D. Usachov

Nitrogen-Doped Graphene: Efficient Growth, Structure, and Electronic Properties

A novel strategy for efficient growth of nitrogen-doped graphene (N-graphene) on a large scale from s-triazine molecules is presented. The growth process has been unveiled in situ using time-dependent photoemission. It has been established that a postannealing of N-graphene after gold intercalation causes a conversion of the N environment from pyridinic to graphitic, allowing to obtain more than 80% of all embedded nitrogen in graphitic form, which is essential for the electron doping in graphene. A band gap, a doping level of 300 meV, and a charge-carrier concentration of ∼8×10(12) electrons per cm2, induced by 0.4 atom % of graphitic nitrogen, have been detected by angle-resolved photoemission spectroscopy, which offers great promise for implementation of this system in next generation electronic devices.

Evidence for a New Two-Dimensional C4H-Type Polymer Based on Hydrogenated Graphene

www.MaterialsViews.com C O M M U N IC A IO N Danny Haberer , * Cristina E. Giusca , Ying Wang , Hermann Sachdev , * Alexander V. Fedorov , Mani Farjam , S. Akbar Jafari , Denis V. Vyalikh , Dmitry Usachov , Xianjie Liu , Uwe Treske , Mandy Grobosch , Oleg Vilkov , Vera K. Adamchuk , Stephan Irle , * S. Ravi P. Silva , Martin Knupfer , Bernd Büchner , and Alexander Grüneis * Evidence for a New Two-Dimensional C 4 H-Type Polymer Based on Hydrogenated Graphene

Quasifreestanding single-layer hexagonal boron nitride as a substrate for graphene synthesis

We demonstrate that freeing a single-atom thick layer of hexagonal boron nitride (h-BN) from tight chemical bonding to a Ni(111) thin film grown on a W(110) substrate can be achieved by intercalation of Au atoms into the interface. This process has been systematically investigated using angle-resolved photoemission spectroscopy, X-ray photoemission and absorption techniques. It has been demonstrated that the transition of the h-BN layer from the “rigid” into the “quasi-freestanding” state is accompanied by a change of its lattice constant. Using chemical vapor deposition, graphene has been successfully synthesized on the insulating, quasi-freestanding h-BN monolayer. We anticipate that the in situ synthesized weakly interacting graphene/h-BN double layered system could be further developed for technological applications and may provide perspectives for further inquiry into the unusual electronic properties of graphene.

The Chemistry of Imperfections in N‑Graphene

Many propositions have been already put forth for the practical use of N-graphene in various devices, such as batteries, sensors, ultracapacitors, and next generation electronics. However, the chemistry of nitrogen imperfections in this material still remains an enigma. Here we demonstrate a method to handle N-impurities in graphene, which allows efficient conversion of pyridinic N to graphitic N and therefore precise tuning of the charge carrier concentration. By applying photoemission spectroscopy and density functional calculations, we show that the electron doping effect of graphitic N is strongly suppressed by pyridinic N. As the latter is converted into the graphitic configuration, the efficiency of doping rises up to half of electron charge per N atom.

Observation of a universal donor-dependent vibrational mode in graphene

Electron-phonon coupling and the emergence of superconductivity in intercalated graphite have been studied extensively. Yet, phonon-mediated superconductivity has never been observed in the 2D equivalent of these materials, doped monolayer graphene. Here we perform angle-resolved photoemission spectroscopy to try to find an electron donor for graphene that is capable of inducing strong electron-phonon coupling and superconductivity. We examine the electron donor species Cs, Rb, K, Na, Li, Ca and for each we determine the full electronic band structure, the Eliashberg function and the superconducting critical temperature Tc from the spectral function. An unexpected low-energy peak appears for all dopants with an energy and intensity that depend on the dopant atom. We show that this peak is the result of a dopant-related vibration. The low energy and high intensity of this peak are crucially important for achieving superconductivity, with Ca being the most promising candidate for realizing superconductivity in graphene.

Controlled assembly of graphene-capped nickel, cobalt and iron silicides

The unique properties of graphene have raised high expectations regarding its application in carbon-based nanoscale devices that could complement or replace traditional silicon technology. This gave rise to the vast amount of researches on how to fabricate high-quality graphene and graphene nanocomposites that is currently going on. Here we show that graphene can be successfully integrated with the established metal-silicide technology. Starting from thin monocrystalline films of nickel, cobalt and iron, we were able to form metal silicides of high quality with a variety of stoichiometries under a Chemical Vapor Deposition grown graphene layer. These graphene-capped silicides are reliably protected against oxidation and can cover a wide range of electronic materials/device applications. Most importantly, the coupling between the graphene layer and the silicides is rather weak and the properties of quasi-freestanding graphene are widely preserved.

Observation of Single-Spin Dirac Fermions at the Graphene/ Ferromagnet Interface

With the discovery and first characterization of graphene, its potential for spintronic applications was recognized immediately. Since then, an active field of research has developed trying to overcome the practical hurdles. One of the most severe challenges is to find appropriate interfaces between graphene and ferromagnetic layers, which are granting efficient injection of spin-polarized electrons. Here, we show that graphene grown under appropriate conditions on Co(0001) demonstrates perfect structural properties and simultaneously exhibits highly spin-polarized charge carriers. The latter was conclusively proven by observation of a single-spin Dirac cone near the Fermi level. This was accomplished experimentally using spin- and angle-resolved photoelectron spectroscopy, and theoretically with density functional calculations. Our results demonstrate that the graphene/Co(0001) system represents an interesting candidate for applications in devices using the spin degree of freedom.

Large spin splitting of metallic surface-state bands at adsorbate-modified gold/silicon surfaces

Finding appropriate systems with a large spin splitting of metallic surface-state band which can be fabricated on silicon using routine technique is an essential step in combining Rashba-effect based spintronics with silicon technology. We have found that originally poor structural and electronic properties of the surface can be substantially improved by adsorbing small amounts of suitable species (e.g., Tl, In, Na, Cs). The resultant surfaces exhibit a highly-ordered atomic structure and spin-split metallic surface-state band with a momentum splitting of up to 0.052 Å−1 and an energy splitting of up to 190 meV at the Fermi level. The family of adsorbate-modified surfaces, on the one hand, is thought to be a fascinating playground for exploring spin-splitting effects in the metal monolayers on a semiconductor and, on the other hand, expands greatly the list of material systems prospective for spintronics applications.

Oxygen Reduction by Lithiated Graphene and Graphene-Based Materials

Oxygen reduction reaction (ORR) plays a key role in lithium-air batteries (LABs) that attract great attention thanks to their high theoretical specific energy several times exceeding that of lithium-ion batteries. Because of their high surface area, high electric conductivity, and low specific weight, various carbons are often materials of choice for applications as the LAB cathode. Unfortunately, the possibility of practical application of such batteries is still under question as the sustainable operation of LABs with carbon cathodes is not demonstrated yet and the cyclability is quite poor, which is usually associated with oxygen reduced species side reactions. However, the mechanisms of carbon reactivity toward these species are still unclear. Here, we report a direct in situ X-ray photoelectron spectroscopy study of oxygen reduction by lithiated graphene and graphene-based materials. Although lithium peroxide (Li2O2) and lithium oxide (Li2O) reactions with carbon are thermodynamically favorable, neither of them was found to react even at elevated temperatures. As lithium superoxide is not stable at room temperature, potassium superoxide (KO2) prepared in situ was used instead to test the reactivity of graphene with superoxide species. In contrast to Li2O2 and Li2O, KO2 was demonstrated to be strongly reactive.

Epitaxial B-Graphene: Large-Scale Growth and Atomic Structure

Embedding foreign atoms or molecules in graphene has become the key approach in its functionalization and is intensively used for tuning its structural and electronic properties. Here, we present an efficient method based on chemical vapor deposition for large scale growth of boron-doped graphene (B-graphene) on Ni(111) and Co(0001) substrates using carborane molecules as the precursor. It is shown that up to 19 at. % of boron can be embedded in the graphene matrix and that a planar C-B sp(2) network is formed. It is resistant to air exposure and widely retains the electronic structure of graphene on metals. The large-scale and local structure of this material has been explored depending on boron content and substrate. By resolving individual impurities with scanning tunneling microscopy we have demonstrated the possibility for preferential substitution of carbon with boron in one of the graphene sublattices (unbalanced sublattice doping) at low doping level on the Ni(111) substrate. At high boron content the honeycomb lattice of B-graphene is strongly distorted, and therefore, it demonstrates no unballanced sublattice doping.