Insight into the electronic structure of the centrosymmetric skyrmion magnet GdRu2Si2.

The discovery of a square magnetic-skyrmion lattice in GdRu2Si2, 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 GdRu2Si2 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. A nice agreement of the ARPES-derived electronic structure with the calculated one has allowed us to characterize the features of the Fermi surface (FS), unveil the nested region along kz at the corner of the 3D FS, and reveal their orbital compositions. Our findings suggest that the Ruderman-Kittel-Kasuya-Yosida interaction plays a decisive role in stabilizing the spiral-like order of Gd 4f moments responsible for the skyrmion physics in GdRu2Si2. Our results provide a deeper understanding of electronic and magnetic properties of this material, which is crucial for predicting and developing novel skyrmion-based systems.

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. This makes metals unattractive for use as components for magnonic devices. Here, we present the metallic antiferromagnet CeCo2P2, which exhibits long-living magnons even in the terahertz (THz) regime. For CeCo2P2, our first-principle calculations predict a suppression of low-energy spin-flip Stoner excitations, which is verified by resonant inelastic X-ray scattering measurements. By comparison to the isostructural compound LaCo2P2, we show how small structural changes can dramatically alter the electronic structure around the Fermi level leading to the classical picture of the strongly damped magnons intrinsic to metallic systems. Our results not only demonstrate that long-lived magnons in the THz regime can exist in bulk metallic systems, but they also open a path for an efficient search for metallic magnetic systems in which undamped THz magnons can be excited.

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 HoRh2Si2 and DyRh2Si2, we investigate the temperature-dependent canting of the 4f moments near the surface. We demonstrate that this canting can be understood in the framework of crystal electric field theory and the exchange magnetic interaction. Using photoelectron spectroscopy, we disclose subtle but certain temperature-dependent changes in the line shape of the 4f multiplet. These changes are directly linked to the canting of the 4f moments, which is different for the individual lanthanide layers near the surface. Our results illustrate the opportunity to monitor the orientation of the 4f-moments with high precision, which is essential for development of novel lanthanide-based nanostructures, interfaces, supramolecular complexes, and single-molecule magnets for various applications.

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 momentum1-3, 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 electrons4 (the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction), and the effect of such conditions on direct spin transfer processes is largely unexplored. Here, we investigate ultrafast magnetization dynamics in 4f antiferromagnets and systematically vary the 4f occupation, thereby altering the magnitude of the RKKY coupling energy. By combining time-resolved soft X-ray diffraction with ab initio calculations, we find that the rate of direct transfer between opposing moments is directly determined by this coupling. Given the high sensitivity of RKKY to the conduction electrons, our results offer a useful approach for fine tuning the speed of magnetic devices.

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

Discovered in 1962, the divalent ferromagnetic semiconductor EuS (TC = 16.5 K, Eg = 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. Because detailed information on the electronic structure of EuS and, in particular, its evolution across TC is not well-represented in the literature but is essential for the development of new functional systems, the present work aims at filling this gap. Our angle-resolved photoemission measurements complemented with first-principles calculations demonstrate how the electronic structure of EuS evolves across a paramagnetic-ferromagnetic transition. Our results emphasize the importance of the strong Eu 4f-S 3p mixing for exchange-magnetic splittings of the sulfur-derived bands as well as coupling between f and d orbitals of neighboring Eu atoms to derive the value of TC accurately. The 4f-3p mixing facilitates the coupling between 4f and 5d orbitals of neighboring Eu atoms, which mainly governs the exchange interaction in EuS.

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. The curious in-plane spin-momentum locking is remarkably robust and remains intact across a paramagnetic-antiferromagnetic transition in spite of spin-orbit interaction on Rh atoms being considerably weaker than the out-of-plane exchange field due to the Tb 4f moments.

Divalent EuRh2Si2 as a reference for the Luttinger theorem and antiferromagnetism in trivalent heavy-fermion YbRh2Si2.

Application of the Luttinger theorem to the Kondo lattice YbRh2Si2 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) EuRh2Si2 in its PM regime. Here we show by angle-resolved photoemission spectroscopy that paramagnetic EuRh2Si2 has a large FS essentially similar to the one seen in YbRh2Si2 down to 1 K. In EuRh2Si2 the onset of AFM order below 24.5 K induces an extensive fragmentation of the FS due to Brillouin zone folding, intersection and resulting hybridization of the Fermi-surface sheets. Our results on EuRh2Si2 indicate that the formation of the AFM state in YbRh2Si2 is very likely also connected with similar changes in the FS, which have to be taken into account in the controversial analysis and discussion of anomalies observed at the quantum critical point in this system.

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 TK 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 TK obtained from thermodynamic measurements. In contrast, the temperature scale Tv at which the valence increases with temperature is almost the same in all investigated materials while the Kondo temperatures differ by almost four orders of magnitude. This observation is in remarkable contradiction to both naive expectation and precise theoretical predictions of the Kondo model, asking for further theoretical work in order to explain our findings. Our data exclude the presence of a quantum critical valence transition in YbRh2Si2.

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. The spin degeneracy of the Shockley state breaks down below ~90 K, and the splitting of the resulting subbands saturates upon cooling at values as high as ~185 meV. The spin splitting of the Dirac state becomes clearly visible around ~60 K, reaching a maximum of ~70 meV. An abrupt increase of surface magnetization at around the same temperature suggests that the Dirac state contributes significantly to the magnetic properties at the Si surface. We also show the possibility to tune the properties of 2DESs by depositing alkali metal atoms. The unique temperature-dependent ferromagnetic properties of the Si-terminated surface in GdRh2Si2 could be exploited when combined with functional adlayers deposited on top for which novel phenomena related to magnetism can be anticipated.

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. Most interestingly, the bulk Ce-4f spectra reveal a fine structure near the Fermi edge reflecting the crystal electric field splitting of the bulk magnetic 4f (1)5/2 state. This structure presents a clear dispersion upon crossing valence states, providing direct evidence of f-d hybridization. Our findings give precise insight into f-d hybridization penomena and highlight their importance in the antiferromagnetic phases of Kondo lattices.

Atomically precise semiconductor--graphene and hBN interfaces by Ge intercalation.

The full exploration of the potential, which graphene offers to nanoelectronics requires its integration into semiconductor technology. So far the real-world applications are limited by the ability to concomitantly achieve large single-crystalline domains on dielectrics and semiconductors and to tailor the interfaces between them. Here we show a new direct bottom-up method for the fabrication of high-quality atomically precise interfaces between 2D materials, like graphene and hexagonal boron nitride (hBN), and classical semiconductor via Ge intercalation. Using angle-resolved photoemission spectroscopy and complementary DFT modelling we observed for the first time that epitaxially grown graphene with the Ge monolayer underneath demonstrates Dirac Fermions unaffected by the substrate as well as an unperturbed electronic band structure of hBN. This approach provides the intrinsic relativistic 2D electron gas towards integration in semiconductor technology. Hence, these new interfaces are a promising path for the integration of graphene and hBN into state-of-the-art semiconductor technology.

Laser-induced transformation of supramolecular complexes: approach to controlled formation of hybrid multi-yolk-shell Au-Ag@a-C:H nanostructures.

In the present work an efficient approach of the controlled formation of hybrid Au-Ag-C nanostructures based on laser-induced transformation of organometallic supramolecular cluster compound is suggested. Herein the one-step process of the laser-induced synthesis of hybrid multi-yolk-shell Au-Ag@a-C:H nanoparticles which are bimetallic gold-silver subnanoclusters dispersed in nanospheres of amorphous hydrogenated a-C:H carbon is reported in details. It has been demonstrated that variation of the experimental parameters such as type of the organometallic precursor, solvent, deposition geometry and duration of laser irradiation allows directed control of nanoparticles' dimension and morphology. The mechanism of Au-Ag@a-C:H nanoparticles formation is suggested: the photo-excitation of the precursor molecule through metal-to-ligand charge transfer followed by rupture of metallophilic bonds, transformation of the cluster core including red-ox intramolecular reaction and aggregation of heterometallic species that results in the hybrid metal/carbon nanoparticles with multi-yolk-shell architecture formation. It has been found that the nanoparticles obtained can be efficiently used for the Surface-Enhanced Raman Spectroscopy label-free detection of human serum albumin in low concentration solution.

Field emission luminescence of nanodiamonds deposited on the aligned carbon nanotube array.

Detonation nanodiamonds (NDs) were deposited on the surface of aligned carbon nanotubes (CNTs) by immersing a CNT array in an aqueous suspension of NDs in dimethylsulfoxide (DMSO). The structure and electronic state of the obtained CNT-ND hybrid material were studied using optical and electron microscopy and Infrared, Raman, X-ray photoelectron and near-edge X-ray absorption fine structure spectroscopy. A non-covalent interaction between NDs and CNT and preservation of vertical orientation of CNTs in the hybrid were revealed. We showed that current-voltage characteristics of the CNT-ND cathode are changed depending on the applied field; below ~3 V/µm they are similar to those of the initial CNT array and at the higher field they are close to the ND behavior. Involvement of the NDs in field emission process resulted in blue luminescence of the hybrid surface at an electric field higher than 3.5 V/µm. Photoluminescence measurements showed that the NDs emit blue-green light, while blue luminescence prevails in the CNT-ND hybrid. The quenching of green luminescence was attributed to a partial removal of oxygen-containing groups from the ND surface as the result of the hybrid synthesis.

Fermi-surface reconstruction and complex phase equilibria in CaFe2As2.

Fermi-surface topology governs the relationship between magnetism and superconductivity in iron-based materials. Using low-temperature transport, angle-resolved photoemission, and x-ray diffraction, we show unambiguous evidence of large Fermi-surface reconstruction in CaFe2As2 at magnetic spin-density-wave and nonmagnetic collapsed-tetragonal (cT) transitions. For the cT transition, the change in the Fermi-surface topology has a different character with no contribution from the hole part of the Fermi surface. In addition, the results suggest that the pressure effect in CaFe2As2 is mainly leading to a rigid-band-like change of the valence electronic structure. We discuss these results and their implications for magnetism and superconductivity in this material.

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.

Strong ferromagnetism at the surface of an antiferromagnet caused by buried magnetic moments.

Carrying a large, pure spin magnetic moment of 7 µB per atom in the half-filled 4f shell, divalent europium is an outstanding element for assembling novel magnetic devices in which a two-dimensional electron gas may be polarized due to exchange interaction with an underlying magnetically-active Eu layer. Here we show that the Si-Rh-Si surface trilayer of the antiferromagnet EuRh2Si2 bears a surface state, which exhibits an unexpected and large spin splitting controllable by temperature. The splitting sets in below ~32.5 K, well above the ordering temperature of the Eu 4f moments (~24.5 K) in the bulk, indicating a larger ordering temperature in the topmost Eu layers. The driving force for the itinerant ferromagnetism at the surface is the aforementioned exchange interaction. Such a splitting may also be induced into states of functional surface layers deposited onto the surface of EuRh2Si2 or similarly ordered magnetic materials with metallic or semiconducting properties.

Effect of Na adsorption on the structural and electronic properties of Si(111)√3 × âˆš3-Au surface.

Adsorption of ∼0.1 ML of Na onto the Si(111)√3 × âˆš3-Au surface held at 300 °C has been found to induce pronounced changes in its structural and electronic properties. Domain wall networks, characteristic of the pristine surface, are removed completely, leading to the formation of a highly ordered homogeneous surface. The original atomic arrangement of the Si(111)√3 × âˆš3-Au is preserved and Na atoms occupy T4 adsorption sites at the centers of surface Si trimers. Upon Na adsorption, a pronounced metallic S1 surface-state band develops. It is characterized by a large spin splitting (momentum splitting at the Fermi level Δk∥ = 0.027 Å(-1) and consequent energy splitting ΔEF = 110 meV), large electron filling (on the order of 0.5 electrons per √3 × âˆš3 unit cell) and small effective electron mass of (0.028 ± 0.006)me. The natural consequence of the latter properties is a high surface conductivity of the Si(111)√3 × âˆš3-(Au, Na) surface.

Discovery of 505-million-year old chitin in the basal demosponge Vauxia gracilenta.

Sponges are probably the earliest branching animals, and their fossil record dates back to the Precambrian. Identifying their skeletal structure and composition is thus a crucial step in improving our understanding of the early evolution of metazoans. Here, we present the discovery of 505-million-year-old chitin, found in exceptionally well preserved Vauxia gracilenta sponges from the Middle Cambrian Burgess Shale. Our new findings indicate that, given the right fossilization conditions, chitin is stable for much longer than previously suspected. The preservation of chitin in these fossils opens new avenues for research into other ancient fossil groups.

Carbon nanowalls: the next step for physical manifestation of the black body coating.

The optical properties of carbon nanowall (CNW) films in the visible range have been studied and reported for the first time. Depending on the film structure, ultra-low total reflectance up to 0.13% can be reached, which makes the CNW films a promising candidate for the black body-like coating, and thus for a wide range of applications as a light absorber. We have estimated important trends in the optical property variation from sample to sample, and identified the presence of edge states and domain boundaries in carbon nanowalls as well as the film mass density variation as the key factors. Also we demonstrated that at much lower film thickness and density than for a carbon nanotube forest the CNWs yield one order higher specific light absorption.

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.