Surface modification on MoO2+x/Mo(110) induced by a local electric potential.

Oxygen adatoms on the MoO2+x/Mo(110) surface are observed to be removed when a sufficiently large bias is applied between the scanning tunneling microscope tip and the surface. Experimental observations, such as the bias polarity dependence of adatom removal and the observation of an intermediate state, indicate that the adatom penetrates the surface oxide layer. Through the comparison of finite element method simulations with various experimental relationships, the electric field is concluded to be the sole contributor to adatom penetration into the surface oxide layer. The energetic barrier to this process is estimated to be approximately 0.45 eV in magnitude. Furthermore, the resolution of this phenomenon is on the atomic scale: individual adatoms can undergo surface penetration whilst their nearest neighbour adatoms, separated by 5 Å, are unaffected. The mechanism reported here has the advantages of not strongly influencing the substrate and is exceptionally localised, which can be beneficial for the synthesis of single atom devices.

Large positive in-plane magnetoresistance induced by localized states at nanodomain boundaries in graphene.

Graphene supports long spin lifetimes and long diffusion lengths at room temperature, making it highly promising for spintronics. However, making graphene magnetic remains a principal challenge despite the many proposed solutions. Among these, graphene with zig-zag edges and ripples are the most promising candidates, as zig-zag edges are predicted to host spin-polarized electronic states, and spin-orbit coupling can be induced by ripples. Here we investigate the magnetoresistance of graphene grown on technologically relevant SiC/Si(001) wafers, where inherent nanodomain boundaries sandwich zig-zag structures between adjacent ripples of large curvature. Localized states at the nanodomain boundaries result in an unprecedented positive in-plane magnetoresistance with a strong temperature dependence. Our work may offer a tantalizing way to add the spin degree of freedom to graphene.

Transport Gap Opening and High On-Off Current Ratio in Trilayer Graphene with Self-Aligned Nanodomain Boundaries.

Trilayer graphene exhibits exceptional electronic properties that are of interest both for fundamental science and for technological applications. The ability to achieve a high on-off current ratio is the central question in this field. Here, we propose a simple method to achieve a current on-off ratio of 10(4) by opening a transport gap in Bernal-stacked trilayer graphene. We synthesized Bernal-stacked trilayer graphene with self-aligned periodic nanodomain boundaries (NBs) on the technologically relevant vicinal cubic-SiC(001) substrate and performed electrical measurements. Our low-temperature transport measurements clearly demonstrate that the self-aligned periodic NBs can induce a charge transport gap greater than 1.3 eV. More remarkably, the transport gap of ∼0.4 eV persists even at 100 K. Our results show the feasibility of creating new electronic nanostructures with high on-off current ratios using graphene on cubic-SiC.

Homolytic cleavage of molecular oxygen by manganese porphyrins supported on Ag(111).

Oxygen binding and cleavage are important for both molecular recognition and catalysis. Mn-based porphyrins in particular are used as catalysts for the epoxidation of alkenes, and in this study the homolytic cleavage of O2 by a surface-supported monolayer of Mn porphyrins on Ag(111) is demonstrated by scanning tunneling microscopy, X-ray absorption, and X-ray photoemission. As deposited, {5,10,15,20-tetraphenylporphyrinato}Mn(III)Cl (MnClTPP) adopts a saddle conformation with the average plane of its macrocycle parallel to the substrate and the axial Cl ligand pointing upward, away from the substrate. The adsorption of MnClTPP on Ag(111) is accompanied by a reduction of the Mn oxidation state from Mn(III) to Mn(II) due to charge transfer between the substrate and the molecule. Annealing the Mn(II)ClTPP monolayer up to 510 K causes the chlorine ligands to desorb from the porphyrins while leaving the monolayer intact. The Mn(II)TPP is stabilized by the surface acting as an axial ligand for the metal center. Exposure of the Mn(II)TPP/Ag(111) system to molecular oxygen results in the dissociation of O2 and forms pairs of Mn(III)OTPP molecules on the surface. Annealing at 445 K reduces the Mn(III)OTPP complex back to Mn(II)TPP/Ag(111). The activation energies for Cl and O removal were found to be 0.35 ± 0.02 eV and 0.26 ± 0.03 eV, respectively.

Rotated domain network in graphene on cubic-SiC(001).

The atomic structure of the cubic-SiC(001) surface during ultra-high vacuum graphene synthesis has been studied using scanning tunneling microscopy (STM) and low-energy electron diffraction. Atomically resolved STM studies prove the synthesis of a uniform, millimeter-scale graphene overlayer consisting of nanodomains rotated by ±13.5° relative to the left angle bracket 110 right angle bracket-directed boundaries. The preferential directions of the domain boundaries coincide with the directions of carbon atomic chains on the SiC(001)-c(2 × 2) reconstruction, fabricated prior to graphene synthesis. The presented data show the correlation between the atomic structures of the SiC(001)-c(2 × 2) surface and the graphene/SiC(001) rotated domain network and pave the way for optimizing large-area graphene synthesis on low-cost cubic-SiC(001)/Si(001) wafers.

Correlation between charge-transfer and rotation of C60 on WO2/W(110).

Understanding molecular switching between different charge states is crucial to further progress in molecule-based nano-electronic devices. Herein we have employed scanning tunnelling microscopy to visualize different charge states of a single C60 molecule within a molecular layer grown on the WO2/W(110) surface. The results obtained demonstrate that individual C60 molecules within the layer switch between neutral and negatively charged states in the temperature range of 220-260 K over the time scale of the experiment. The charging of the C60 causes changes in the local density of electron states and consequently a variation in tunnelling current. Using density functional theory calculations, it was found that the charged state corresponds to the negatively charged C60(-), which has accepted an electron. The switching of the molecule into the charged state is triggered continuously by tunnelling electrons when the STM tip is static above an individual C60 molecule with a bias applied. Molecular movement accompanies the molecule's switching between these states.