Fabrication of Single-Crystalline CoCrFeNi Thin Films by DC Magnetron Sputtering: A Route to Surface Studies of High-Entropy Alloys.

High-entropy alloys (HEAs) with their almost limitless number of possible compositions have raised widespread attention in material science. Next to wear and corrosion resistive coatings, their application as tunable electrocatalysts has recently moved into the focus. On the other hand, fundamental properties of HEA surfaces like atomic and electronic structure, surface segregation and diffusion as well as adsorption on HEA surfaces are barely explored. The lack of research is caused by the limited availability of single-crystalline samples. In the present work, the epitaxial growth of face centered cubic (fcc) CoCrFeNi films on MgO(100) is reported. Their characterization by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM) demonstrates that the layers with a homogeneous and close to equimolar elemental composition are oriented in [100] direction and aligned with the substrate to which they form an abrupt interface. X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED), and angle-resolved photoelectron spectroscopy are employed to study chemical composition and atomic and electronic structure of CoCrFeNi(100). It is demonstrated that epitaxially grown HEA films have the potential to fill the sample gap, allowing for fundamental studies of properties of and processes on well-defined HEA surfaces over the full compositional space.

Modulation doping and charge density wave transition in layered PbSe-VSe2 ferecrystal heterostructures.

Controlling charge carrier concentrations remains a major challenge in the application of quasi-two-dimensional materials. A promising approach is the modulation doping of transport channels via charge transfer from neighboring layers in stacked heterostructures. Ferecrystals, which are metastable layered structures created from artificial elemental precursors, are a perfect model system to investigate modulation doping, as they offer unparalleled freedom in the combination of different constituents and variable layering sequences. In this work, differently stacked combinations of rock-salt structured PbSe and VSe2 were investigated using X-ray photoelectron spectroscopy. The PbSe layers act as electron donors in all heterostructures, with about 0.1 to 0.3 donated electrons per VSe2 unit cell. While they initially retain their inherent semiconducting behavior, they themselves become metallic when combined with a larger number of VSe2 layers, as evidenced by a change of the XPS core level lineshape. Additional analysis of the valence band structure was performed for selected stacking orders at different sample temperatures to investigate a predicted charge density wave (CDW) transition. While there appear to be hints of a gap opening, the data so far is inconclusive and the application of spatially resolved techniques such as scanning tunneling microscopy is encouraged for further studies.

Surface Transport Properties of Pb-Intercalated Graphene.

Intercalation experiments on epitaxial graphene are attracting a lot of attention at present as a tool to further boost the electronic properties of 2D graphene. In this work, we studied the intercalation of Pb using buffer layers on 6H-SiC(0001) by means of electron diffraction, scanning tunneling microscopy, photoelectron spectroscopy and in situ surface transport. Large-area intercalation of a few Pb monolayers succeeded via surface defects. The intercalated Pb forms a characteristic striped phase and leads to formation of almost charge neutral graphene in proximity to a Pb layer. The Pb intercalated layer consists of 2 ML and shows a strong structural corrugation. The epitaxial heterostructure provides an extremely high conductivity of σ=100 mS/□. However, at low temperatures (70 K), we found a metal-insulator transition that we assign to the formation of minigaps in epitaxial graphene, possibly induced by a static distortion of graphene following the corrugation of the interface layer.

Challenging the Durability of Intermetallic Mo-Ni Compounds in the Hydrogen Evolution Reaction.

Molybdenum-nickel materials are catalysts of industrial interest for the hydrogen evolution reaction (HER). Well-characterized surfaces of the single-phase intermetallic compounds Ni7Mo7, Ni3Mo, and Ni4Mo were subjected to accelerated durability tests (ADTs) and thorough characterization to unravel whether crystallographic ordering affects the activity. Their intrinsic instability leads to molybdenum leaching, resulting in higher specific surface areas and nickel-enriched surfaces. These are more prone to form Ni(OH)2 layers, which leads to deactivation of the Mo-Ni materials. The crystal structure of the intermetallic compounds has, due to the intrinsic instability of the materials in alkaline media, no effect on the activity. Ni7Mo7, identified earlier as durable, proves to be highly unstable in the applied ADTs. The results show that the enhanced activity of unsupported bulk Mo-Ni electrodes can solely be ascribed to increased specific surface areas.

Substrate induced nanoscale resistance variation in epitaxial graphene.

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 is still an open issue. Here, we quantitatively investigate local transport properties of graphene prepared by polymer assisted sublimation growth using scanning tunneling potentiometry. These samples exhibit 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 silicon carbide substrate and with the distance between the graphene and the substrate. Our results experimentally quantify the impact of the graphene-substrate interaction on the local transport properties of graphene.

From a Cerium-Doped Polynuclear Bismuth Oxido Cluster to ß-Bi2O3:Ce.

The simultaneous hydrolysis of Bi(NO3)3·5H2O and Ce(NO3)3·6H2O results in the formation of novel heterometallic bismuth oxido clusters with the general formula [Bi38O45(NO3)24(DMSO)28+δ]:Ce (DMSO = dimethyl sulfoxide; cerium content <1.50%), which is demonstrated by single-crystal X-ray diffraction analysis. The incorporation of cerium into the cluster core is a result of the interplay of hydrolysis and condensation of the metal nitrates in the presence of oxygen. Diffuse-reflectance UV-vis and X-ray photoelectron spectroscopy reveal the presence of CeIV in the final bismuth oxido clusters as a result of oxidation of the cerium source. The cerium atoms are statistically distributed mainly on the bismuth atom positions of the central [Bi6O9] motif of the [Bi38O45] cluster core. Hydrolysis and subsequent annealing of the bismuth oxido clusters in the temperature range of 300-400 °C provides ß-Bi2O3:Ce samples with slightly lowered band gaps of approximately 2.3 eV compared to the undoped ß-Bi2O3 (approximately 2.4 eV). The sintering behavior of ß-Bi2O3 is significantly affected by the cerium dopant. Finally, differences in the efficiency of the as-prepared ß-Bi2O3:Ce and undoped ß-Bi2O3 samples in the photocatalytic decomposition of the biocide triclosan in an aqueous solution under visible-light irradiation are demonstrated.

Direct observation of grain boundaries in graphene through vapor hydrofluoric acid (VHF) exposure.

The shape and density of grain boundary defects in graphene strongly influence its electrical, mechanical, and chemical properties. However, it is difficult and elaborate to gain information about the large-area distribution of grain boundary defects in graphene. An approach is presented that allows fast visualization of the large-area distribution of grain boundary-based line defects in chemical vapor deposition graphene after transferring graphene from the original copper substrate to a silicon dioxide surface. The approach is based on exposing graphene to vapor hydrofluoric acid (VHF), causing partial etching of the silicon dioxide underneath the graphene as VHF diffuses through graphene defects. The defects can then be identified using optical microscopy, scanning electron microscopy, or Raman spectroscopy. The methodology enables simple evaluation of the grain sizes in polycrystalline graphene and can therefore be a valuable procedure for optimizing graphene synthesis processes.

Charge transfer in (PbSe)1+δ (NbSe2)2 and (SnSe)1+δ (NbSe2)2 ferecrystals investigated by photoelectron spectroscopy.

Rotationally disordered, layered (PbSe)[Formula: see text](NbSe2)2 and (SnSe)[Formula: see text](NbSe2)2 ferecrystal heterostructures, consisting of stacked two-dimensional bilayers of either PbSe or SnSe alternating with two planes of NbSe2, were synthesized from modulated elemental reactants. The electronic structure of these ternary systems was investigated using x-ray photoelectron spectroscopy and compared to the binary bulk compounds PbSe, SnSe and NbSe2. The Pb and Sn core level spectra show a significant shift towards lower binding energies and the peak shape becomes asymmetric in the ferecrystals, while the electronic structure of the NbSe2 layers does not change compared to the bulk. This is interpreted in terms of an interlayer interaction in the form of a charge transfer of electrons from PbSe or SnSe into the NbSe2 layers, which is supported by valence band spectra and is consistent with prior results from transport measurements.

Structural Changes in 2D BiSe Bilayers as n Increases in (BiSe)1+δ(NbSe2)n (n = 1-4) Heterostructures.

(BiSe)1+δ(NbSe2)n heterostructures with n = 1-4 were synthesized using modulated elemental reactants. The BiSe bilayer structure changed from a rectangular basal plane with n = 1 to a square basal plane for n = 2-4. The BiSe in-plane structure was also influenced by small changes in the structure of the precursor, without significantly changing the out-of-plane diffraction pattern or value of the misfit parameter, δ. Density functional theory calculations on isolated BiSe bilayers showed that its lattice is very flexible, which may explain its readiness to adjust shape and size depending on the environment. Correlated with the changes in the BiSe basal plane structure, analysis of scanning transmission electron microscope images revealed that the occurrence of antiphase boundaries, found throughout the n = 1 compound, is dramatically reduced for the n = 2-4 compounds. X-ray photoelectron spectroscopy measurements showed that the Bi 5d3/2, 5d5/2 doublet peaks narrowed toward higher binding energies as n increased from 1 to 2, also consistent with a reduction in the number of antiphase boundaries. Temperature-dependent electrical resistivity and Hall coefficient measurements of nominally stoichiometric samples in conjunction with structural refinements and XPS data suggest a constant amount of interlayer charge transfer independent of n. Constant interlayer charge transfer is surprising given the changes in the BiSe in-plane structure. The structural flexibility of the BiSe layer may be useful in designing multiple constituent heterostructures as an interlayer between structurally dissimilar constituents.

Ultrafast electron dynamics in epitaxial graphene investigated with time- and angle-resolved photoemission spectroscopy.

In order to exploit the intriguing optical properties of graphene it is essential to gain a better understanding of the light-matter interaction in the material on ultrashort timescales. Exciting the Dirac fermions with intense ultrafast laser pulses triggers a series of processes involving interactions between electrons, phonons and impurities. Here we study these interactions in epitaxial graphene supported on silicon carbide (semiconducting) and iridium (metallic) substrates using ultrafast time- and angle-resolved photoemission spectroscopy (TR-ARPES) based on high harmonic generation. For the semiconducting substrate we reveal a complex hot carrier dynamics that manifests itself in an elevated electronic temperature and an increase in linewidth of the π band. By analyzing these effects we are able to disentangle electron relaxation channels in graphene. On the metal substrate this hot carrier dynamics is found to be severely perturbed by the presence of the metal, and we find that the electronic system is much harder to heat up than on the semiconductor due to screening of the laser field by the metal.

Tunable carrier multiplication and cooling in graphene.

Time- and angle-resolved photoemission measurements on two doped graphene samples displaying different doping levels reveal remarkable differences in the ultrafast dynamics of the hot carriers in the Dirac cone. In the more strongly (n-)doped graphene, we observe larger carrier multiplication factors (>3) and a significantly faster phonon-mediated cooling of the carriers back to equilibrium compared to in the less (p-)doped graphene. These results suggest that a careful tuning of the doping level allows for an effective manipulation of graphene's dynamical response to a photoexcitation.

Luminescence, patterned metallic regions, and photon-mediated electronic changes in single-sided fluorinated graphene sheets.

Single-sided fluorination has been predicted to open an electronic band gap in graphene and to exhibit unique electronic and magnetic properties; however, this has not been substantiated by experimental reports. Our comprehensive experimental and theoretical study of this material on a SiC(0001) substrate shows that single-sided fluorographene exhibits two phases, a stable one with a band gap of ∼6 eV and a metastable one, induced by UV irradiation, with a band gap of ∼2.5 eV. The metastable structure, which reverts to the stable "ground-state" phase upon annealing under emission of blue light, in our view is induced by defect states, based on the observation of a nondispersive electronic state at the top of the valence band, not unlike that found in organic molecular layers. Our structural data show that the stable C2F ground state has a "boat" structure, in agreement with our X-ray magnetic circular dichroism data, which show the absence of an ordered magnetic phase. A high flux of UV or X-ray photons removes the fluorine atoms, demonstrating the possibility of lithographically patterning conducting regions into an otherwise semiconducting 2D material.

Surface-induced hybridization between graphene and titanium.

Carbon-based materials such as graphene sheets and carbon nanotubes have inspired a broad range of applications ranging from high-speed flexible electronics all the way to ultrastrong membranes. However, many of these applications are limited by the complex interactions between carbon-based materials and metals. In this work, we experimentally investigate the structural interactions between graphene and transition metals such as palladium (Pd) and titanium (Ti), which have been confirmed by density functional simulations. We find that the adsorption of titanium on graphene is more energetically favorable than in the case of most metals, and density functional theory shows that a surface induced p-d hybridization occurs between atomic carbon and titanium orbitals. This strong affinity between the two materials results in a short-range ordered crystalline deposition on top of graphene as well as chemical modifications to graphene as seen by Raman and X-ray photoemission spectroscopy (XPS). This induced hybridization is interface-specific and has major consequences for contacting graphene-nanoelectronic devices as well as applications toward metal-induced chemical functionalization of graphene.

Ultrafast dynamics of massive dirac fermions in bilayer graphene.

Bilayer graphene is a highly promising material for electronic and optoelectronic applications since it is supporting massive Dirac fermions with a tunable band gap. However, no consistent picture of the gap's effect on the optical and transport behavior has emerged so far, and it has been proposed that the insulating nature of the gap could be compromised by unavoidable structural defects, by topological in-gap states, or that the electronic structure could be altogether changed by many-body effects. Here, we directly follow the excited carriers in bilayer graphene on a femtosecond time scale, using ultrafast time- and angle-resolved photoemission. We find a behavior consistent with a single-particle band gap. Compared to monolayer graphene, the existence of this band gap leads to an increased carrier lifetime in the minimum of the lowest conduction band. This is in sharp contrast to the second substate of the conduction band, in which the excited electrons decay through fast, phonon-assisted interband transitions.

A universal transfer route for graphene.

Often synthetic graphene requires transfer onto an arbitrary substrate prior to use because the substrate it was originally synthesized on is inappropriate for either electrical measurement or characterization. While a variety of routes have been developed they are substrate dependant and often involve the use of harsh treatments. Here we present a facile and cheap route that can be applied to graphene over any substrate. This universal transfer route is based on a wet chemical reaction producing gaseous species which can intercalate between the substrate and the graphene and thus gently delaminate the two.

Strong plasmon reflection at nanometer-size gaps in monolayer graphene on SiC.

We employ tip-enhanced infrared near-field microscopy to study the plasmonic properties of epitaxial quasi-free-standing monolayer graphene on silicon carbide. The near-field images reveal propagating graphene plasmons, as well as a strong plasmon reflection at gaps in the graphene layer, which appear at the steps between the SiC terraces. When the step height is around 1.5 nm, which is two orders of magnitude smaller than the plasmon wavelength, the reflection signal reaches 20% of its value at graphene edges, and it approaches 50% for step heights as small as 5 nm. This intriguing observation is corroborated by numerical simulations and explained by the accumulation of a line charge at the graphene termination. The associated electromagnetic fields at the graphene termination decay within a few nanometers, thus preventing efficient plasmon transmission across nanoscale gaps. Our work suggests that plasmon propagation in graphene-based circuits can be tailored using extremely compact nanostructures, such as ultranarrow gaps. It also demonstrates that tip-enhanced near-field microscopy is a powerful contactless tool to examine nanoscale defects in graphene.

Observation of 4 nm pitch stripe domains formed by exposing graphene to ambient air.

We study epitaxial graphene on the 6H-SiC(0001) surface under ambient conditions using frequency-modulation atomic force microscopy. We observe large terraces with a self-assembled stripe structure within a highly adsorbate covered surface on top of the graphene. To identify the origin of the structure, we compare the experimental data on graphene with calculations and experiments on graphite that predict the formation of a solid-gas monolayer in the solid-liquid interface of hydrophobic surfaces.

Fabry-Perot enhanced Faraday rotation in graphene.

We demonstrate that giant Faraday rotation in graphene in the terahertz range due to the cyclotron resonance is further increased by constructive Fabry-Perot interference in the supporting substrate. Simultaneously, an enhanced total transmission is achieved, making this effect doubly advantageous for graphene-based magneto-optical applications. As an example, we present far-infrared spectra of epitaxial multilayer graphene grown on the C-face of 6H-SiC, where the interference fringes are spectrally resolved and a Faraday rotation up to 0.15 radians (9°) is attained. Further, we discuss and compare other ways to increase the Faraday rotation using the principle of an optical cavity.

Coexisting massive and massless Dirac fermions in symmetry-broken bilayer graphene.

Charge carriers in bilayer graphene are widely believed to be massive Dirac fermions that have a bandgap tunable by a transverse electric field. However, a full transport gap, despite its importance for device applications, has not been clearly observed in gated bilayer graphene, a long-standing puzzle. Moreover, the low-energy electronic structure of bilayer graphene is widely held to be unstable towards symmetry breaking either by structural distortions, such as twist, strain, or electronic interactions that can lead to various ground states. Which effect dominates the physics at low energies is hotly debated. Here we show both by direct band-structure measurements and by calculations that a native imperfection of bilayer graphene, a distribution of twists whose size is as small as ~0.1°, is sufficient to generate a completely new electronic spectrum consisting of massive and massless Dirac fermions. The massless spectrum is robust against strong electric fields, and has a unusual topology in momentum space consisting of closed arcs having an exotic chiral pseudospin texture, which can be tuned by varying the charge density. The discovery of this unusual Dirac spectrum not only complements the framework of massive Dirac fermions, widely relevant to charge transport in bilayer graphene, but also supports the possibility of valley Hall transport.

Direct view of hot carrier dynamics in graphene.

The ultrafast dynamics of excited carriers in graphene is closely linked to the Dirac spectrum and plays a central role for many electronic and optoelectronic applications. Harvesting energy from excited electron-hole pairs, for instance, is only possible if these pairs can be separated before they lose energy to vibrations, merely heating the lattice. Until now, the hot carrier dynamics in graphene could only be accessed indirectly. Here, we present a dynamical view on the Dirac cone by time- and angle-resolved photoemission spectroscopy. This allows us to show the quasi-instant thermalization of the electron gas to a temperature of ≈2000 K, to determine the time-resolved carrier density, and to disentangle the subsequent decay into excitations of optical phonons and acoustic phonons (directly and via supercollisions).