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Register a new userX-ray absorption spectroscopy and X-ray magnetic circular dichroism studies of transition-metal-co-doped ZnO nano-particles
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We report on x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) studies of the paramagnetic (Mn,Co)-co-doped ZnO and ferromagnetic (Fe,Co)-co-doped ZnO nano-particles. Both the surface-sensitive total-electron-yield mode and the bulk-sensitive total-fluorescence-yield mode have been employed to extract the valence and spin states of the surface and inner core regions of the nano-particles. XAS spectra reveal that significant part of the doped Mn and Co atoms are found in the trivalent and tetravalent state in particular in the surface region while majority of Fe atoms are found in the trivalent state both in the inner core region and surface region. The XMCD spectra show that the Fe$^{3+}$ ions in the surface region give rise to the ferromagnetism while both the Co and Mn ions in the surface region show only paramagnetic behaviors. The transition-metal atoms in the inner core region do not show magnetic signals, meaning that they are antiferromagnetically coupled. The present result combined with the previous results on transition-metal-doped ZnO nano-particles and nano-wires suggest that doped holes, probably due to Zn vacancy formation at the surfaces of the nano-particles and nano-wires, rather than doped electrons are involved in the occurrence of ferromagnetism in these systems.
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We have investigated the electronic structure of ZnO:Mn and ZnO:Mn,N thin films using x-ray magnetic circular dichroism (XMCD) and resonance-photoemission spectroscopy. From the Mn 2$p$$rightarrow3d$ XMCD results, it is shown that, while XMCD signals only due to paramagnetic Mn$^{2+}$ ions were observed in ZnO:Mn, nonmagnetic, paramagnetic and ferromagnetic Mn$^{2+}$ ions coexist in ZnO:Mn,N. XMCD signals of ZnO:Mn,N revealed that the localized Mn$^{2+}$ ground state and Mn$^{2+}$ state hybridized with ligand hole coexisted, implying $p$-$d$ exchange coupling. In the valence-band spectra, spectral weight near the Fermi level was suppressed, suggesting that interaction between magnetic moments in ZnO:Mn,N has localized nature.
GdNi is a ferrimagnetic material with a Curie temperature Tc = 69 K which exhibits a large magnetocaloric effect, making it useful for magnetic refrigerator applications. We investigate the electronic structure of GdNi by carrying out x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) at T = 25 K in the ferrimagnetic phase. We analyze the Gd M$_{4,5}$-edge ($3d$ - $4f$) and Ni L$_{2,3}$-edge ($2p$ - $3d$) spectra using atomic multiplet and cluster model calculations, respectively. The atomic multiplet calculation for Gd M$_{4,5}$-edge XAS indicates that Gd is trivalent in GdNi, consistent with localized $4f$ states. On the other hand, a model cluster calculation for Ni L$_{2,3}$-edge XAS shows that Ni is effectively divalent in GdNi and strongly hybridized with nearest neighbour Gd states, resulting in a $d$-electron count of 8.57. The Gd M$_{4,5}$-edge XMCD spectrum is consistent with a ground state configuration of S = 7/2 and L=0. The Ni L$_{2,3}$-edge XMCD results indicate that the antiferromagnetically aligned Ni moments exhibit a small but finite magnetic moment ( $m_{tot}$ $sim$ 0.12 $mu_B$ ) with the ratio $m_{o}/m_{s}$ $sim$ 0.11. Valence band hard x-ray photoemission spectroscopy shows Ni $3d$ features at the Fermi level, confirming a partially filled $3d$ band, while the Gd $4f$ states are at high binding energies away from the Fermi level. The results indicate that the Ni $3d$ band is not fully occupied and contradicts the charge-transfer model for rare-earth based alloys. The obtained electronic parameters indicate that GdNi is a strongly correlated charge transfer metal with the Ni on-site Coulomb energy being much larger than the effective charge-transfer energy between the Ni $3d$ and Gd $4f$ states.
We have performed x-ray magnetic circular dichroism (XMCD) and valence-band photoemission studies of the diluted ferromagnetic semiconductor Zn$_{1-x}$Cr$_x$Te. XMCD signals due to ferromagnetism were observed at the Cr 2p absorption edge. Comparison with atomic multiplet calculations suggests that the magnetically active component of the Cr ion was divalent under the tetrahedral crystal field with tetragonal distortion along the crystalline a-, b-, and c-axes. In the valence-band spectra, spectral weight near the Fermi level was strongly suppressed, suggesting the importance of Jahn-Teller effect and the strong Coulomb interaction between the Cr 3d electrons.
In this study, X-ray absorption spectroscopy (XAS) experiments for Ni45Co5Mn36.7In13.3 metamagnetic shape memory alloy were performed under high magnetic fields up to 12 T using a pulsed magnet. Field-induced reverse transformation to austenite phase caused considerable changes in the magnetic circular dichroism (MCD) signals and the magnetic moments of the ferromagnetic coupling between Mn, Ni, and Co were determined. The spin magnetic moment, Mspin, and orbital magnetic moment, Morb, of Mn atom in the induced austenite ferromagnetic phase, estimated based on the magneto-optical sum rule, were 3.2 and 0.13 {mu}B, respectively, resulting in an Morb / Mspin ratio of 0.04. In the element-specific magnetization curves recorded at 150 K, metamagnetic behavior associated with the field-induced reverse transformation is clearly observed and reverse transformation finishing magnetic field and martensitic transformation starting magnetic field are detected. There was almost no difference in the magnetically averaged XAS spectrum for Mn-L2,3 edges between in the martensite and in the magnetic field-induced austenite phases, however, it was visible for Ni, indicating that Ni 3d-electrons mainly contribute to martensitic transformation.
Motivated by the recent synthesis of Ba$_2$CuO$_{3+delta}$ (BCO), a high temperature superconducting cuprate with putative $d_{3z^2-r^2}$ ground state symmetry, we investigated its electronic structure by means of Cu $L_3$ x-ray absorption (XAS) and resonant inelastic x-ray scattering (RIXS) at the Cu $L_3$ edge on a polycrystalline sample. We show that the XAS profile of BCO is characterised by two peaks associated to inequivalent Cu sites, and that its RIXS response features a single, sharp peak associated to crystal-field excitations. We argue that these observations are only partially compatible with the previously proposed crystal structure of BCO. Based on our spectroscopic results and on previously published powder diffraction measurements, we propose a crystalline structure characterized by two inequivalent Cu sites located at alternated planes along the $c$ axis: nominally trivalent Cu(1) belonging to very short Cu-O chains, and divalent Cu(2) in the oxygen deficient CuO$_ {1.5}$ planes. We also analyze the low-energy region of the RIXS spectra to estimate the magnitude of the magnetic interactions in BCO and find that in-plane nearest neighbor superexchange exceeds 120~meV, similarly to that of other layered cuprates. Although these results do not support the pure $d_{3z^2-r^2}$ ground state scenario, they hint at a significant departure from the common quasi-2D electronic structure of superconducting cuprates of pure $d_{x^2-y^2}$ symmetry.
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