Atomic and Electronic Structure of a Multidomain GeTe Crystal.

Renewed interest in the ferroelectric semiconductor germanium telluride was recently triggered by the direct observation of a giant Rashba effect and a 30-year-old dream about a functional spin field-effect transistor. In this respect, all-electrical control of the spin texture in this material in combination with ferroelectric properties at the nanoscale would create advanced functionalities in spintronics and data information processing. Here, we investigate the atomic and electronic properties of GeTe bulk single crystals and their (111) surfaces. We succeeded in growing crystals possessing solely inversion domains of ∼10 nm thickness parallel to each other. Using HAADF-TEM we observe two types of domain boundaries, one of them being similar in structure to the van der Waals gap in layered materials. This structure is responsible for the formation of surface domains with preferential Te-termination (∼68%) as we determined using photoelectron diffraction and XPS. The lateral dimensions of the surface domains are in the range of ∼10-100 nm, and both Ge- and Te-terminations reveal no reconstruction. Using spin-ARPES we establish an intrinsic quantitative relationship between the spin polarization of pure bulk states and the relative contribution of different terminations, a result that is consistent with a reversal of the spin texture of the bulk Rashba bands for opposite configurations of the ferroelectric polarization within individual nanodomains. Our findings are important for potential applications of ferroelectric Rashba semiconductors in nonvolatile spintronic devices with advanced memory and computing capabilities at the nanoscale.

Layer-by-Layer Graphene Growth on ß-SiC/Si(001).

The mechanism of few-layer graphene growth on the technologically relevant cubic-SiC/Si(001) substrate is uncovered using high-resolution core-level and angle-resolved photoelectron spectroscopy, low-energy electron microscopy, and microspot low-energy electron diffraction. The thickness of the graphitic overlayer supported on the silicon carbide substrate and related changes in the surface structure are precisely controlled by monitoring the progress of the surface graphitization in situ during high-temperature graphene synthesis, using a combination of microspectroscopic techniques. The experimental data reveal gradual changes in the preferential graphene lattice orientations at the initial stages of the few-layer graphene growth on SiC(001) and can act as reference data for controllable growth of single-, double-, and triple-layer graphene on silicon carbide substrates.

A photochemical approach for a fast and self-limited covalent modification of surface supported graphene with photoactive dyes.

Herein, we report a simple method for a covalent modification of surface supported graphene with photoactive dyes. Graphene was fabricated on cubic-SiC/Si(001) wafers due to their low cost and suitability for mass-production of continuous graphene fit for electronic applications on millimetre scale. Functionalisation of the graphene surface was carried out in solution via white light induced photochemical generation of phenazine radicals from phenazine diazonium salt. The resulting covalently bonded phenazine-graphene hybrid structure was characterised by scanning tunnelling microscopy (STM) and spectroscopy (STS), Raman spectroscopy and density functional theory (DFT) calculations. It was found that phenazine molecules form an overlayer, which exhibit a short range order with a rectangular unit cell on the graphene surface. DFT calculations based on STM results reveal that molecules are standing up in the overlayer with the maximum coverage of 0.25 molecules per graphene unit cell. Raman spectroscopy and STM results show that the growth is limited to one monolayer of standing molecules. STS reveals that the phenazine-graphene hybrid structure has a band gap of 0.8 eV.

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.