Determining the Oxygen Stoichiometry of Cobaltite Thin Films

Zhang, Shenli; Chiu, I-Ting; Lee, Min-Han; Gunn, Brandon; Feng, Mingzhen; Park, Tae Joon; Shafer, Padraic; N’Diaye, Alpha T.; Rodolakis, Fanny; Ramanathan, Shriram; Frañó, Alex; Schuller, Ivan K.; Takamura, Yayoi; Galli, Giulia

doi:10.1021/acs.chemmater.1c03338

Determining the Oxygen Stoichiometry of Cobaltite Thin Films

Journal Article · Wed Feb 23 00:00:00 EST 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.1c03338· OSTI ID:1868557

^[1]; Chiu, I-Ting ^[2]; ^[3]; Gunn, Brandon ^[4]; ^[2]; Park, Tae Joon ^[5]; ^[6]; N’Diaye, Alpha T. ^[6]; Rodolakis, Fanny ^[7]; Ramanathan, Shriram ^[5]; Frañó, Alex ^[4]; ^[3]; ^[2]; ^[8]

Univ. of Chicago, IL (United States)
Univ. of California, Davis, CA (United States)
Univ. of California San Diego, La Jolla, CA (United States); Univ. of California San Diego, La Jolla, CA (United States). Center for Advanced Nanoscience
Univ. of California San Diego, La Jolla, CA (United States)
Purdue Univ., West Lafayette, IN (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)
Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)

Transition metal oxides (TMO) are promising materials to realize low-power neuromorphic devices. Their physical properties critically depend on their oxygen vacancy concentrations, whose experimental determination remains a challenging task. Here we focus on cobaltites, in particular La_1-xSr_xCoO_3-d (LSCO), and we present a strategy to identify fingerprints of oxygen vacancies in X-ray absorption (XA) spectra. Using a combination of experiment and theory, we show that the variation of the oxygen vacancy concentration in the perovskite phase of LSCO is correlated with the change of the relative peak positions of the O K-edge XA spectra. Furthermore, we also identify an additional geometrical fingerprint that captures both the changes of the Co-O bond length and Co-O-Co bond angle in the material due to the presence of oxygen vacancies. Finally, we predict the oxygen vacancy concentration of experimental samples and show how the resistivity of the oxide material may be tuned as a function of the defect concentration present in the system.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; SC0019273

OSTI ID:: 1868557

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 5 Vol. 34; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (64)

Insights into Nanoscale Electrochemical Reduction in a Memristive Oxide: the Role of Three-Phase Boundaries Lenser, Christian; Patt, Marten; Menzel, Stephan Advanced Functional Materials, Vol. 24, Issue 28 https://doi.org/10.1002/adfm.201304233	journal	April 2014
Strain Control of Oxygen Vacancies in Epitaxial Strontium Cobaltite Films Petrie, Jonathan R.; Mitra, Chandrima; Jeen, Hyoungjeen Advanced Functional Materials, Vol. 26, Issue 10 https://doi.org/10.1002/adfm.201504868	journal	January 2016
Room‐Temperature AFM Electric‐Field‐Induced Topotactic Transformation between Perovskite and Brownmillerite SrFeO _x with Sub‐Micrometer Spatial Resolution Ferreiro‐Vila, Elías; Blanco‐Canosa, Santiago; Lucas del Pozo, Irene Advanced Functional Materials, Vol. 29, Issue 48 https://doi.org/10.1002/adfm.201901984	journal	September 2019
Topotactic Phase Transformation of the Brownmillerite SrCoO _2.5 to the Perovskite SrCoO _3- _δ Jeen, H.; Choi, W. S.; Freeland, J. W. Advanced Materials, Vol. 25, Issue 27 https://doi.org/10.1002/adma.201300531	journal	July 2013
Topotactic Metal-Insulator Transition in Epitaxial SrFeO _x Thin Films Khare, Amit; Shin, Dongwon; Yoo, Tae Sup Advanced Materials, Vol. 29, Issue 37 https://doi.org/10.1002/adma.201606566	journal	July 2017
Interrelation between Structure - Magnetic Properties in La _0.5 Sr _0.5 CoO ₃ Biegalski, Michael. D.; Takamura, Yayoi; Mehta, Apurva Advanced Materials Interfaces, Vol. 1, Issue 8 https://doi.org/10.1002/admi.201400203	journal	July 2014
Memristors for Energy-Efficient New Computing Paradigms Jeong, Doo Seok; Kim, Kyung Min; Kim, Sungho Advanced Electronic Materials, Vol. 2, Issue 9 https://doi.org/10.1002/aelm.201600090	journal	August 2016
Topotactic Phase Transformation in Epitaxial SrCo _1‐ _x Fe _x O ₃₋ _δ Thin Films Nguyen, Hien Thi Dieu; Granville, Simon; Seidel, Jan Advanced Electronic Materials, Vol. 6, Issue 4 https://doi.org/10.1002/aelm.201901204	journal	February 2020
Crystal Structure and Metal–Insulator Transition of La1−xSrxCoO3 Mineshige, Atsushi; Inaba, Minoru; Yao, Takeshi Journal of Solid State Chemistry, Vol. 121, Issue 2 https://doi.org/10.1006/jssc.1996.0058	journal	February 1996
Pseudopotentials periodic table: From H to Pu Dal Corso, Andrea Computational Materials Science, Vol. 95 https://doi.org/10.1016/j.commatsci.2014.07.043	journal	December 2014
Efficient implementation of core-excitation Bethe–Salpeter equation calculations Gilmore, K.; Vinson, John; Shirley, E. L. Computer Physics Communications, Vol. 197 https://doi.org/10.1016/j.cpc.2015.08.014	journal	December 2015
The PseudoDojo: Training and grading a 85 element optimized norm-conserving pseudopotential table van Setten, M. J.; Giantomassi, M.; Bousquet, E. Computer Physics Communications, Vol. 226 https://doi.org/10.1016/j.cpc.2018.01.012	journal	May 2018
In situ TEM studies of oxygen vacancy migration for electrically induced resistance change effect in cerium oxides Gao, Peng; Wang, Zhenzhong; Fu, Wangyang Micron, Vol. 41, Issue 4 https://doi.org/10.1016/j.micron.2009.11.010	journal	June 2010
Topotactic phase transformations by concerted dual-ion migration of B-site cation and oxygen in multivalent cobaltite La–Sr–Co–Ox films Li, Jia; Guan, Meng-Xue; Nan, Peng-Fei Nano Energy, Vol. 78 https://doi.org/10.1016/j.nanoen.2020.105215	journal	December 2020
Investigations of the electronic structure of d0 transition metal oxides belonging to the perovskite family Eng, Hank W.; Barnes, Paris W.; Auer, Benjamin M. Journal of Solid State Chemistry, Vol. 175, Issue 1 https://doi.org/10.1016/s0022-4596(03)00289-5	journal	October 2003
Mechanical properties of LaCoO3 based ceramics Orlovskaya, Nina; Kleveland, Kjersti; Grande, Tor Journal of the European Ceramic Society, Vol. 20, Issue 1 https://doi.org/10.1016/s0955-2219(99)00084-9	journal	January 2000
Resistive switching in transition metal oxides Sawa, Akihito Materials Today, Vol. 11, Issue 6 https://doi.org/10.1016/s1369-7021(08)70119-6	journal	June 2008
Predicting the Onset of Metal–Insulator Transitions in Transition Metal Oxides—A First Step in Designing Neuromorphic Devices Zhang, Shenli; Vo, Hien; Galli, Giulia Chemistry of Materials, Vol. 33, Issue 9 https://doi.org/10.1021/acs.chemmater.1c00061	journal	April 2021
Oxygen Evolution Reaction on La _{1– x} Sr _x CoO ₃ Perovskites: A Combined Experimental and Theoretical Study of Their Structural, Electronic, and Electrochemical Properties Cheng, Xi; Fabbri, Emiliana; Nachtegaal, Maarten Chemistry of Materials, Vol. 27, Issue 22 https://doi.org/10.1021/acs.chemmater.5b03138	journal	November 2015
Controlling Metal–Insulator Transitions in Vanadium Oxide Thin Films by Modifying Oxygen Stoichiometry Lee, Min-Han; Kalcheim, Yoav; Valle, Javier del ACS Applied Materials & Interfaces, Vol. 13, Issue 1 https://doi.org/10.1021/acsami.0c18327	journal	December 2020
In Situ Observation of Oxygen Vacancy Dynamics and Ordering in the Epitaxial LaCoO ₃ System Jang, Jae Hyuck; Kim, Young-Min; He, Qian ACS Nano, Vol. 11, Issue 7 https://doi.org/10.1021/acsnano.7b02188	journal	June 2017
O-K and Co-L XANES Study on Oxygen Intercalation in Perovskite SrCoO_3-δ Karvonen, Lassi; Valkeapaa, Markus; Liu, Ru-Shi Chemistry of Materials, Vol. 22, Issue 1, p. 70-76 https://doi.org/10.1021/cm9021563	journal	January 2010
Time-Resolved in Situ Studies of Oxygen Intercalation into SrCoO_2.5, Performed by Neutron Diffraction and X-ray Absorption Spectroscopy Le Toquin, Ronan; Paulus, Werner; Cousson, Alain Journal of the American Chemical Society, Vol. 128, Issue 40, p. 13161-13174 https://doi.org/10.1021/ja063207m	journal	October 2006
X-ray Absorption Spectroscopic Study on La _0.6 Sr _0.4 CoO _3−δ Cathode Materials Related with Oxygen Vacancy Formation Orikasa, Yuki; Ina, Toshiaki; Nakao, Takayuki The Journal of Physical Chemistry C, Vol. 115, Issue 33 https://doi.org/10.1021/jp2029642	journal	August 2011
Anomalous Interface and Surface Strontium Segregation in (La _{1– y} Sr _y ) ₂ CoO _4±δ /La _{1– x} Sr _x CoO _3−δ Heterostructured Thin Films Feng, Zhenxing; Yacoby, Yizhak; Gadre, Milind J. The Journal of Physical Chemistry Letters, Vol. 5, Issue 6 https://doi.org/10.1021/jz500293d	journal	March 2014
Direct observation of oxygen vacancy-driven structural and resistive phase transitions in La2/3Sr1/3MnO3 Yao, Lide; Inkinen, Sampo; van Dijken, Sebastiaan Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14544	journal	February 2017
Reversible redox reactions in an epitaxially stabilized SrCoOx oxygen sponge Jeen, Hyoungjeen; Choi, Woo Seok; Biegalski, Michael D. Nature Materials, Vol. 12, Issue 11 https://doi.org/10.1038/nmat3736	journal	August 2013
Understanding the metal-to-insulator transition in La1−xSrxCoO3−δ and its applications for neuromorphic computing Zhang, Shenli; Galli, Giulia npj Computational Materials, Vol. 6, Issue 1 https://doi.org/10.1038/s41524-020-00437-w	journal	November 2020
Resistive switching materials for information processing Wang, Zhongrui; Wu, Huaqiang; Burr, Geoffrey W. Nature Reviews Materials, Vol. 5, Issue 3 https://doi.org/10.1038/s41578-019-0159-3	journal	January 2020
Physics for neuromorphic computing Marković, Danijela; Mizrahi, Alice; Querlioz, Damien Nature Reviews Physics, Vol. 2, Issue 9 https://doi.org/10.1038/s42254-020-0208-2	journal	July 2020
Epitaxial La0.5Sr0.5CoO3 thin films: Structure, magnetism, and transport Torija, M. A.; Sharma, M.; Fitzsimmons, M. R. Journal of Applied Physics, Vol. 104, Issue 2 https://doi.org/10.1063/1.2955725	journal	July 2008
Lattice mismatch accommodation via oxygen vacancy ordering in epitaxial La _0.5 Sr _0.5 CoO _3-δ thin films Gazquez, J.; Bose, Shameek; Sharma, M. APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4809547	journal	July 2013
Tuning interfacial exchange interactions via electronic reconstruction in transition-metal oxide heterostructures Li, Binzhi; Chopdekar, Rajesh V.; N'Diaye, Alpha T. Applied Physics Letters, Vol. 109, Issue 15 https://doi.org/10.1063/1.4964407	journal	October 2016
Tutorial: Concepts for closely mimicking biological learning with memristive devices: Principles to emulate cellular forms of learning Ziegler, M.; Wenger, Ch.; Chicca, E. Journal of Applied Physics, Vol. 124, Issue 15 https://doi.org/10.1063/1.5042040	journal	October 2018
Challenges in materials and devices for resistive-switching-based neuromorphic computing del Valle, Javier; Ramírez, Juan Gabriel; Rozenberg, Marcelo J. Journal of Applied Physics, Vol. 124, Issue 21 https://doi.org/10.1063/1.5047800	journal	December 2018
Modification of magnetocrystalline anisotropy via ion-implantation Lee, Michael S.; Chopdekar, Rajesh V.; Shafer, Padraic AIP Advances, Vol. 10, Issue 4 https://doi.org/10.1063/1.5134867	journal	April 2020
Oxygen vacancies: The (in)visible friend of oxide electronics Gunkel, F.; Christensen, D. V.; Chen, Y. Z. Applied Physics Letters, Vol. 116, Issue 12 https://doi.org/10.1063/1.5143309	journal	March 2020
Volatile and non-volatile behavior of metal–insulator transition in VO ₂ through oxygen vacancies tunability for memory applications Moatti, Adele; Sachan, Ritesh; Narayan, Jagdish Journal of Applied Physics, Vol. 128, Issue 4 https://doi.org/10.1063/5.0006671	journal	July 2020
Carrier localization in perovskite nickelates from oxygen vacancies Kotiuga, Michele; Zhang, Zhen; Li, Jiarui Proceedings of the National Academy of Sciences, Vol. 116, Issue 44 https://doi.org/10.1073/pnas.1910490116	journal	October 2019
Operando characterization of conductive filaments during resistive switching in Mott VO ₂ Cheng, Shaobo; Lee, Min-Han; Li, Xing Proceedings of the National Academy of Sciences, Vol. 118, Issue 9 https://doi.org/10.1073/pnas.2013676118	journal	February 2021
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502 https://doi.org/10.1088/0953-8984/21/39/395502	journal	September 2009
Device and materials requirements for neuromorphic computing Islam, Raisul; Li, Haitong; Chen, Pai-Yu Journal of Physics D: Applied Physics, Vol. 52, Issue 11 https://doi.org/10.1088/1361-6463/aaf784	journal	January 2019
Topotactic transition between perovskite and brownmillerite phases for epitaxial LaCoO _{3− δ} films and effects thus resulted Huang, Hailin; Zhang, Jine; Zhang, Hui Journal of Physics D: Applied Physics, Vol. 53, Issue 15 https://doi.org/10.1088/1361-6463/ab6bef	journal	February 2020
Advanced capabilities for materials modelling with Quantum ESPRESSO Giannozzi, P.; Andreussi, O.; Brumme, T. Journal of Physics: Condensed Matter, Vol. 29, Issue 46 https://doi.org/10.1088/1361-648x/aa8f79	journal	October 2017
Direct Measurement of the Low-Temperature Spin-State Transition in LaCoO 3 Klie, R. F.; Zheng, J. C.; Zhu, Y. Physical Review Letters, Vol. 99, Issue 4 https://doi.org/10.1103/PhysRevLett.99.047203	journal	July 2007
Evolution of Metallicity in Vanadium Dioxide by Creation of Oxygen Vacancies Zhang, Zhen; Zuo, Fan; Wan, Chenghao Physical Review Applied, Vol. 7, Issue 3 https://doi.org/10.1103/physrevapplied.7.034008	journal	March 2017
Intrinsic luminescence excitation spectrum and extended x-ray absorption fine structure above the K edge in Ca F 2 Bianconi, A.; Jackson, D.; Monahan, K. Physical Review B, Vol. 17, Issue 4 https://doi.org/10.1103/physrevb.17.2021	journal	February 1978
Electronic structure and spin-state transition of LaCoO 3 Abbate, M.; Fuggle, J. C.; Fujimori, A. Physical Review B, Vol. 47, Issue 24 https://doi.org/10.1103/physrevb.47.16124	journal	June 1993
Thermally induced insulator-metal transition in LaCoO 3 : A view based on the Mott transition Tokura, Y.; Okimoto, Y.; Yamaguchi, S. Physical Review B, Vol. 58, Issue 4 https://doi.org/10.1103/physrevb.58.r1699	journal	July 1998
Hole-state density of La 1 − x Sr x CoO 3 − δ ( 0 <~ x <~ 0 . 5 ) across the insulator/metal phase boundary Moodenbaugh, A.; Nielsen, B.; Sambasivan, Sharadha Physical Review B, Vol. 61, Issue 8, p. 5666-5671 https://doi.org/10.1103/physrevb.61.5666	journal	February 2000
Pressure-induced insulating state in ( L a , S r ) CoO 3 Lengsdorf, R.; Ait-Tahar, M.; Saxena, S. S. Physical Review B, Vol. 69, Issue 14 https://doi.org/10.1103/physrevb.69.140403	journal	April 2004
Tuning the magnetic properties of La Co O 3 thin films by epitaxial strain Fuchs, D.; Arac, E.; Pinta, C. Physical Review B, Vol. 77, Issue 1 https://doi.org/10.1103/physrevb.77.014434	journal	January 2008
Bethe-Salpeter equation calculations of core excitation spectra Vinson, J.; Rehr, J. J.; Kas, J. J. Physical Review B, Vol. 83, Issue 11 https://doi.org/10.1103/physrevb.83.115106	journal	March 2011
Optimized norm-conserving Vanderbilt pseudopotentials Hamann, D. R. Physical Review B, Vol. 88, Issue 8 https://doi.org/10.1103/physrevb.88.085117	journal	August 2013
Role of oxygen vacancy in the spin-state change and magnetic ordering in SrCoO 3 − δ Lim, Jinyoung; Yu, Jaejun Physical Review B, Vol. 98, Issue 8 https://doi.org/10.1103/physrevb.98.085106	journal	August 2018
Evolution of Magnetic Oxygen States in Sr-Doped LaCoO 3 Medling, S.; Lee, Y.; Zheng, H. Physical Review Letters, Vol. 109, Issue 15 https://doi.org/10.1103/physrevlett.109.157204	journal	October 2012
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
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
Ionic tuning of cobaltites at the nanoscale Gilbert, Dustin A.; Grutter, Alexander J.; Murray, Peyton D. Physical Review Materials, Vol. 2, Issue 10 https://doi.org/10.1103/physrevmaterials.2.104402	journal	October 2018
X-ray nanodiffraction studies of ionically controlled nanoscale phase separation in cobaltites Rippy, Geoffery; Trinh, Lacey; Kane, Alexander M. Physical Review Materials, Vol. 3, Issue 8 https://doi.org/10.1103/physrevmaterials.3.082001	journal	August 2019
Cation and anion topotactic transformations in cobaltite thin films leading to Ruddlesden-Popper phases Chiu, I-Ting; Lee, Min-Han; Cheng, Shaobo Physical Review Materials, Vol. 5, Issue 6 https://doi.org/10.1103/physrevmaterials.5.064416	journal	June 2021
Suppression of Metal-Insulator Transition in VO2 by Electric Field-Induced Oxygen Vacancy Formation Jeong, J.; Aetukuri, N.; Graf, T. Science, Vol. 339, Issue 6126 https://doi.org/10.1126/science.1230512	journal	March 2013
Electrochemistry of Mixed Oxygen Ion and Electron Conducting Electrodes in Solid Electrolyte Cells Chueh, William C.; Haile, Sossina M. Annual Review of Chemical and Biomolecular Engineering, Vol. 3, Issue 1 https://doi.org/10.1146/annurev-chembioeng-073009-101000	journal	July 2012
Quantum materials for brain sciences and artificial intelligence Ramanathan, Shriram MRS Bulletin, Vol. 43, Issue 7 https://doi.org/10.1557/mrs.2018.147	journal	July 2018

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Cation and anion topotactic transformations in cobaltite thin films leading to Ruddlesden-Popper phases

Journal Article · Wed Jun 23 20:00:00 EDT 2021 · Physical Review Materials · OSTI ID:1798563

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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defects in solids
oxygen
perovskites
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Determining the Oxygen Stoichiometry of Cobaltite Thin Films

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