Atomic and electronic structure of graphene oxide/Cu interface

The results of X-ray photoemission (XPS) and valence bands spectroscopy, optically stimulated electron emission (OSEE) measurements and density functional theory based modeling of graphene oxide (GO) placed on Cu via an electrophoretic deposition (EPD) are reported. The comparison of XPS spectra of EPD prepared GO/Cu composites with those of as prepared GO, strongly reduced GO, pure and oxidized copper demonstrate the partial (until C/O ratio about two) removal of oxygen-containing functional groups from GO simultaneously with the formation of copper oxide-like layers over the metallic substrate. OSEE measurements evidence the presence of copper oxide phase in the systems simultaneously with the absence of contributions from GO with corresponding energy gap. All measurements demonstrate the similarity of the results for different thickness of GO cover of the copper surface. Theoretical modeling demonstrates favorability of migration of oxygen-containing functional groups from GO to the copper substrate only for the case of C/O ratio below two and formation of Cu-O-C bonds between substrate and GO simultaneously with the vanishing of the energy gap in GO layer. Basing on results of experimental measurements and theoretical calculations we suggest the model of atomic structure for Cu/GO interface as Cu/CuO/GO with C/O ratio in gapless GO about two.Comment: 22 pages, 14 figures, accepted to Thin Solid Films journa

Influence of Alkali Treatment on Anodized Titanium Alloys in Wollastonite Suspension

The surface modification of titanium alloys is an effective method to improve their biocompatibility and tailor the material to the desired profile of implant functionality. In this work, technologically-advanced titanium alloys—Ti-15Mo, Ti-13Nb-13Zr and Ti-6Al-7Nb—were anodized in suspensions, followed by treatment in alkali solutions, with wollastonite deposition from the powder phase suspended in solution. The anodized samples were immersed in NaOH or KOH solution with various concentrations with a different set of temperatures and exposure times. Based on their morphologies (observed by scanning electron microscope), the selected samples were investigated by Raman and X-ray photoelectron spectroscopy (XPS). Titaniate compounds were formed on the previously anodized titanium surfaces. The surface wettability significantly decreased, mainly on the modified Ti-15Mo alloy surface. Titanium alloy compounds had an influence on the results of the titanium alloys’ surface modification, which caused the surfaces to exhibit differential physical properties. In this paper, we present the influence of the anodization procedure on alkali treatment effects and the properties of obtained hybrid coatings

Selective Area Band Engineering of Graphene using Cobalt-Mediated Oxidation

This study reports a scalable and economical method to open a band gap in single layer graphene by deposition of cobalt metal on its surface using physical vapor deposition in high vacuum. At low cobalt thickness, clusters form at impurity sites on the graphene without etching or damaging the graphene. When exposed to oxygen at room temperature, oxygen functional groups form in proportion to the cobalt thickness that modify the graphene band structure. Cobalt/Graphene resulting from this treatment can support a band gap of 0.30 eV, while remaining largely undamaged to preserve its structural and electrical properties. A mechanism of cobalt-mediated band opening is proposed as a two-step process starting with charge transfer from metal to graphene, followed by formation of oxides where cobalt has been deposited. Contributions from the formation of both CoO and oxygen functional groups on graphene affect the electronic structure to open a band gap. This study demonstrates that cobalt-mediated oxidation is a viable method to introduce a band gap into graphene at room temperature that could be applicable in electronics applications

Pronounced, Reversible, and in Situ Modification of the Electronic Structure of Graphene Oxide via Buckling below 160 K

We have shown that the electronic structure of graphene oxide is strongly, but reversibly, affected by temperature. Below 160 K, graphene oxide is much more completely oxidized, removing any last remaining π-conjugated network. Through DFT simulations, we have shown that this is due to buckling-induced oxidation. As temperature is reduced, the lightly oxidized, graphene-like zones attempt to expand due to a negative thermal expansion coefficient (TEC), but the heavily oxidized zones, with a TEC that is near zero, prevent this from happening. This contributes to localized buckling. The deformed regions oxidize much more readily, and the 1,2-epoxide groups form a new type of functional group never before seen: a triply bonded oxygen, bonded at the 1,3,5 sites of the hexagonal carbon rings. We have called this group TB-epoxide. Stable only under buckling, the TB-epoxide groups revert back to 1,2-epoxides once the lattice relaxes to a flatter profile. We have shown that one can alter the electronic structure of graphene oxide to induce temporary, but more complete, oxidation via strain

Spectral and magnetic properties of Na2RuO3

We present measurements of resistivity, x-ray absorption (XAS) and emission (XES) spectroscopy together with ab initio band structure calculations for quasi two dimensional ruthenate Na2RuO3. Density function calculations (DFT) and XAS and XES spectra both show that Na2RuO3 is a semiconductor with an activation energy of ∼80 meV. Our DFT calculations reveal large magneto-elastic coupling in Na2RuO3 and predict that the ground state of Na2RuO3 should be antiferromagnetic zig-zag. © 2017 IOP Publishing Lt