The complex refractive index of many materials is poorly known in the soft X-ray range across absorption edges. This is due to saturation effects that occur there in total-electron-yield and fluorescence-yield spectroscopy and that are strongest at resonance energies. Aiming to obtain reliable optical constants, a procedure that reconciles electron-yield measurements and reflection spectroscopy by correcting these saturation effects is presented. The procedure takes into account the energy- and polarization-dependence of the photon penetration depth as well as the creation efficiency for secondary electrons and their escape length. From corrected electron-yield spectra the absorption constants and the imaginary parts of the refractive index of the material are determined. The real parts of the index are subsequently obtained through a Kramers-Kronig transformation. These preliminary optical constants are refined by simulating reflection spectra and adapting them, so that measured reflection spectra are reproduced best. The efficacy of the new procedure is demonstrated for graphite. The optical constants that have been determined for linearly polarized synchrotron light incident with p- and s-geometry provide a detailed and reliable representation of the complex refractive index of the material near π- and σ-resonances. They are also suitable for allotropes of graphite such as graphene.

The complex refractive index has been determined for graphene for linearly polarised light in p- and s-geometry at energies across the carbon 1s edge. The imaginary part was measured with absorption spectroscopy. The real part was derived using Kramers-Kronig transformations. Results have been validated by X-ray reflectometry of substrate-supported graphene. Theoretical modelling demonstrates that reflection spectra are strongly affected by the relative difference between the reflectance of graphene and its substrate. Measured reflection spectra show that graphene is often sandwiched between a carbonaceous layer of surface-adsorbates and another carbonaceous layer between graphene and substrate. Reflectometry distinguishes adventitious layers from the graphene because of a different energy-dependence of the refractive index. The carbonaceous interface layers can be modelled well with the refractive index function measured for an adventitious surface layer on silicon. The carbon observed at the substrate-interface may originate from the transfer of a graphene sheet from a deposition-substrate. The optically-effective thickness and anisotropy of adventitious carbonaceous layers can be extracted from reflectance spectra. The bonds of adventitious carbon tend to be normal to the basal plane of graphene. Transferred graphene typically has a substrate-interface three times its own thickness and is covered by one layer of surface adsorbates.

Using polarization analysis of linearly polarized synchrotron radiation we demonstrate the existence of a giant magneto-optical Faraday effect at the carbon 1s edge of single-layer graphene on Co, reaching Faraday rotation angles of 2.9 x 10(5)deg/mm. This value is of the order of those observed at the Co 3p and 2p edges. Using element-selective magnetic hysteresis curves we find that graphene on Co exhibits ferromagnetic order. The magnetism in graphene is found to be carried by and be strongly enhanced by aligned n orbitals of carbon atoms. It is induced by hybridization with the Co 3d(z)2 orbitals while carbon a bonds show negligible magnetism due to insignificant hybridization with Co. From additional x-ray magnetic circular dichroism and transversal magneto-optical Kerr effect spectra a magnetic moment of 0.14 mu(B) is estimated for graphene. From Faraday spectra the complete set of x-ray magneto-optical constants of graphene has been deduced which allows for future modeling of magneto-optical devices based on graphene. The strong magnetism in graphene results from hybridization of carbon p(z) and metal 3d orbitals. Atoms of the graphene sublattice A, placed on top of Co, lead to strongest hybridization with Co 3d(z)( )(2)orbitals. Carbon atoms of sublattice B, and those of rotated graphene domains without Co atoms beneath, hybridize with each other and with 3d(xy) and 3d(yz) orbitals of neighboring Co atoms forming tilted p(z) bonds. We show that the related reduction of A-B symmetry leads to a splitting of the spin-polarized density of conduction-band states which is responsible for the strong magneto-optical Faraday effect.

The existence of ferromagnetic ordering in graphene on cobalt is demonstrated by means of resonant magnetic reflection spectroscopy exploiting the transversal magneto-optical Kerr-effect (T-MOKE). Using linearly polarized synchrotron radiation in the soft x-ray range with energies spanning the carbon 1s edge, the π- and σ- bonds of graphene were excited individually, showing that magnetism in graphene is carried by the π – orbitals. Magnetic signals were detected over a wide energy range from 257 – 340 eV with a T-MOKE peak value of 1.1 % at the π – resonance energy near 285 eV. By comparison with corresponding spectra measured at the 2p edges of the Co substrate, a large induced magnetic moment of 0.14 μB was derived for graphene. Individual hysteresis curves monitored at the Co 2p and C 1s edges show that the carbon magnetism is induced by the Co substrate.

Near edge x-ray absorption fine structure spectroscopy was performed to determine the imaginary part of the refractive index of graphite and graphene at wavelengths spanning the carbon K-edge. The real part of the refractive index has been derived from this measured imaginary part via piecewise polynomial Kramers-Kronig transformations. This paper presents the first comparison of simulated reflection spectra using these data with measured reflection spectra.

The existence of natural birefringence in x-ray reflection on graphene is demonstrated at energies spanning the carbon 1s absorption edge. This new x-ray effect has been discovered with precision measurements of the polarization-plane rotation and the polarization-ellipticity changes that occur upon reflection of linearly polarized synchrotron radiation on monolayer graphene. Extraordinarily large polarization-plane rotations of up to 30 degrees, accompanied by a change from linearly to circularly polarized radiation have been measured for graphene on copper. Graphene on single crystalline cobalt, grown on tungsten, exhibits rotation values of up to 17 degrees. Both graphene systems show resonantly enhanced effects at the pi* and sigma* energies. The results are referenced against those obtained for polycrystalline carbon and highly oriented pyrolytic graphite (HOPG), respectively. As expected, polycrystalline carbon shows negligible rotation, whereas a huge maximum rotation of 140 degrees has been observed for HOPG that may be considered a graphene multilayer system. HOPG is found to exhibit such large rotation values over a broad energy range, even well beyond the pi* resonance energy due to the contributions of numerous graphene layers. To explain the origin of the observed natural birefringence of graphene, the Stokes parameters as well as the x-ray natural linear dichroism in reflection have been determined. It is shown that the birefringence directly results from the optical anisotropy related to the orthogonal alignment of pi* and sigma* bonds in the graphene layer. Our polarization analysis reveals a strong bonding of graphene on Co with a reduced sigma* excitation energy and a strong tilt of 50% of the p(z) orbitals towards diagonal orientation. In contrast, graphene on Cu is weakly bound with an orthogonal orientation of the p(z) orbitals. Exhibiting such a large natural birefringence that can be controlled through substrate choice, and because of excellent heat conductivity, graphene materials have a potential to be used as tunable x-ray phase shifting lambda/4 or lambda/2 plates in the design of future high-intensity light sources.

Reflectivity measurements on graphitic materials such as graphene at energies across the carbon K-edge are frustrated by significant intensity loss due to adventitious carbon on beamline mirrors. Such intensity reduction enhances effects due to perturbing high-order harmonics in the beam. These effects distort the actual structure of the reflectance curve. In order to overcome this limitation, a correction technique has been developed and demonstrated first with measurements for highly ordered pyrolytic graphite. The same approach may be applied to other graphitic materials such as graphene and it may be used with other synchrotron beamlines. The fraction of high-order harmonics was determined by passing the incident beam through a 87nm thin silicon nitride absorber that can be well modeled. Using the corrected measurements the x-ray natural linear dichroism of the sample has been determined.

In graphene oxide, the graphite lattice is intercalated with oxygen groups that bond to carbon atoms. These groups have a bearing on the possibility of using graphene oxide as a precursor to make graphene. The nature of carbon bonds in graphene oxide has been characterized with soft x-ray reflection spectroscopy across the carbon K-edge. Results distinguish graphene oxide synthesized with Hummers' method from that made using a method suggested by Tour. The observed spectra are consistent with those from near-edge x-ray absorption fine structure (NEXAFS) measurements. In particular, the expected carbon K-edge resonances associated with excitations into molecular *- and sigma*-states of CC bonds can be identified. Importantly, the greater oxidation efficiency of the method by Tour may be the reason for the observation of additional resonances that have been assigned to carbon bonding with molecular groups containing oxygen. The additional resonances have been interpreted as the excitations of carbon 1s electrons into the carbonyl *(CO) orbital in the molecular group -COOH and into the hydroxyl *(COH) orbital, respectively. Copyright (c) 2015 John Wiley & Sons, Ltd.

We report an investigation of the influence of the crystal structure of Co thin films on the X-ray magnetic linear dichroism (XMLD) spectrum. We compare XMLD spectra measured in reflection at the 3p-edges for two distinct orientations of the magnetization in the crystalline Co film with ab initio calculated spectra. The latter was computed for the face-centered cubic as well as the hexagonal-close packed crystal structures of Co. We find that the XMLD signal is strongly dependent on the magnetization direction with respect to the crystal axes as well as strongly influenced by the crystal structure.

X-ray magnetic linear dichroism spectra measured in reflection (XMLD-R) on crystalline bcc Fe thin films across the 3 p absorption edges are reported. A series of measurements with varying orientation of the electric field vector of the linear polarized synchrotron radiation with respect to the crystal axes reveals a strong magnetocrystalline anisotropy in the XMLD-R spectra. The spectra agree well with theoretical spectra calculated within the framework of the density-functional theory accounting for the spin-orbital and exchange splitting of the 3 p semicore states on an equal footing.

The magnetocrystalline anisotropy of X-ray magnetic linear dichroism (XMLD) reflection spectra measured on single-crystalline bcc Fe films across the 3p and 2p edges are presented. The XMLD spectra were obtained from a series of reflection spectra by aligning the electric field vector of linearly polarized undulator radiation with respect to the crystal axes. Our results show the presence of a huge magnetocrystalline anisotropy in the XMLD reflection spectra. The XMLD signal is further investigated as a function of the Fe film thickness in Au/Fe/Ag/GaAs layered systems. Simulations of the reflection spectra reveal the influences of interference effects, which can enhance or diminish the XMLD signals. The measured spectra are in good agreement with ab initio calculated spectra.