No Arabic abstract
A series of (ZnO)m(CoO)n digital alloys and superlattices grown by atomic layer deposition has been investigated by a range of experimental methods. The data provide evidences that the Co interdiffusion in the digital alloy structures is sufficient to produce truly random Zn1-xCoxO mixed crystals with x up to 40%. Conversely, in the superlattice structures the interdiffusion is not strong enough to homogenize the Co content along the growth direction results in the formation of (Zn,Co)O films with spatially modulated Co concentrations. All structures deposited at 160circC show magnetic properties specific to dilute magnetic semiconductors with localized spins S = 3/2 coupled by strong but short range antiferromagnetic interactions that lead to low temperature spin-glass freezing. It is demonstrated that ferromagnetic-like features, visible exclusively in layers grown at 200circC and above, are associated with an interfacial mesh of metallic Co granules residing between the substrate and the (Zn,Co)O layer. This explains why the magnitude of ferromagnetic signal is virtually independent of the film thickness as well as elucidates the origin of magnetic anisotropy. Our conclusions have been derived for layers in which the Co concentration, distribution, and aggregation have been determined by: secondary-ion mass spectroscopy, electron probe micro-analysis, high-resolution transmission electron microscopy with capabilities allowing for chemical analysis; x-ray absorption near-edge structure; extended x-ray absorption fine-structure; x-ray photoemission spectroscopy, and x-ray circular magnetic dichroism. Macroscopic properties of these layers have been investigated by superconducting quantum interference device magnetometery and microwave dielectric losses allowing to confirm the important role of metallic inclusions.
We demonstrate that room temperature ferromagnetic response (RT FR) of ZnCoO films grown at low temperature by the Atomic layer Deposition (ALD) method is due to Co metal accumulations at the ZnCoO/substrate interface region. The accumulated experimental evi evidences allow us to reject several other explanations of this effect in our samples, despite the fact that some of them are likely to be responsible for the low temperature FM in this class of the material.
Using the spectroscopies based upon x-ray absorption, we have studied the structural and magnetic properties of Zn$_{1-x}$Co$_{x}$O films ($x$ = 0.1 and 0.25) produced by reactive magnetron sputtering. These films show ferromagnetism with a Curie temperature $T_{mathrm{C}}$ above room temperature in bulk magnetization measurements. Our results show that the Co atoms are in a divalent state and in tetrahedral coordination, thus substituting Zn in the wurtzite-type structure of ZnO. However, x-ray magnetic circular dichroism at the Co textit{L}$_{2,3}$ edges reveals that the Co 3textit{d} sublattice is paramagnetic at all temperatures down to 2 K, both at the surface and in the bulk of the films. The Co 3textit{d} magnetic moment at room temperature is considerably smaller than that inferred from bulk magnetisation measurements, suggesting that the Co 3textit{d} electrons are not directly at the origin of the observed ferromagnetism.
In order to elucidate the nature of ferromagnetic signatures observed in (Zn,Co)O we have examined experimentally and theoretically magnetic properties and spin-dependent quantum localization effects that control low-temperature magnetoresistance. Our findings, together with a through structural characterization, substantiate the model assigning spontaneous magnetization of (Zn,Co)O to uncompensated spins at the surface of antiferromagnetic nanocrystal of Co-rich wurtzite (Zn,Co)O. The model explains a large anisotropy observed in both magnetization and magnetoresistance in terms of spin hamiltonian of Co ions in the crystal field of the wurtzite lattice.
The magnetic properties of Zn$_{1-x}$Co$_x$O ($x=0.07$ and 0.10) thin films, which were homo-epitaxially grown on a ZnO(0001) substrates with varying relatively high oxygen pressure, have been investigated using x-ray magnetic circular dichroism (XMCD) at Co $2p$ core-level absorption edge. The line shapes of the absorption spectra are the same in all the films and indicate that the Co$^{2+}$ ions substitute for the Zn sites. The magnetic-field and temperature dependences of the XMCD intensity are consistent with the magnetization measurements, indicating that except for Co there are no additional sources for the magnetic moment, and demonstrate the coexistence of paramagnetic and ferromagnetic components in the homo-epitaxial Zn$_{1-x}$Co$_{x}$O thin films, in contrast to the ferromagnetism in the hetero-epitaxial Zn$_{1-x}$Co$_{x}$O films studied previously. The analysis of the XMCD intensities using the Curie-Weiss law reveals the presence of antiferromagnetic interaction between the paramagnetic Co ions. Missing XMCD intensities and magnetization signals indicate that most of Co ions are non-magnetic probably because they are strongly coupled antiferromagnetically with each other. Annealing in a high vacuum reduces both the paramagnetic and ferromagnetic signals. We attribute the reductions to thermal diffusion and aggregation of Co ions with antiferromagnetic nanoclusters in Zn$_{1-x}$Co$_{x}$O.
Electronic structures of Zn$_{1-x}$Co$_x$O have been investigated using photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS). The Co 3d states are found to lie near the top of the O $2p$ valence band, with a peak around $sim 3$ eV binding energy. The Co $2p$ XAS spectrum provides evidence that the Co ions in Zn$_{1-x}$Co$_{x}$O are in the divalent Co$^{2+}$ ($d^7$) states under the tetrahedral symmetry. Our finding indicates that the properly substituted Co ions for Zn sites will not produce the diluted ferromagnetic semiconductor property.