skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Glass-Like Through-Plane Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La 0.5Sr 0.5CoO 3– δ [Glass-Like Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La 0.5Sr 0.5CoO 3– δ]

Abstract

Here, ultrafast time-domain thermoreflectance (TDTR) is utilized to extract the through-plane thermal conductivity (Λ LSCO) of epitaxial La 0.5Sr 0.5CoO 3–δ (LSCO) of varying thickness (<20 nm) on LaAlO 3 and SrTiO 3 substrates. These LSCO films possess ordered oxygen vacancies as the primary means of lattice mismatch accommodation with the substrate, which induces compressive/tensile strain and thus controls the orientation of the oxygen vacancy ordering (OVO). TDTR results demonstrate that the room-temperature Λ LSCO of LSCO on both substrates (1.7 W m –1 K –1) are nearly a factor of four lower than that of bulk single-crystal LSCO (6.2 W m –1 K –1). Remarkably, this approaches the lower limit of amorphous oxides (e.g., 1.3 W m –1 K –1 for glass), with no dependence on the OVO orientation. Through theoretical simulations, origins of the glass-like thermal conductivity of LSCO are revealed as a combined effect resulting from oxygen vacancies (the dominant factor), Sr substitution, size effects, and the weak electron/phonon coupling within the LSCO film. The absence of OVO dependence in the measured Λ LSCO is rationalized by two main effects: (1) the nearly isotropic phononic thermal conductivity resulting from the imperfect OVO planes when δ is small;more » (2) the missing electronic contribution to Λ LSCO along the through-plane direction for these ultrathin LSCO films on insulating substrates.« less

Authors:
 [1];  [1];  [2];  [1];  [3];  [3];  [4];  [4];  [2];  [1];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Purdue Univ., West Lafayette, IN (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Univ. Complutense de Madrid, Madrid (Spain)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF); Spanish Ministerio de Economia y Competitividad (MINECO); USDOE
OSTI Identifier:
1415607
Alternate Identifier(s):
OSTI ID: 1407813
Grant/Contract Number:  
AC02-06CH11357; FG02-06ER46275; SC0016371
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 27; Journal Issue: 47; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Boltzmann transport equation; LSCO; TDTR; molecular dynamics simulation; nanoscale epitaxial LSCO; oxygen vacancies; perovskite; thermal conductivity; time-domain thermoreflectance

Citation Formats

Wu, Xuewang, Walter, Jeff, Feng, Tianli, Zhu, Jie, Zheng, Hong, Mitchell, John F., Biskup, Neven, Varela, Maria, Ruan, Xiulin, Leighton, Chris, and Wang, Xiaojia. Glass-Like Through-Plane Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La0.5Sr0.5CoO3–δ [Glass-Like Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La0.5Sr0.5CoO3–δ]. United States: N. p., 2017. Web. doi:10.1002/adfm.201704233.
Wu, Xuewang, Walter, Jeff, Feng, Tianli, Zhu, Jie, Zheng, Hong, Mitchell, John F., Biskup, Neven, Varela, Maria, Ruan, Xiulin, Leighton, Chris, & Wang, Xiaojia. Glass-Like Through-Plane Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La0.5Sr0.5CoO3–δ [Glass-Like Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La0.5Sr0.5CoO3–δ]. United States. doi:10.1002/adfm.201704233.
Wu, Xuewang, Walter, Jeff, Feng, Tianli, Zhu, Jie, Zheng, Hong, Mitchell, John F., Biskup, Neven, Varela, Maria, Ruan, Xiulin, Leighton, Chris, and Wang, Xiaojia. Thu . "Glass-Like Through-Plane Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La0.5Sr0.5CoO3–δ [Glass-Like Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La0.5Sr0.5CoO3–δ]". United States. doi:10.1002/adfm.201704233. https://www.osti.gov/servlets/purl/1415607.
@article{osti_1415607,
title = {Glass-Like Through-Plane Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La0.5Sr0.5CoO3–δ [Glass-Like Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La0.5Sr0.5CoO3–δ]},
author = {Wu, Xuewang and Walter, Jeff and Feng, Tianli and Zhu, Jie and Zheng, Hong and Mitchell, John F. and Biskup, Neven and Varela, Maria and Ruan, Xiulin and Leighton, Chris and Wang, Xiaojia},
abstractNote = {Here, ultrafast time-domain thermoreflectance (TDTR) is utilized to extract the through-plane thermal conductivity (ΛLSCO) of epitaxial La0.5Sr0.5CoO3–δ (LSCO) of varying thickness (<20 nm) on LaAlO3 and SrTiO3 substrates. These LSCO films possess ordered oxygen vacancies as the primary means of lattice mismatch accommodation with the substrate, which induces compressive/tensile strain and thus controls the orientation of the oxygen vacancy ordering (OVO). TDTR results demonstrate that the room-temperature ΛLSCO of LSCO on both substrates (1.7 W m–1 K–1) are nearly a factor of four lower than that of bulk single-crystal LSCO (6.2 W m–1 K–1). Remarkably, this approaches the lower limit of amorphous oxides (e.g., 1.3 W m–1 K–1 for glass), with no dependence on the OVO orientation. Through theoretical simulations, origins of the glass-like thermal conductivity of LSCO are revealed as a combined effect resulting from oxygen vacancies (the dominant factor), Sr substitution, size effects, and the weak electron/phonon coupling within the LSCO film. The absence of OVO dependence in the measured ΛLSCO is rationalized by two main effects: (1) the nearly isotropic phononic thermal conductivity resulting from the imperfect OVO planes when δ is small; (2) the missing electronic contribution to ΛLSCO along the through-plane direction for these ultrathin LSCO films on insulating substrates.},
doi = {10.1002/adfm.201704233},
journal = {Advanced Functional Materials},
number = 47,
volume = 27,
place = {United States},
year = {2017},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Atomic-Resolution Imaging of Spin-State Superlattices in Nanopockets within Cobaltite Thin Films
journal, March 2011

  • Gazquez, Jaume; Luo, Weidong; Oxley, Mark P.
  • Nano Letters, Vol. 11, Issue 3, p. 973-976
  • DOI: 10.1021/nl1034896

Structure-thermal property correlation of aligned silicon dioxide nanorod arrays
journal, June 2016

  • Zhu, Jie; Zhu, Yu; Wu, Xuewang
  • Applied Physics Letters, Vol. 108, Issue 23
  • DOI: 10.1063/1.4953625

Revealing the Origins of 3D Anisotropic Thermal Conductivities of Black Phosphorus
journal, March 2016

  • Zhu, Jie; Park, Haechan; Chen, Jun-Yang
  • Advanced Electronic Materials, Vol. 2, Issue 5
  • DOI: 10.1002/aelm.201600040

Thermoelectric and magnetic properties of nanocrystalline La 0.7 Sr 0.3 CoO 3
journal, March 2012

  • Durá, O. J.; Rogl, P.; Falmbigl, M.
  • Journal of Applied Physics, Vol. 111, Issue 6
  • DOI: 10.1063/1.3699038

Oxygen Permeation Through Perovskite-Type Oxides
journal, November 1985

  • Teraoka, Yasutake; Zhang, Hua-Min; Furukawa, Shoichi
  • Chemistry Letters, Vol. 14, Issue 11
  • DOI: 10.1246/cl.1985.1743

Reversible redox reactions in an epitaxially stabilized SrCoOx oxygen sponge
journal, August 2013

  • Jeen, Hyoungjeen; Choi, Woo Seok; Biegalski, Michael D.
  • Nature Materials, Vol. 12, Issue 11
  • DOI: 10.1038/nmat3736

Lattice mismatch accommodation via oxygen vacancy ordering in epitaxial La 0.5 Sr 0.5 CoO 3-δ thin films
journal, July 2013

  • Gazquez, J.; Bose, Shameek; Sharma, M.
  • APL Materials, Vol. 1, Issue 1
  • DOI: 10.1063/1.4809547

Electrical and magnetic properties of La0.5Sr0.5CoO3 thin films
journal, April 2000

  • Luo, G. P.; Wang, Y. S.; Chen, S. Y.
  • Applied Physics Letters, Vol. 76, Issue 14
  • DOI: 10.1063/1.126208

Mixed-valence manganites
journal, November 2009


Metal–insulator transition and phonon scattering mechanisms in La1−xSrxCoO3
journal, May 2006


Complex thermoelectric materials
journal, February 2008

  • Snyder, G. Jeffrey; Toberer, Eric S.
  • Nature Materials, Vol. 7, Issue 2, p. 105-114
  • DOI: 10.1038/nmat2090

Ferroelectric Ceramics: History and Technology
journal, April 1999


Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Analysis of heat flow in layered structures for time-domain thermoreflectance
journal, December 2004

  • Cahill, David G.
  • Review of Scientific Instruments, Vol. 75, Issue 12
  • DOI: 10.1063/1.1819431

Magnetic phase separation in SrCoOx (2.5 ≤ x ≤ 3)
journal, August 2011

  • Xie, C.; Nie, Y.; Wells, B.
  • Applied Physics Letters, Vol. 99, Issue 5, Article No. 052503
  • DOI: 10.1063/1.3622644

Large thermoelectric performance of heavily Nb-doped SrTiO3 epitaxial film at high temperature
journal, August 2005

  • Ohta, Shingo; Nomura, Takashi; Ohta, Hiromichi
  • Applied Physics Letters, Vol. 87, Issue 9
  • DOI: 10.1063/1.2035889

Lower limit to the thermal conductivity of disordered crystals
journal, September 1992

  • Cahill, David G.; Watson, S. K.; Pohl, R. O.
  • Physical Review B, Vol. 46, Issue 10, p. 6131-6140
  • DOI: 10.1103/PhysRevB.46.6131

Bond-length fluctuations and the spin-state transition in L CoO 3 ( L = La , Pr, and Nd)
journal, April 2004


Origin of ferroelectricity in perovskite oxides
journal, July 1992


Thermal conductivity reduction in oxygen-deficient strontium titanates
journal, May 2008

  • Yu, Choongho; Scullin, Matthew L.; Huijben, Mark
  • Applied Physics Letters, Vol. 92, Issue 19
  • DOI: 10.1063/1.2930679

Atomic Resolution Analysis of the Defect Chemistry and Microdomain Structure of Brownmillerite-Type Strontium Cobaltite
journal, April 2002


Impact of stress on oxygen vacancy ordering in epitaxial (La0.5Sr0.5)CoO3−∂ thin films
journal, May 2003

  • Klenov, Dmitri O.; Donner, Wolfgang; Foran, Brendan
  • Applied Physics Letters, Vol. 82, Issue 20
  • DOI: 10.1063/1.1575503

Oxygen Ion Migration in Perovskite-Type Oxides
journal, August 1995

  • Cherry, M.; Islam, M. S.; Catlow, C. R. A.
  • Journal of Solid State Chemistry, Vol. 118, Issue 1
  • DOI: 10.1006/jssc.1995.1320

Direct real space observation of magneto-electronic inhomogeneity in ultra-thin film La0.5Sr0.5CoO3−δ on SrTiO3(001)
journal, September 2014

  • Kelly, S.; Galli, F.; Aarts, J.
  • Applied Physics Letters, Vol. 105, Issue 11
  • DOI: 10.1063/1.4896283

Mixed electronic and ionic conductivity of LaCo(M)O3 (M=Ga, Cr, Fe or Ni)I. Oxygen transport in perovskites LaCoO3–LaGaO3
journal, December 1997


Defect chemistry and surface properties of LaCoO3
journal, January 2000

  • Read, Mark S. D.; Saiful Islam, M.; Watson, Graeme W.
  • Journal of Materials Chemistry, Vol. 10, Issue 10
  • DOI: 10.1039/b002168g

Strain Control of Oxygen Vacancies in Epitaxial Strontium Cobaltite Films
journal, January 2016

  • Petrie, Jonathan R.; Mitra, Chandrima; Jeen, Hyoungjeen
  • Advanced Functional Materials, Vol. 26, Issue 10
  • DOI: 10.1002/adfm.201504868

Tetragonal domain structure and magnetoresistance of La 1 x Sr x CoO 3
journal, July 1996


A Localized‐Electron to Collective‐Electron Transition in the System (La, Sr)CoO 3
journal, February 1968

  • Raccah, P. M.; Goodenough, J. B.
  • Journal of Applied Physics, Vol. 39, Issue 2
  • DOI: 10.1063/1.1656227

Electrical conductivity relaxation studies of an epitaxial La0.5Sr0.5CoO3−δ thin film
journal, February 2002


Epitaxial La0.5Sr0.5CoO3 thin films: Structure, magnetism, and transport
journal, July 2008

  • Torija, M. A.; Sharma, M.; Fitzsimmons, M. R.
  • Journal of Applied Physics, Vol. 104, Issue 2
  • DOI: 10.1063/1.2955725

Interpreting picosecond acoustics in the case of low interface stiffness
journal, November 2012

  • Hohensee, Gregory T.; Hsieh, Wen-Pin; Losego, Mark D.
  • Review of Scientific Instruments, Vol. 83, Issue 11
  • DOI: 10.1063/1.4766957

Topotactic Phase Transformation of the Brownmillerite SrCoO 2.5 to the Perovskite SrCoO 3- δ
journal, July 2013


High dielectric constant and tunability of epitaxial SrTiO3 thin film capacitors
journal, May 1999

  • Fuchs, D.; Schneider, C. W.; Schneider, R.
  • Journal of Applied Physics, Vol. 85, Issue 10
  • DOI: 10.1063/1.369363

Thermal conductivity, thermopower, and figure of merit of La 1 x Sr x Co O 3
journal, October 2005


Thermal Transport across Surfactant Layers on Gold Nanorods in Aqueous Solution
journal, March 2016

  • Wu, Xuewang; Ni, Yuxiang; Zhu, Jie
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 16
  • DOI: 10.1021/acsami.5b12163

Perovskite as a Cathode Material: A Review of its Role in Solid-Oxide Fuel Cell Technology
journal, January 2016


Intergranular Giant Magnetoresistance in a Spontaneously Phase Separated Perovskite Oxide
journal, January 2005


Oxygen Vacancy Ordering: a Degree of Freedom that can Control the Structural, Electronic and Magnetic Properties of Transition-Metal Oxide Films
journal, August 2014


Interfacial thermal conductance in spun-cast polymer films and polymer brushes
journal, July 2010

  • Losego, Mark D.; Moh, Lionel; Arpin, Kevin A.
  • Applied Physics Letters, Vol. 97, Issue 1
  • DOI: 10.1063/1.3458802

Scattering of phonons by vacancies
journal, November 1987

  • Ratsifaritana, C. A.; Klemens, P. G.
  • International Journal of Thermophysics, Vol. 8, Issue 6
  • DOI: 10.1007/BF00500791

Zirconates as New Materials for Thermal Barrier Coatings
journal, August 2000


Tuning thermal conductivity in homoepitaxial SrTiO 3 films via defects
journal, August 2015

  • Brooks, Charles M.; Wilson, Richard B.; Schäfer, Anna
  • Applied Physics Letters, Vol. 107, Issue 5
  • DOI: 10.1063/1.4927200

Correlated electrons in high-temperature superconductors
journal, July 1994


Perovskite thin Films for High-Frequency Capacitor Applications
journal, August 1998


Resistive switching in transition metal oxides
journal, June 2008


Effect of Growth Induced (Non)Stoichiometry on the Structure, Dielectric Response, and Thermal Conductivity of SrTiO 3 Thin Films
journal, December 2011

  • Breckenfeld, E.; Wilson, R.; Karthik, J.
  • Chemistry of Materials, Vol. 24, Issue 2
  • DOI: 10.1021/cm203042q

Oxide materials for high temperature thermoelectric energy conversion
journal, March 2012


Cross-plane electronic and thermal transport properties of p-type La 0.67 Sr 0.33 MnO 3 /LaMnO 3 perovskite oxide metal/semiconductor superlattices
journal, September 2012

  • Jha, Pankaj; Sands, Timothy D.; Cassels, Laura
  • Journal of Applied Physics, Vol. 112, Issue 6
  • DOI: 10.1063/1.4754514

Glassy ferromagnetism and magnetic phase separation in La 1 x Sr x CoO 3
journal, May 2003


Effect of strain on the local perovskite structure: La 0.5 Sr 0.5 CoO 3
journal, April 2011

  • Woicik, J. C.; Xie, C. K.; Wells, B. O.
  • Journal of Applied Physics, Vol. 109, Issue 8
  • DOI: 10.1063/1.3564934

Large Thermal Conductivity Reduction Induced by La/O Vacancies in the Thermoelectric LaCoO 3 System
journal, May 2011

  • Wang, Yang; Li, Fang; Xu, Luxiang
  • Inorganic Chemistry, Vol. 50, Issue 10
  • DOI: 10.1021/ic200178x

Multiferroics progress and prospects in thin films
journal, January 2007

  • Ramesh, R.; Spaldin, Nicola A.
  • Nature Materials, Vol. 6, Issue 1, p. 21-29
  • DOI: 10.1038/nmat1805

Recent development of n-type perovskite thermoelectrics
journal, September 2016


Thermoelectric properties of perovskite-type oxide La1−xSrxCoO3 (x=0, 0.1) prepared by solid state reactions
journal, March 2006


La0.5Sr0.5CoO3−δ nanotubes sensor for room temperature detection of ammonia
journal, August 2008


Chemically Driven Nanoscopic Magnetic Phase Separation at the SrTiO3(001)/La1-xSrxCoO3 Interface
journal, April 2011

  • Torija, Maria A.; Sharma, Manish; Gazquez, Jaume
  • Advanced Materials, Vol. 23, Issue 24
  • DOI: 10.1002/adma.201100417

Epitaxial Strain-Induced Chemical Ordering in La 0.5 Sr 0.5 CoO 3−δ Films on SrTiO 3
journal, February 2011

  • Donner, Wolfgang; Chen, Chonglin; Liu, Ming
  • Chemistry of Materials, Vol. 23, Issue 4
  • DOI: 10.1021/cm102657v

Thermal Conductivity of High-Modulus Polymer Fibers
journal, June 2013

  • Wang, Xiaojia; Ho, Victor; Segalman, Rachel A.
  • Macromolecules, Vol. 46, Issue 12, p. 4937-4943
  • DOI: 10.1021/ma400612y

Thermal transport across carbon nanotube-graphene covalent and van der Waals junctions
journal, July 2015

  • Shi, Jingjing; Dong, Yalin; Fisher, Timothy
  • Journal of Applied Physics, Vol. 118, Issue 4
  • DOI: 10.1063/1.4927273

High-temperature thermoelectric response of double-doped SrTiO 3 epitaxial films
journal, October 2010


A computational modelling study of oxygen vacancies at LaCoO3 perovskite surfaces
journal, January 2006

  • Khan, S.; Oldman, R. J.; Cor?, F.
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 44
  • DOI: 10.1039/b602753a

Magnetic compounds wtth perovskite structure III. ferromagnetic compounds of cobalt
journal, January 1953


Interrelation between Structure - Magnetic Properties in La 0.5 Sr 0.5 CoO 3
journal, July 2014

  • Biegalski, Michael. D.; Takamura, Yayoi; Mehta, Apurva
  • Advanced Materials Interfaces, Vol. 1, Issue 8
  • DOI: 10.1002/admi.201400203