Aqueous solution/metal interfaces investigated in operando by photoelectron spectroscopy.

We describe a new in operando approach for the investigation of heterogeneous processes at solid/liquid interfaces with elemental and chemical specificity which combines the preparation of thin liquid films using the meniscus method with standing wave ambient pressure X-ray photoelectron spectroscopy [Nemsák et al., Nat. Commun., 5, 5441 (2014)]. This technique provides information about the chemical composition across liquid/solid interfaces with sub-nanometer depth resolution and under realistic conditions of solution composition and concentration, pH, as well as electrical bias. In this article, we discuss the basics of the technique and present the first results of measurements on KOH/Ni interfaces.

Electronic superlattice revealed by resonant scattering from random impurities in Sr3Ru2O7.

Resonant elastic x-ray scattering (REXS) is an exquisite element-sensitive tool for the study of subtle charge, orbital, and spin superlattice orders driven by the valence electrons, which therefore escape detection in conventional x-ray diffraction (XRD). Although the power of REXS has been demonstrated by numerous studies of complex oxides performed in the soft x-ray regime, the cross section and photon wavelength of the material-specific elemental absorption edges ultimately set the limit to the smallest superlattice amplitude and periodicity one can probe. Here we show--with simulations and REXS on Mn-substituted Sr3Ru2O7--that these limitations can be overcome by performing resonant scattering experiments at the absorption edge of a suitably-chosen, dilute impurity. This establishes that--in analogy with impurity-based methods used in electron-spin-resonance, nuclear-magnetic resonance, and Mössbauer spectroscopy--randomly distributed impurities can serve as a non-invasive, but now momentum-dependent probe, greatly extending the applicability of resonant x-ray scattering techniques.

Magnetic structure of RuSr2GdCu2O8 determined by resonant x-ray diffraction.

X-ray diffraction with photon energies near the Ru L2-absorption edge was used to detect resonant reflections characteristic of a G-type superstructure in RuSr2GdCu2O8 single crystals. A polarization analysis confirms that these reflections are due to magnetic order of Ru moments, and the azimuthal-angle dependence of the scattering amplitude reveals that the moments lie along a low-symmetry axis with substantial components parallel and perpendicular to the RuO2 layers. Complemented by susceptibility data and a symmetry analysis of the magnetic structure, these results reconcile many of the apparently contradictory findings reported in the literature.

Orbital ordering transition in Ca2RuO4 observed with resonant X-ray diffraction.

Resonant x-ray diffraction performed at the L(II) and L(III) absorption edges of Ru has been used to investigate the magnetic and orbital ordering in Ca2RuO4 single crystals. A large resonant enhancement due to electric dipole 2p-->4d transitions is observed at the wave-vector characteristic of antiferromagnetic ordering. Besides the previously known antiferromagnetic phase transition at T(N)=110 K, an additional phase transition, between two paramagnetic phases, is observed around 260 K. Based on the polarization and azimuthal angle dependence of the diffraction signal, this transition can be attributed to orbital ordering of the Ru t(2g) electrons. The propagation vector of the orbital order is inconsistent with some theoretical predictions for the orbital state of Ca2RuO4.

Oxygen superstructures throughout the phase diagram of (Y,Ca)Ba2Cu3O6+x.

The doping dependence of short-range lattice superstructures in (Y,Ca)Ba2Cu3O6+x has been studied with high-energy x-ray scattering. We observe diffuse features with a well defined periodicity which depend on the oxygen concentration but not on the charge carrier concentration. In addition, we find that diffuse scattering is absent in underdoped YBa2Cu4O8, which does not sustain oxygen defects. Our combined data highlight that the diffuse scattering arises from short-range oxygen ordering and associated lattice distortions. Signatures of stripe ordering or fluctuations are not seen and therefore must be much weaker.