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Role of interface in ferromagnetism of (Zn,Co)O films

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 Added by Elzbieta Guziewicz
 Publication date 2011
  fields Physics
and research's language is English




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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.



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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.
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.
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.
Magnetic and magnetotransport properties of oriented polycrystalline Pr0.58Ca0.42MnO3 thin films prepared in flowing oxygen and air ambient has been investigated. The magnetic ground state of both the films is a frozen cluster glass. In the air annealed film charge order (CO) is quenched and ferromagnetic (FM) transition, which appears at TC=148 K is followed by antiferromagnetic (AFM) transition at TN=104 K. This film shows self-field hysteretic insulator-metal transition (IMT) at TIMC=89 K and TIMW=148 K in the cooling and warming cycle, respectively. Application of magnetic field (H) gradually enhances TIMC and TIMW, reduces the thermoresistive hysteresis and TIM diminishes. In contrast, the film annealed in flowing oxygen shows a CO transition, which is followed by FM and AFM transitions. This film shows appreciably smaller magnetic moment and does not show IMT upto H=20 kOe. As H is increased to H=30 kOe, IMT having strong thermoresistive hysteresis and sharp resistivity jumps appears in the cooling and warming cycles. As H increases to higher values the thermoresistive hysteresis is reduced, resistivity jumps are observed to disappear and TIM decreases. In the lower temperature regime the resistivity first decreases slowly with H and then shows sharp drop. The virgin cycle is not recoverable in subsequent cycles. The decrement far more pronounced in the oxygen annealed film and occurs at much higher H suggesting that the frozen cluster glass state is more robust in this film. The microstructural analysis of the two set of films shows CO quenching, FM transition and self-field IMT in air annealed film is caused by higher density of microstructural disorder and lattice defects. The difference in growth ambience of the two films could give rise to such microstructural perturbations.
148 - E. Haltz , R. Weil , J. Sampaio 2018
Ferrimagnetic TbFe or TbFeCo amorphous alloy thin films have been grown by co-evaporation in ultra-high vacuum. They exhibit an out-of-plane magnetic anisotropy up to their Curie temperature with a nucleation and propagation reversal mechanism suitable for current induced domain wall motion. Rutherford back scattering experiments confirmed a fine control of the Tb depth-integrated composition within the evaporation process. However, a large set of experimental techniques were used to evidence an interface related contribution in such thin films as compared to much thicker samples. In particular, scanning transmission electron microscopy experiments evidence a depth dependent composition and perturbed top and bottom interfaces with preferential oxidation and diffusion of terbium. Despite of that, amorphous and homogeneous alloy film remains in a bulk-like part. The composition of that bulk-like part of the magnetic layer, labeled as effective composition, is biased when compared with the depth-integrated composition. The magnetic properties of the film are mostly dictated by this effective composition, which we show changes with different top and bottom interfaces.
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