Topotactic Reduction‐Driven Crystal Field Excitations in Brownmillerite Manganite Thin Films

Jin, Feng; Fan, Shiyu; Gu, Mingqiang; Lv, Qiming; Ge, Min; Zhang, Zixun; Zhang, Jinfeng; Lu, Jingdi; Kim, Taehun; Bhartiya, Vivek; Huang, Zhen; Wang, Lingfei; Bisogni, Valentina; Pelliciari, Jonathan; Wu, Wenbin

doi:10.1002/adfm.202501893

Topotactic Reduction‐Driven Crystal Field Excitations in Brownmillerite Manganite Thin Films

Journal Article · Wed Feb 19 00:00:00 EST 2025 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.202501893· OSTI ID:2525844

^[1]; Fan, Shiyu ^[2]; Gu, Mingqiang ^[3]; Lv, Qiming ^[1]; Ge, Min ^[1]; Zhang, Zixun ^[1]; Zhang, Jinfeng ^[1]; Lu, Jingdi ^[1]; Kim, Taehun ^[2]; Bhartiya, Vivek ^[2]; Huang, Zhen ^[4]; Wang, Lingfei ^[1]; Bisogni, Valentina ^[2]; Pelliciari, Jonathan ^[2]; Wu, Wenbin ^[5]

University of Science and Technology of China, Hefei (China)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Southern University of Science and Technology (SUSTech), Shenzhen (China); Sun Yat‐sen University, Shenzhen (China)
Anhui University, Hefei (China)
University of Science and Technology of China, Hefei (China); Anhui University, Hefei (China); Chinese Academy of Sciences (CAS), Hefei (China)

Topotactic reduction of perovskite oxides offers a powerful approach for discovering novel phenomena, such as superconducting infinite-layer nickelates and polar metallicity, and is commonly accompanied by the emergence of multiple valence states and/or complex crystal fields of transition metals. However, understanding the complex interplay between crystal chemistry, electronic structure, and physical properties at the spin- and orbital-resolved levels in these reduced systems remains elusive. Here, in this study, x-ray absorption spectroscopy, resonant inelastic x-ray scattering (RIXS), and density functional theory calculations are used to uncover topotactic metal-insulator transition and orbital-specific crystal field excitations in brownmillerite La_0.67Ca_0.33MnO_2.5 thin films. The Mn valence states are found to be Mn²⁺/Mn³⁺, along with their corresponding populations at octahedral and tetrahedral sites, which effectively weaken the Mn-O hybridization compared to the parent perovskite phase. As a result, La_0.67Ca_0.33MnO_2.5 films exhibit an antiferromagnetic insulating ground state. Moreover, by combining the RIXS measurements on selected single-valence manganites, specifically MnO, LaMnO₃, and CaMnO₃, with orbital- and spin-resolved density-of-states calculations, the study identifies the dd excitations of octahedrally and tetrahedrally coordinated Mn²⁺/Mn³⁺ ions, directly linking the microscopic electronic structure to the macroscopic magnetic/electrical properties.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: Guangdong Innovative and Entrepreneurial Research Team Program; National Key Research and Development Program of China; National Natural Science Foundation of China (NSFC); Natural Science Foundation of Anhui Province; Natural Science Foundation of Guangdong Province; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2525844

Report Number(s):: BNL--227627-2025-JAAM

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 28 Vol. 35; ISSN 1616-301X; ISSN 1616-3028

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

Versatile and Highly Efficient Controls of Reversible Topotactic Metal–Insulator Transitions through Proton Intercalation Chen, Shanquan; Zhou, Haiping; Ye, Xing Advanced Functional Materials, Vol. 29, Issue 50 https://doi.org/10.1002/adfm.201907072	journal	September 2019
Topotactic Transition: A Promising Opportunity for Creating New Oxides Meng, Ziang; Yan, Han; Qin, Peixin Advanced Functional Materials, Vol. 33, Issue 46 https://doi.org/10.1002/adfm.202305225	journal	June 2023
Epitaxial Oxygen Getter for a Brownmillerite Phase Transformation in Manganite Films Ferguson, J. D.; Kim, Y.; Kourkoutis, L. Fitting Advanced Materials, Vol. 23, Issue 10 https://doi.org/10.1002/adma.201003581	journal	January 2011
Structure and Properties of Functional Oxide Thin Films: Insights From Electronic-Structure Calculations Rondinelli, James M.; Spaldin, Nicola A. Advanced Materials, Vol. 23, Issue 30 https://doi.org/10.1002/adma.201101152	journal	July 2011
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
Electron-Beam-Induced Perovskite-Brownmillerite-Perovskite Structural Phase Transitions in Epitaxial La _2/3 Sr _1/3 MnO ₃ Films Yao, Lide; Majumdar, Sayani; Äkäslompolo, Laura Advanced Materials, Vol. 26, Issue 18 https://doi.org/10.1002/adma.201305656	journal	February 2014
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
Reversible Control of Physical Properties via an Oxygen-Vacancy-Driven Topotactic Transition in Epitaxial La _0.7 Sr _0.3 MnO ₃₋ _δ Thin Films Cao, Lei; Petracic, Oleg; Zakalek, Paul Advanced Materials, Vol. 31, Issue 7 https://doi.org/10.1002/adma.201806183	journal	December 2018
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
Magnetic Structure and Electronic Study of Complex Oxygen‐Deficient Manganites Cortés‐Gil, Raquel; Hernando, María; Ruiz‐González, M. Luisa Chemistry – A European Journal, Vol. 14, Issue 29 https://doi.org/10.1002/chem.200800723	journal	August 2008
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
In-situ investigation on the oxygen vacancy-driven topotactic phase transition in charge-orbital ordered Nd0.5Sr0.5MnO3 films Xiao, Andong; Liu, Yao; Yang, Tianzi Acta Materialia, Vol. 245 https://doi.org/10.1016/j.actamat.2022.118616	journal	February 2023
Atomic-scale observation of strain-dependent reversible topotactic transition in La0.7Sr0.3MnOx films under an ultra-high vacuum environment Hu, Kejun; Zhang, Xinyu; Chen, Pingfan Materials Today Physics, Vol. 29 https://doi.org/10.1016/j.mtphys.2022.100922	journal	December 2022
Synthesis and Structural Characterization of La _{1− x} A _x MnO _2.5 (A = Ba, Sr, Ca) Phases: Mapping the Variants of the Brownmillerite Structure Parsons, Thomas G.; D’Hondt, Hans; Hadermann, Joke Chemistry of Materials, Vol. 21, Issue 22 https://doi.org/10.1021/cm902535m	journal	November 2009
Infinite-layer iron oxide with a square-planar coordination Tsujimoto, Y.; Tassel, C.; Hayashi, N. Nature, Vol. 450, Issue 7172, p. 1062-1065 https://doi.org/10.1038/nature06382	journal	December 2007
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
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
Emergent phenomena at oxide interfaces Hwang, H. Y.; Iwasa, Y.; Kawasaki, M. Nature Materials, Vol. 11, Issue 2 https://doi.org/10.1038/nmat3223	journal	January 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
Symmetry mismatch-driven perpendicular magnetic anisotropy for perovskite/brownmillerite heterostructures Zhang, Jing; Zhong, Zhicheng; Guan, Xiangxiang Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04304-7	journal	May 2018
Electronic structure of the parent compound of superconducting infinite-layer nickelates Hepting, M.; Li, D.; Jia, C. J. Nature Materials, Vol. 19, Issue 4 https://doi.org/10.1038/s41563-019-0585-z	journal	January 2020
Superconductivity in a quintuple-layer square-planar nickelate Pan, Grace A.; Ferenc Segedin, Dan; LaBollita, Harrison Nature Materials, Vol. 21, Issue 2 https://doi.org/10.1038/s41563-021-01142-9	journal	November 2021
Absence of 3a0 charge density wave order in the infinite-layer nickelate NdNiO2 Parzyck, C. T.; Gupta, N. K.; Wu, Y. Nature Materials, Vol. 23, Issue 4 https://doi.org/10.1038/s41563-024-01797-0	journal	January 2024
A correlated ferromagnetic polar metal by design Zhang, Jianbing; Shen, Shengchun; Puggioni, Danilo Nature Materials, Vol. 23, Issue 7 https://doi.org/10.1038/s41563-024-01856-6	journal	April 2024
Current-driven dynamics and ratchet effect of skyrmion bubbles in a ferrimagnetic insulator Vélez, Saül; Ruiz-Gómez, Sandra; Schaab, Jakob Nature Nanotechnology, Vol. 17, Issue 8 https://doi.org/10.1038/s41565-022-01144-x	journal	July 2022
Superconductivity in an infinite-layer nickelate Li, Danfeng; Lee, Kyuho; Wang, Bai Yang Nature, Vol. 572, Issue 7771 https://doi.org/10.1038/s41586-019-1496-5	journal	August 2019
Geometric frustration of Jahn–Teller order in the infinite-layer lattice Kim, Woo Jin; Smeaton, Michelle A.; Jia, Chunjing Nature, Vol. 615, Issue 7951 https://doi.org/10.1038/s41586-022-05681-2	journal	February 2023
Signatures of superconductivity near 80 K in a nickelate under high pressure Sun, Hualei; Huo, Mengwu; Hu, Xunwu Nature, Vol. 621, Issue 7979 https://doi.org/10.1038/s41586-023-06408-7	journal	July 2023
Spatially Confined Spin Polarization and magnetic sublattice control in (La,Sr)MnO3−δ Thin Films by Oxygen Vacancy Ordering Moreau, Magnus; Selbach, Sverre M.; Tybell, Thomas Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-04103-y	journal	June 2017
Single-crystal epitaxial thin films of SrFeO2 with FeO2 “infinite layers” Inoue, Satoru; Kawai, Masanori; Shimakawa, Yuichi Applied Physics Letters, Vol. 92, Issue 16 https://doi.org/10.1063/1.2913164	journal	April 2008
Reversible changes of epitaxial thin films from perovskite LaNiO3 to infinite-layer structure LaNiO2 Kawai, Masanori; Inoue, Satoru; Mizumaki, Masaichiro Applied Physics Letters, Vol. 94, Issue 8 https://doi.org/10.1063/1.3078276	journal	February 2009
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
Labyrinth-type domain structure of heteroepitaxial SrMnO _2.5 film Kobayashi, Shunsuke; Ikuhara, Yuichi; Yamamoto, Takahisa Applied Physics Letters, Vol. 102, Issue 23 https://doi.org/10.1063/1.4811152	journal	June 2013
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
Strain-driven formation of epitaxial nanostructures in brownmillerite strontium cobaltite thin films Han, Hyeon; Deniz, Hakan; Parkin, Stuart S. P. Proceedings of the National Academy of Sciences, Vol. 120, Issue 12 https://doi.org/10.1073/pnas.2221651120	journal	March 2023
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators Liechtenstein, A. I.; Anisimov, V. I.; Zaanen, J. Physical Review B, Vol. 52, Issue 8 https://doi.org/10.1103/PhysRevB.52.R5467	journal	August 1995
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Resonant inelastic x-ray scattering study of the hole-doped manganites La 1 − x Sr x MnO 3 ( x = 0.2 , 0.4) Ishii, K.; Inami, T.; Ohwada, K. Physical Review B, Vol. 70, Issue 22 https://doi.org/10.1103/PhysRevB.70.224437	journal	December 2004
Mn valence instability in La 2 ∕ 3 Ca 1 ∕ 3 Mn O 3 thin films Valencia, S.; Gaupp, A.; Gudat, W. Physical Review B, Vol. 73, Issue 10 https://doi.org/10.1103/PhysRevB.73.104402	journal	March 2006
Assessing the Perdew-Burke-Ernzerhof exchange-correlation density functional revised for metallic bulk and surface systems Ropo, M.; Kokko, K.; Vitos, L. Physical Review B, Vol. 77, Issue 19 https://doi.org/10.1103/PhysRevB.77.195445	journal	May 2008
Theoretical analysis of resonant inelastic x-ray scattering spectra in LaMnO 3 Semba, Taeko; Takahashi, Manabu; Igarashi, Jun-ichi Physical Review B, Vol. 78, Issue 15 https://doi.org/10.1103/PhysRevB.78.155111	journal	October 2008
Jahn-Teller distortion and magnetic structure in LaMnO 3 : A first-principles theoretical study with full structure optimizations Hashimoto, T.; Ishibashi, S.; Terakura, K. Physical Review B, Vol. 82, Issue 4 https://doi.org/10.1103/PhysRevB.82.045124	journal	July 2010
Multiplet ligand-field theory using Wannier orbitals Haverkort, M. W.; Zwierzycki, M.; Andersen, O. K. Physical Review B, Vol. 85, Issue 16 https://doi.org/10.1103/PhysRevB.85.165113	journal	April 2012
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
Crystal structure and electronic properties of bulk and thin film brownmillerite oxides Young, Joshua; Rondinelli, James M. Physical Review B, Vol. 92, Issue 17 https://doi.org/10.1103/PhysRevB.92.174111	journal	November 2015
d − d Excitations in Manganites Probed by Resonant Inelastic X-Ray Scattering Grenier, S.; Hill, J. P.; Kiryukhin, V. Physical Review Letters, Vol. 94, Issue 4 https://doi.org/10.1103/PhysRevLett.94.047203	journal	February 2005
Orientation control of oxygen vacancy channels in brownmillerite SrFe O 2.5 Saleem, Muhammad Shahrukh; Song, Cheng; Gu, Youdi Physical Review Materials, Vol. 4, Issue 1 https://doi.org/10.1103/PhysRevMaterials.4.014403	journal	January 2020
Effects of dimensionality on the electronic structure of Ruddlesden-Popper chromates Srn+1CrnO3n+1 Doyle, Spencer; Takana, Lerato; Anderson, Margaret A. Physical Review Materials, Vol. 8, Issue 7 https://doi.org/10.1103/PhysRevMaterials.8.L071602	journal	July 2024
Resonant inelastic x-ray scattering studies of elementary excitations Ament, Luuk J. P.; van Veenendaal, Michel; Devereaux, Thomas P. Reviews of Modern Physics, Vol. 83, Issue 2 https://doi.org/10.1103/RevModPhys.83.705	journal	June 2011
Magnetic excitations in infinite-layer nickelates Lu, H.; Rossi, M.; Nag, A. Science, Vol. 373, Issue 6551 https://doi.org/10.1126/science.abd7726	journal	July 2021
Reversible oxygen migration and phase transitions in hafnia-based ferroelectric devices Nukala, Pavan; Ahmadi, Majid; Wei, Yingfen Science, Vol. 372, Issue 6542 https://doi.org/10.1126/science.abf3789	journal	May 2021

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