Y. F. Wang

The Effect of Thermal Reduction on the Photoluminescence and Electronic Structures of Graphene Oxides

Electronic structures of graphene oxide (GO) and hydro-thermally reduced graphene oxides (rGOs) processed at low temperatures (120–180°C) were studied using X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). C K-edge XANES spectra of rGOs reveal that thermal reduction restores C = C sp2 bonds and removes some of the oxygen and hydroxyl groups of GO, which initiates the evolution of carbonaceous species. The combination of C K-edge XANES and Kα XES spectra shows that the overlapping π and π* orbitals in rGOs and GO are similar to that of highly ordered pyrolytic graphite (HOPG), which has no band-gap. C Kα RIXS spectra provide evidence that thermal reduction changes the density of states (DOSs) that is generated in the π-region and/or in the gap between the π and π* levels of the GO and rGOs. Two-dimensional C Kα RIXS mapping of the heavy reduction of rGOs further confirms that the residual oxygen and/or oxygen-containing functional groups modify the π and σ features, which are dispersed by the photon excitation energy. The dispersion behavior near the K point is approximately linear and differs from the parabolic-like dispersion observed in HOPG.

Effect of geometry on the magnetic properties of CoFe2O4–PbTiO3 multiferroic composites

In this study, X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), X-ray magnetic circular dichroism (XMCD) and element- and site-specific magnetic hysteresis (ESMH) are used to elucidate the effect of geometry (0-3- and 2-2-type) on the magnetic properties of CoFe2O4–PbTiO3 (CFO–PTO) multiferroic composites by comparison with those of the reference CFO and PTO powders. Magnetic Co ions in CFO have been confirmed to be located at both the tetrahedral (A)- and octahedral (B)-sites. CFO retains its mixed-spinel structure as verified by the EXAFS, XMCD and ESMH measurements. ESMH measurements further demonstrate that the magnetic moments of Co2+ and Fe3+/Fe2+ cations at both the A- and B-sites in the composites are smaller than those of the CFO powder. The reduction of the magnetic moments in the 2-2-type composite was larger than that in the 0-3-type composite. The reduction of the magnetic moments in the composites was attributable to the formation of anti-phase boundaries owing to the compressive strain in CFO, which is the largest strain in the 2-2-type composite. Based on the Ti L3,2-edge XMCD measurements of the CFO–PTO composites, no induced magnetic moment was observed at the Ti sites in the PTO matrix, excluding the possibility that the Ti ions in the PTO matrix affect the magnetic properties of these CFO–PTO composites.

Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy.

This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature. Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based on experimental results and first-principles calculations, the variation in magnetic behavior from GO to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups on GO sheets.

Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques.

The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, nu2009>u20092)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples.

Defect induced room temperature ferromagnetism in single crystal, poly-crystal, and nanorod ZnO: A comparative study

A comparative study has been made for the defect induced room temperature ferromagnetism of single crystal, poly-crystal, and nanorod zinc oxide (ZnO), based on the magnetic properties and electronic properties by means of X-ray absorption near edge structure spectroscopy (XANES), X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy (UPS), valence band photoemission spectroscopy (VB-PES), and SQUID-type magnetometry. Magnetic measurement demonstrates the defect-induced ferromagnetic nature at room temperature in different ZnO films and a strong correlation between their electronic properties and magnetic responses. The higher ferromagnetic behaviour in polycrystalline ZnO is attributed to the increasing number of surface defects and native defect sites (oxygen vacancies and zinc interstitials) present in ZnO. XANES studies reveal that the number of unoccupied p states in polycrystalline ZnO is higher than single crystal ZnO as well as nanorod ZnO. The more amount of oxygen vacancy caus...

Magnetic anisotropic properties of Pd/Co/Pd trilayer films studied by X-ray absorption spectroscopy and magnetic circular dichroism

We study the magnetic anisotropic properties of as-grown and annealed Pd/Co/Pd trilayer films based on their atomic and electronic structures using extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES) spectroscopy and magnetic circular dichroism (XMCD) measurements. The annealed film exhibits interesting perpendicular magnetic anisotropy (PMA) whereas the as-grown film exhibits in-plane anisotropy. Cross-sectional transmission electron microscopic analysis together with the Co K-edge EXAFS results confirm the formation of an ordered-alloy CoPd phase in the annealed film, whereas the as-grown film has an hcp Co-like phase. Co L3,2-edge XMCD measurements reveal an enhanced ratio of the Co 3d orbital to spin moments of the annealed film providing evidence of the observed PMA upon annealing.

Effect of defects and film thickness on the optical properties of ZnO–Au hybrid films

Electronic structure and optical properties of ZnO(y nm)–Au(10 nm) hybrid films, with y = 20, 50 and 150, have been investigated for effective coupling of surface plasmon resonance (SPR) of Au nanoparticles (NPs) with ZnO band structure to enhance their optical properties. The films have been synthesized by a pulsed laser deposition method and studied by UV-Visible absorption, Raman, Photoluminescence, and X-ray absorption near-edge structural analyses. The effect of defects on coupling of SPR with ZnO band structure has been discussed based on optical and electronic structural studies. The local electronic structure analysis at the O K-edge reveals that, in the thinnest film more unoccupied states are introduced in ZnO due to hybridization of O 2p–Au 5d/6s orbitals. The increased density of states causes the enhanced optical properties of ZnO–Au hybrid films via increasing the population at the conduction band of ZnO. Our experimental findings demonstrate that in the thickest film, the exponential decay of SPR induced local field and defects are the main factors affecting the coupling of SPR with the ZnO band structure.

The electronic and magnetic properties of La0.85Zr0.15MnO3 deposited on SrTiO3 and MgO substrates

The electronic and magnetic properties of tetravalent-ion-doped La0.85Zr0.15MnO3 (LZMO) thin films that were epitaxially grown on SrTiO3 (STO) and MgO substrates were studied using temperature-dependent x-ray diffraction (XRD), x-ray absorption near-edge structure, x-ray linear dichroism, and x-ray magnetic circular dichroism at the Mn L3,2- and K-edge. XRD studies reveal that the LZMO thin films have compressive and tensile strains (along the c-axis) on the STO and MgO substrates, respectively. As the temperature is reduced from room temperature to below magnetic transition temperature, the preferentially occupied Mn majority-spin eg orbital changes from the in-plane dx2-y2 to the out-of-plane d3z2-r2 orbital for LZMO/STO, and vice versa for LZMO/MgO. Experimental results suggest that the new hopping path that is mediated by the Mn2+ ions triggers a stronger d3z2-r2 orbital ordering of Mn3+ ions and enhances the ferromagnetic coupling between the Mn spin moments of t2g electrons in LZMO/STO, whereas the ...

Anisotropy in the thermal hysteresis of resistivity and charge density wave nature of single crystal SrFeO 3-δ : X-ray absorption and photoemission studies

The local electronic and atomic structures of the high-quality single crystal of SrFeO3-δ (δ~0.19) were studied using temperature-dependent x-ray absorption and valence-band photoemission spectroscopy (VB-PES) to investigate the origin of anisotropic resistivity in the ab-plane and along the c-axis close to the region of thermal hysteresis (near temperature for susceptibility maximum, Tm~78u2009K). All experiments herein were conducted during warming and cooling processes. The Fe L3,2-edge X-ray linear dichroism results show that during cooling from room temperature to below the transition temperature, the unoccupied Fe 3d eg states remain in persistently out-of-plane 3d3z2-r2 orbitals. In contrast, in the warming process below the transition temperature, they change from 3d3z2-r2 to in-plane 3dx2-y2 orbitals. The nearest-neighbor (NN) Fe-O bond lengths also exhibit anisotropic behavior in the ab-plane and along the c-axis below Tm. The anisotropic NN Fe-O bond lengths and Debye-Waller factors stabilize the in-plane Fe 3dx2-y2 and out-of-plane 3d3z2-r2 orbitals during warming and cooling, respectively. Additionally, a VB-PES study further confirms that a relative band gap opens at low temperature in both the ab-plane and along the c-axis, providing the clear evidence of the charge-density-wave nature of SrFeO3-δ (δ~0.19) single crystal.

Observation of DNA and protein distributions in mammalian cell nuclei using STXM

A whole A549 cell and isolated nuclei of HeLa S3 cells in the apoptotic process were investigated by using a scanning transmission X-ray microscope (STXM) in the UVSOR Synchrotron (Okazaki, Japan). Near edge X-ray absorption fine structures (NEXAFS) of DNA and histone in the N K-edge region were measured as reference and their distribution in the nuclei was determined by using these reference spectra. The four stages of the apoptosis were successfully distinguished.