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.
We have studied the electronic structure of the molecular ferromagnet $beta$-Mn phthalocyanine ($beta$-MnPc) in a polycrystalline form, which has been reported to show ferromagnetism at T$<$8.6 K, by x-ray absorption spectroscopy (XAS) and x-ray magn
etic circular dichroism (XMCD). From the experimental results and subsequent cluster-model calculation, we find that the ferromagnetic Mn ion in $beta$-MnPc is largely in the $^4$$E$$_g$ ground state arising from the ($e$$_{g}$)$^3$($b$$_{2g}$)$^1$($a$$_{1g}$)$^1$ [($d_{xz,yz}$)$^3$($d_{xy}$)$^1$($d_{z^{2}}$)$^1$] configuration of the Mn$^{2+}$ state. Considering that the highest occupied molecular orbital (HOMO) of MnPc with the $^4$$E$$_g$ ground state originates from the $a$$_{1g}$ orbital of the Mn$^{2+}$ ion, it is proposed that $a$$_{1g}$-$a$$_{1g}$ exchange coupling via the $pi$ orbitals of the phthalocyanine ring plays a crucial role in the ferromagnetism of $beta$-MnPc.
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.
We have studied the electronic structure and the magnetism of Cu-doped ZnO nanowires, which have been reported to show ferromagnetism at room temperature [G. Z. Xing ${et}$ ${al}$., Adv. Mater. {bf 20}, 3521 (2008).], by x-ray photoemission spectrosc
opy (XPS), x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD). From the XPS and XAS results, we find that the Cu atoms are in the Cu$^{3+}$ state with mixture of Cu$^{2+}$ in the bulk region ($sim$ 100 nm), and that Cu$^{3+}$ ions are dominant in the surface region ($sim$ 5 nm), i.e., the surface electronic structure of the surface region differs from the bulk one. From the magnetic field and temperature dependences of the XMCD intensity, we conclude that the ferromagnetic interaction in ZnO:Cu NWs comes from the Cu$^{2+}$ and Cu$^{3+}$ states in the bulk region, and that most of the doped Cu ions are magnetically inactive probably because they are antiferromagnetically coupled with each other.
We have studied magnetism in Ti_[1-x]Co_xO_[2-delta] thin films with various x and delta by soft x-ray magnetic circular dichroism (XMCD) measurements at the Co L_[2,3] absorption edges. The estimated ferromagnetic moment by XMCD was 0.15-0.24 mubeta
/Co in the surface, while in the bulk it was 0.82-2.25 mubeta/Co, which is in the same range as the saturation magnetization of 1.0-1.5 mubeta/Co. Theseresults suggest that the intrinsic origin of the erromagnetism. The smaller moment of Co atom at surface is an indication of a magnetically dead layer of a few nm thick at the surface of the thin films.
We have performed x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) studies of the diluted ferromagnetic semiconductor Zn$_{1-textit{x}}$Cr$_textit{x}$Te doped with iodine (I) or nitrogen (N), corresponding to electron
or hole doping, respectively. From the shape of the Cr $2p$ absorption peak in the XAS spectra, it was concluded that Cr ions in the undoped, I-doped and lightly N-doped samples are divalent (Cr$^{2+}$), while Cr$^{2+}$ and trivalent (Cr$^{3+}$) coexist in the heavily N-doped sample. This result indicates that the doped nitrogen atoms act as acceptors but that doped holes are located on the Cr ions. In the magnetic-field dependence of the XMCD signal at the Cr $2p$ absorption edge, ferromagnetic behaviors were observed in the undoped, I-doped, and lightly N-doped samples, while ferromagnetism was considerably suppressed in heavily N-doped sample, which is consistent with the results of magnetization measurements.
We have studied the electronic structure of Zn$_{0.9}$Fe$_{0.1}$O nano-particles, which have been reported to show ferromagnetism at room temperature, by x-ray photoemission spectroscopy (XPS), resonant photoemission spectroscopy (RPES), x-ray absorp
tion spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD). From the experimental and cluster-model calculation results, we find that Fe atoms are predominantly in the Fe$^{3+}$ ionic state with mixture of a small amount of Fe$^{2+}$ and that Fe$^{3+}$ ions are dominant in the surface region of the nano-particles. It is shown that the room temperature ferromagnetism in the Zn$_{0.9}$Fe$_{0.1}$O nano-particles is primarily originated from the antiferromagnetic coupling between unequal amounts of Fe$^{3+}$ ions occupying two sets of nonequivalent positions in the region of the XMCD probing depth of $sim$ 2-3 nm.
