Layer Resolved Cr Oxidation State Modulation in Epitaxial SrFe0.67Cr0.33O3−δ Thin Films

Koirala, Krishna Prasad; Hossain, Mohammad Delower; Wang, Le; Zhuo, Zengqing; Yang, Wanli; Bowden, Mark E.; Spurgeon, Steven R.; Wang, Chongmin; Sushko, Peter V.; Du, Yingge

doi:10.1021/acs.nanolett.4c03660

Layer Resolved Cr Oxidation State Modulation in Epitaxial SrFe_0.67Cr_0.33O_3−δ Thin Films

Journal Article · Thu Oct 31 00:00:00 EDT 2024 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.4c03660· OSTI ID:2543078

Koirala, Krishna Prasad ^[1]; Hossain, Mohammad Delower ^[1]; ^[1]; ^[2]; ^[2]; ^[1]; ^[3]; ^[1]; ^[1]; ^[1]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); University of Washington, Seattle, WA (United States)

Understanding how doping influences physicochemical properties of ABO₃ perovskite oxides is critical for tailoring their functionalities. In this study, SrFe_0.67Cr_0.33O_3−δ epitaxial thin films were used to examine the effects of Fe and Cr competition on structure and B-site cation oxidation states. The films exhibit a perovskite-like structure near the film/substrate interface, while a brownmillerite-like structure with horizontal oxygen vacancy channels predominates near the surface. Electron energy loss spectroscopy shows Fe remains Fe³⁺, while Cr varies from ∼Cr³⁺ (tetrahedral layers) to ∼Cr⁴⁺ (octahedral layers) within brownmillerite phases and becomes ∼Cr^4.5+ in perovskite-like phases. Theoretical simulations indicate that Cr–O bond arrangements and the way oxygen vacancies interact with Cr and Fe drive Cr charge disproportionation. High-valent Cr cations introduce additional densities of states near the Fermi level, reducing the optical bandgap from ∼2.0 eV (SrFeO_2.5) to ∼1.7 eV (SrFe_0.67Cr_0.33O_3−δ). In conclusion, these findings offer insights into B-site cation doping in the perovskite oxide framework.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: National Energy Research Scientific Computing Center (NERSC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC05-76RL01830

OSTI ID:: 2543078

Alternate ID(s):: OSTI ID: 2573772

Report Number(s):: PNNL-SA--202083; ark:/13030/qt96j651mn; https://escholarship.org/uc/item/96j651mn

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 45 Vol. 24; ISSN 1530-6992; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (64)

Tuning Bifunctional Oxygen Electrocatalysts by Changing the A-Site Rare-Earth Element in Perovskite Nickelates Wang, Le; Stoerzinger, Kelsey A.; Chang, Lei Advanced Functional Materials, Vol. 28, Issue 39 https://doi.org/10.1002/adfm.201803712	journal	August 2018
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
Orienting Oxygen Vacancies for Fast Catalytic Reaction Jeen, Hyoungjeen; Bi, Zhonghe; Choi, Woo Seok Advanced Materials, Vol. 25, Issue 44 https://doi.org/10.1002/adma.201302919	journal	October 2013
Control of Functional Responses Via Reversible Oxygen Loss in La _{1- x} Sr _x FeO _3-δ Films Xie, Yujun; Scafetta, Mark D.; Sichel-Tissot, Rebecca J. Advanced Materials, Vol. 26, Issue 9 https://doi.org/10.1002/adma.201304374	journal	November 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
A Ferrite Synaptic Transistor with Topotactic Transformation Ge, Chen; Liu, Chang‐xiang; Zhou, Qing‐li Advanced Materials, Vol. 31, Issue 19 https://doi.org/10.1002/adma.201900379	journal	March 2019
Topotactic Phase Transition Driving Memristive Behavior Nallagatla, Venkata R.; Heisig, Thomas; Baeumer, Christoph Advanced Materials, Vol. 31, Issue 40 https://doi.org/10.1002/adma.201903391	journal	August 2019
Nanoscale Topotactic Phase Transformation in SrFeO _x Epitaxial Thin Films for High‐Density Resistive Switching Memory Tian, Junjiang; Wu, Haijun; Fan, Zhen Advanced Materials, Vol. 31, Issue 49 https://doi.org/10.1002/adma.201903679	journal	October 2019
Activating Lattice Oxygen in Perovskite Oxide by B‐Site Cation Doping for Modulated Stability and Activity at Elevated Temperatures Chen, Huijun; Lim, Chaesung; Zhou, Mengzhen Advanced Science, Vol. 8, Issue 22 https://doi.org/10.1002/advs.202102713	journal	October 2021
Anion Doping: A New Strategy for Developing High-Performance Perovskite-Type Cathode Materials of Solid Oxide Fuel Cells Zhang, Zhenbao; Zhu, Yinlong; Zhong, Yijun Advanced Energy Materials, Vol. 7, Issue 17 https://doi.org/10.1002/aenm.201700242	journal	May 2017
Deciphering the oxygen absorption pre‐edge: a caveat on its application for probing oxygen redox reactions in batteries Roychoudhury, Subhayan; Qiao, Ruimin; Zhuo, Zengqing ENERGY & ENVIRONMENTAL MATERIALS https://doi.org/10.1002/eem2.12119	journal	August 2020
Evidence for a Crucial Role Played by Oxygen Vacancies in LaMnO3 Resistive Switching Memories Xu, Zhong-tang; Jin, Kui-juan; Gu, Lin Small, Vol. 8, Issue 8 https://doi.org/10.1002/smll.201101796	journal	February 2012
Electrical Properties of the Ferrite SrFeOy at High Temperatures Kozhevnikov, V. L.; Leonidov, I. A.; Patrakeev, M. V. Journal of Solid State Chemistry, Vol. 158, Issue 2 https://doi.org/10.1006/jssc.2001.9120	journal	May 2001
Exploring the Spatial Control of Topotactic Phase Transitions Using Vertically Oriented Epitaxial Interfaces Zhang, Wenrui; Zhang, Jie; Cheng, Shaobo Nano-Micro Letters, Vol. 14, Issue 1 https://doi.org/10.1007/s40820-021-00752-x	journal	December 2021
The crystal and magnetic structures of Sr2CoFeO5 Battle, P. D.; Gibb, T. C.; Lightfoot, P. Journal of Solid State Chemistry, Vol. 76, Issue 2 https://doi.org/10.1016/0022-4596(88)90227-7	journal	October 1988
A study of the oxygen-deficient perovskite system Sr2Fe2−xCrxO5+y by Mössbauer spectroscopy Gibb, T. C.; Matsuo, M. Journal of Solid State Chemistry, Vol. 86, Issue 2 https://doi.org/10.1016/0022-4596(90)90131-G	journal	June 1990
Preparation and gas-sensing properties of perovskite-type SrFeO3 oxide Wang, Yude; Chen, Jingbo; Wu, Xinghui Materials Letters, Vol. 49, Issue 6 https://doi.org/10.1016/S0167-577X(00)00400-6	journal	July 2001
Controlling the A-site deficiency and oxygen vacancies by donor-doping in pre-reductive-sintered thermoelectric SrTiO3 ceramics Fu, Qing-Qiao; Gu, Hui; Xing, Juan-Juan Acta Materialia, Vol. 229 https://doi.org/10.1016/j.actamat.2022.117785	journal	May 2022
Alternative B-site-doped La0.6Sr0.4Co0.2Fe0.8-xMxO3 (M = Ni, Cu, Nb; x = 0, 0.1, 0.2) as innovative cathode material for LT-SOFC with enhanced charge transfer and oxygen ion diffusion Jia, Weihua; Wang, Yuqi; Huang, Jianbing Applied Energy, Vol. 353 https://doi.org/10.1016/j.apenergy.2023.122096	journal	January 2024
Determination of chromium valence over the range Cr(0)–Cr(VI) by electron energy loss spectroscopy Daulton, Tyrone L.; Little, Brenda J. Ultramicroscopy, Vol. 106, Issue 7 https://doi.org/10.1016/j.ultramic.2006.02.005	journal	May 2006
Synthesis and Characterization of SrFe_xMn_1–x(O,F)_3−δ Oxide (δ = 0 and 0.5) and Oxyfluoride Perovskite Films Wang, Jiayi; Lefler, Benjamin M.; May, Steven J. Inorganic Chemistry, Vol. 59, Issue 14 https://doi.org/10.1021/acs.inorgchem.0c01148	journal	July 2020
Dynamics of Anisotropic Oxygen-Ion Migration in Strained Cobaltites Zhang, Qinghua; Meng, Fanqi; Gao, Ang Nano Letters, Vol. 21, Issue 24 https://doi.org/10.1021/acs.nanolett.1c04057	journal	December 2021
Oxygen Vacancy Induced Room-Temperature Metal–Insulator Transition in Nickelate Films and Its Potential Application in Photovoltaics Wang, Le; Dash, Sibashisa; Chang, Lei ACS Applied Materials & Interfaces, Vol. 8, Issue 15 https://doi.org/10.1021/acsami.6b00650	journal	April 2016
Directing Oxygen Vacancy Channels in SrFeO _2.5 Epitaxial Thin Films Khare, Amit; Lee, Jaekwang; Park, Jaeseoung ACS Applied Materials & Interfaces, Vol. 10, Issue 5 https://doi.org/10.1021/acsami.7b17377	journal	January 2018
Electric Field Control of Phase Transition and Tunable Resistive Switching in SrFeO _2.5 Saleem, Muhammad Shahrukh; Cui, Bin; Song, Cheng ACS Applied Materials & Interfaces, Vol. 11, Issue 6 https://doi.org/10.1021/acsami.8b18251	journal	January 2019
Self-Assembled Multiphase Nanocomposite SrCo_1–xFe_xO_3-δ Thin Films with Voltage-Controlled Magnetism for Spintronic Applications Cho, Eunsoo; Kumar, Abinash; Ning, Shuai ACS Applied Nano Materials, Vol. 5, Issue 10 https://doi.org/10.1021/acsanm.2c03019	journal	September 2022
Direct Mapping of Fluorine in Cation Disordered Rocksalt Cathodes Koirala, Krishna Prasad; Jiang, Lin; Patil, Shripad ACS Energy Letters, Vol. 9, Issue 1 https://doi.org/10.1021/acsenergylett.3c02154	journal	November 2023
Voltage Control of Magnetism above Room Temperature in Epitaxial SrCo _{1– x} Fe _x O _3−δ Ning, Shuai; Zhang, Qiqi; Occhialini, Connor ACS Nano, Vol. 14, Issue 7 https://doi.org/10.1021/acsnano.0c03750	journal	June 2020
Control of Oxygen Vacancy Ordering in Brownmillerite Thin Films via Ionic Liquid Gating Han, Hyeon; Sharma, Arpit; Meyerheim, Holger L. ACS Nano, Vol. 16, Issue 4 https://doi.org/10.1021/acsnano.2c00012	journal	April 2022
Effect of Antisite Defects on the Formation of Oxygen Vacancies in Sr ₂ FeMoO ₆ : Implications for Ion and Electron Transport Muñoz-García, Ana B.; Pavone, Michele; Carter, Emily A. Chemistry of Materials, Vol. 23, Issue 20 https://doi.org/10.1021/cm201799c	journal	October 2011
Local and Average Structures and Magnetic Properties of Sr ₂ FeMnO _{5+ y} , y = 0.0, 0.5. Comparisons with Ca ₂ FeMnO ₅ and the Effect of the A-Site Cation Ramezanipour, Farshid; Greedan, John E.; Siewenie, Joan Inorganic Chemistry, Vol. 50, Issue 16 https://doi.org/10.1021/ic200919m	journal	August 2011
A Vacancy-Disordered, Oxygen-Deficient Perovskite with Long-Range Magnetic Ordering: Local and Average Structures and Magnetic Properties of Sr ₂ Fe _1.5 Cr _0.5 O ₅ Ramezanipour, Farshid; Greedan, John E.; Siewenie, Joan Inorganic Chemistry, Vol. 51, Issue 4 https://doi.org/10.1021/ic202590r	journal	January 2012
Factors Governing Oxygen Vacancy Formation in Oxide Perovskites Wexler, Robert B.; Gautam, Gopalakrishnan Sai; Stechel, Ellen B. Journal of the American Chemical Society, Vol. 143, Issue 33 https://doi.org/10.1021/jacs.1c05570	journal	August 2021
Electric-field control of tri-state phase transformation with a selective dual-ion switch Lu, Nianpeng; Zhang, Pengfei; Zhang, Qinghua Nature, Vol. 546, Issue 7656 https://doi.org/10.1038/nature22389	journal	May 2017
Anisotropic oxygen diffusion at low temperature in perovskite-structure iron oxides Inoue, Satoru; Kawai, Masanori; Ichikawa, Noriya Nature Chemistry, Vol. 2, Issue 3, p. 213-217 https://doi.org/10.1038/nchem.547	journal	February 2010
Reversible nano-structuring of SrCrO3-δ through oxidation and reduction at low temperature Zhang, K. H. L.; Sushko, P. V.; Colby, R. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5669	journal	August 2014
Probing oxygen vacancy concentration and homogeneity in solid-oxide fuel-cell cathode materials on the subunit-cell level Kim, Young-Min; He, Jun; Biegalski, Michael D. Nature Materials, Vol. 11, Issue 10 https://doi.org/10.1038/nmat3393	journal	August 2012
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
Atomic-resolution imaging of electrically induced oxygen vacancy migration and phase transformation in SrCoO2.5-σ Zhang, Qinghua; He, Xu; Shi, Jinan Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00121-6	journal	July 2017
Probing dopant segregation in distinct cation sites at perovskite oxide polycrystal interfaces Yoon, Hye-In; Lee, Dong-Kyu; Bae, Hyung Bin Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01134-x	journal	November 2017
Near-room temperature ferromagnetic insulating state in highly distorted LaCoO2.5 with CoO5 square pyramids Zhang, Qinghua; Gao, Ang; Meng, Fanqi Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-22099-y	journal	March 2021
Emergent and robust ferromagnetic-insulating state in highly strained ferroelastic LaCoO3 thin films Li, Dong; Wang, Hongguang; Li, Kaifeng Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-39369-6	journal	June 2023
Guided anisotropic oxygen transport in vacancy ordered oxides Yang, Zhenzhong; Wang, Le; Dhas, Jeffrey A. Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-40746-4	journal	September 2023
Phase contrast scanning transmission electron microscopy imaging of light and heavy atoms at the limit of contrast and resolution Yücelen, Emrah; Lazić, Ivan; Bosch, Eric G. T. Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-20377-2	journal	February 2018
Disorder and compositional dependences in Urbach-Martienssen tails in amorphous (GeTe)x(Sb2Te3)1−x alloys Shportko, K. V. Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-42634-8	journal	April 2019
Oxygen-Vacancy-Induced Antiferromagnetism to Ferromagnetism Transformation in Eu0.5Ba0.5TiO3−δ Multiferroic Thin Films Li, Weiwei; Zhao, Run; Wang, Le Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02618	journal	September 2013
First-principles exploration of oxygen vacancy impact on electronic and optical properties of ABO _3−δ (A = La, Sr; B = Cr, Mn) perovskites Park, Jongwoo; Wu, Yu-Ning; Saidi, Wissam A. Physical Chemistry Chemical Physics, Vol. 22, Issue 46 https://doi.org/10.1039/D0CP05445C	journal	January 2020
Interface-related phenomena in epitaxial complex oxide ferroics across different thin film platforms: opportunities and challenges MacManus-Driscoll, Judith L.; Wu, Rui; Li, Weiwei Materials Horizons, Vol. 10, Issue 4 https://doi.org/10.1039/D2MH01527G	journal	January 2023
The effect of the B-site cation and oxygen stoichiometry on the local and average crystal and magnetic structures of Sr2Fe1.9M0.1O5+y (M = Mn, Cr, Co; y = 0, 0.5) Ramezanipour, Farshid; Greedan, John E.; Cranswick, Lachlan M. D. Journal of Materials Chemistry, Vol. 22, Issue 19 https://doi.org/10.1039/c2jm30957b	journal	January 2012
The origin of oxygen in oxide thin films: Role of the substrate Schneider, C. W.; Esposito, M.; Marozau, I. Applied Physics Letters, Vol. 97, Issue 19 https://doi.org/10.1063/1.3515849	journal	November 2010
Irradiation induced modification in transport properties of LaNiO₃ thin films: An x-ray absorption study Kumar, Yogesh; Pratap Singh, Abhinav; Sharma, S. K. Applied Physics Letters, Vol. 101, Issue 11 https://doi.org/10.1063/1.4752005	journal	September 2012
Brownmillerite phase formation and evolution in epitaxial strontium ferrite heterostructures Wang, Le; Yang, Zhenzhong; Bowden, Mark E. Applied Physics Letters, Vol. 114, Issue 23 https://doi.org/10.1063/1.5096769	journal	June 2019
Extending the Kinetic and Thermodynamic Limits of Molecular-Beam Epitaxy Utilizing Suboxide Sources or Metal-Oxide-Catalyzed Epitaxy Vogt, Patrick; Hensling, Felix V. E.; Azizie, Kathy Physical Review Applied, Vol. 17, Issue 3 https://doi.org/10.1103/PhysRevApplied.17.034021	journal	March 2022
Insulator-metal transition and giant magnetoresistance in La 1 − x Sr x MnO 3 Urushibara, A.; Moritomo, Y.; Arima, T. Physical Review B, Vol. 51, Issue 20 https://doi.org/10.1103/PhysRevB.51.14103	journal	May 1995
Strain-controlled oxygen vacancy formation and ordering in CaMnO 3 Aschauer, Ulrich; Pfenninger, Reto; Selbach, Sverre M. Physical Review B, Vol. 88, Issue 5 https://doi.org/10.1103/PhysRevB.88.054111	journal	August 2013
Hole-induced insulator-to-metal transition in L a 1 − x S r x Cr O 3 epitaxial films Zhang, K. H. L.; Du, Y.; Sushko, P. V. Physical Review B, Vol. 91, Issue 15 https://doi.org/10.1103/PhysRevB.91.155129	journal	April 2015
Hole-induced electronic and optical transitions in L a 1 − x S r x Fe O 3 epitaxial thin films Wang, Le; Du, Yingge; Sushko, Peter V. Physical Review Materials, Vol. 3, Issue 2 https://doi.org/10.1103/PhysRevMaterials.3.025401	journal	February 2019
Oxygen diffusion in oxide thin films grown on SrTi O 3 Schneider, Christof W.; Döbeli, Max; Richter, Christoph Physical Review Materials, Vol. 3, Issue 12 https://doi.org/10.1103/PhysRevMaterials.3.123401	journal	December 2019
Band Alignment and Charge Transfer in Complex Oxide Interfaces Zhong, Zhicheng; Hansmann, Philipp Physical Review X, Vol. 7, Issue 1 https://doi.org/10.1103/PhysRevX.7.011023	journal	March 2017
Chemical Expansivity of Electrochemical Ceramics Adler, Stuart B. Journal of the American Ceramic Society, Vol. 84, Issue 9 https://doi.org/10.1111/j.1151-2916.2001.tb00968.x	journal	September 2001
Epitaxial BiFeO₃ Multiferroic Thin Film Heterostructures Wang, J.; Neaton, J. B.; Zheng, H. Science, Vol. 299, Issue 5613, p. 1719-1722 https://doi.org/10.1126/science.1080615	journal	March 2003
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles Suntivich, J.; May, K. J.; Gasteiger, H. A. Science, Vol. 334, Issue 6061 https://doi.org/10.1126/science.1212858	journal	October 2011
Visibility of Single Atoms Crewe, A. V.; Wall, J.; Langmore, J. Science, Vol. 168, Issue 3937 https://doi.org/10.1126/science.168.3937.1338	journal	June 1970
Scanning transmission electron microscopy for advanced characterization of ferroic materials Cabral, Matthew J.; Chen, Zibin; Liao, Xiaozhou Microstructures, Vol. 3, Issue 4 https://doi.org/10.20517/microstructures.2023.39	journal	October 2023

Similar Records

Structural studies of SrFeO{sub 3} and SrFe{sub 0.5}Nb{sub 0.5}O{sub 3} by employing XRD and XANES spectroscopic techniques

Journal Article · Sat Oct 15 00:00:00 EDT 2011 · Materials Characterization · OSTI ID:22066342

Synthesis and characterization of Mo-doped SrFeO_3-δ as cathode materials for solid oxide fuel cells

Journal Article · Wed Feb 29 23:00:00 EST 2012 · Journal of Power Sources · OSTI ID:1383110

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
STEAM/EELS
SrFeO2.5
SrFeO2.5
brownmillerite
cation doping
cations
epitaxial thin films
layers
oxidation state
oxygen

Layer Resolved Cr Oxidation State Modulation in Epitaxial SrFe0.67Cr0.33O3−δ Thin Films

Citation Formats

References (64)

Similar Records

Related Subjects

Layer Resolved Cr Oxidation State Modulation in Epitaxial SrFe_0.67Cr_0.33O_3−δ Thin Films