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Rare-earth tuned magnetism and magnetocaloric effects in double perovskites $R_2$NiMnO$_6$

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 Added by Yogesh Singh
 Publication date 2021
  fields Physics
and research's language is English




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We present a comprehensive experimental study of magnetization and magnetocaloric effect (MCE) in double perovskite (DP) materials $R_2$NiMnO$_6$ with $R =$ Pr, Nd, Sm, Gd, Tb, and Dy. While a paramagnetic to ferromagnetic transition, with T$_{rm C}$ in the range $sim 100 - 200~$K, is a common feature that can be attributed to the ordering of Mn$^{4+}$ and Ni$^{2+}$ magnetic moments, qualitatively distinct behavior depending on the choice of $R$ is observed at low temperatures. These low-temperature anomalies in magnetization are also manifest in the change in magnetic entropy, $-Delta S_{M}$, whose sign depends on the choice of $R$. In order to understand these results, we present theoretical analysis based on mean-field approximation and Monte Carlo simulations on a minimal spin model. The model correctly captures the key features of the experimental observations.



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We present combined experimental and theoretical investigations on the magnetic and magnetocaloric behavior of Nd$_2$NiMnO$_6$. The relative cooling power (RCP) which quantifies the usefulness of a magnetocaloric (MC) material is estimated to be $approx 300$ J/Kg near the ferromagnetic transition at $T_C approx 195$ K. This RCP is comparable to the best known MC materials. Additionally, the magnetic entropy change has a broad profile ($T_C - 50~{rm K} < T < T_C + 50~{rm K}$) leading to an enhancement in the working-range of temperatures for magnetocaloric based cooling. These features make Nd$_2$NiMnO$_6$ a superior magnetocaloric material compared for example, to the nonmagnetic counterpart Y$_2$NiMnO$_6$. We identify the mechanism for the enhanced RCP which can guide search for future MC materials.
The magnetism of the double perovskite compounds SLFCOx ($x$ = 0, 1, 2) are contrasted using magnetization, neutron diffraction and electron paramagnetic resonance with the support from density functional theory calculations. LFCO is identified as a long-range ordered antiferromagnet displaying a near-room temperature transition at $T_N$ = 270~K, accompanied by a low temperature structural phase transition at $T_S$ = 200~K. The structural phase transformation at $T_S$ occurs from $Roverline{3}c$ at 300~K to $Pnma$ at 200~K. The density functional theory calculations support an insulating non-compensated AFM structure. The long-range ordered magnetism of LFCO transforms to short-range glassy magnetism as La is replaced with Sr in the other two compounds. The magnetism of LFCO is differentiated from the non-equilibrium glassy features of SFCO and SLFCO using the {em cooling-and-heating-in-unequal-fields} (CHUF) magnetization protocols. This contransting magnetism in the SLFCOx series is evidenced in electron paramegnetic resonance studies. The electronic density-of-states estimated using the density functional theory calculations contrast the insulating feature of LFCO from the metallic nature of SFCO. From the present suite of experimental and computational results on SLFCOx, it emerges that the electronic degrees of freedom, along with antisite disorder, play an important role in controlling the magnetism observed in double perovskites.
The Fe electronic structure and magnetism in (i) monoclinic Ca$_2$FeReO$_6$ with a metal-insulator transition at $T_{MI} sim 140$ K and (ii) quasi-cubic half-metallic Ba$_2$FeReO$_6$ ceramic double perovskites are probed by soft x-ray absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD). These materials show distinct Fe $L_{2,3}$ XAS and XMCD spectra, which are primarily associated with their different average Fe oxidation states (close to Fe$^{3+}$ for Ca$_2$FeReO$_6$ and intermediate between Fe$^{2+}$ and Fe$^{3+}$ for Ba$_2$FeReO$_6$) despite being related by an isoelectronic (Ca$^{2+}$/Ba$^{2+}$) substitution. For Ca$_2$FeReO$_6$, the powder-averaged Fe spin moment along the field direction ($B = 5$ T), as probed by the XMCD experiment, is strongly reduced in comparison with the spontaneous Fe moment previously obtained by neutron diffraction, consistent with a scenario where the magnetic moments are constrained to remain within an easy plane. For $B=1$ T, the unsaturated XMCD signal is reduced below $T_{MI}$ consistent with a magnetic transition to an easy-axis state that further reduces the powder-averaged magnetization in the field direction. For Ba$_2$FeReO$_6$, the field-aligned Fe spins are larger than for Ca$_2$FeReO$_6$ ($B=5$ T) and the temperature dependence of the Fe magnetic moment is consistent with the magnetic ordering transition at $T_C^{Ba} = 305$ K. Our results illustrate the dramatic influence of the specific spin-orbital configuration of Re $5d$ electrons on the Fe $3d$ local magnetism of these Fe/Re double perovskites.
190 - Q. J. Li , L. M. Xu , C. Fan 2013
We report a systematic study on the crystal growth of the rare-earth titanates $R_2$Ti$_2$O$_7$ ($R$ = Gd, Tb, Dy, Ho, Y, Er, Yb and Lu) and Y-doped Tb$_{2-x}$Y$_x$Ti$_2$O$_7$ ($x$ = 0.2 and 1) using an optical floating-zone method. High-quality single crystals were successfully obtained and the growth conditions were carefully optimized. The oxygen pressure was found to be the most important parameter and the appropriate ones are 0.1--0.4 MPa, depending on the radius of rare-earth ions. The growth rate is another parameter and was found to be 2.5--4 mm/h for different rare-earth ions. X-ray diffraction data demonstrated the good crystallinity of these crystals. The basic physical properties of these crystals were characterized by the magnetic susceptibility and specific heat measurements.
We have studied Ir spin and orbital magnetic moments in the double perovskites La$_{2-x}$Sr$_x$CoIrO$_6$ by x-ray magnetic circular dichroism. In La$_2$CoIrO$_6$, Ir$^{4+}$ couples antiferromagnetically to the weak ferromagnetic moment of the canted Co$^{2+}$ sublattice and shows an unusually large negative total magnetic moment (-0.38,$mu_{text B}$/f.u.) combined with strong spin-orbit interaction. In contrast, in Sr$_2$CoIrO$_6$, Ir$^{5+}$ has a paramagnetic moment with almost no orbital contribution. A simple kinetic-energy-driven mechanism including spin-orbit coupling explains why Ir is susceptible to the induction of substantial magnetic moments in the double perovskite structure.
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