Oxidation behavior of graphene-coated copper at intrinsic graphene defects of different origins

The development of ultrathin barrier films is vital to the advanced semiconductor industry. Graphene appears to hold promise as a protective coating; however, the polycrystalline and defective nature of engineered graphene hinders its practical applications. Here, we investigate the oxidation behavior of graphene-coated Cu foils at intrinsic graphene defects of different origins. Macro-scale information regarding the spatial distribution and oxidation resistance of various graphene defects is readily obtained using optical and electron microscopies after the hot-plate annealing. The controlled oxidation experiments reveal that the degree of structural deficiency is strongly dependent on the origins of the structural defects, the crystallographic orientations of the underlying Cu grains, the growth conditions of graphene, and the kinetics of the graphene growth. The obtained experimental and theoretical results show that oxygen radicals, decomposed from water molecules in ambient air, are effectively inverted at Stone-Wales defects into the graphene/Cu interface with the assistance of facilitators

Inverted orbital polarization in strained correlated oxide films

Manipulating the orbital occupation of valence electrons via epitaxial strain in an effort to induce new functional properties requires considerations of how changes in the local bonding environment affect the band structure at the Fermi level. Using synchrotron radiation to measure the x-ray linear dichroism of epitaxially strained films of the correlated oxide CaFeO3, we demonstrate that the orbital polarization of the Fe valence electrons is opposite from conventional understanding. Although the energetic ordering of the Fe 3d orbitals is confirmed by multiplet ligand field theory analysis to be consistent with previously reported strain-induced behavior, we find that the nominally higher energy orbital is more populated than the lower. We ascribe this inverted orbital polarization to an anisotropic bandwidth response to strain in a compound with nearly filled bands. These findings provide an important counterexample to the traditional understanding of strain-induced orbital polarization and reveal a method to engineer otherwise unachievable orbital occupations in correlated oxides

Distinguishing electronic contributions of surface and sub-surface transition metal atoms in Ti-based MXenes

MXenes are a rapidly-expanding family of 2D transition metal carbides and nitrides that have attracted attention due to their excellent performance in applications ranging from energy storage to electromagnetic interference shielding. Numerous other electronic and magnetic properties have been computationally predicted, but not yet realized due to the experimental difficulty in obtaining uniform surface terminations (Tx), necessitating new design approaches for MXenes that are independent of surface terminations. In this study, we distinguished the contributions of surface and sub-surface Ti atoms to the electronic structure of four Ti-containing MXenes (Ti2CTx, Ti3C2Tx, Cr2TiC2Tx, and Mo2TiC2Tx) using soft x-ray absorption spectroscopy. For MXenes with no Ti atoms on the surface transition metal layers, such as Mo2TiC2Tx and Cr2TiC2Tx, our results show minimal changes in the spectral features between the parent MAX phase and its MXene. In contrast, for MXenes with surface Ti atoms, here Ti3C2Tx and Ti2CTx, the Ti L-edge spectra are significantly modified compared to their parent MAX phase compounds. First principles calculations provide similar trends in the partial density of states derived from surface and sub-surface Ti atoms, corroborating the spectroscopic measurements. These results reveal that electronic states derived from sub-surface M-site layers are largely unperturbed by the surface terminations, indicating a relatively short length scale over which the Tx terminations alter the nominal electron count associated with Ti atoms and suggesting that desired band features should be hosted by sub-surface M-sites that are electronically more robust than their surface M-site counterparts

Real-time observation of epitaxial graphene domain reorientation

Graphene films grown by vapor deposition tend to be polycrystalline due to the nucleation and growth of islands with different in-plane orientations. Here, using low-energy electron microscopy, we find that micron-sized graphene islands on Ir(111) rotate to a preferred orientation during thermal annealing. We observe three alignment mechanisms: the simultaneous growth of aligned domains and dissolution of rotated domains, i.e., "ripening"; domain-boundary motion within islands; and continuous lattice-rotation of entire domains. By measuring the relative growth velocity of domains during ripening, we estimate that the driving force for alignment is on the order of 0.1 meV per C atom and increases with rotation angle. A simple model of the orientation-dependent energy associated with the moir\'e corrugation of the graphene sheet due to local variations in the graphene-substrate interaction reproduces the results. This work suggests new strategies for improving the van der Waals epitaxy of 2D materials