Results for “NaMnBi” | Engineering Papers

DOE OSTI2020

Materials Data on NaMnBi by Materials Project

NaMnBi is Matlockite structured and crystallizes in the tetragonal P4/nmm space group. The structure is three-dimensional. Na is bonded in a 5-coordinate geometry to four equivalent Mn and five equivalent Bi atoms. All Na–Mn bond lengths are 3.53 Å. There are one shorter (3.32 Å) and four longer (3.34 Å) Na–Bi bond lengths. Mn is bonded to four equivalent Na and four equivalent Bi atoms to form a mixture of distorted edge and face-sharing MnNa4Bi4 tetrahedra. All Mn–Bi bond lengths are 2.86 Å. Bi is bonded in a 9-coordinate geometry to five equivalent Na and four equivalent Mn atoms.

36 MATERIALS SCIENCE↗

DOE OSTI2023

From Layered Antiferromagnet to 3D Ferromagnet: LiMnBi-to-MnBi Magneto-Structural Transformation

Here, the intermetallic compound LiMnBi was synthesized by the two-step solid-state reaction from the elements. The synthesis temperature of 850 K was selected based on in-situ high-temperature powder X-ray diffraction data. LiMnBi crystalizes in the layered-like PbClF structure type (a = 4.3131(7) Å, c = 7.096(1) Å at 100 K, P4/nmm space group, Z = 2). LiMnBi structure is built of the alternating [MnBi] and Li layers, as determined from single-crystal X-ray diffraction data. Magnetic properties measurements and solid-state 7 Li Nuclear Magnetic Resonance data collected for polycrystalline LiMnBi samples indicate the long-range antiferromagnetic ordering of Mn sublattice at ~340 K, with no superconductivity down to 5 K detected. LiMnBi is air- and water-sensitive. In aerobic conditions, Li can be extracted from LiMnBi structure to form Li 2 O/LiOH and MnBi (NiAs structure type, P6 3 /mmc). The obtained MnBi polymorph was previously reported to be one of the strongest rare-earth-free ferromagnets, yet its bulk synthesis in powder form is cumbersome. The proposed magneto-structural transformation from ternary LiMnBi to ferromagnetic MnBi involves condensation of the MnBi4 tetrahedra upon Li deintercalation and is exclusive to LiMnBi. In contrast, ferromagnetic MnBi cannot be obtained from either isostructural NaMnBi and KMnBi, or from the structurally related CaMn 2 Bi 2 . Such a distinctive transformation in the case of LiMnBi is presumed to be due to its fitting reactivity to yield MnBi and favorable interlayer distance between [MnBi] layers, while the interlayer distance in NaMnBi and KMnBi structural analogs is unfavorably long. The studies of delithiation from the layered-like LiMnBi under different chemical environments indicate that the yield of the MnBi depends on the type of solvent used and the kinetics of the reaction. A slow rate and mild reaction media lead to a high fraction of the MnBi product. The saturation magnetization of the “as-prepared” MnBi is ~50 % of the expected value of 81.3 emu/g. Overall, this study adds a missing member to the family of ternary pnictides and illustrates how soft-chemistry methods can be used to obtain “difficult-to-synthesize” compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Charge density modulation and defect ordering in the $Na_xMnBi_y$ magnetic semimetal

The I-Mn-V antiferromagnet, NaMnBi, develops a very large positive magnetoresistance (MR) up to 10 000% at 2 K and 9 T in crystals showing a semiconductor-to-metal transition (SMT). In the absence of an SMT, a modest (20%) MR is achieved. Here, we show that upon cooling below the magnetic transition, a spatial modulation appears giving rise to new Bragg peaks due to charge and defect ordering in a checkerboard pattern, with two kinds of modulation vectors, $q_1 = \left( \frac{2}{3}, 0, 1 \right)$ and $q_2 = \left( \frac{2}{3}, \frac{1}{3}, \frac {1}{2} \right)$. This constitutes a superlattice transition ($T_s$) that lowers the symmetry from the high-temperature centrosymmetric $P4/nmm$ to the noncentrosymmetric $P\overline{4}m2$. In crystals with a large MR, a close to room temperature $T_s$ is observed with $q_1$ appearing first, followed by $q_2$. In crystals with low MR, however, $T_s$ is much lower and only $q_1$ is observed. Finally, the charge modulation and spin fluctuations may both contribute to the enhancement of MR.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗