperature. X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED) data show that this process yields an increase in h-BN average film thickness linearly proportional to the number of BCl3/NH3 cycles, with BN layers in azimuthal registry with each other and with the Co(0001) substrate. LEED diffraction spot profile data indicate an average BN domain size of at least 1900 Å. Optical microscopy data indicate the presence of some domains as large as ∼20 μm. Transmission electron microscopy (TEM) and ambient exposure studies demonstrate macroscopic and microscopic continuity of the h-BN film, with the h-BN film highly conformal to the Co substrate. Photoemission data show that the h-BN(0001) film is p-type, with band bending near the Co/h-BN interface. Growth of graphene by molecular beam epitaxy (MBE) is observed on the surface of multilayer h-BN(0001) at temperatures of 800 K. LEED data indicate azimuthal graphene alignment with the h-BN and Co(0001) lattices, with domain size similar to BN. The evidence of multilayer BN and graphene azimuthal alignment with the lattice of the Co(0001) substrate demonstrates that this procedure is suitable for scalable production of heterojunctions for spintronic applications.

The local physical structure of amorphous hydrogenated boron carbide: insights from magic angle spinning solid-state NMR spectroscopy

Magic angle spinning solid-state nuclear magnetic resonance spectroscopy techniques are applied to the elucidation of the local physical structure of an intermediate product in the plasma-enhanced chemical vapour deposition of thin-film amorphous hydrogenated boron carbide (B(x)C:H(y)) from an orthocarborane precursor. Experimental chemical shifts are compared with theoretical shift predictions from ab initio calculations of model molecular compounds to assign atomic chemical environments, while Lee-Goldburg cross-polarization and heteronuclear recoupling experiments are used to confirm atomic connectivities. A model for the B(x)C:H(y) intermediate is proposed wherein the solid is dominated by predominantly hydrogenated carborane icosahedra that are lightly cross-linked via nonhydrogenated intraicosahedral B atoms, either directly through B-B bonds or through extraicosahedral hydrocarbon chains. While there is no clear evidence for extraicosahedral B aside from boron oxides, ∼40% of the C is found to exist as extraicosahedral hydrocarbon species that are intimately bound within the icosahedral network rather than in segregated phases.

Sublattice-induced symmetry breaking and band-gap formation in graphene

A reduction of symmetry from C6v to C3v leads to the opening of a band gap in the otherwise gapless semiconductor graphene. Simple models provide a fairly complete picture of this mechanism for opening a band gap and in fact can be discussed in terms of the tight-binding approximation, accurately resolving the wave-vector space to a very high accuracy. This picture is consistent with experiments that yield a band gap due to A and B graphene-site symmetry breaking due to substrate interactions.

The electronic and chemical structure of the a-B3CO0.5:Hy-to-metal interface from photoemission spectroscopy: implications for Schottky barrier heights

The electronic and chemical structure of the metal-to-semiconductor interface was studied by photoemission spectroscopy for evaporated Cr, Ti, Al and Cu overlayers on sputter-cleaned as-deposited and thermally treated thin films of amorphous hydrogenated boron carbide (a-B(x)C:H(y)) grown by plasma-enhanced chemical vapor deposition. The films were found to contain ~10% oxygen in the bulk and to have approximate bulk stoichiometries of a-B(3)CO(0.5):H(y). Measured work functions of 4.7/4.5 eV and valence band maxima to Fermi level energy gaps of 0.80/0.66 eV for the films (as-deposited/thermally treated) led to predicted Schottky barrier heights of 1.0/0.7 eV for Cr, 1.2/0.9 eV for Ti, 1.2/0.9 eV for Al, and 0.9/0.6 eV for Cu. The Cr interface was found to contain a thick partial metal oxide layer, dominated by the wide-bandgap semiconductor Cr(2)O(3), expected to lead to an increased Schottky barrier at the junction and the formation of a space-charge region in the a-B(3)CO(0.5):H (y) layer. Analysis of the Ti interface revealed a thick layer of metal oxide, comprising metallic TiO and Ti (2)O (3), expected to decrease the barrier height. A thinner, insulating Al(2)O(3) layer was observed at the Al-to-a-B(3)CO(0.5):H(y) interface, expected to lead to tunnel junction behavior. Finally, no metal oxides or other new chemical species were evident at the Cu-to-a-B(3)CO(0.5):H(y) interface in either the core level or valence band photoemission spectra, wherein characteristic metallic Cu features were observed at very thin overlayer coverages. These results highlight the importance of thin-film bulk oxygen content on the metal-to-semiconductor junction character as well as the use of Cu as a potential Ohmic contact material for amorphous hydrogenated boron carbide semiconductor devices such as high-efficiency direct-conversion solid-state neutron detectors.

Semiconducting boron carbides with better charge extraction through the addition of pyridine moieties

The plasma-enhanced chemical vapor (PECVD) co-deposition of pyridine and 1,2 dicarbadodecaborane, 1,2-B10C2H12 (orthocarborane) results in semiconducting boron carbide composite films with a significantly better charge extraction than plasma-enhanced chemical vapor deposited semiconducting boron carbide synthesized from orthocarborane alone. The PECVD pyridine/orthocarborane based semiconducting boron carbide composites, with pyridine/orthocarborane ratios ~3:1 or 9:1 exhibit indirect band gaps of 1.8 eV or 1.6 eV, respectively. These energies are less than the corresponding exciton energies of 2.0 eV–2.1 eV. The capacitance/voltage and current/voltage measurements indicate the hole carrier lifetimes for PECVD pyridine/orthocarborane based semiconducting boron carbide composites (3:1) films of ~350 µs compared to values of ≤35 µs for the PECVD semiconducting boron carbide films fabricated without pyridine. The hole carrier lifetime values are significantly longer than the initial exciton decay times in the region of ~0.05 ns and 0.27 ns for PECVD semiconducting boron carbide films with and without pyridine, respectively, as suggested by the time-resolved photoluminescence. These data indicate enhanced electron–hole separation and charge carrier lifetimes in PECVD pyridine/orthocarborane based semiconducting boron carbide and are consistent with the results of zero bias neutron voltaic measurements indicating significantly enhanced charge collection efficiency.

Atomic layer-by-layer deposition of h-BN(0001) on cobalt: a building block for spintronics and graphene electronics

X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and Raman measurements demonstrate that macroscopically continuous hexagonal BN(0001) (h-BN) multilayer layer films can be grown by atomic layer deposition on Co(0001) substrates. The growth procedure involves alternating exposures of BCl3 and NH3 at 550 K, followed by annealing in ultrahigh vacuum above 700 K to induce long-range order. XPS data demonstrate that the films have a consistent B:N atomic ratio of 1:1. LEED data show that the BN layers are azimuthally in registry, with an estimated domain size of ~170 A. The films are continuous over a macroscopic (1 cm × 1 cm) area as demonstrated by the fact that exposure of a h-BN(0001) bi-layer film to ambient at room temperature yields no observable Co oxidation, although some N oxidation is observed, and long range order is lost. The ability to grow large area, continuous multilayer BN films on Co, with atomic level control of film thickness, makes possible an array of magnetic tunnel junction and spin filter applications.

Work function characterization of solution-processed cobalt silicide

Cobalt silicide thin films were prepared by spin-coating liquid cyclohexasilane-based inks onto silicon substrates followed by a thermal treatment. The work function of the solution-processed Co–Si was determined by both capacitance–voltage (C–V) measurements of metal–oxide–semiconductor (MOS) structures as well as by ultraviolet photoemission spectroscopy (UPS). Variable frequency C–V of MOS structures with silicon oxide layers of variable thickness showed that solution-processed metal silicide films exhibit a work function of 4.36 eV with one Co–Si film on Si � 100 � giving a UPS-derived work function of 4.80 eV. Similar work function measurements were collected for vapor-deposited MOS capacitors where Al thin films were prepared according to standard class 100 cleanroom handling techniques. In both instances, the work function values established by the electrical measurements were lower than those measured by UPS and this difference appears to be a consequence of parasitic series resistance.

Nucleation of graphene layers on magnetic oxides: Co3O4(111) and Cr2O3(0001) from theory and experiment

We report directly grown strongly adherent graphene on Co3O4(111) by carbon molecular beam epitaxy (C MBE) at 850 K and density functional theory (DFT) findings that the first graphene layer is reconstructed to fit the Co3O4 surface, while subsequent layers retain normal graphene structure. This adherence to the Co3O4 structure results from partial bonding of half the carbons to top oxygens of the substrate. This structure is validated by X-ray photoelectron spectroscopy and low-energy electron diffraction studies, showing layer-by-layer graphene growth with ∼0.08 electrons/carbon atom transferred to the oxide from the first graphene layer, in agreement with DFT. In contrast, for Cr2O3 DFT finds no strong bonding to the surface and C MBE on Cr2O3(0001) yields only graphite formation at 700 K, with C desorption above 800 K. Thus strong graphene-to-oxide charge transfer aids nucleation of graphene on incommensurate oxide substrates and may have implications for spintronics.