Structural and electronic properties of the first iridium containing mixed B-site spinel oxide: Cu[Ir1.5Cu0.5]O4

Wallace, M. K.; Li, Jun; Labarre, P. G.; Svadlenak, S.; Haskel, D.; Kim, J.; Sterbinsky, G. E.; Rodolakis, F.; Park, H.; Ramirez, A. P.; Subramanian, M. A.

doi:10.1103/physrevmaterials.5.094410

Title: Structural and electronic properties of the first iridium containing mixed B-site spinel oxide: $Cu [{Ir}_{1.5} {Cu}_{0.5}] O_{4}$

Journal Article · Mon Sep 27 00:00:00 EDT 2021 · Physical Review Materials

DOI:https://doi.org/10.1103/physrevmaterials.5.094410· OSTI ID:1839091

^[1];

^[1]; Labarre, P. G. ^[2];

^[1]; Haskel, D. ^[3];

^[3]; Sterbinsky, G. E. ^[3];

^[3]; Park, H. ^[4]; Ramirez, A. P. ^[2];

^[1]

Oregon State Univ., Corvallis, OR (United States)
Univ. of California, Santa Cruz, CA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division

Geometrically frustrated systems populated with large spin-orbit coupled ions are an ideal setting for the exploration of novel exotic states of matter. In this study we present an example of iridium on a mixed B-site spinel oxide structure: $Cu [{Ir}_{1.498 (2)} {Cu}_{0.502 (2)}] O_{4}$ . Synchrotron XRD refinements reveal a face-centered-cubic structure with space group $F d \bar{3} m$ and mixed Cu-Ir site disorder within the $B_{2} O_{4}$ rocksalt substructure. Electrical properties reveal a metallic state within the 50–600-K range with a Kondo effect at $T < 50 K$ . X-ray absorption spectroscopy (XAS) measurements show a mixed ${Cu}^{1 + / 2 +}$ and ${Ir}^{3 + / 4 +}$ charge partitioned picture, which suggests a metallic/band description with reduced on-site Coulomb interactions. Spin-glass-like freezing is seen at $T_{g} = 49 K$ , and the hysteresis behavior for $T > T_{g}$ resembles that of a strongly frustrated magnet. DFT calculations show sizable hybridization between the Cu $3 d$ and Ir $5 d$ states with an effective mixed ${Ir}^{3 + / 4 +}$ charge partitioned picture, supporting the electronic and XAS results.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; SC0017862; DMR-1508527

OSTI ID:: 1839091

Journal Information:: Physical Review Materials, Vol. 5, Issue 9; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (41)

Interplay of Spin-Orbit Interactions, Dimensionality, and Octahedral Rotations in Semimetallic ${SrIrO}_{3}$ Nie, Y. F.; King, P. D. C.; Kim, C. H. Physical Review Letters, Vol. 114, Issue 1 https://doi.org/10.1103/PhysRevLett.114.016401	journal	January 2015
Pressure-induced insulating state in ${Ba}_{1 - x} R_{x} {IrO}_{3}$ ( $R = Gd$ , Eu) single crystals Korneta, O. B.; Chikara, S.; Parkin, S. Physical Review B, Vol. 81, Issue 4 https://doi.org/10.1103/PhysRevB.81.045101	journal	January 2010
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Formation of isomorphic Ir3+ and Ir4+ octamers and spin dimerization in the spinel CuIr2S4 Radaelli, Paolo G.; Horibe, Y.; Gutmann, Matthias J. Nature, Vol. 416, Issue 6877 https://doi.org/10.1038/416155a	journal	March 2002
Electronic structure, local magnetism, and spin-orbit effects of Ir(IV)-, Ir(V)-, and Ir(VI)-based compounds Laguna-Marco, M. A.; Kayser, P.; Alonso, J. A. Physical Review B, Vol. 91, Issue 21 https://doi.org/10.1103/PhysRevB.91.214433	journal	June 2015
X-ray scattering study of pyrochlore iridates: Crystal structure, electronic, and magnetic excitations Clancy, J. P.; Gretarsson, H.; Lee, E. K. H. Physical Review B, Vol. 94, Issue 2 https://doi.org/10.1103/PhysRevB.94.024408	journal	July 2016
Valence-electron transfer and a metal-insulator transition in a strongly correlated perovskite oxide Ramirez, A. P.; Lawes, G.; Li, D. Solid State Communications, Vol. 131, Issue 3-4 https://doi.org/10.1016/j.ssc.2004.04.014	journal	July 2004
Observation of heavy spin-orbit excitons propagating in a nonmagnetic background: The case of ${(Ba, Sr)}_{2} {YIrO}_{6}$ Kusch, M.; Katukuri, V. M.; Bogdanov, N. A. Physical Review B, Vol. 97, Issue 6 https://doi.org/10.1103/PhysRevB.97.064421	journal	February 2018
Crystal-Field Splitting and Correlation Effect on the Electronic Structure of $A_{2} {IrO}_{3}$ Gretarsson, H.; Clancy, J. P.; Liu, X. Physical Review Letters, Vol. 110, Issue 7 https://doi.org/10.1103/PhysRevLett.110.076402	journal	February 2013
Structural and magnetic studies of ${Sr}_{2}$ ${IrO}_{4}$ Crawford, M. K.; Subramanian, M. A.; Harlow, R. L. Physical Review B, Vol. 49, Issue 13 https://doi.org/10.1103/PhysRevB.49.9198	journal	April 1994
Novel $J_{eff} = 1 / 2$ Mott State Induced by Relativistic Spin-Orbit Coupling in ${Sr}_{2} {IrO}_{4}$ Kim, B. J.; Jin, Hosub; Moon, S. J. Physical Review Letters, Vol. 101, Issue 7 https://doi.org/10.1103/PhysRevLett.101.076402	journal	August 2008
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
Unoccupied electronic structure and core-hole effects in the x-ray-absorption spectra of ${Cu}_{2}$ O Grioni, M.; van Acker, J. F.; Czyžyk, M. T. Physical Review B, Vol. 45, Issue 7 https://doi.org/10.1103/PhysRevB.45.3309	journal	February 1992
Tunneling into the Mott insulator ${Sr}_{2}$ ${IrO}_{4}$ Nichols, John; Bray-Ali, Noah; Ansary, Armin Physical Review B, Vol. 89, Issue 8 https://doi.org/10.1103/PhysRevB.89.085125	journal	February 2014
MERIX—Next generation medium energy resolution inelastic X-ray scattering instrument at the APS Shvyd’ko, Yu. V.; Hill, J. P.; Burns, C. A. Journal of Electron Spectroscopy and Related Phenomena, Vol. 188 https://doi.org/10.1016/j.elspec.2012.09.003	journal	June 2013
Anomalous dispersion calculations near to and on the long-wavelength side of an absorption edge Cromer, D. T.; Liberman, D. A. Acta Crystallographica Section A, Vol. 37, Issue 2 https://doi.org/10.1107/S0567739481000600	journal	March 1981
Magnetic Excitations across the Metal-Insulator Transition in the Pyrochlore Iridate ${Eu}_{2} {Ir}_{2} O_{7}$ Chun, Sae Hwan; Yuan, Bo; Casa, Diego Physical Review Letters, Vol. 120, Issue 17 https://doi.org/10.1103/PhysRevLett.120.177203	journal	April 2018
${LiV}_{2} O_{4}$ : A Heavy Fermion Transition Metal Oxide Kondo, S.; Johnston, D. C.; Swenson, C. A. Physical Review Letters, Vol. 78, Issue 19 https://doi.org/10.1103/PhysRevLett.78.3729	journal	May 1997
Evolution of magnetic and orbital properties in the magnetically diluted $A$ -site spinel ${Cu}_{1 - x} {Zn}_{x} {Rh}_{2} O_{4}$ Zakrzewski, A. V.; Gangopadhyay, S.; MacDougall, G. J. Physical Review B, Vol. 97, Issue 21 https://doi.org/10.1103/PhysRevB.97.214411	journal	June 2018
High-Pressure Synthesis, Crystal Structure, and Electromagnetic Properties of CdRh ₂ O ₄ : an Analogous Oxide of the Postspinel Mineral MgAl ₂ O ₄ Wang, Xia; Guo, Yanfeng; Shi, Youguo Inorganic Chemistry, Vol. 51, Issue 12 https://doi.org/10.1021/ic300628m	journal	June 2012
Determination of Spin- and Orbital-Moment Anisotropies in Transition Metals by Angle-Dependent X-Ray Magnetic Circular Dichroism Stöhr, J.; König, H. Physical Review Letters, Vol. 75, Issue 20 https://doi.org/10.1103/PhysRevLett.75.3748	journal	November 1995
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Magnetic Frustration in Iridium Spinel Compound ${CuIr}_{2} S_{4}$ Kojima, K. M.; Kadono, R.; Miyazaki, M. Physical Review Letters, Vol. 112, Issue 8 https://doi.org/10.1103/PhysRevLett.112.087203	journal	February 2014
Excitonic quasiparticles in a spin–orbit Mott insulator Kim, Jungho; Daghofer, M.; Said, A. H. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5453	journal	July 2014
Anomalous magnetoresistance in the spinel superconductor LiTi2O4 Jin, K.; He, G.; Zhang, X. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8183	journal	May 2015
Charge partitioning and anomalous hole doping in Rh-doped ${Sr}_{2} {IrO}_{4}$ Chikara, S.; Fabbris, G.; Terzic, J. Physical Review B, Vol. 95, Issue 6 https://doi.org/10.1103/PhysRevB.95.060407	journal	February 2017
Electron-doped ${Sr}_{2} {IrO}_{4 - δ}$ $(0 \leq δ \leq 0.04)$ : Evolution of a disordered $J_{eff} = \frac{1}{2}$ Mott insulator into an exotic metallic state Korneta, O. B.; Qi, Tongfei; Chikara, S. Physical Review B, Vol. 82, Issue 11 https://doi.org/10.1103/PhysRevB.82.115117	journal	September 2010
${LiV}_{2} O_{4}$ Spinel as a Heavy-Mass Fermi Liquid: Anomalous Transport and Role of Geometrical Frustration Urano, C.; Nohara, M.; Kondo, S. Physical Review Letters, Vol. 85, Issue 5 https://doi.org/10.1103/PhysRevLett.85.1052	journal	July 2000
Local Probe for Spin-Orbit Interaction van der Laan, G.; Thole, B. T. Physical Review Letters, Vol. 60, Issue 19 https://doi.org/10.1103/PhysRevLett.60.1977	journal	May 1988
High temperature superconductivity in the LiTiO ternary system Johnston, D. C.; Prakash, H.; Zachariasen, W. H. Materials Research Bulletin, Vol. 8, Issue 7 https://doi.org/10.1016/0025-5408(73)90183-9	journal	July 1973
Orbital Magnetism and Spin-Orbit Effects in the Electronic Structure of ${BaIrO}_{3}$ Laguna-Marco, M. A.; Haskel, D.; Souza-Neto, N. Physical Review Letters, Vol. 105, Issue 21 https://doi.org/10.1103/PhysRevLett.105.216407	journal	November 2010
Multiple-scattering calculations of x-ray-absorption spectra Zabinsky, S. I.; Rehr, J. J.; Ankudinov, A. Physical Review B, Vol. 52, Issue 4 https://doi.org/10.1103/PhysRevB.52.2995	journal	July 1995
Origin of magnetic moments and presence of spin-orbit singlets in ${Ba}_{2} {YIrO}_{6}$ Nag, Abhishek; Bhowal, Sayantika; Chakraborty, Atasi Physical Review B, Vol. 98, Issue 1 https://doi.org/10.1103/PhysRevB.98.014431	journal	July 2018
Spherical analyzers and monochromators for resonant inelastic hard X-ray scattering: a compilation of crystals and reflections Gog, Thomas; Casa, Diego M.; Said, Ayman H. Journal of Synchrotron Radiation, Vol. 20, Issue 1 https://doi.org/10.1107/S0909049512043154	journal	November 2012
Momentum-resolved electronic excitations in the Mott insulator ${Sr}_{2} {IrO}_{4}$ studied by resonant inelastic x-ray scattering Ishii, K.; Jarrige, I.; Yoshida, M. Physical Review B, Vol. 83, Issue 11 https://doi.org/10.1103/PhysRevB.83.115121	journal	March 2011
Ordering and Antiferromagnetism in Ferrites Anderson, P. W. Physical Review, Vol. 102, Issue 4 https://doi.org/10.1103/PhysRev.102.1008	journal	May 1956
${Sr}_{2} {Ir}_{1 - x} {Rh}_{x} O_{4} (x < 0.5)$ : An inhomogeneous $j_{eff} = \frac{1}{2}$ Hubbard system Chikara, Shalinee; Haskel, Daniel; Sim, Jae-Hoon Physical Review B, Vol. 92, Issue 8 https://doi.org/10.1103/PhysRevB.92.081114	journal	August 2015
Three-Dimensional Topological Insulators on the Pyrochlore Lattice Guo, H. -M.; Franz, M. Physical Review Letters, Vol. 103, Issue 20 https://doi.org/10.1103/PhysRevLett.103.206805	journal	November 2009
Testing the Validity of the Strong Spin-Orbit-Coupling Limit for Octahedrally Coordinated Iridate Compounds in a Model System ${Sr}_{3} {CuIrO}_{6}$ Liu, X.; Katukuri, Vamshi M.; Hozoi, L. Physical Review Letters, Vol. 109, Issue 15 https://doi.org/10.1103/PhysRevLett.109.157401	journal	October 2012
Mott Insulators in the Strong Spin-Orbit Coupling Limit: From Heisenberg to a Quantum Compass and Kitaev Models Jackeli, G.; Khaliullin, G. Physical Review Letters, Vol. 102, Issue 1 https://doi.org/10.1103/PhysRevLett.102.017205	journal	January 2009

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Title: Structural and electronic properties of the first iridium containing mixed B-site spinel oxide: Cu [ Ir 1.5 Cu 0.5 ] O 4

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Title: Structural and electronic properties of the first iridium containing mixed B-site spinel oxide: $Cu [{Ir}_{1.5} {Cu}_{0.5}] O_{4}$