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Title: Non-Griffiths-like clustered phase above the Curie temperature of the doped perovskite cobaltite La{sub x-1}Sr{sub x}CoO{sub 3}.

Abstract

The existence of preformed clusters above the Curie temperature of the doped perovskite manganites is well established and, in many cases, conforms to the expectations for a Griffiths phase. We show here that the canonical perovskite cobaltite (La{sub 1?x}Sr{sub x}CoO{sub 3}) also exhibits a clustered state above the Curie point in the ferromagnetic phase. The formation of magnetic clusters at a well-defined temperature (T*) is revealed in the small-angle neutron scattering and dc susceptibility. Remarkably, the characteristics of this clustered state appear quite unlike those of a Griffiths phase; the deviation from Curie-Weiss behavior is opposite to expectations and is field independent, while T* does not correspond to the undiluted Curie temperature. These results demonstrate that, although the Griffiths model may apply to many systems with quenched disorder, it is not universally applicable to randomly doped transition metal oxides.

Authors:
; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF); ACS PRF; National Institute of Standards and Technology (NIST)
OSTI Identifier:
920574
Report Number(s):
ANL/MSD/JA-60556
TRN: US0805298
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Phys. Rev. B; Journal Volume: 76; Journal Issue: 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; CURIE POINT; NEUTRONS; OXIDES; PEROVSKITE; SCATTERING; TRANSITION ELEMENTS

Citation Formats

He, C., Torija, M. A., Wu, J., Lynn, J. W., Zheng, H., Mitchell, J. F., Leighton, C., Materials Science Division, Univ. Minnesota, and NIST. Non-Griffiths-like clustered phase above the Curie temperature of the doped perovskite cobaltite La{sub x-1}Sr{sub x}CoO{sub 3}.. United States: N. p., 2007. Web. doi:10.1103/PhysRevB.76.014401.
He, C., Torija, M. A., Wu, J., Lynn, J. W., Zheng, H., Mitchell, J. F., Leighton, C., Materials Science Division, Univ. Minnesota, & NIST. Non-Griffiths-like clustered phase above the Curie temperature of the doped perovskite cobaltite La{sub x-1}Sr{sub x}CoO{sub 3}.. United States. doi:10.1103/PhysRevB.76.014401.
He, C., Torija, M. A., Wu, J., Lynn, J. W., Zheng, H., Mitchell, J. F., Leighton, C., Materials Science Division, Univ. Minnesota, and NIST. Mon . "Non-Griffiths-like clustered phase above the Curie temperature of the doped perovskite cobaltite La{sub x-1}Sr{sub x}CoO{sub 3}.". United States. doi:10.1103/PhysRevB.76.014401.
@article{osti_920574,
title = {Non-Griffiths-like clustered phase above the Curie temperature of the doped perovskite cobaltite La{sub x-1}Sr{sub x}CoO{sub 3}.},
author = {He, C. and Torija, M. A. and Wu, J. and Lynn, J. W. and Zheng, H. and Mitchell, J. F. and Leighton, C. and Materials Science Division and Univ. Minnesota and NIST},
abstractNote = {The existence of preformed clusters above the Curie temperature of the doped perovskite manganites is well established and, in many cases, conforms to the expectations for a Griffiths phase. We show here that the canonical perovskite cobaltite (La{sub 1?x}Sr{sub x}CoO{sub 3}) also exhibits a clustered state above the Curie point in the ferromagnetic phase. The formation of magnetic clusters at a well-defined temperature (T*) is revealed in the small-angle neutron scattering and dc susceptibility. Remarkably, the characteristics of this clustered state appear quite unlike those of a Griffiths phase; the deviation from Curie-Weiss behavior is opposite to expectations and is field independent, while T* does not correspond to the undiluted Curie temperature. These results demonstrate that, although the Griffiths model may apply to many systems with quenched disorder, it is not universally applicable to randomly doped transition metal oxides.},
doi = {10.1103/PhysRevB.76.014401},
journal = {Phys. Rev. B},
number = 2007,
volume = 76,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • Years of intensive work on perovskite manganites has led to a detailed understanding of the phenomena that emerge from competition between the electronic and lattice degrees of freedom in these correlated electron systems. It is well understood that the related cobaltites provide an additional spin-state degree of freedom. Here, we use the magnetic properties of a particular cobaltite, Pr{sub 1-x}Sr{sub x}CoO{sub 3}, to demonstrate the vital role played by a further ingredient often negligible in manganites; magnetocrystalline anisotropy. Pr{sub 1-x}Sr{sub x}CoO{sub 3} exhibits an anomalous 'double magnetic transition' that cannot be ascribed to a spin-state transition or the usual charge/orbital/antiferromagneticmore » ordering and has thus far evaded explanation. We show that this is actually due to a coupled structural/magnetocrystalline anisotropy transition driven, in this case, by Pr-O hybridization. The results point to the existence of a distinct class of phenomena in the cobaltites due to the unique interplay between structure and magnetic anisotropy.« less
  • The properties of La{sub 1-x}Sr{sub x}CoO{sub 3} (x = 0, 0.15, 0.20, 0.30) solid solutions are investigated using neutron diffraction, positive-muon spin relaxation (precession) measurements, and extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectroscopy. The results obtained are interpreted within the model of phase separation into ferromagnetic regions enriched with Sr{sup 2+} ions and nonmagnetic regions similar in composition to the LaCoO{sub 3} compound.
  • 3d metal K-shell X-ray absorption spectra of perovskites with the composition La{sub 1-x}Ca{sub x}CoO{sub 3-{delta}} (x=0, 0.2, 0.4, 0.5, 0.6, 0.8), La{sub 1-x}Sr{sub x}CoO{sub 3-{delta}} (x=0, 0.1, 0.2, 0.3, 0.4, 0.5) and La{sub 1-x}Sr{sub x}FeO{sub 3-{delta}} (x=0, 0.2, 0.4, 0.5, 0.6, 0.8) are compared on the basis of pre-edges, white line features and extended fine structures. The measurements were performed at 300 K and for La{sub 1-x}Ca{sub x}CoO{sub 3-{delta}} also at temperatures as low as 10-20 K. Going to low-temperature the measurements indicate an increase in t{sub 2g}{sup Low-Asterisk} and a decrease in e{sub g}{sup Low-Asterisk} orbital occupancy, which ismore » most accentuated in the LaCoO{sub 3} sample. Virtually no Co K-edge shift was observed for the La{sub 1-x}Ca{sub x}CoO{sub 3-{delta}} and La{sub 1-x}Sr{sub x}CoO{sub 3-{delta}} compounds and the Co-O distances are also not significantly reduced when La{sup 3+} is partially substituted by Ca{sup 2+} or Sr{sup 2+}. From the pre-edge features of these perovskites we are tended to conclude that the t{sub 2g}{sup Low-Asterisk} orbitals are less, and the e{sub g}{sup Low-Asterisk} orbitals are more occupied with increasing x in the Ca and Sr substituted compounds, whereas the total d-electron density is not changing. These results indicate that cobalt prefers a valence state of 3{sup +} in these Co perovskites. This could also be confirmed with iodometric titrations. The Fe perovskites behave differently. In contrast to the Co perovskites, for La{sub 1-x}Sr{sub x}FeO{sub 3-{delta}} perovskites the Fe K-edge is shifted, the pre-edge features intensity is increasing and the Fe-O bond length is decreasing with increasing x. The valence states of the iron in the La{sub 1-x}Sr{sub x}FeO{sub 3-{delta}} perovskites in fact increase as much as x increases. - Graphical abstract: Co K and Fe K pre-edge of La{sub 1-x}Ca{sub x}CoO{sub 3-{delta}} and La{sub 1-x}Sr{sub x}FeO{sub 3-{delta}} perovskites one of the evidences in favor of {delta}=x/2 for the Co-perovskites and {delta}=0 for the Fe-perovskites. Highlights: Black-Right-Pointing-Pointer XAS a valuable tool to evaluate the valence states of Co and Fe perovskites. Black-Right-Pointing-Pointer For La{sub 1-x}Ca{sub x}CoO{sub 3-{delta}} and La{sub 1-x}Sr{sub x}CoO{sub 3-{delta}} perovskites {delta} is close to x/2. Black-Right-Pointing-Pointer For La{sub 1-x}Sr{sub x}FeO{sub 3-{delta}} series {delta} is close to 0. Black-Right-Pointing-Pointer Discussion of the x dependency of the pre-edge bands.« less
  • We present a temperature-dependent extended x-ray absorption fine structure (EXAFS)/x-ray absorption near edge structure (XANES) investigation of La{sub 1-x}Sr{sub x}CoO{sub 3} (LSCO) over a wide doping concentration range (0 {le} x {le} 0.35). Five of the samples are nanoparticles (x = 0.15, 0.20, 0.25, 0.30, and 0.35) and four are bulk powders (x = 0, 0.15, 0.20, and 0.30). From the EXAFS analysis, we find that the Co-O bonds are well ordered for both bulk and nanoparticle materials and there is no clear evidence for a Jahn-Teller (JT) distortion in the LSCO system (either static or dynamic). The distortion ofmore » the Co-O bond with increasing T, parameterized by the width of the pair distribution function (PDF), {sigma} (T), can easily be modeled using a correlated Debye model with a high correlated Debye temperature {approx} 800 K. There is also no evidence for a step in plots of {sigma}{sup 2} vs T. In addition, the very small nonthermal contribution to {sigma}{sup 2} for the Co-O (PDF), {sigma}{sup 2} static, sets an upper limit on the extent of any Jahn-Teller distortion at low T. These experiments are inconsistent with the existence of a significant fraction of Co sites with an intermediate spin (IS) state, for which there is a JT active e{sub g} electron on the Co atoms. We cannot, however, exclude the possibility of a tiny fraction of sites having a JT distortion or some other (non-JT active) means of producing an IS state. The bulk samples are well ordered out to at least the third neighbors (Co-Co) while the nanoparticles show increased disorder and a reduction in coordination for Co-Co. XANES data are also presented, and, for both bulk and nanoparticle samples, there is essentially no edge shift with increasing Sr concentration. Bond-valence sums also indicate no change in effective Co valence. These results indicate that when holes are introduced via Sr doping, they have little Co(3d) character and the Co configuration remains close to 3d{sup 6}; we argue that the holes have mostly O(2p) character and are localized more on the O sites.« less
  • Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr 2+ substitution into La 1-xSr xCoO 3-δ. We attempt tomore » rationalize the high activities of La 1-xSr xCoO 3-δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO 2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.« less