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@PHDTHESIS{He:1048648,
author = {He, Suqin},
title = {{T}opotactic phase transition in {L}a0.6{S}r0.4{C}o{O}3-δ
thin films: oxygen content, dynamics and reversibility},
volume = {116},
school = {RWTH Aachen University},
type = {Dissertation},
address = {Jülich},
publisher = {Forschungszentrum Jülich GmbH Zentralbibliothek, Verlag},
reportid = {FZJ-2025-04778},
isbn = {978-3-95806-868-1},
series = {Schriften des Forschungszentrums Jülich Reihe Information
/ Information},
pages = {ix, 137},
year = {2025},
note = {Dissertation, RWTH Aachen University, 2025},
abstract = {Topotactic phase transitions induced by changes in oxygen
vacancy concentration can significantly alter the physical
properties of complex oxides, including electronic and
magnetic properties. Such tunable properties are critical
for developing novel electronic and spintronic devices,
where control of magnetic and electronic functionalities is
essential. This thesis investigates an
oxygen-vacancy-induced topotactic phase transition from
perovskite (PV) to brownmillerite (BM) in epitaxial
La0.6Sr0.4CoO3−δ (LSCO) thin films. Depth-sensitive
polarized neutron reflectometry (PNR) enable quantitative
analysis of magnetization and oxygen content, revealing a
continuous transition from La0.6Sr0.4CoO2.97 to
La0.6Sr0.4CoO2.5. BM formation occurs at an oxygen content
of 2.67, while the electronic metal-to-insulator transition
(MIT) and magnetic ferromagnet-to-non-ferromagnet
(FM-to-non-FM) transition occur above an oxygen content of
2.77, without a BM signature. These findings demonstrate
that the MIT, FM-to-non-FM, and PV-to-BM transitions are
interrelated but distinct processes. To further understand
the phase transition, the reversibility between PV and BM
was studied over 20 cycles. XRD showed that, although the PV
and BM structures were maintained, the intensities of both
peaks decreased by half, suggesting lattice incoherence or
decomposition. Magnetometry indicated no change in magnetic
properties, while electronic transport measurements showed
partially reversible behaviour. X-ray Photoelectron
Spectroscopy (XPS) showed that the Co core-level spectra
remained unchanged for both the as-grown and redox-treated
PV phases. However, the BM-to-PV transition introduced new
features in the A-site core-level spectrum, indicating
surface chemical changes during this process. The activation
energy for the phase transition was found to be between 0.72
and 0.9 eV by in-situ XRD measurements, which is consistent
with that of oxygen surface exchange in LSCO. Using platinum
to accelerate the surface exchange process further enhanced
the phase transition. These suggest that surface exchange is
likely the rate-limiting step. Finally, the study was
extended to a free-standing LSCO + SrTiO3 membrane. It
exhibited similar structural and magnetic transitions from
the PV to BM phase and from a ferromagnetic to
non-ferromagnetic state, indicating that the membrane has
similar functionalities as the thin film. These findings
highlight the potential of oxygen defect engineering to
enable control of topotactic phase transitions, paving the
way for perovskite-based devices with tailored
functionalities.},
cin = {PGI-7},
cid = {I:(DE-Juel1)PGI-7-20110106},
pnm = {5233 - Memristive Materials and Devices (POF4-523)},
pid = {G:(DE-HGF)POF4-5233},
typ = {PUB:(DE-HGF)3 / PUB:(DE-HGF)11},
doi = {10.34734/FZJ-2025-04778},
url = {https://juser.fz-juelich.de/record/1048648},
}