C. W. Pao

Observation of the origin of d0 magnetism in ZnO nanostructures using X-ray-based microscopic and spectroscopic techniques

Efforts have been made to elucidate the origin of d(0) magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites. Specifically, the results of O K-edge scanning transmission X-ray microscopy (STXM) and the corresponding X-ray-absorption near-edge structure (XANES) spectroscopy demonstrated that the impurity (non-stoichiometric) region in ZnO NCs contains a greater defect population than the thick region. The intensity of O K-edge STXM-XANES in the impurity region is more predominant in ZnO NCs than in NWs. The increase in the unoccupied (occupied) density of states at/above (at/below) the conduction-band minimum (valence-band maximum) or the Fermi level is related to the population of defects at the O sites, as revealed by comparing the ZnO NCs to the NWs. The results of O K-edge and Zn L3,2-edge X-ray magnetic circular dichroism demonstrated that the origin of magnetization is attributable to the O 2p orbitals rather than the Zn d orbitals. Further, the local density approximation (LDA) + U verified that vacancies in the form of dangling or unpaired 2p states (due to Zn vacancies) induced a significant local spin moment in the nearest-neighboring O atoms to the defect center, which was determined from the uneven local spin density by analyzing the partial density of states of O 2p in ZnO.

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.

Comparison of the electronic structures of Zn1−xCoxO and Zn1−xMgxO nanorods using x-ray absorption and scanning photoelectron microscopies

X-ray absorption near-edge structure (XANES) and scanning photoelectron microscopy (SPEM) measurements have been performed for Zn1−xCoxO and Zn1−xMgxO to elucidate the effects of the doping of Co and Mg, which have very different electronegativities, on the electronic structures of ZnO nanorods. The intensities of O K-edge near-edge features in the XANES spectra of Zn1−xCoxO and Zn1−xMgxO nanorods are found to be lower than those of ZnO, which suggests that both Co and Mg substitutions of the Zn ions enhance the effective charge on the O ion. The valence-band SPEM measurements show that Mg doping does not increase the density of near-Fermi-level states, which implies that Mg doping will not improve field emission of ZnO nanorods. It is surprising to find that both Co and Mg substitutions of Zn increase the numbers of O 2p dominated valence-band states, despite that Co and Mg have larger and smaller electronegativities than that of Zn.

Charge transfer in nanocrystalline-Au/ZnO nanorods investigated by x-ray spectroscopy and scanning photoelectron microscopy

O K- and Zn and Au L3-edge x-ray absorption near-edge structure (XANES), x-ray emission spectroscopy (XES), and scanning photoelectron microscopy (SPEM) are performed to investigate the electronic structure of ZnO nanorods with nanocrystalline (nc)-Au particles grown on the surfaces. The XANES spectra of nc-Au∕ZnO nanorods reveal the decrease of the number of both O 2p and Zn 4s∕3d unoccupied states with the increase of the nc-Au particle size. The number of Au 6s∕5d unoccupied states increases when the size of nc-Au particle decreases, indicating that the deposition of nc-Au particles on the surface of ZnO nanorods promotes charge transfer from the ZnO nanorods to nc-Au particles. Excitation energy dependent XES and SPEM spectra show that the number of electrons in the valence band of O 2p-Zn 4sp hybridized states decreases as the nc-Au particle size increases, revealing that more electrons are excited from the valence band to the conduction band of ZnO nanorods and the storage of electrons in nc-Au part...

Mg-induced increase of band gap in Zn1−xMgxO nanorods revealed by x-ray absorption and emission spectroscopy

X-ray absorption near-edge structure (XANES) and x-ray emission spectroscopy (XES) measurements were used to investigate the effect of Mg doping in ZnO nanorods. The intensities of the features in the O K-edge XANES spectra of Zn{sub 1-x}Mg{sub x}O nanorods are lower than those of pure ZnO nanorods, suggesting that Mg doping increases the negative effective charge of O ions. XES and XANES spectra of O 2p states indicate that Mg doping raises (lowers) the conduction-band-minimum (valence-band-maximum) and increases the bandgap. The bandgap is found to increase linearly with the Mg content, as revealed by photoluminescence and combined XANES and XES measurements.

Effect of Co, Ni, and Cu substitution on the electronic structure of hexagonal YMnO3 studied by x-ray absorption spectroscopy

X-ray absorption spectroscopy measurements have been performed to elucidate local electronic and atomic structures of orthorhombic 3d-transition metal-doped yttrium manganites (YMnO3) with chemical formulae YMn2/3Me1/3O3 (Me=Co, Ni, and Cu). The Mn L3- and K-edges x-ray absorption near-edge structure (XANES) demonstrate the direct substitution of Me2+ for Mn3+, so that the positive effective charge of Mn ions are increased. Me-doping is also found to induce substantial broadening of the Mn L3-edge feature, which suggests enhancement of the delocalization of Mn 3d eg subbands and conductivity. Local spin density approximation (LSDA)+U (Hubbard U parameter) calculations were used to understand their electronic structures.

Role of valence-band Co 3d states on ferromagnetism in Zn1−xCoxO nanorods

This work investigates the electronic and ferromagnetic properties of Zn1−xCoxO nanorods using x-ray absorption, x-ray magnetic circular dichroism, and scanning photoelectron microscopy methods. The magnetic moment of Co ions in Zn1−xCoxO nanorods is found greatly reduced relative to that of the Co metal. The intensities of valence-band features near the valence-band maximum/Fermi level (EF) of ferromagnetic nanorods are substantially larger than those of weaker ferromagnetic nanorods, suggesting that the occupation of near-EF valence-band Co 3d states is important in determining the ferromagnetic behavior in Zn1−xCoxO nanorods.

Electronic and magnetic properties of the Ag-doped Fe3O4 films studied by x-ray absorption spectroscopy

The electronic and magnetic properties of Ag-doped Fe3O4 films were studied by x-ray absorption near-edge structure (XANES), extended x-ray absorption fine structure (EXAFS), and x-ray magnetic circular dichroism (XMCD) measurements. A comparison between the Ag K-edge EXAFS Fourier transform spectra of Ag-doped Fe3O4 and the Ag metal shows that Ag atoms aggregate into Ag granules. The O K-edge and Ag L3-edge XANES spectra consistently indicate an electron transfer from the Fe3O4 host into Ag granules. The Fe L3,2-edge XMCD spectra and hysteresis measurements reveal that Ag granules reduce the average magnetic moment of Fe ions and the saturation magnetization of Fe3O4.

Determination of the microstructure of Eu-treated ZnO nanowires by x-ray absorption

X-ray absorption near-edge structure (XANES), extended x-ray absorption fine structures (EXAFS), and photoluminescence measurements were used to elucidate the microstructural and photoluminescence properties of ZnO nanowires (ZnO-NWs) that had been treated with Eu by thermal diffusion. The O K- and Eu L3-edge XANES and EXAFS spectra at the Zn K- and Eu L3-edge verified the formation of Eu2O3-like layer on the surface of ZnO-NWs. X-ray diffraction, XANES and EXAFS measurements consistently suggest the lack of substitutional doping of Eu ions at the Zn ion sites in the interior of ZnO-NWs. The clear sharp and intense emission bands in the range 610–630 nm of Eu-treated ZnO-NWs originated from the intra-4f transition of Eu ions in the Eu2O3-like surface layer.

Electronic structure and magnetic properties of Al-doped Fe3O4 films studied by x-ray absorption and magnetic circular dichroism

The electronic structure and magnetic properties of Al-doped Fe3O4 films at various Al concentrations were investigated by Al and OK-edge x-ray absorption near-edge structure (XANES) and FeL3,2-edge magnetic circular dichroism (MCD) measurements. The OK-edge XANES spectra reveal that the intensity of O2p–Fe3d hybridized states decreases linearly as the Al concentration increases, suggesting that nonmagnetic Al substitution reduces couplings of the O2p with Fe3d orbitals. The FeL3-edge MCD spectra show that the intensities of MCD features decrease as the Al concentration increases, which suggests that Al substitution reduces the magnetic moments of Fe ions. The FeL3,2 XANES spectra suggest the absence of mixed valence states in agreement with previous x-ray resonance scattering measurements.