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

Title: 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

Abstract

Ionic-liquid/gel-based transistors have emerged as a potentially ideal means to accumulate high charge-carrier densities at the surfaces of materials such as oxides, enabling control over electronic phase transitions. Substantial gaps remain in the understanding of gating mechanisms, however, particularly with respect to charge carrier vs oxygen defect creation, one contributing factor being the dearth of experimental probes beyond electronic transport. Here we demonstrate the use of synchrotron hard x-ray diffraction and polarized neutron reflectometry as in operando probes of ion-gel transistors based on ferromagnetic La 0.5Sr 0.5CoO 3-δ. An asymmetric gate-bias response is confirmed to derive from electrostatic hole accumulation at negative gate bias vs oxygen vacancy formation at positive bias. The latter is detected via a large gate-induced lattice expansion (up to 1%), complementary bulk measurements and density functional calculations enabling quantification of the bias-dependent oxygen vacancy density. Remarkably, the gate-induced oxygen vacancies proliferate through the entire thickness of 30-40-unit-cell-thick films, quantitatively accounting for changes in the magnetization depth profile. In conclusion, these results directly elucidate the issue of electrostatic vs redox-based response in electrolyte-gated oxides, also demonstrating powerful approaches to their in operando investigation.

Authors:
 [1];  [1];  [1];  [2];  [2];  [2];  [3];  [3];  [1];  [1];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1466375
Alternate Identifier(s):
OSTI ID: 1414041
Grant/Contract Number:  
AC02-06CH11357; FG02-06ER46275; SC0016371
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 1; Journal Issue: 7; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Walter, Jeff, Yu, Guichuan, Yu, Biqiong, Grutter, Alexander, Kirby, Brian, Borchers, Julie, Zhang, Zhan, Zhou, Hua, Birol, Turan, Greven, Martin, and Leighton, Chris. Ion-gel-gating-induced oxygen vacancy formation in epitaxial La0.5Sr0.5CoO3–δ films from in operando x-ray and neutron scattering. United States: N. p., 2017. Web. doi:10.1103/PhysRevMaterials.1.071403.
Walter, Jeff, Yu, Guichuan, Yu, Biqiong, Grutter, Alexander, Kirby, Brian, Borchers, Julie, Zhang, Zhan, Zhou, Hua, Birol, Turan, Greven, Martin, & Leighton, Chris. Ion-gel-gating-induced oxygen vacancy formation in epitaxial La0.5Sr0.5CoO3–δ films from in operando x-ray and neutron scattering. United States. doi:10.1103/PhysRevMaterials.1.071403.
Walter, Jeff, Yu, Guichuan, Yu, Biqiong, Grutter, Alexander, Kirby, Brian, Borchers, Julie, Zhang, Zhan, Zhou, Hua, Birol, Turan, Greven, Martin, and Leighton, Chris. Tue . "Ion-gel-gating-induced oxygen vacancy formation in epitaxial La0.5Sr0.5CoO3–δ films from in operando x-ray and neutron scattering". United States. doi:10.1103/PhysRevMaterials.1.071403. https://www.osti.gov/servlets/purl/1466375.
@article{osti_1466375,
title = {Ion-gel-gating-induced oxygen vacancy formation in epitaxial La0.5Sr0.5CoO3–δ films from in operando x-ray and neutron scattering},
author = {Walter, Jeff and Yu, Guichuan and Yu, Biqiong and Grutter, Alexander and Kirby, Brian and Borchers, Julie and Zhang, Zhan and Zhou, Hua and Birol, Turan and Greven, Martin and Leighton, Chris},
abstractNote = {Ionic-liquid/gel-based transistors have emerged as a potentially ideal means to accumulate high charge-carrier densities at the surfaces of materials such as oxides, enabling control over electronic phase transitions. Substantial gaps remain in the understanding of gating mechanisms, however, particularly with respect to charge carrier vs oxygen defect creation, one contributing factor being the dearth of experimental probes beyond electronic transport. Here we demonstrate the use of synchrotron hard x-ray diffraction and polarized neutron reflectometry as in operando probes of ion-gel transistors based on ferromagnetic La0.5Sr0.5CoO3-δ. An asymmetric gate-bias response is confirmed to derive from electrostatic hole accumulation at negative gate bias vs oxygen vacancy formation at positive bias. The latter is detected via a large gate-induced lattice expansion (up to 1%), complementary bulk measurements and density functional calculations enabling quantification of the bias-dependent oxygen vacancy density. Remarkably, the gate-induced oxygen vacancies proliferate through the entire thickness of 30-40-unit-cell-thick films, quantitatively accounting for changes in the magnetization depth profile. In conclusion, these results directly elucidate the issue of electrostatic vs redox-based response in electrolyte-gated oxides, also demonstrating powerful approaches to their in operando investigation.},
doi = {10.1103/PhysRevMaterials.1.071403},
journal = {Physical Review Materials},
number = 7,
volume = 1,
place = {United States},
year = {2017},
month = {12}
}

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

Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: (more » a) Device and experimental setup schematic for synchrotron x-ray diffraction on epitaxial La0.5Sr0.5CoO3δ films. (b) Gate-bias-(Vg)-dependent specular diffraction (00L) scans, where L is in reciprocal lattice units (r.l.u.) of the LAO substrate. (c) Change in c-axis lattice parameter (Δcop, left axis) and cell volume (ΔV, right axis) with Vg. (d) Change in Scherrer thickness (Δts, left axis), and ts itself (right axis), vs Vg. (e) Change in film thickness from Laue fringes (Δtf), and tf itself (right axis), vs Vg. Blue dotted lines are guides to the eye.« less

Save / Share:

Works referenced in this record:

Crystal-Facet-Dependent Metallization in Electrolyte-Gated Rutile TiO 2 Single Crystals
journal, August 2013

  • Schladt, Thomas D.; Graf, Tanja; Aetukuri, Nagaphani B.
  • ACS Nano, Vol. 7, Issue 9
  • DOI: 10.1021/nn403340d

Oxygen reaction on strontium-doped lanthanum cobaltite dense electrodes at intermediate temperatures
journal, February 2001


Nonstoichiometry of the perovskite-type oxides La1−xSrxCoO3−δ
journal, May 1989


Oxygen stoichiometry, crystal structure, and magnetism of La 0.5 Sr 0.5 CoO 3  
journal, August 2004


2D Insulator-Metal Transition in Aerosol-Jet-Printed Electrolyte-Gated Indium Oxide Thin Film Transistors
journal, February 2017

  • Xie, Wei; Zhang, Xin; Leighton, Chris
  • Advanced Electronic Materials, Vol. 3, Issue 3
  • DOI: 10.1002/aelm.201600369

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

Gate-tunable gigantic lattice deformation in VO 2
journal, January 2014

  • Okuyama, D.; Nakano, M.; Takeshita, S.
  • Applied Physics Letters, Vol. 104, Issue 2
  • DOI: 10.1063/1.4861901

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

Low-Temperature Transport Properties of Holes Introduced by Ionic Liquid Gating in Hydrogen-Terminated Diamond Surfaces
journal, July 2013

  • Yamaguchi, Takahide; Watanabe, Eiichiro; Osato, Hirotaka
  • Journal of the Physical Society of Japan, Vol. 82, Issue 7
  • DOI: 10.7566/JPSJ.82.074718

Insulator to metal transition in WO3 induced by electrolyte gating
journal, July 2017


Collective bulk carrier delocalization driven by electrostatic surface charge accumulation
journal, July 2012


Cobalt spin states and hyperfine interactions in LaCoO 3 investigated by LDA + U calculations
journal, September 2010


Suppression of Metal-Insulator Transition in VO2 by Electric Field-Induced Oxygen Vacancy Formation
journal, March 2013


Discovery of superconductivity in KTaO3 by electrostatic carrier doping
journal, May 2011

  • Ueno, K.; Nakamura, S.; Shimotani, H.
  • Nature Nanotechnology, Vol. 6, Issue 7
  • DOI: 10.1038/nnano.2011.78

Studies on room-temperature electric-field effect in ionic-liquid gated VO 2 three-terminal devices
journal, January 2012

  • Yang, Zheng; Zhou, You; Ramanathan, Shriram
  • Journal of Applied Physics, Vol. 111, Issue 1
  • DOI: 10.1063/1.3665399

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Superconducting Dome in a Gate-Tuned Band Insulator
journal, November 2012


Electrostatic modification of novel materials
journal, November 2006

  • Ahn, C. H.; Bhattacharya, A.; Di Ventra, M.
  • Reviews of Modern Physics, Vol. 78, Issue 4, p. 1185-1212
  • DOI: 10.1103/RevModPhys.78.1185

Electric-Field Control of the Metal-Insulator Transition in Ultrathin NdNiO3 Films
journal, October 2010

  • Scherwitzl, Raoul; Zubko, Pavlo; Lezama, I. Gutierrez
  • Advanced Materials, Vol. 22, Issue 48
  • DOI: 10.1002/adma.201003241

Effect of gate voltage polarity on the ionic liquid gating behavior of NdNiO 3 /NdGaO 3 heterostructures
journal, May 2017

  • Dong, Yongqi; Xu, Haoran; Luo, Zhenlin
  • APL Materials, Vol. 5, Issue 5
  • DOI: 10.1063/1.4983617

Superconductor–insulator transition in La2 − xSr x CuO4 at the pair quantum resistance
journal, April 2011


Electrically Induced Ferromagnetism at Room Temperature in Cobalt-Doped Titanium Dioxide
journal, May 2011


Electric-field-induced superconductivity in an insulator
journal, October 2008

  • Ueno, K.; Nakamura, S.; Shimotani, H.
  • Nature Materials, Vol. 7, Issue 11, p. 855-858
  • DOI: 10.1038/nmat2298

“Cut and Stick” Rubbery Ion Gels as High Capacitance Gate Dielectrics
journal, July 2012

  • Lee, Keun Hyung; Kang, Moon Sung; Zhang, Sipei
  • Advanced Materials, Vol. 24, Issue 32
  • DOI: 10.1002/adma.201200950

Large Electric Field Effect in Electrolyte-Gated Manganites
journal, March 2009


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


Accessing the transport properties of graphene and its multilayers at high carrier density
journal, July 2011

  • Ye, Jianting; Craciun, Monica F.; Koshino, Mikito
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 32
  • DOI: 10.1073/pnas.1018388108

Ab initiomolecular dynamics for liquid metals
journal, January 1993


In operando evidence of deoxygenation in ionic liquid gating of YBa 2 Cu 3 O 7-X
journal, December 2016

  • Perez-Muñoz, Ana M.; Schio, Pedro; Poloni, Roberta
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 2
  • DOI: 10.1073/pnas.1613006114

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

High-Density Carrier Accumulation in ZnO Field-Effect Transistors Gated by Electric Double Layers of Ionic Liquids
journal, April 2009

  • Yuan, Hongtao; Shimotani, Hidekazu; Tsukazaki, Atsushi
  • Advanced Functional Materials, Vol. 19, Issue 7
  • DOI: 10.1002/adfm.200801633

High Conductance 2D Transport around the Hall Mobility Peak in Electrolyte-Gated Rubrene Crystals
journal, December 2014


Oxygen Displacement in Cuprates under Ionic Liquid Field-Effect Gating
journal, August 2016

  • Dubuis, Guy; Yacoby, Yizhak; Zhou, Hua
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep32378

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

Suppression of Ionic Liquid Gate-Induced Metallization of SrTiO 3 (001) by Oxygen
journal, September 2013

  • Li, Mingyang; Han, Wei; Jiang, Xin
  • Nano Letters, Vol. 13, Issue 10
  • DOI: 10.1021/nl402088f

Modulation of the Electrical Properties of VO 2 Nanobeams Using an Ionic Liquid as a Gating Medium
journal, May 2012

  • Ji, Heng; Wei, Jiang; Natelson, Douglas
  • Nano Letters, Vol. 12, Issue 6
  • DOI: 10.1021/nl300741h

Phase-sensitive specular neutron reflectometry for imaging the nanometer scale composition depth profile of thin-film materials
journal, February 2012

  • Kirby, B. J.; Kienzle, P. A.; Maranville, B. B.
  • Current Opinion in Colloid & Interface Science, Vol. 17, Issue 1
  • DOI: 10.1016/j.cocis.2011.11.001

Hopping transport and the Hall effect near the insulator–metal transition in electrochemically gated poly(3-hexylthiophene) transistors
journal, January 2012

  • Wang, Shun; Ha, Mingjing; Manno, Michael
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms2213

Electrostatic Gating of Ultrathin Films
journal, July 2014


Electric-field control of tri-state phase transformation with a selective dual-ion switch
journal, May 2017

  • Lu, Nianpeng; Zhang, Pengfei; Zhang, Qinghua
  • Nature, Vol. 546, Issue 7656
  • DOI: 10.1038/nature22389

Glass-Like Through-Plane Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La 0.5 Sr 0.5 CoO 3− δ
journal, November 2017

  • Wu, Xuewang; Walter, Jeff; Feng, Tianli
  • Advanced Functional Materials, Vol. 27, Issue 47
  • DOI: 10.1002/adfm.201704233

Oxygen transport in La1−xSrxMn1−yCoyO3±δ perovskites Part I. Oxygen tracer diffusion
journal, February 1998


Electrostatic Control of the Evolution from a Superconducting Phase to an Insulating Phase in Ultrathin YBa 2 Cu 3 O 7 x Films
journal, July 2011


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

Tuning of the metal-insulator transition in electrolyte-gated NdNiO3 thin films
journal, October 2010

  • Asanuma, S.; Xiang, P. -H.; Yamada, H.
  • Applied Physics Letters, Vol. 97, Issue 14
  • DOI: 10.1063/1.3496458

    Works referencing / citing this record:

    Wide-voltage-window reversible control of electronic transport in electrolyte-gated epitaxial BaSnO 3
    journal, July 2019


    Voltage‐Control of Magnetism in All‐Solid‐State and Solid/Liquid Magnetoelectric Composites
    journal, February 2019


    Voltage‐Control of Magnetism in All‐Solid‐State and Solid/Liquid Magnetoelectric Composites
    journal, February 2019


    Wide-voltage-window reversible control of electronic transport in electrolyte-gated epitaxial BaSnO 3
    journal, July 2019


      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.