Simulating high-pressure surface reactions with molecular beams.

Using a reactive molecular beam with high kinetic energy (), it is possible to speed gas-surface reactions involving high activation barriers (), which would require elevated pressures () if a random gas with a Maxwell-Boltzmann distribution is used. By simply computing the number of molecules that overcome the activation barrier in a random gas at and in a molecular beam at = , we establish an - equivalence curve, through which we postulate that molecular beams are ideal tools to investigate gas-surface reactions that involve high activation energies. In particular, we foresee the use of molecular beams to simulate gas surface reactions within the industrial-range (>10 bar) using surface-sensitive ultra-high vacuum (UHV) techniques, such as X-ray photoemission spectroscopy (XPS).

Insight into the electronic structure of the centrosymmetric skyrmion magnet GdRuSi.

The discovery of a square magnetic-skyrmion lattice in GdRuSi, with the smallest so far found skyrmion size and without a geometrically frustrated lattice, has attracted significant attention. In this work, we present a comprehensive study of surface and bulk electronic structures of GdRuSi by utilizing momentum-resolved photoemission (ARPES) measurements and first-principles calculations. We show how the electronic structure evolves during the antiferromagnetic transition when a peculiar helical order of 4f magnetic moments within the Gd layers sets in.

Long-lived spin waves in a metallic antiferromagnet.

Collective spin excitations in magnetically ordered crystals, called magnons or spin waves, can serve as carriers in novel spintronic devices with ultralow energy consumption. The generation of well-detectable spin flows requires long lifetimes of high-frequency magnons. In general, the lifetime of spin waves in a metal is substantially reduced due to a strong coupling of magnons to the Stoner continuum.

Insight into the Temperature-Dependent Canting of 4f Magnetic Moments from 4f Photoemission.

The orientation of the 4f moments offers an additional degree of freedom for engineering the spin-related properties in spintronic nanostructures of lanthanides. Yet, precise monitoring of the direction of magnetic moments remains a challenge. Here, on the example of the antiferromagnets HoRhSi and DyRhSi, we investigate the temperature-dependent canting of the 4f moments near the surface.

Estimating the Orientation of 4f Magnetic Moments by Classical Photoemission.

To use efficiently the magnetic functionalities emerging at the surfaces or interfaces of novel lanthanides-based materials, there is a need for complementary methods to probe the atomic-layer resolved magnetic properties. Here, we show that 4f photoelectron spectroscopy is highly sensitive to the collective orientation of 4f magnetic moments and, thus, a powerful tool for characterizing the related properties. To demonstrate this, we present the results of systematic study of a family of layered crystalline 4f-materials, which are crystallized in the body-centered tetragonal ThCrSi structure.

Exchange scaling of ultrafast angular momentum transfer in 4f antiferromagnets.

Ultrafast manipulation of magnetism bears great potential for future information technologies. While demagnetization in ferromagnets is governed by the dissipation of angular momentum, materials with multiple spin sublattices, for example antiferromagnets, can allow direct angular momentum transfer between opposing spins, promising faster functionality. In lanthanides, 4f magnetic exchange is mediated indirectly through the conduction electrons (the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction), and the effect of such conditions on direct spin transfer processes is largely unexplored.

High-Quality Graphene Using Boudouard Reaction.

Following the game-changing high-pressure CO (HiPco) process that established the first facile route toward large-scale production of single-walled carbon nanotubes, CO synthesis of cm-sized graphene crystals of ultra-high purity grown during tens of minutes is proposed. The Boudouard reaction serves for the first time to produce individual monolayer structures on the surface of a metal catalyst, thereby providing a chemical vapor deposition technique free from molecular and atomic hydrogen as well as vacuum conditions. This approach facilitates inhibition of the graphene nucleation from the CO/CO mixture and maintains a high growth rate of graphene seeds reaching large-scale monocrystals.

Interlayer Coupling of a Two-Dimensional Kondo Lattice with a Ferromagnetic Surface in the Antiferromagnet CeCoP.

The f-driven temperature scales at the surfaces of strongly correlated materials have increasingly come into the focus of research efforts. Here, we unveil the emergence of a two-dimensional Ce Kondo lattice, which couples ferromagnetically to the ordered Co lattice below the P-terminated surface of the antiferromagnet CeCoP. In its bulk, Ce is passive and behaves tetravalently.

Insight into the Temperature Evolution of Electronic Structure and Mechanism of Exchange Interaction in EuS.

Discovered in 1962, the divalent ferromagnetic semiconductor EuS ( = 16.5 K, = 1.65 eV) has remained constantly relevant to the engineering of novel magnetically active interfaces, heterostructures, and multilayer sequences and to combination with topological materials.

Atomically-Precise Texturing of Hexagonal Boron Nitride Nanostripes.

Monolayer hexagonal boron nitride (hBN) is attracting considerable attention because of its potential applications in areas such as nano- and opto-electronics, quantum optics and nanomagnetism. However, the implementation of such functional hBN demands precise lateral nanostructuration and integration with other two-dimensional materials, and hence, novel routes of synthesis beyond exfoliation. Here, a disruptive approach is demonstrated, namely, imprinting the lateral pattern of an atomically stepped one-dimensional template into a hBN monolayer.

Extreme Biomimetics: Designing of the First Nanostructured 3D Spongin-Atacamite Composite and its Application.

The design of new composite materials using extreme biomimetics is of crucial importance for bioinspired materials science. Further progress in research and application of these new materials is impossible without understanding the mechanisms of formation, as well as structural features at the molecular and nano-level. It presents a challenge to obtain a holistic understanding of the mechanisms underlying the interaction of organic and inorganic phases under conditions of harsh chemical reactions for biopolymers.

Electronic Structures and Surface Reconstructions in Magnetic Superconductor RbEuFeAs.

In pnictide RbEuFeAs, superconductivity sets in at 36 K and coexists, below 15-19 K, with the long-range magnetic ordering of Eu 4f spins. Here we report scanning tunneling experiments performed on cold-cleaved single crystals of the compound. The data revealed the coexistence of large Rb-terminated and small Eu-terminated terraces, both manifesting 1 × 2 and reconstructions.

Cubic Rashba Effect in the Surface Spin Structure of Rare-Earth Ternary Materials.

Spin-orbit interaction and structure inversion asymmetry in combination with magnetic ordering is a promising route to novel materials with highly mobile spin-polarized carriers at the surface. Spin-resolved measurements of the photoemission current from the Si-terminated surface of the antiferromagnet TbRh_{2}Si_{2} and their analysis within an ab initio one-step theory unveil an unusual triple winding of the electron spin along the fourfold-symmetric constant energy contours of the surface states. A two-band k·p model is presented that yields the triple winding as a cubic Rashba effect.

Divalent EuRhSi as a reference for the Luttinger theorem and antiferromagnetism in trivalent heavy-fermion YbRhSi.

Application of the Luttinger theorem to the Kondo lattice YbRhSi suggests that its large 4f-derived Fermi surface (FS) in the paramagnetic (PM) regime should be similar in shape and volume to that of the divalent local-moment antiferromagnet (AFM) EuRhSi in its PM regime. Here we show by angle-resolved photoemission spectroscopy that paramagnetic EuRhSi has a large FS essentially similar to the one seen in YbRhSi down to 1 K. In EuRhSi the onset of AFM order below 24.

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 2p and Co 3d states.

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.

Similar temperature scale for valence changes in Kondo lattices with different Kondo temperatures.

The Kondo model predicts that both the valence at low temperatures and its temperature dependence scale with the characteristic energy T of the Kondo interaction. Here, we study the evolution of the 4f occupancy with temperature in a series of Yb Kondo lattices using resonant X-ray emission spectroscopy. In agreement with simple theoretical models, we observe a scaling between the valence at low temperature and T obtained from thermodynamic measurements.

Effect of the fluorination technique on the surface-fluorination patterning of double-walled carbon nanotubes.

Double-walled carbon nanotubes (DWCNTs) are fluorinated using (1) fluorine F at 200 °C, (2) gaseous BrF at room temperature, and (3) CF radio-frequency plasma functionalization. These have been comparatively studied using transmission electron microscopy and infrared, Raman, X-ray photoelectron, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. A formation of covalent C-F bonds and a considerable reduction in the intensity of radial breathing modes from the outer shells of DWCNTs are observed for all samples.

Raman Spectroscopy of Lattice-Matched Graphene on Strongly Interacting Metal Surfaces.

Regardless of the widely accepted opinion that there is no Raman signal from single-layer graphene when it is strongly bonded to a metal surface, we present Raman spectra of a graphene monolayer on Ni(111) and Co(0001) substrates. The high binding energy of carbon to these surfaces allows formation of lattice-matched (1 × 1) structures where graphene is significantly stretched. This is reflected in a record-breaking shift of the Raman G band by more than 100 cm relative to the case of freestanding graphene.

Spin Orientation of Two-Dimensional Electrons Driven by Temperature-Tunable Competition of Spin-Orbit and Exchange-Magnetic Interactions.

Finding ways to create and control the spin-dependent properties of two-dimensional electron states (2DESs) is a major challenge for the elaboration of novel spin-based devices. Spin-orbit and exchange-magnetic interactions (SOI and EMI) are two fundamental mechanisms that enable access to the tunability of spin-dependent properties of carriers. The silicon surface of HoRhSi appears to be a unique model system, where concurrent SOI and EMI can be visualized and controlled by varying the temperature.

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.

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.

Robust and tunable itinerant ferromagnetism at the silicon surface of the antiferromagnet GdRh2Si2.

Spin-polarized two-dimensional electron states (2DESs) at surfaces and interfaces of magnetically active materials attract immense interest because of the idea of exploiting fermion spins rather than charge in next generation electronics. Applying angle-resolved photoelectron spectroscopy, we show that the silicon surface of GdRh2Si2 bears two distinct 2DESs, one being a Shockley surface state, and the other a Dirac surface resonance. Both are subject to strong exchange interaction with the ordered 4f-moments lying underneath the Si-Rh-Si trilayer.

ARPES view on surface and bulk hybridization phenomena in the antiferromagnetic Kondo lattice CeRh2Si2.

The hybridization between localized 4f electrons and itinerant electrons in rare-earth-based materials gives rise to their exotic properties like valence fluctuations, Kondo behaviour, heavy-fermions, or unconventional superconductivity. Here we present an angle-resolved photoemission spectroscopy (ARPES) study of the Kondo lattice antiferromagnet CeRh2Si2, where the surface and bulk Ce-4f spectral responses were clearly resolved. The pronounced 4f (0) peak seen for the Ce terminated surface gets strongly suppressed in the bulk Ce-4f spectra taken from a Si-terminated crystal due to much larger f-d hybridization.