H. M. Tsai

Diameter dependence of the electronic structure of ZnO nanorods determined by x-ray absorption spectroscopy and scanning photoelectron microscopy

OK-, ZnL3, and K-edges x-ray absorption near-edge structure (XANES) spectra and scanning photoelectron microscopy (SPEM) spectra were obtained for ZnO nanorods with various diameters. The analysis of the XANES spectra revealed increased numbers of O2p and Zn4p unoccupied states with the downsizing of the nanorods, which reflects the enhancement of surface states when the diameter is decreased. Valence-band photoemission spectra show a significant narrowing of the valence band for the 45nm diameter nanorod. The Zn3d intensities in the Zn3d SPEM spectra are drastically diminished for all nanorods as compared to the ZnO reference film, which can be interpreted as a reduction in density of itinerant final states or in transition probability.

Electronic structure of ZnO nanorods studied by angle-dependent x-ray absorption spectroscopy and scanning photoelectron microscopy

Angle-dependent x-ray absorption near-edge structure (XANES) and scanning photoelectron microscopy measurements were performed to differentiate local electronic structures at the tips and sidewalls of highly aligned ZnO nanorods. The overall intensity of the O K-edge XANES spectra is greatly enhanced for small photon incident angles. In contrast, the overall intensity of the Zn K-edge XANES is much less sensitive to the photon incident angle. Both valence-band photoemission and O K-edge XANES spectra show substantial enhancement of O 2p derived states near the valence band maximum and conduction band minimum, respectively. The spatially resolved Zn 3d core level spectra from tip and sidewall regions show the lack of chemical shift. All the results consistently suggest that the tip surfaces of the highly aligned ZnO nanorods are terminated by O ions and the nanorods are oriented in the [0001] direction.

Structural, electrical transport and x-ray absorption spectroscopy studies of LaFe1−xNixO3 (x⩽0.6)

Electronic structures of LaFe1−xNixO3 (x⩽0.6) have been studied by x-ray absorption near edge structure spectra of OK, FeL2,3 and LaM4,5 edges. Upon substitution of Ni at Fe site in LaFeO3, the OK-edge spectra show a feature about 2.0eV lower than that of LaFeO3. This feature is growing as the concentration of Ni is increasing. This is consistent with our resistivity data which show that the resistivity decreases very fast with Ni substitution from GΩcm for LaFeO3 to a few mΩcm for the sample with 60% Ni substitution. The resistivity data have been fitted with a variable-range hopping model and it is found that the gap parameter reduces from 2eV to 2.1meV with the Ni substitution. This gap parameter decreases very systematically with the increase in Ni concentration. The structural analysis of these samples shows that they have single-phase orthorhombic structure with space-group Pnma in the studied range (0⩽x⩽0.6). The study of FeL2,3-edge structures confirm the trivalent state of Fe. The observed featur...

Electronic properties of a‐CNx thin films: An x-ray-absorption and photoemission spectroscopy study

The electronic properties of amorphous carbon nitride were studied by x-ray-absorption near-edge structure (XANES) and valence-band photoelectron spectroscopy (PES). The nitrogen incorporation was found to induce graphitization, as evidenced by an increase of the sp2 cluster in C and N K-edge XANES spectra. The structure is found to be similar to pyridine. Hybridized C–N bond lengths were determined from the position of the σ* resonance of XANES spectra and the obtained results suggest sp2 hybridization. A valence-band PES spectrum showed that the p‐π band became more intense than the p‐σ band upon higher at. % nitrogen addition, which confirmed the role played by the π bonds in controlling the electronic structure of a‐CNx films.

X-ray absorption spectroscopy (XAS) study of dip deposited a-C:H(OH) thin films

This work measures the C and O K-edge x-ray absorption near-edge structure (XANES) spectra of hydrogenated amorphous carbon (a-C:H) films deposited at various baking temperatures Tb (Tb = 300–500 °C at 50 °C). The C–H σ* peak related to the content of the sp2 graphite-like bonding in the C K-edge spectra was found to yield to the C–H π* peak related to the sp3 diamond-like bonding at high temperature (500 °C). We find that the intensities of both the sp2 and sp3 features in the C K-edge XANES spectra decrease with increase of Tb, which suggests an increase of the defect concentration with Tb. The intensities of the O K-edge XANES spectra are found to decrease with increase of Tb, which suggests thermally induced decomposition of carbonyl contaminants on the surface. The elemental analysis C/O (or O/C) ratio was obtained from XPS spectra and indicates that films are not hydrogenated amorphous carbon but rather oxyhydrogenated amorphous carbon thin films.

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.

Electron- and hole-doping effects on the electronic structure of manganite studied by x-ray absorption spectroscopy

The electronic structures of hole-doped La0.7Ca0.3MnO3 and electron-doped La0.7Ce0.3MnO3 manganites are investigated by x-ray absorption near-edge structure spectroscopy at the O and Mn K-, and Mn L3,2-edges. The Mn K- and L3,2-edge results show that Ce dopants increase the occupation of the Mn 4p and majority-spin eg orbitals and reduce the positive effective charge of some Mn ions. However, Ce doping also induces holes in O 2p derived states. As for La0.7Ca0.3MnO3, in contrast to previous understanding that Ca doping converts some Mn ions into the Mn4+ state, we find that Ca dopants actually increase the number of majority-spin eg electrons. We find instead that the holes created by Ca dopants are in the O 2p derived states.

Atomistic nucleation sites of Pt nanoparticles on N-doped carbon nanotubes

The atomistic nucleation sites of Pt nanoparticles (Pt NPs) on N-doped carbon nanotubes (N-CNTs) were investigated using C and N K-edge and Pt L3-edge X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy. Transmission electron microscopy and XANES/EXAFS results revealed that the self-organized Pt NPs on N-CNTs are uniformly distributed because of the relatively high binding energies of the adsorbed Pt atoms at the imperfect sites. During the atomistic nucleation process of Pt NPs on N-CNTs, stable Pt-C and Pt-N bonds are presumably formed, and charge transfer occurs at the surface/interface of the N-CNTs. The findings in this study were consistent with density functional theory calculations performed using cluster models for the undoped, substitutional-N-doped and pyridine-like-N-doped CNTs.

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.

Electronic and bonding structures of B-C-N thin films investigated by x-ray absorption and photoemission spectroscopy

X-ray absorption near-edge structure (XANES) and valence-band photoelectron spectroscopy (PES) were used to investigate the electronic and bonding structures of B-C-N thin films. The intensities of the sp2-bonded features in the C K-edge XANES spectra are found to generally decrease as the C concentration increases, whereas the intensities of the sp2-bonded features in the spectra of N K-edge XANES increase with the N concentration. The decrease of the intensities of the sp2-bonded features in the C and N K-edges XANES spectra correlates with the increase of the C/B and N/B concentration ratios and the increase of Young’s modulus. Valence-band PES spectra are found to be insensitive to the variations of the B and C concentrations in B-C-N compounds