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تسجيل مستخدم جديدHigh oxygen pressure floating zone growth and crystal structure of the layered nickelates R$_4$Ni$_3$O$_{10}$ (R=La, Pr)
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Single crystals of the metallic Ruddlesden-Popper trilayer nickelates R$_4$Ni$_3$O$_{10}$ (R=La, Pr) were successfully grown using an optical-image floating zone furnace under oxygen pressure (pO$_2$) of 20 bar for La$_4$Ni$_3$O$_{10}$ and 140 bar for Pr$_4$Ni$_3$O$_{10}$. A combination of synchrotron and laboratory x-ray single crystal diffraction, high-resolution synchrotron x-ray powder diffraction and measurements of physical properties revealed that R$_4$Ni$_3$O$_{10}$ (R=La, Pr) crystallizes in the monoclinic $P$2$_1$/$a$ (Z=2) space group at room temperature, and that a metastable orthorhombic phase ($Bmab$) can be trapped by post-growth rapid cooling. Both La$_4$Ni$_3$O$_{10}$ and Pr$_4$Ni$_3$O$_{10}$ crystals undergo a metal-to-metal transition (MMT) below room temperature. In the case of Pr$_4$Ni$_3$O$_{10}$, the MMT is found at ~157.6 K. For La$_4$Ni$_3$O$_{10}$, the MMT depends on the lattice symmetry: 147.5 K for $Bmab$ vs. 138.6 K for $P$2$_1$/$a$. Lattice anomalies were found at the MMT that, when considered together with the pronounced dependence of the transition temperature on subtle structural differences between $Bmab$ and $P$2$_1$/$a$ phases, demonstrates a not insignificant coupling between electronic and lattice degrees of freedom in these trilayer nickelates.
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We investigate the low temperature structural and physical properties of the trilayer nickelates R4Ni3O10 (R = La, Pr and Nd) using resistivity, thermopower, thermal conductivity, specific heat, high-resolution synchrotron powder X-ray diffraction an
d thermal expansion experiments. We show that all three compounds crystallize with a monoclinic symmetry, and undergo a metal-to-metal (MMT) transition at 135 K (La), 156 K (Pr) and 160 K (Nd). At MMT, the lattice parameters show distinct anomalies; however, without any lowering of the lattice symmetry. Unambiguous signatures of MMT are also seen in magnetic and thermal measurements, which suggest a strong coupling between the electronic, magnetic and structural degrees of freedom in these nickelates. Analysis of thermal expansion yields hydrostatic pressure dependence of MMT in close agreement with experiments. We show that the 9-fold coordinated Pr ions in the rocksalt (RS) layers have a crystal field (CF) split doublet ground state with possible antiferromagnetic ordering at 5 K. The Pr ions located in the perovskite block (PB) layers with 12-fold coordination, however, exhibit a non-magnetic singlet ground state. The CF ground state of Nd in both RS and PB layers is a Kramers doublet. Heat capacity of R = Nd shows a Schottky-like anomaly near35 K, and an upturn below T = 10 K suggesting the presence of short-range correlations between the Nd moments. However, no signs of long-range ordering could be found down to 2 K despite a sizeable theta_p ~ -40 K. The strongly suppressed magnetic long-range ordering in both R = Pr and Nd suggests the presence of strong magnetic frustration in these compounds. The low-temperature resistivity shows a T^0.5 dependence. No evidence for the heavy fermion behavior could be found in any of the three compounds.
Single crystals of PrNiO3 were grown under an oxygen pressure of 295 bar using a unique high-pressure optical-image floating zone furnace. The crystals, with volume in excess of 1 mm3, were characterized structurally using single crystal and powder X
-ray diffraction. Resistivity, specific heat, and magnetic susceptibility were measured, all of which evidenced an abrupt, first order metal-insulator transition (MIT) at ~130 K, in agreement with previous literature reports on polycrystalline specimens. Temperature-dependent single crystal diffraction was performed to investigate changes through the MIT. Our study demonstrates the opportunity space for high fugacity, reactive environments for single crystal growth specifically of perovskite nickelates but more generally to correlated electron oxides.
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