Search

Bismuth compounds are of growing interest with regard to potential applications in catalysis, medicine and electronics, for which their environmentally benign nature is one of the key factors. The most common starting material is bismuth nitrate, which easily hydrolyses to give a large number of condensation products. The so-called bismuth subnitrates are composed of bismuth oxido clusters of varying composition and nuclearity. One reason that hampers the further development of bismuth oxido-based materials, however is the low solubility of the subnitrates, which makes targeted immobilisation on substrates challenging. We present an approach towards solubilisation of bismuth oxido clusters by introducing an amino carboxylate as functional group and a study of the growth mode of these atom-precise nanoclusters on gold surfaces. For this purpose the bismuth oxido cluster [Bi38O45(NO3)20(dmso)28](NO3)4*4dmso (dmso=dimethyl sulfoxide) was reacted with the sodium salt of tert-butyloxycabonyl(Boc)-protected phenylalanine (Phe) to give the soluble and chiral nanocluster [Bi38O45(Boc-Phe)24(dmso)9]. The hydrodynamic diameter of the cluster was estimated with (1.4-1.6) nm (in CH3CN) and (2.2 nm-2.9) nm (in Ethanol) based on dynamic light scattering (DLS). The full exchange of the nitrates by the amino carboxylates was proven by NMR and FTIR as well as elemental analysis (EA) and XPS. The solubility of the bismuth oxido cluster in a protic as well as an aprotic polar organic solvent and the growth mode of the clusters on Au upon spin-, dip-, and drop-coating on gold surfaces were studied. Successful deposition of bismuth oxido cluster was proven by powder XRD, FTIR, and XPS while the microstructure of the resulting films was investigated as a function of the deposition method and the solvent used by SEM, AFM, and optical microscopy.

Generally, it is supposed that the Fermi level in epitaxial graphene is controlled by two effects: p-type polarization doping induced by the bulk of the hexagonal SiC(0001) substrate and overcompensation by donor-like states related to the buffer layer. In this work, we evidence that this effect is also related to the specific underlying SiC terrace. We fabricated a periodic sequence of non-identical SiC terraces, which are unambiguously attributed to specific SiC surface terminations. A clear correlation between the SiC termination and the electronic graphene properties is experimentally observed and confirmed by various complementary surface-sensitive methods. We attribute this correlation to a proximity effect of the SiC termination-dependent polarization doping on the overlying graphene layer. Our findings open a new approach for a nano-scale doping-engineering by self-patterning of epitaxial graphene and other 2D layers on dielectric polar substrates.

Graphene, the first true two-dimensional material still reveals the most remarkable transport properties among the growing class of two-dimensional materials. Although many studies have investigated fundamental scattering processes, the surprisingly large variation in the experimentally determined resistances associated with a localized defect is still an open issue. Here, we quantitatively investigate the local transport properties of graphene prepared by polymer assisted sublimation growth (PASG) using scanning tunneling potentiometry. PASG graphene is characterized by a spatially homogeneous current density, which allows to analyze variations in the local electrochemical potential with high precision. We utilize this possibility by examining the local sheet resistance finding a significant variation of up to 270% at low temperatures. We identify a correlation of the sheet resistance with the stacking sequence of the 6H-SiC substrate as well as with the distance between the graphene sheet and the substrate. Our results experimentally quantify the strong impact of the graphene-substrate interaction on the local transport properties of graphene., Comment: 27 pages main text, 4 figures and 11 pages supplementary information, 17 figures. This is a pre-print of an article published in Nature Communications

In this study, we first show that the argon flow during epitaxial graphene growth is an important parameter to control the quality of the buffer and the graphene layer. Atomic force microscopy (AFM) and low-energy electron diffraction (LEED) measurements reveal that the decomposition of the SiC substrate strongly depends on the Ar mass flow rate while pressure and temperature are kept constant. Our data are interpreted by a model based on the competition of the SiC decomposition rate, controlled by the Ar flow, with a uniform graphene buffer layer formation under the equilibrium process at the SiC surface. The proper choice of a set of growth parameters allows the growth of defect-free, ultra-smooth and coherent graphene-free buffer layer and bilayer-free monolayer graphene sheets which can be transformed into large-area high-quality quasi-freestanding monolayer and bilayer graphene (QFMLG and QFBLG) by hydrogen intercalation. AFM, scanning tunneling microscopy (STM), Raman spectroscopy and electronic transport measurements underline the excellent homogeneity of the resulting quasi-freestanding layers. Electronic transport measurements in four-point probe configuration reveal a homogeneous low resistance anisotropy on both {\mu}m- and mm scales., Comment: Supplementary data is included

One of the ways to use graphene in field effect transistors is to introduce a band gap by quantum confinement effect [1]. That is why narrow graphene nanoribbons (GNRs) with width less than 50nm are considered to be essential components in future graphene electronics. The growth of graphene on sidewalls of SiC(0001) mesa structures using scalable photolithography was shown to produce high quality GNR with excellent transport properties [2-7]. Such epitaxial graphene nanoribbons are very important in fundamental science but if GNR are supposed to be used in advanced nanoelectronics, high quality thin (<50nm) nanoribbons should be produced on a large (wafer) scale. Here we present a technique for scalable template growth of high quality GNR on Si-face of SiC(0001) and provide detailed structural information along with transport properties. We succeeded to grow GNR along both [1-100] and [11-20] crystallographic directions. The quality of the grown nanoribbons was confirmed by comprehensive characterization with high resolution STM, dark field LEEM and transport measurements.

We present a new fabrication method for epitaxial graphene on SiC which enables the growth of ultra-smooth defect- and bilayer-free graphene sheets with an unprecedented reproducibility, a necessary prerequisite for wafer-scale fabrication of high quality graphene-based electronic devices. The inherent but unfavorable formation of high SiC surface terrace steps during high temperature sublimation growth is suppressed by rapid formation of the graphene buffer layer which stabilizes the SiC surface. The enhanced nucleation is enforced by decomposition of polymer adsorbates which act as a carbon source. With most of the steps well below 0.75 nm pure monolayer graphene without bilayer inclusions is formed with lateral dimensions only limited by the size of the substrate. This makes the polymer assisted sublimation growth technique the most promising method for commercial wafer scale epitaxial graphene fabrication. The extraordinary electronic quality is evidenced by quantum resistance metrology at 4.2 K with until now unreached precision and high electron mobilities on mm scale devices., Comment: 20 pages, 6 Figures

We have realized nanometer size constrictions in ballistic graphene nanoribbons grown on sidewalls of SiC mesa structures. The high quality of our devices allows the observation of a number of electronic quantum interference phenomena. The transmissions of Fabry-Perot like resonances were probed by in-situ transport measurements at various temperatures. The energies of the resonances are determined by the size of the constrictions which can be controlled precisely using STM lithography. The temperature and size dependence of the measured conductances are in quantitative agreement with tight-binding calculations. The fact that these interference effects are visible even at room temperature makes the reported devices attractive as building blocks for future carbon based electronics., Comment: to appear in Phys. Rev. Lett

The collective electronic excitations of arrays of Au chains on regularly stepped Si(553) and Si(775) surfaces were studied using electron loss spectroscopy with simultaneous high energy and momentum resolution (ELS-LEED) in combination with low energy electron diffraction (SPA-LEED) and tunneling microscopy. Both surfaces contain a double chain of gold atoms per terrace. Although one-dimensional metallicity and plasmon dispersion is observed only along the wires, two-dimensional effects are important, since plasmon dispersion explicitly depends both on the structural motif of the wires and the terrace width. The electron density on each terrace turns out to be modulated, as seen by tunneling spectroscopy (STS). The effective wire width of 7.5\,\AA\ for Si(553)-Au -- 10.2\,\AA\ for Si(775)-Au -- , determined from plasmon dispersion is in good agreement with STS data. Clear evidence for coupling between wires is seen beyond nearest neighbor coupling., Comment: 5 pages, 4 figures

The electrical transport properties of epitaxial graphene layers are correlated with the SiC surface morphology. In this study we show by atomic force microscopy and Raman measurements that the surface morphology and the structure of the epitaxial graphene layers change significantly when different pretreatment procedures are applied to nearly on-axis 6H-SiC(0001) substrates. It turns out that the often used hydrogen etching of the substrate is responsible for undesirable high macro steps evolving during graphene growth. A more advantageous type of sub-nanometer stepped graphene layers is obtained with a new method: a high-temperature conditioning of the SiC surface in argon atmosphere. The results can be explained by the observed graphene buffer layer domains after the conditioning process which suppress giant step bunching and graphene step flow growth. The superior electronic quality is demonstrated by a less extrinsic resistance anisotropy obtained in nano-probe transport experiments and by the excellent quantization of the Hall resistance in low-temperature magneto-transport measurements. The quantum Hall resistance agrees with the nominal value (half of the von Klitzing constant) within a standard deviation of 4.5*10(-9) which qualifies this method for the fabrication of electrical quantum standards., Comment: This is an author-created, un-copyedited version of an article accepted for publication in J. Phys.: Condensed Matter. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it

Among the many anticipated applications of graphene, some - such as transistors for Si microelectronics - would greatly benefit from the possibility to deposit graphene directly on a semiconductor grown on a Si wafer. We report that Ge(001) layers on Si(001) wafers can be uniformly covered with graphene at temperatures between 800{\deg}C and the melting temperature of Ge. The graphene is closed, with sheet resistivity strongly decreasing with growth temperature, weakly decreasing with the amount of deposited C, and reaching down to 2 kOhm/sq. Activation energy of surface roughness is low (about 0.66 eV) and constant throughout the range of temperatures in which graphene is formed. Density functional theory calculations indicate that the major physical processes affecting the growth are: (1) substitution of Ge in surface dimers by C, (2) interaction between C clusters and Ge monomers, and (3) formation of chemical bonds between graphene edge and Ge(001), and that the processes 1 and 2 are surpassed by CH$_{2}$ surface diffusion when the C atoms are delivered from CH$_{4}$. The results of this study indicate that graphene can be produced directly at the active region of the transistor in a process compatible with the Si technology.

Topological insulators are guaranteed to support metallic surface states on an insulating bulk, and one should thus expect that the electronic transport in these materials is dominated by the surfaces states. Alas, due to the high remaining bulk conductivity, surface contributions to transport have so-far only been singled out indirectly via quantum oscillations, or for devices based on gated and doped topological insulator thin films, a situation in which the surface carrier mobility could be limited by defect and interface scattering. Here we present the first direct measurement of surface-dominated conduction on an atomically clean surface of bulk-insulating Bi$_2$Te$_2$Se. Using nano-scale four point setups with variable contact distance, we show that the transport at 30 K is two-dimensional rather than three-dimensional and by combining these measurements with angle-resolved photoemission results from the same crystals, we find a surface state mobility of 390(30) cm$^{2}$V$^{-1}$s$^{-1}$ at 30 K at a carrier concentration of 8.71(7)$\times 10^{12}$ cm$^{-2}$.

Growth of large-scale graphene is still accompanied by imperfections. By means of a four-tip STM/SEM the local structure of graphene grown on SiC(0001) was correlated with scanning electron microscope images and spatially resolved transport measurements. The systematic variation of probe spacings and substrate temperature has clearly revealed two-dimensional transport regimes of Anderson localization as well as of diffusive transport. The detailed analysis of the temperature dependent data demonstrates that the local on-top nano-sized contacts do not induce significant strain to the epitaxial graphene films., Comment: 3 figures

Graphene electronics has motivated much of graphene science for the past decade. A primary goal was to develop high mobility semiconducting graphene with a band gap that is large enough for high performance applications. Graphene ribbons were thought to be semiconductors with these properties, however efforts to produce ribbons with useful bandgaps and high mobility has had limited success. We show here that high quality epitaxial graphene nanoribbons 40 nm in width, with annealed edges, grown on sidewall SiC are not semiconductors, but single channel room temperature ballistic conductors for lengths up to at least 16 micrometers. Mobilities exceeding one million corresponding to a sheet resistance below 1 Ohm have been observed, thereby surpassing two dimensional graphene by 3 orders of magnitude and theoretical predictions for perfect graphene by more than a factor of 10. The graphene ribbons behave as electronic waveguides or quantum dots. We show that transport in these ribbons is dominated by two components of the ground state transverse waveguide mode, one that is ballistic and temperature independent, and a second thermally activated component that appears to be ballistic at room temperature and insulating at cryogenic temperatures. At room temperature the resistance of both components abruptly increases with increasing length, one at a length of 160 nm and the other at 16 micrometers. These properties appear to be related to the lowest energy quantum states in the charge neutral ribbons. Since epitaxial graphene nanoribbons are readily produced by the thousands, their room temperature ballistic transport properties can be used in advanced nanoelectronics as well.

The electronic excitation of a conjugated molecule-insulator interface, as exemplified by the adsorption of benzoic acid and its phenolic derivative on NaCl(001) surface, is addressed by many-body Green's function methods. By solving the two-particle Bethe-Salpeter equation on top of the $GW$ quasiparticle energies, it turns out that instead of the intramolecular $\pi-\pi^\ast$ transition of the adsorbate, the lowest singlet excited state of the adsorbate system, being a charge transfer excitonic effect, is essentially assigned to the transition from the surface valence band maximum to the $\pi-\pi^\ast$ state of the molecule. An accurate description of this lowest electronic excitations confined at the interface requires the knowledge of a full excitonic Hamiltonian due to the sizable electron-hole exchange interaction., Comment: 5 pages, 3 figures

We present in this work the electronic structure and transition energies (both thermodynamic and optical) of Cl vacancies in NaCl by hybrid density functionals. The underestimated transition energies by the semi-local functional inherited from the band gap problem are recovered by the PBE0 hybrid functional through the non-local exact exchange, whose amount is adjusted to reproduce the experimental band gap. The hybrid functional also gives a better account of the lattice relaxation for the defect systems arising from the reduced self-interaction. On the other hand, the quantitative agreement with experimental vertical transition energy cannot be achieved with hybrid functionals due to the inaccurate descriptions of the ionization energies of the localized defect and the positions of the band edges., Comment: 13 pages, 6 figures

It is commonly believed that organic molecules are physisorbed on the ideal non-polar surfaces of wide band gap insulators with limited variation of the electronic properties of the adsorbate molecule. On the basis of first principles calculations within density functional theory (DFT) and $GW$ approximation, we show that this is not generally true. We find that the molecular frontier orbitals undergo significant changes when a hydroxy acid (here we chose gluconic acid) is adsorbed on MgSO$_4$$\cdot$H$_2$O(100) surface due to the complex interaction between the molecule and the insulating surface. The predicted trend of the adsorption effect on the energy gap obtained by DFT is reversed when the surface polarization effect is taken into account via the many-body corrections., Comment: 5 pages, 3 figures