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Absence of zero-field-cooled exchange bias effect in single crystalline La2-xAxCoMnO6 (A = Ca, Sr) compounds

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 Added by Eduardo Bittar
 Publication date 2021
  fields Physics
and research's language is English




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Magnetic properties of A2BBO6 (A = rare or alkaline earth ions; B,B = transition metal ions) double perovskites are of great interest due to their potential spintronic applications. Particularly fascinating is the zero field cooled exchange bias (ZEB) effect observed for the hole doped La2-xAxCoMnO6 polycrystalline samples. In this work we synthesize La2CoMnO6, La1.5Ca0.5CoMnO6, and La1.5Sr0.5CoMnO6 single crystals by the floating zone method and study their magnetic behavior. The three materials are ferromagnetic. Surprisingly, we observe no zero or even conventional exchange bias effect for the Ca and Sr doped single crystals, in sharp contrast to polycrystalline samples. This absence indicates that the lack of grain boundaries and spin glass-like behavior, not observed in our samples, might be key ingredients for the spontaneous exchange bias phenomena seen in polycrystalline samples.



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We report a giant zero field cooled exchange bias (ZEB) effect (~0.65 T) in La1.5Sr0.5CoMnO6 sample. Magnetic study has revealed a reentrant spin glass ~90 K, phase separation to spin glass and ferromagnetic phases below 50 K and canted antiferromagnetic transition ~10 K. A small conventional exchange bias (CEB) is established with the advent of spontaneous phase separation down to 10 K. Giant ZEB and enhanced CEB effects are found only below 10 K and are attributed to the large unidirectional anisotropy at the interface of isothermally field induced ferromagnetic phase and canted antiferromagnetic background.
In the zero-field-cooled exchange bias (ZEB) effect the unidirectional magnetic anisotropy is set at low temperatures even when the system is cooled in the absence of external magnetic field. La$_{1.5}$Sr$_{0.5}$CoMnO$_{6}$ stands out as presenting the largest ZEB reported so far, while for La$_{1.5}$Ca$_{0.5}$CoMnO$_{6}$ the exchange bias field ($H_{EB}$) is one order of magnitude smaller. Here we show that La$_{1.5}$Ba$_{0.5}$CoMnO$_{6}$ also exhibits a pronounced shift of its magnetic hysteresis loop, with intermediate $H_{EB}$ value in respect to Ca- and Sr-doped samples. In order to figure out the microscopic mechanisms responsible for this phenomena, these compounds were investigated by means of synchrotron X-ray powder diffraction, Raman spectroscopy, muon spin rotation and relaxation, AC and DC magnetization, X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD). The parent compound La$_{2}$CoMnO$_{6}$ was also studied for comparison, as a reference of a non-ZEB material. Our results show that the Ba-, Ca- and Sr-doped samples present a small amount of phase segregation, and that the ZEB effect is strongly correlated to the systems structure. We also observed that mixed valence states Co$^{2+}$/Co$^{3+}$ and Mn$^{4+}$/Mn$^{3+}$ are already present at the La$_{2}$CoMnO$_{6}$ parent compound, and that Ba$^{2+}$/Ca$^{2+}$/Sr$^{2+}$ partial substitution at La$^{3+}$ site leads to a large increase of Co average valence, with a subtle augmentation of Mn formal valence. Estimates of the Co and Mn valences from the $L$-edge XAS indicate the presence of oxygen vacancies in all samples (0.05$leq delta leq$0.1). Our XMCD results show a great decrease of Co moment for the doped compounds, and indicate that the shift of the hysteresis curves for these samples is related to uncompensated antiferromagnetic coupling between Co and Mn.
We report exchange bias (EB) effect in the Au-Fe3O4 composite nanoparticle system, where one or more Fe3O4 nanoparticles are attached to an Au seed particle forming dimer and cluster morphologies, with the clusters showing much stronger EB in comparison with the dimers. The EB effect develops due to the presence of stress in the Au-Fe3O4 interface which leads to the generation of highly disordered, anisotropic surface spins in the Fe3O4 particle. The EB effect is lost with the removal of the interfacial stress. Our atomistic Monte-Carlo studies are in excellent agreement with the experimental results. These results show a new path towards tuning EB in nanostructures, namely controllably creating interfacial stress, and open up the possibility of tuning the anisotropic properties of biocompatible nanoparticles via a controllable exchange coupling mechanism.
Doping at the rare-earth site by divalent alkaline-earth ions in perovskite lattice has witnessed a variety of magnetic and electronic orders with spatially correlated charge, spin and orbital degrees of freedom. Here, we report an antisite disorder driven spontaneous exchange bias effect as a result of hole carrier (Sr2+) doping in La2-xSrxCoMnO6 (0 < x < 1) double perovskites. X-ray diffraction and Raman spectroscopy have evidenced an increase in disorder with the increase of Sr content up to x = 0.5 and thereby decreases from x = 0.5 to 1. X-ray absorption spectroscopy has revealed that only Co is present in mixed valent Co2+ and Co3+ states with Sr doping to compensate the charge neutrality. Magnetotransport is strongly correlated with the increase of antisite disorder. The antisite disorder at the B-site interrupts the long-range ferromagnetic order by introducing various magnetic interactions and instigates reentrant glassy dynamics, phase separation and canted type antiferromagnetic behavior with the decrease of temperature. This leads to novel magnetic microstructure with unidirectional anisotropy that causes spontaneous exchange bias effect that can be tuned with the amount of antisite disorder.
Magnetic and transport properties of (Pr1/3Sm2/3)2/3A1/3MnO3 (A = Ca, Sr and Ba) compounds, prepared by the citrate gel route, have been investigated. These compounds are found to crystallize in the orthorhombic structure. Charge ordering transport behavior is indicated only in Ca-substituted compound. The Sr- and Ba-substituted compounds show metal-insulator transition and semiconducting-like behavior, respectively. The magnetoresistance is highest in the Ba substituted compound. All the three samples show irreversibility in magnetization as a function of temperature in zero-field cooled (ZFC) and field cooled (FC) plots. The non-saturating magnetization, even at 5K and 4 Tesla field, are observed in Ca as well Ba-substituted compounds.
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