Ferromagnetic Layers in a Topological Insulator (Bi,Sb)2Te3 Crystal Doped with Mn.

Magnetic topological insulators (MTIs) have recently become a subject of poignant interest; among them, Z2 topological insulators with magnetic moment ordering caused by embedded magnetic atoms attract special attention. In such systems, the case of magnetic anisotropy perpendicular to the surface that holds a topologically nontrivial surface state is the most intriguing one. Such materials demonstrate the quantum anomalous Hall effect, which manifests itself as chiral edge conduction channels that can be manipulated by switching the polarization of magnetic domains. In the present paper, we uncover the atomic structure of the bulk and the surface of Mn0.06Sb1.22Bi0.78Te3.06 in conjunction with its electronic and magnetic properties; this material is characterized by naturally formed ferromagnetic layers inside the insulating matrix, where the Fermi level is tuned to the bulk band gap. We found that in such mixed crystals septuple layers (SLs) of Mn(Bi,Sb)2Te4 form structures that feature three SLs, each of which is separated by two or three (Bi,Sb)2Te3 quintuple layers (QLs); such a structure possesses ferromagnetic properties. The surface obtained by cleavage includes terraces with different terminations. Manganese atoms preferentially occupy the central positions in the SLs and in a very small proportion can appear in the QLs, as indirectly indicated by a reshaped Dirac cone.

Tunneling current modulation in atomically precise graphene nanoribbon heterojunctions.

Lateral heterojunctions of atomically precise graphene nanoribbons (GNRs) hold promise for applications in nanotechnology, yet their charge transport and most of the spectroscopic properties have not been investigated. Here, we synthesize a monolayer of multiple aligned heterojunctions consisting of quasi-metallic and wide-bandgap GNRs, and report characterization by scanning tunneling microscopy, angle-resolved photoemission, Raman spectroscopy, and charge transport. Comprehensive transport measurements as a function of bias and gate voltages, channel length, and temperature reveal that charge transport is dictated by tunneling through the potential barriers formed by wide-bandgap GNR segments. The current-voltage characteristics are in agreement with calculations of tunneling conductance through asymmetric barriers. We fabricate a GNR heterojunctions based sensor and demonstrate greatly improved sensitivity to adsorbates compared to graphene based sensors. This is achieved via modulation of the GNR heterojunction tunneling barriers by adsorbates.

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.

The Influence of Cu and Al Additives on Reduction of Iron(III) Oxide: In Situ XRD and XANES Study.

The reduction of Fe-based nanocomposite catalysts doped with Al and Cu has been studied using in situ X-ray diffraction (XRD), in situ X-ray absorption near-edge structure (XANES), and temperature-programmed reduction (TPR) techniques. The catalysts have been synthesized by melting of iron, aluminum, and copper salts. According to XRD, the catalysts consist mainly of Fe2O3 and Al2O3 phases. Alumina is in an amorphous state, whereas iron oxide forms nanoparticles with the protohematite structure. The Al3+ cations are partially dissolved in the Fe2O3 lattice. Due to strong alumina-iron oxide interaction, the specific surface area of the catalysts increases significantly. TPR and XANES data indicate that copper forms highly dispersed surface CuO nanoparticles and partially dissolves in iron oxide. It has been shown that the reduction of iron(III) oxide by CO proceeds via two routes: a direct two-stage reduction of iron(III) oxide to metal (Fe2O3 → Fe3O4 → Fe) or an indirect three-stage reduction with the formation of FeO intermediate phases (Fe2O3 → Fe3O4 → FeO → Fe). The introduction of Al into Fe2O3 leads to a decrease in the rate for all reduction steps. In addition, the introduction of Al stabilizes small Fe3O4 particles and prevents further sintering of the iron oxide. The mechanism of stabilization is associated with the formation of Fe3- xAl xO4 solid solution. The addition of copper to the Fe-Al catalyst leads to the formation of highly dispersed CuO particles on the catalyst surface and a mixed oxide with a spinel-type crystalline structure similar to that of CuFe2O4. The low-temperature reduction of Cu2+ to Cu0 accelerates the Fe2O3 → Fe3O4 and FeO → Fe transformations but does not affect the Fe3O4 → FeO/Fe stages. These changes in the reduction properties significantly affect the catalytic performance of the Fe-based nanocomposite catalysts in the low-temperature oxidation of CO.

Spin-polarized Fermi surface, hole-doping and band gap in graphene with boron impurities.

Embedding foreign atoms in graphene and interchanging the underlying substrate are proved to be efficient methods for manipulating the properties of graphene. Combining ARPES experiments with DFT calculations we show that boron-doped graphene (B-graphene) grown on a Co(0001) substrate by chemical vapor deposition (CVD) becomes hole doped and its Fermi surface near the K-point reveals strongly spin-polarized states. The latter stems from the spin-polarized mini Dirac cone that is an intrinsic two-dimensional feature of the graphene/Co(0001) interface and is formed by a mixture of C 2pz and Co 3d states. Since the CVD method allows the achievement of up to 20 at% of incorporated B atoms, this provides a certain flexibility for handling the spin-polarized properties of the system. We also show that the bonding of the B-graphene layer to the Co(0001) substrate can be released by intercalation of Li into the interface. This allows the exploration of the doping effect in detail. Finally, our ARPES data indicate a gap opening in the Dirac cone as a result of the highly unbalanced boron concentrations in the two graphene sublattices.

Boron-Doped Graphene Nanoribbons: Electronic Structure and Raman Fingerprint.

We investigate the electronic and vibrational properties of bottom-up synthesized aligned armchair graphene nanoribbons of N = 7 carbon atoms width periodically doped by substitutional boron atoms (B-7AGNRs). Using angle-resolved photoemission spectroscopy and density functional theory calculations, we find that the dopant-derived valence and conduction band states are notably hybridized with electronic states of Au substrate and spread in energy. The interaction with the substrate leaves the bands with pure carbon character rather unperturbed. This results in an identical effective mass of ≈0.2 m0 for the next-highest valence band compared with pristine 7AGNRs. We probe the phonons of B-7AGNRs by ultrahigh-vacuum (UHV) Raman spectroscopy and reveal the existence of characteristic splitting and red shifts in Raman modes due to the presence of substitutional boron atoms. Comparing the Raman spectra for three visible lasers (red, green, and blue), we find that interaction with gold suppresses the Raman signal from B-7AGNRs and the energy of the green laser (2.33 eV) is closer to the resonant E22 transition. The hybridized electronic structure of the B-7AGNR-Au interface is expected to improve electrical characteristics of contacts between graphene nanoribbon and Au. The Raman fingerprint allows the easy identification of B-7AGNRs, which is particularly useful for device fabrication.

Cobalt-assisted recrystallization and alignment of pure and doped graphene.

Recrystallization of bulk materials is a well-known phenomenon, which is widely used in commercial manufacturing. However, for low-dimensional materials like graphene, this process still remains an unresolved puzzle. Thus, the understanding of the underlying mechanisms and the required conditions for recrystallization in low dimensions is essential for the elaboration of routes towards the inexpensive and reliable production of high-quality nanomaterials. Here, we unveil the details of the efficient recrystallization of one-atom-thick pure and boron-doped polycrystalline graphene layers on a Co(0001) surface. By applying photoemission and electron diffraction, we show how more than 90% of the initially misoriented graphene grains can be reconstructed into a well-oriented and single-crystalline layer. The obtained recrystallized graphene/Co interface exhibits high structural quality with a pronounced sublattice asymmetry, which is important for achieving an unbalanced sublattice doping of graphene. By exploring the kinetics of recrystallization for native and B-doped graphene on Co, we were able to estimate the activation energy and propose a mechanism of this process.

Large-Scale Sublattice Asymmetry in Pure and Boron-Doped Graphene.

The implementation of future graphene-based electronics is essentially restricted by the absence of a band gap in the electronic structure of graphene. Options of how to create a band gap in a reproducible and processing compatible manner are very limited at the moment. A promising approach for the graphene band gap engineering is to introduce a large-scale sublattice asymmetry. Using photoelectron diffraction and spectroscopy we have demonstrated a selective incorporation of boron impurities into only one of the two graphene sublattices. We have shown that in the well-oriented graphene on the Co(0001) surface the carbon atoms occupy two nonequivalent positions with respect to the Co lattice, namely top and hollow sites. Boron impurities embedded into the graphene lattice preferably occupy the hollow sites due to a site-specific interaction with the Co pattern. Our theoretical calculations predict that such boron-doped graphene possesses a band gap that can be precisely controlled by the dopant concentration. B-graphene with doping asymmetry is, thus, a novel material, which is worth considering as a good candidate for electronic applications.

A curious interplay in the films of N-heterocyclic carbene Pt(II) complexes upon deposition of alkali metals.

The recently synthesized series of Pt(II) complexes containing cyclometallating (phenylpyridine or benzoquinoline) and N-heterocyclic carbene ligands possess intriguing structures, topologies, and light emitting properties. Here, we report curious physicochemical interactions between in situ PVD-grown films of a typical representative of the aforementioned Pt(II) complex compounds and Li, Na, K and Cs atoms. Based on a combination of detailed core-level photoelectron spectroscopy and quantum-chemical calculations at the density functional theory level, we found that the deposition of alkali atoms onto the molecular film leads to unusual redistribution of electron density: essential modification of nitrogen sites, reduction of the coordination Pt(II) centre to Pt(0) and decrease of electron density on the bromine atoms. A possible explanation for this is formation of a supramolecular system "Pt complex-alkali metal ion"; the latter is supported by restoration of the system to the initial state upon subsequent oxygen treatment. The discovered properties highlight a considerable potential of the Pt(II) complexes for a variety of biomedical, sensing, chemical, and electronic applications.

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.

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.

Acoustic properties of rarefied gases inside pores of simple geometries.

Analytical solutions describing propagation of monochromatic acoustic waves inside long pores of simple geometries and narrow flat slits are obtained with accounting for gas rarefaction effects. It is assumed that molecular nature of gas is important in Knudsen layers near solid boundaries. Outside the Knudsen layers, the continuum approach is used. This model allows for extension of acoustic analysis to regions of low pressures and microscopic cross-sectional sizes of channels. The problem is solved using linearized Navier-Stokes equations with the boundary conditions that resulted from the first-order approximation with respect to small Knudsen number Kn. For slits and pores of circular and square cross sections, the theoretical dependencies of the dynamic density in the low-frequency range are compared with those that resulted from known experimental data on steady-state flows of rarefied gases in uniform channels. Despite the formal restriction Kn << 1 of asymptotic analysis, the theoretical model agrees well with experiments up to Kn approximately 5. It is shown that the molecular phenomena affect acoustic characteristics of micro-channels and pores starting from relatively small Knudsen numbers Kn > 0.01, especially at low frequencies. The obtained results may be used for analyses of acoustic properties of waveguides, perforated panels, micro-channels and pores in wide range of gas pressures as well as for stationary flows of rarefied gases through long uniform pipes etc.