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

Abstract

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.

Authors:

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)

Publication Date:: Tue May 15 00:00:00 EDT 2018

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

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

OSTI Identifier:: 1439293

Alternate Identifier(s):: OSTI ID: 1437205

Report Number(s):: BNL-205701-2018-JAAM
Journal ID: ISSN 2475-9953; PRMHAR; TRN: US1900594

Grant/Contract Number:: SC0012704; 16-039

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Physical Review Materials

Additional Journal Information:: Journal Volume: 2; Journal Issue: 5; Journal ID: ISSN 2475-9953

Publisher:: American Physical Society (APS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Jeong, Jong Seok, Wu, Wangzhou, Topsakal, Mehmet, Yu, Guichuan, Sasagawa, Takao, Greven, Martin, and Mkhoyan, K. Andre. Decomposition of La2–xSrxCuO4 into several La2O3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope.  United States: N. p., 2018. 
        Web.  doi:10.1103/PhysRevMaterials.2.054801.

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                    Jeong, Jong Seok, Wu, Wangzhou, Topsakal, Mehmet, Yu, Guichuan, Sasagawa, Takao, Greven, Martin, & Mkhoyan, K. Andre. Decomposition of La2–xSrxCuO4 into several La2O3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope.  United States.  https://doi.org/10.1103/PhysRevMaterials.2.054801

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                    Jeong, Jong Seok, Wu, Wangzhou, Topsakal, Mehmet, Yu, Guichuan, Sasagawa, Takao, Greven, Martin, and Mkhoyan, K. Andre. 2018.  
        "Decomposition of La2–xSrxCuO4 into several La2O3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope".  United States.  https://doi.org/10.1103/PhysRevMaterials.2.054801.  https://www.osti.gov/servlets/purl/1439293.

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@article{osti_1439293,

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

  author       = {Jeong, Jong Seok and Wu, Wangzhou and Topsakal, Mehmet and Yu, Guichuan and Sasagawa, Takao and Greven, Martin and Mkhoyan, K. Andre},

  abstractNote = {Here, we report the decomposition of La2–xSrxCuO4 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 LaM4,5 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.},

  doi          = {10.1103/PhysRevMaterials.2.054801},

  url          = {https://www.osti.gov/biblio/1439293},
  journal      = {Physical Review Materials},

  issn         = {2475-9953},

  number       = 5,

  volume       = 2,

  place        = {United States},

  year         = {Tue May 15 00:00:00 EDT 2018},

  month        = {Tue May 15 00:00:00 EDT 2018}

}

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https://doi.org/10.1103/PhysRevMaterials.2.054801

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FIG. 1: Low-magnification BF-TEM image (a) and highresolution HAADF-STEM image (b) from a [110]-oriented La_2−xSr_xCuO₄ (x = 0.03) specimen. The inset to (a) is a corresponding SAED pattern. The scale bar of the inset is 2 nm⁻¹. The atomic-resolution HAADF-STEM image shows the K₂NiF₄ structure, which is the structure ofmore »

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Similar Records

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

Abstract

Citation Formats

Figures / Tables:

alpha-Manganese(III) Oxide --- a C-Type Sesquioxide of Orthorhombic Symmetry. journal, January 1967

Phase separation in superoxygenated La2-xSrxCuO4+y journal, April 2006

Phase Equilibria of the La 2 O 3 -SrO-CuO System at 950°C and 10 kbar journal, December 1996

Defect Chemistry of La2−xSrxCuO4−δ: Oxygen Nonstoichiometry and Thermodynamic Stability journal, June 1997

Magnetic excitations in pure, lightly doped, and weakly metallic La 2 CuO 4 journal, December 1992

Distortion in the crystal structure of α-Mn2O3 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) 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 journal, February 2012

From quantum matter to high-temperature superconductivity in copper oxides 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 journal, November 2002

exciting: a full-potential all-electron package implementing density-functional theory and many-body perturbation theory journal, August 2014

Die Struktur des Kaliumnickelfluorids, K2NiF journal, August 1955

A new form of La2O3 journal, April 1969

The Strain-Driven Pyrochlore to “Defect Fluorite” Phase Transition in Rare Earth Sesquioxide Stabilized Cubic Zirconias 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 journal, May 1998

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces journal, April 2008

Effect of chemical inhomogeneity in bismuth-based copper oxide superconductors journal, February 2004

Thermal decomposition and chemical stabilization of mercurocuprate high-temperature superconductors journal, March 2000

Strong charge fluctuations manifested in the high-temperature Hall coefficient of high- T c cuprates 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 journal, December 2017

Frustrated electronic phase separation and high-temperature superconductors journal, May 1993

Radiolytic purification of CaO by electron beams journal, July 2006

Thermodynamic stability of ternary oxides in LnMO (Ln = La, Pr, Nd; M = Co, Ni, Cu) systems journal, November 1988

Electron Energy-Loss Spectroscopy in the Electron Microscope book, January 2011

Addressing electron-hole correlation in core excitations of solids: An all-electron many-body approach from first principles journal, April 2017

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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

alpha-Manganese(III) Oxide --- a C-Type Sesquioxide of Orthorhombic Symmetry.
journal, January 1967

Phase separation in superoxygenated La2-xSrxCuO4+y
journal, April 2006

Phase Equilibria of the La ₂ O ₃ -SrO-CuO System at 950°C and 10 kbar
journal, December 1996

Defect Chemistry of La2−xSrxCuO4−δ: Oxygen Nonstoichiometry and Thermodynamic Stability
journal, June 1997

Magnetic excitations in pure, lightly doped, and weakly metallic ${La}_{2}$ ${CuO}_{4}$
journal, December 1992

Distortion in the crystal structure of α-Mn2O3
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)
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
journal, February 2012

From quantum matter to high-temperature superconductivity in copper oxides
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
journal, November 2002

exciting: a full-potential all-electron package implementing density-functional theory and many-body perturbation theory
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Die Struktur des Kaliumnickelfluorids, K₂NiF
journal, August 1955

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journal, April 1969

The Strain-Driven Pyrochlore to “Defect Fluorite” Phase Transition in Rare Earth Sesquioxide Stabilized Cubic Zirconias
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
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Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
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Effect of chemical inhomogeneity in bismuth-based copper oxide superconductors
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Thermal decomposition and chemical stabilization of mercurocuprate high-temperature superconductors
journal, March 2000

Strong charge fluctuations manifested in the high-temperature Hall coefficient of high- $T_{c}$ cuprates
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
journal, December 2017

Frustrated electronic phase separation and high-temperature superconductors
journal, May 1993

Radiolytic purification of CaO by electron beams
journal, July 2006

Thermodynamic stability of ternary oxides in LnMO (Ln = La, Pr, Nd; M = Co, Ni, Cu) systems
journal, November 1988

Electron Energy-Loss Spectroscopy in the Electron Microscope
book, January 2011

Addressing electron-hole correlation in core excitations of solids: An all-electron many-body approach from first principles
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