Decomposition of La2–xSrxCuO4 into several La2O3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope

Jeong, Jong Seok; Wu, Wangzhou; Topsakal, Mehmet; Yu, Guichuan; Sasagawa, Takao; Greven, Martin; Mkhoyan, K. Andre

doi:10.1103/PhysRevMaterials.2.054801

Title: Decomposition of $L a_{2 - x} S r_{x} Cu O_{4}$ into several $L a_{2} O_{3}$ phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope

Journal Article · Tue May 15 00:00:00 EDT 2018 · Physical Review Materials

DOI:https://doi.org/10.1103/PhysRevMaterials.2.054801· OSTI ID:1439293

Jeong, Jong Seok ^[1]; Wu, Wangzhou ^[1];

^[2]; Yu, Guichuan ^[1]; Sasagawa, Takao ^[3]; Greven, Martin ^[1]; Mkhoyan, K. Andre ^[1]

Univ. of Minnesota, Minneapolis, MN (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Tokyo Institute of Technology, Kanagawa (Japan)

Here, we report the decomposition of La_2–xSr_xCuO₄ into La₂O₃ and Cu nanoparticles in ultrahigh vacuum, observed by in situ heating experiments in a transmission electron microscope. The analysis of electron diffraction data reveals that the phase decomposition process starts at about 150°C and is considerably expedited in the temperature range of 350°C–450°C. Two major resultant solid phases are identified as metallic Cu and La₂O₃ by electron diffraction, simulation, and electron energy-loss spectroscopy (EELS) analyses. With the aid of calculations, La₂O₃ phases are further identified to be derivatives of a fluorite structure—fluorite, pyrochlore, and (distorted) bixbyite—characterized by different oxygen-vacancy order. Additionally, the bulk plasmon energy and the fine structures of the O K and LaM_4,5 EELS edges are reported for these structures, along with simulated O K x-ray absorption near-edge structure. The resultant Cu nanoparticles and La₂O₃ phases remain unchanged after cooling to room temperature.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; 16-039

OSTI ID:: 1439293

Alternate ID(s):: OSTI ID: 1437205

Report Number(s):: BNL-205701-2018-JAAM; PRMHAR; TRN: US1900594

Journal Information:: Physical Review Materials, Vol. 2, Issue 5; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 2 works

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References (27)

alpha-Manganese(III) Oxide --- a C-Type Sesquioxide of Orthorhombic Symmetry. Norrestam, Rolf; Ingri, Nils; Östlund, Eric Acta Chemica Scandinavica, Vol. 21 https://doi.org/10.3891/acta.chem.scand.21-2871	journal	January 1967
Phase separation in superoxygenated La2-xSrxCuO4+y Mohottala, Hashini E.; Wells, Barrett O.; Budnick, Joseph I. Nature Materials, Vol. 5, Issue 5 https://doi.org/10.1038/nmat1633	journal	April 2006
Phase Equilibria of the La ₂ O ₃ -SrO-CuO System at 950°C and 10 kbar Geny, Joel; Meen, James K.; Elthon, Don Journal of the American Ceramic Society, Vol. 79, Issue 12 https://doi.org/10.1111/j.1151-2916.1996.tb08080.x	journal	December 1996
Defect Chemistry of La2−xSrxCuO4−δ: Oxygen Nonstoichiometry and Thermodynamic Stability Kanai, Hideki; Mizusaki, Junichiro; Tagawa, Hiroaki Journal of Solid State Chemistry, Vol. 131, Issue 1 https://doi.org/10.1006/jssc.1997.7377	journal	June 1997
Magnetic excitations in pure, lightly doped, and weakly metallic ${La}_{2}$ ${CuO}_{4}$ Keimer, B.; Belk, N.; Birgeneau, R. J. Physical Review B, Vol. 46, Issue 21 https://doi.org/10.1103/PhysRevB.46.14034	journal	December 1992
Distortion in the crystal structure of α-Mn2O3 Geller, S.; Cape, J. A.; Grant, R. W. Physics Letters A, Vol. 24, Issue 7 https://doi.org/10.1016/0375-9601(67)90929-2	journal	March 1967
EXAFS study at the La LIII X-ray absorption edge of superconducting materials obtained by fluorination of La2−xSrxCuO4 oxides (0≤x≤0.15) Tuilier, M. H.; Chevalier, B.; Tressaud, A. Physica C: Superconductivity, Vol. 200, Issue 1-2 https://doi.org/10.1016/0921-4534(92)90327-9	journal	September 1992
Effect of Strontium doping on the Oxygen Diffusion in La _2−x Sr _x CuO _4±δ samples Investigated by Oxygen Isotope Back Exchange Sura, R.; Ceretti, M.; Prestipino, C. Journal of Physics: Conference Series, Vol. 340 https://doi.org/10.1088/1742-6596/340/1/012110	journal	February 2012
From quantum matter to high-temperature superconductivity in copper oxides Keimer, B.; Kivelson, S. A.; Norman, M. R. Nature, Vol. 518, Issue 7538 https://doi.org/10.1038/nature14165	journal	February 2015
Bulk magnetic properties and phase diagram of Li-doped ${La}_{2} {CuO}_{4} :$ Common magnetic response of hole-doped ${CuO}_{2}$ planes Sasagawa, T.; Mang, P. K.; Vajk, O. P. Physical Review B, Vol. 66, Issue 18 https://doi.org/10.1103/PhysRevB.66.184512	journal	November 2002
exciting: a full-potential all-electron package implementing density-functional theory and many-body perturbation theory Gulans, Andris; Kontur, Stefan; Meisenbichler, Christian Journal of Physics: Condensed Matter, Vol. 26, Issue 36 https://doi.org/10.1088/0953-8984/26/36/363202	journal	August 2014
Die Struktur des Kaliumnickelfluorids, K₂NiF Balz, D.; Plieth, K. Zeitschrift für Elektrochemie, Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 59, Issue 6 https://doi.org/10.1002/bbpc.19550590613	journal	August 1955
A new form of La2O3 Felsche, J. Die Naturwissenschaften, Vol. 56, Issue 4 https://doi.org/10.1007/BF01166817	journal	April 1969
The Strain-Driven Pyrochlore to “Defect Fluorite” Phase Transition in Rare Earth Sesquioxide Stabilized Cubic Zirconias Tabira, Y.; Withers, R. L.; Barry, J. C. Journal of Solid State Chemistry, Vol. 159, Issue 1 https://doi.org/10.1006/jssc.2001.9139	journal	June 2001
First-Order Vortex-Lattice Phase Transition in $({La}_{1 - x} {Sr}_{x})_{2} {CuO}_{4}$ Single Crystals: Universal Scaling of the Transition Lines in High-Temperature Superconductors Sasagawa, T.; Kishio, K.; Togawa, Y. Physical Review Letters, Vol. 80, Issue 19 https://doi.org/10.1103/PhysRevLett.80.4297	journal	May 1998
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
Effect of chemical inhomogeneity in bismuth-based copper oxide superconductors Eisaki, H.; Kaneko, N.; Feng, D. L. Physical Review B, Vol. 69, Issue 6 https://doi.org/10.1103/PhysRevB.69.064512	journal	February 2004
Thermal decomposition and chemical stabilization of mercurocuprate high-temperature superconductors Peacock, G. B.; Haydon, S. K.; Ellis, A. J. Superconductor Science and Technology, Vol. 13, Issue 4 https://doi.org/10.1088/0953-2048/13/4/313	journal	March 2000
Strong charge fluctuations manifested in the high-temperature Hall coefficient of high- $T_{c}$ cuprates Ono, S.; Komiya, Seiki; Ando, Yoichi Physical Review B, Vol. 75, Issue 2 https://doi.org/10.1103/PhysRevB.75.024515	journal	January 2007
Ion-gel-gating-induced oxygen vacancy formation in epitaxial $L a_{0.5} S r_{0.5} Co O_{3 - δ}$ films from in operando x-ray and neutron scattering Walter, Jeff; Yu, Guichuan; Yu, Biqiong Physical Review Materials, Vol. 1, Issue 7 https://doi.org/10.1103/PhysRevMaterials.1.071403	journal	December 2017
Frustrated electronic phase separation and high-temperature superconductors Emery, V. J.; Kivelson, S. A. Physica C: Superconductivity, Vol. 209, Issue 4 https://doi.org/10.1016/0921-4534(93)90581-A	journal	May 1993
Radiolytic purification of CaO by electron beams Mkhoyan, K. A.; Silcox, J.; Mcguire, M. A. Philosophical Magazine, Vol. 86, Issue 19 https://doi.org/10.1080/14786430600658025	journal	July 2006
Thermodynamic stability of ternary oxides in LnMO (Ln = La, Pr, Nd; M = Co, Ni, Cu) systems Petrov, A. N.; Cherepanov, V. A.; Zuyev, A. Yu. Journal of Solid State Chemistry, Vol. 77, Issue 1 https://doi.org/10.1016/0022-4596(88)90083-7	journal	November 1988
Electron Energy-Loss Spectroscopy in the Electron Microscope Egerton, R. F. https://doi.org/10.1007/978-1-4419-9583-4	book	January 2011
Addressing electron-hole correlation in core excitations of solids: An all-electron many-body approach from first principles Vorwerk, Christian; Cocchi, Caterina; Draxl, Claudia Physical Review B, Vol. 95, Issue 15 https://doi.org/10.1103/PhysRevB.95.155121	journal	April 2017
Phase decomposition and chemical inhomogeneity in ${Nd}_{2 - x} {Ce}_{x} {CuO}_{4 \pm δ}$ Mang, P. K.; Larochelle, S.; Mehta, A. Physical Review B, Vol. 70, Issue 9 https://doi.org/10.1103/PhysRevB.70.094507	journal	September 2004
Pseudogaps, dopants, and strong disorder in cuprate high-temperature superconductors Phillips, J. C.; Saxena, A.; Bishop, A. R. Reports on Progress in Physics, Vol. 66, Issue 12 https://doi.org/10.1088/0034-4885/66/12/R02	journal	November 2003