This study investigates the strong photoluminescence (PL) and X-ray excited optical luminescence observed in nitrogen-functionalized 2D graphene nanoflakes (GNFs:N), which arise from the significantly enhanced density of states in the region of π states and the gap between π and π* states. The increase in the number of the sp 2 clusters in the form of pyridine-like N−C, graphite-N-like, and the CO bonding and the resonant energy transfer from the N and O atoms to the sp 2 clusters were found to be responsible for the blue shift and the enhancement of the main PL emission feature. The enhanced PL is strongly related to the induced changes of the electronic structures and bonding properties, which were revealed by the X-ray absorption near-edge structure, X-ray emission spectroscopy, and resonance inelastic X-ray scattering. The study demonstrates that PL emission can be tailored through appropriate tuning of the nitrogen and oxygen contents in GNFs and pave the way for new optoelectronic devices.
Various synchrotron radiation-based spectroscopic and microscopic techniques are used to elucidate the room-temperature ferromagnetism of carbon-doped ZnO-nanowires (ZnO-C:NW) via a mild C+ ion implantation method. The photoluminescence and magnetic hysteresis loops reveal that the implantation of C reduces the number of intrinsic surface defects and increases the saturated magnetization of ZnO-NW. The interstitial implanted C ions constitute the majority of defects in ZnO-C:NW as confirmed by the X-ray absorption spectroscopic studies. The X-ray magnetic circular dichroism spectra of O and C K-edge respectively indicate there is a reduction in the number of unpaired/dangling O 2p bonds in the surface region of ZnO-C:NW and the C 2p-derived states of the implanted C ions strongly affect the net spin polarization in the surface and bulk regions of ZnO-C:NW. Furthermore, these findings corroborate well with the first-principles calculations of C-implanted ZnO in surface and bulk regions, which highlight the stability of implanted C for the suppression and enhancement of the ferromagnetism of the ZnO-C:NW in the surface region and bulk phase, respectively.
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−, n > 2)]. 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.
The in-situ X-ray absorption spectroscopy of three tungsten oxide films was performed to study the electronic and atomic structures following repeated cycles of coloration and bleaching processes. The transparent tungsten oxide films become deep blue upon intercalation of Li + ions in the WO 6 octahedra when an external electrical bias was applied. These films reverted to transparent when a reverse external electrical bias was applied. W L 3 -edge X-ray absorption near-edge structure (XANES) measurements of the nanocrystalline and crystalline tungsten oxide films revealed that the intensity of the white-line feature decreases after coloration and recoverably increases after bleaching owing to the filling and unfilling of the W 5d-O 2p conduction band states. The second derivative of the W L 3 -edge XANES spectra indicated an increase in structural disordering following repeated cycles of coloration and bleaching. However, the extended X-ray absorption fine structure analysis showed that the nearestneighbor W-O bond distances in the samples overall remain unchanged by coloration and bleaching.The nanocrystalline tungsten oxide film exhibited more effective recovery ($97% after first cycle) of the electronic structures than the other two crystalline samples in terms of the filling and unfilling of the W 5d-O 2p conduction band states after repeated coloration and bleaching. These results show that the nanocrystalline tungsten oxide sample has superior electrochromic properties to the crystalline samples.
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 causes the highest intensity the O 1 s peak to appear in the XANES spectra of polycrystalline ZnO. In polycrystalline ZnO, the binding energy of the Zn 2p3/2 core level peak shifted to lower energy that further confirms the increase of the valence band maximum (VBM) position. The VBM of single crystal, poly-crystal, and nanorod-ZnO is 3.64 eV, 3.99 eV, and 3.71 eV, respectively, obtained from UPS (He-I) measurements. VB-PES studies confirm that the number of electrons in the valence band of O 2p - Zn 4sp hybridized states of poly-crystal ZnO is higher than single crystal and nanorod-ZnO.
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~78 K). All experiments herein were conducted during warming and cooling processes. The Fe L 3,2-edge X-ray linear dichroism results show that during cooling from room temperature to below the transition temperature, the unoccupied Fe 3d e g states remain in persistently out-of-plane 3d 3z 2 -r 2 orbitals. In contrast, in the warming process below the transition temperature, they change from 3d 3z 2 -r 2 to in-plane 3d x 2 -y 2 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 3d x 2 -y 2 and out-of-plane 3d 3z 2 -r 2 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.
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.
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