Stability of boron-doped graphene/copper interface: DFT, XPS and OSEE studies

Two different types of boron-doped graphene/copper interfaces synthesized using two different flow rates of Ar through the bubbler containing the boron source were studied. X-ray photoelectron spectra (XPS) and optically stimulated electron emission (OSEE) measurements have demonstrated that boron-doped graphene coating provides a high corrosion resistivity of Cu-substrate with the light traces of the oxidation of carbon cover. The density functional theory calculations suggest that for the case of substitutional (graphitic) boron-defect only the oxidation near boron impurity is energetically favorable and creation of the vacancies that can induce the oxidation of copper substrate is energetically unfavorable. In the case of non-graphitic boron defects oxidation of the area, a nearby impurity is metastable that not only prevent oxidation but makes boron-doped graphene. Modeling of oxygen reduction reaction demonstrates high catalytic performance of these materials.Comment: 15 pages, 8 figures, to appear in Appl. Surf. Sc

Atomic and electronic structure of a copper/graphene interface as prepared and 1.5 years after

We report the results of X-ray spectroscopy and Raman measurements of as-prepared graphene on a high quality copper surface and the same materials after 1.5 years under different conditions (ambient and low humidity). The obtained results were compared with density functional theory calculations of the formation energies and electronic structures of various structural defects in graphene/Cu interfaces. For evaluation of the stability of the carbon cover, we propose a two-step model. The first step is oxidation of the graphene, and the second is perforation of graphene with the removal of carbon atoms as part of the carbon dioxide molecule. Results of the modeling and experimental measurements provide evidence that graphene grown on high-quality copper substrate becomes robust and stable in time (1.5 years). However, the stability of this interface depends on the quality of the graphene and the number of native defects in the graphene and substrate. The effect of the presence of a metallic substrate with defects on the stability and electronic structure of graphene is also discussed.Comment: 18 pages, 6 figures, accepted to Appl. Surf. Sc

Residual stresses in Ti6Al4V alloy after surface texturing by femtosecond laser pulses

Surface topography and residual stresses in surface layers of α + β titanium alloy Ti6Al4V textured by 1030-nm, 320-fs-laser pulses were studied by scanning electron microscopy and X-ray diffraction analysis. It was found that multipulse laser processing leads to the formation of laser-induced periodic surface structures (LIPSS) on the surface of Ti6Al4V alloy. XRD studies showed that depending on the laser pulse fluence, both tensile and compressive residual stresses are formed in thin near-surface layer

XPS and DFT study of pulsed Bi-implantation of bulk and thin-films of ZnO - the role of oxygen imperfections

An atomic and electronic structure of the bulk and thin-film morphologies of ZnO were modified using pulsed Bi-ion implantation (1x1017 cm-2 fluence, 70 min exposure under Bi-ion beam, EBi+ = 30 keV, pulsed ion-current density of not more than 0.8 mA/cm2 with a repetition rate of 12.5 Hz). The final samples were qualified by X-ray photoelectron core-level and valence band mapping spectroscopy applying ASTM materials science standard. The spectroscopy data obtained was discussed on the basis of DFT-models for Bi-embedding into ZnO host-matrices. It was established that in the case of direct Bi-impurities insertion into the employed ZnO-host for both studied morphologies neither the only "pure" Bi2O3-like phase nor the only "pure" Bi-metal will be preferable to appear as a secondary phase. An unfavorability of the large cluster agglomeration of Bi-impurities in ZnO-hosts has been shown and an oxygen 2s electronic states pleomorphizm was surely established.Comment: 20 pages, 8 figures, 2 tables, accepted to Appl. Surf. Sc

Formation of the oxide coating on the titanium surface by multipulse femtosecond laser irradiation

The effect of the femtosecond laser irradiation on the formation of oxide layers on the surface of a commercially pure titanium VT1-0 was studied. The methods of X-ray analysis, scanning electron and transmission electron microscopies were used to study the structural and phase state of oxide layers. As a result of the femtosecond laser irradiation, the porous multi-phase nanocrystalline oxide coating with a thickness of 50 µm is formed on the titanium surfac

Structural defects induced by Fe-ion implantation in TiO2

X-ray photoelectron spectroscopy (XPS) and resonant x-ray emission spectroscopy (RXES) measurements of pellet and thin film forms of TiO$_2$ with implanted Fe ions are presented and discussed. The findings indicate that Fe-implantation in a TiO$_2$ pellet sample induces heterovalent cation substitution (Fe$^{2+}\rightarrow$ Ti$^{4+}$) beneath the surface region. But in thin film samples, the clustering of Fe atoms is primarily detected. In addition to this, significant amounts of secondary phases of Fe$^{3+}$ are detected on the surface of all doped samples due to oxygen exposure. These experimental findings are compared with density functional theory (DFT) calculations of formation energies for different configurations of structural defects in the implanted TiO$_2$:Fe system. According to our calculations, the clustering of Fe-atoms in TiO$_2$:Fe thin films can be attributed to the formation of combined substitutional and interstitial defects. Further, the differences due to Fe doping in pellet and thin film samples can ultimately be attributed to different surface to volume ratios.Comment: 7+ pages, 3 Figure, to appear in J. Appl. Phy

Optical transparency and local electronic structure of Yb-doped Y 2 O 3 ceramics with tetravalent additives

The results of optical transmission and X-ray core-level spectra measurements of Yb:Y 2 O 3 ceramics with different tetravalent sintering additives (ZrO 2 , CeO 2 and HfO 2 ) fabricated from nanopowders (produced by the laser ablation method) and then annealed at 1400 °C in air for 2 h are presented. It is found that the transmission values for ZrO 2 - and HfO 2 -doped ceramics at the lasing wavelengths are higher than those of CeO 2 -doped samples. The X-ray photoelectron spectra (XPS) O 1s spectra show that the relative intensity of oxygen defect peak detected for 3Yb:Y 2 O 3 + 5CeO 2 ceramics decreases substantially and consistently compared to that of 5Yb:Y 2 O 3 + 5HfO 2 and 3Yb:Y 2 O 3 + 5ZrO 2 samples. This can be attributed to a more complete filling of oxygen vacancies due to annealing-induced oxygen diffusion into the highly defective sintered ceramics. The measurements of XPS Ce 3d spectra showed that the insufficiently complete filling of the oxygen vacancies in the 3Yb:Y 2 O 3 + 5CeO 2 compound is due to the appreciable presence of trivalent cerium ions. © 2019 by the authors.Ministry of Education and Science of the Russian Federation, Minobrnauka: 3.7270.2017/8.9This study was supported by FASO (Theme "Electron" No. AAAA-A18-118020190098-5). The XPS measurements were supported by the Ministry of Education and Science of the Russian Federation (Project No. 3.7270.2017/8.9) and the Government of the Russian Federation (Act 211, agreement No. 02.A03.21.0006). Fabrication of ceramic samples was performed in the framework of the state task of IEP UB RAS