Chemical Trends of the Bulk and Surface Termination-Dependent Electronic Structure of Metal-Intercalated Transition Metal Dichalcogenides.

The addition of metal intercalants into the van der Waals gaps of transition metal dichalcogenides has shown great promise as a method for controlling their functional properties. For example, chiral helimagnetic states, current-induced magnetization switching, and a giant valley-Zeeman effect have all been demonstrated, generating significant renewed interest in this materials family. Here, we present a combined photoemission and density-functional theory study of three such compounds: , , and , to investigate chemical trends of the intercalant species on their bulk and surface electronic structure. Our resonant photoemission measurements indicate increased hybridization with the itinerant NbS2-derived conduction states with increasing atomic number of the intercalant, leading to pronounced mixing of the nominally localized intercalant states at the Fermi level. Using spatially and angle-resolved photoemission spectroscopy, we show how this impacts surface-termination-dependent charge transfers and leads to the formation of new dispersive states of mixed intercalant-Nb character at the Fermi level for the intercalant-terminated surfaces. This provides an explanation for the origin of anomalous states previously reported in this family of compounds and paves the way for tuning the nature of the magnetic interactions in these systems via control of the hybridization of the magnetic ions with the itinerant states.

Hierarchy of Lifshitz Transitions in the Surface Electronic Structure of Sr_{2}RuO_{4} under Uniaxial Compression.

We report the evolution of the electronic structure at the surface of the layered perovskite Sr_{2}RuO_{4} under large in-plane uniaxial compression, leading to anisotropic B_{1g} strains of ϵ_{xx}-ϵ_{yy}=-0.9±0.1%. From angle-resolved photoemission, we show how this drives a sequence of Lifshitz transitions, reshaping the low-energy electronic structure and the rich spectrum of van Hove singularities that the surface layer of Sr_{2}RuO_{4} hosts. From comparison to tight-binding modeling, we find that the strain is accommodated predominantly by bond-length changes rather than modifications of octahedral tilt and rotation angles. Our study sheds new light on the nature of structural distortions at oxide surfaces, and how targeted control of these can be used to tune density of state singularities to the Fermi level, in turn paving the way to the possible realization of rich collective states at the Sr_{2}RuO_{4} surface.

Electronically driven spin-reorientation transition of the correlated polar metal Ca3Ru2O7.

The interplay between spin-orbit coupling and structural inversion symmetry breaking in solids has generated much interest due to the nontrivial spin and magnetic textures which can result. Such studies are typically focused on systems where large atomic number elements lead to strong spin-orbit coupling, in turn rendering electronic correlations weak. In contrast, here we investigate the temperature-dependent electronic structure of [Formula: see text], a [Formula: see text] oxide metal for which both correlations and spin-orbit coupling are pronounced and in which octahedral tilts and rotations combine to mediate both global and local inversion symmetry-breaking polar distortions. Our angle-resolved photoemission measurements reveal the destruction of a large hole-like Fermi surface upon cooling through a coupled structural and spin-reorientation transition at 48 K, accompanied by a sudden onset of quasiparticle coherence. We demonstrate how these result from band hybridization mediated by a hidden Rashba-type spin-orbit coupling. This is enabled by the bulk structural distortions and unlocked when the spin reorients perpendicular to the local symmetry-breaking potential at the Ru sites. We argue that the electronic energy gain associated with the band hybridization is actually the key driver for the phase transition, reflecting a delicate interplay between spin-orbit coupling and strong electronic correlations and revealing a route to control magnetic ordering in solids.

One-step nondestructive functionalization of graphene oxide paper with amines.

Direct functionalization of prefabricated free-standing graphene oxide paper (GOP) is the only approach suitable for systematic tuning of its mechanical, thermal and electronic characteristics. However, the traditional liquid-phase functionalization can compromise physical integrity of the paper-like material up to its total disintegration. In the present paper, we attempted to apply an alternative, solvent-free strategy for facile and nondestructive functionalization of GOP with 1-octadecylamine (ODA) and 1,12-diaminododecane (DAD) as representatives of aliphatic amines, and with 1-aminopyrene (AP) and 1,5-diaminonaphthalene (DAN) as examples of aromatic amines. The functionalization can be carried out under moderate heating at 150-180 °C for 2 h in vacuum, and proceeds through both amidation and epoxy ring opening reactions. Comparative characterization of pristine and amine-modified GOP samples was carried out by means of Fourier-transform infrared, Raman, and X-ray photoelectron spectroscopy, thermogravimetric and differential thermal analysis, scanning electron and atomic force microscopy. In addition, we compared stability in water, wettability, electrical conductivity and elastic (Young's) modulus of GOP samples before and after functionalization. The highest content of amine species was obtained in the case of GOP-ODA, followed by GOP-DAD, GOP-AP and GOP-DAN. The functionalization increased mechanical and thermal stability, as well as the electrical conductivity of GOP. The magnitude of each effect depends on the structure of amine employed, which allows for tuning a given GOP characteristic. Morphological characterization showed that, compared to pristine graphene oxide paper, amine-modified mats become relatively ordered layered structures, in which individual GO sheets are organized in a near-parallel fashion.