Structure and properties of α-NaFeO{sub 2}-type ternary sodium iridates

Journal Article · Sat Feb 15 00:00:00 EST 2014 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2013.11.017· OSTI ID:22274215

Baroudi, Kristen ^[1]; Yim, Cindi ^[1]; Wu, Hui ^[2]; Huang, Qingzhen ^[2]; Roudebush, John H. ^[1]; Vavilova, Eugenia ^[3]; Grafe, Hans-Joachim; Kataev, Vladislav ^[3]; Buechner, Bernd ^[3]; Ji, Huiwen ^[1]; Kuo, Changyang; Hu, Zhiwei; Pi, Tun-Wen ^[4]; Pao, Chiwen; Lee, Jyhfu ^[5]; Mikhailova, Daria; Hao Tjeng, Liu ^[4]; Cava, R. J. ^[1]

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1. Department of Chemistry, Princeton University, Princeton, NJ 08544 (United States)
2. NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States)
3. Leibniz Institute for Solid State and Materials Research IFW, Dresden (Germany)
4. Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Straße 40, 01187 Dresden (Germany)
5. National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan, ROC (China)

The synthesis, structure, and elementary magnetic and electronic properties are reported for layered compounds of the type Na{sub 3−x}MIr{sub 2}O{sub 6} and Na{sub 3−x}M{sub 2}IrO{sub 6}, where M is a transition metal from the 3d series (M=Zn, Cu, Ni, Co, Fe and Mn). The rhombohedral structures, in space group R−3m, were determined by refinement of neutron and synchrotron powder diffraction data. No clear evidence for long range 2:1 or 1:2 honeycomb-like M/Ir ordering was found in the neutron powder diffraction patterns except in the case of M=Zn, and thus in general the compounds are best designated as sodium deficient α-NaFeO{sub 2}-type phases with formulas Na{sub 1−x}M{sub 1/3}Ir{sub 2/3}O{sub 2} or Na{sub 1−x}M{sub 2/3}Ir{sub 1/3}O{sub 2}. Synchrotron powder diffraction patterns indicate that several of the compounds likely have honeycomb in-plane metal–iridium ordering with disordered stacking of the layers. All the compounds are sodium deficient under our synthetic conditions and are black and insulating. Weiss constants derived from magnetic susceptibility measurements indicate that Na{sub 0.62}Mn{sub 0.61}Ir{sub 0.39}O{sub 2}, Na{sub 0.80}Fe{sub 2/3}Ir{sub 1/3}O{sub 2}, Na{sub 0.92}Ni{sub 1/3}Ir{sub 2/3}O{sub 2}, Na{sub 0.86}Cu{sub 1/3}Ir{sub 2/3}O{sub 2}, and Na{sub 0.89}Zn{sub 1/3}Ir{sub 2/3}O{sub 2} display dominant antiferromagnetic interactions. For Na{sub 0.90}Co{sub 1/3}Ir{sub 2/3}O{sub 2} the dominant magnetic interactions at low temperature are ferromagnetic while at high temperatures they are antiferromagnetic; there is also a change in the effective moment. Low temperature specific heat measurements (to 2 K) on Na{sub 0.92}Ni{sub 1/3}Ir{sub 2/3}O{sub 2} indicate the presence of a broad magnetic ordering transition. X-ray absorption spectroscopy shows that iridium is at or close to the 4+ oxidation state in all compounds. {sup 23}Na nuclear magnetic resonance measurements comparing Na{sub 2}IrO{sub 3} to Na{sub 0.92}Ni{sub 1/3}Ir{sub 2/3}O{sub 2} and Na{sub 0.89}Zn{sub 1/3}Ir{sub 2/3}O{sub 2} provide strong indications that the electron spins are short-range ordered in the latter two materials. Na{sub 0.62}Mn{sub 0.61}Ir{sub 0.39}O{sub 2}, Na{sub 0.80}Fe{sub 2/3}Ir{sub 1/3}O{sub 2}, Na{sub 0.90}Co{sub 1/3}Ir{sub 2/3}O{sub 2}, Na{sub 0.92}Ni{sub 1/3}Ir{sub 2/3}O{sub 2}, Na{sub 0.86}Cu{sub 1/3}Ir{sub 2/3}O{sub 2} and Na{sub 0.89}Zn{sub 1/3}Ir{sub 2/3}O{sub 2} are spin glasses. (CSD-numbers: Na{sub 0.62}Mn{sub 0.61}Ir{sub 0.39}O{sub 2}: 426657, Na{sub 0.80}Fe{sub 2/3}Ir{sub 1/3}O{sub 2}: 426659, Na{sub 0.90}Co{sub 1/3}Ir{sub 2/3}O{sub 2}: 426658, Na{sub 0.92}Ni{sub 1/3}Ir{sub 2/3}O{sub 2}: 426656, Na{sub 0.86}Cu{sub 1/3}Ir{sub 2/3}O{sub 2}: 426655, and Na{sub 2.8}ZnIr{sub 2}O{sub 6}: 426660.) - Graphical abstract: Diffraction patterns of Na{sub 0.92}Ni{sub 1/3}Ir{sub 2/3}O{sub 2}, Na{sub 0.86}Cu{sub 1/3}Ir{sub 2/3}O{sub 2} and Na{sub 0.89}Zn{sub 1/3}Ir{sub 2/3}O{sub 2}: neutron diffraction patterns in the main panel and synchrotron diffraction in the insets. The patterns show a small amount of ordering in the transition metal iridium layer. Display Omitted - Highlights: • We report six ternary sodium iridates with the α-NaFeO{sub 2} structure. • Compounds Na{sub 1−x}M{sub 1/3}Ir{sub 2/3}O{sub 2}, M=Co, Ni, Cu, Zn and Na{sub 1−x}M{sub 2/3}Ir{sub 1/3}O{sub 2}, M=Mn, Fe. • Rietveld refinement of powder neutron diffraction data. • All compounds are spin glasses. • NMR comparison to Na{sub 2}IrO{sub 3}.

• OSTI ID: 22274215
• Journal Information: Journal of Solid State Chemistry, Vol. 210, Issue 1; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTROSCOPY
ANTIFERROMAGNETISM
INTERACTIONS
IRIDIUM
MAGNETIC SUSCEPTIBILITY
MAGNETIZATION
NEUTRON DIFFRACTION
NEUTRONS
NUCLEAR MAGNETIC RESONANCE
POWDERS
SODIUM
SPACE GROUPS
SPECIFIC HEAT
SPIN GLASS STATE
SYNCHROTRONS
SYNTHESIS
TRIGONAL LATTICES
X-RAY SPECTROSCOPY