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Title: Strain-induced majority carrier inversion in ferromagnetic epitaxial LaCo O 3 - δ thin films

Journal Article · · Physical Review Materials

Tensile-strained LaCoO3-δ thin films are ferromagnetic, in sharp contrast to the zero-spin bulk, although no clear consensus has emerged as to the origin of this phenomenon. While magnetism has been heavily studied, relatively little attention has been paid to electronic transport, due to the insulating nature of the strain-stabilized ferromagnetic state. Here, structure, magnetism, and transport are studied in epitaxial LaCoO3-δ films (10–22-nm thick) on various substrates (from 1.4% compressive to 2.5% tensile strain), using synchrotron x-ray diffraction, scanning probe and transmission electron microscopy, magnetometry, polarized neutron reflectometry, resistivity, and Hall effect. High quality, smooth films are obtained, exhibiting superstructures associated with both oxygen vacancy ordering and periodic in-plane ferroelastic domains. Consistent with prior work, ferromagnetism with an approximately 80–85 K Curie temperature is observed under tension; polarized neutron reflectometry confirms a relatively uniform magnetization depth profile, albeit with interfacial dead layer formation. Electrical transport is found to have similar semiconducting nature to bulk, but with reduced resistivity and activation energy. Hall effect measurements, however, reveal a striking inversion of the majority carrier type, from p-type in the bulk and under compression to n-type under tension. While thus far overlooked, ferromagnetism in epitaxial LaCoO3-δ films is thus directly correlated with n-type behavior, providing important insight into the ferromagnetic state in this system. Here, aided by density functional theory calculations, these results are interpreted in terms of tensile-strain-induced orbital occupation and band structure changes, including a rapid decrease in effective mass at the eg-derived conduction band minimum, and corresponding increase at the valence band maximum.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357; SC0016371
OSTI ID:
1614758
Journal Information:
Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 3 Vol. 4; ISSN PRMHAR; ISSN 2475-9953
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

References (83)

Chemically Driven Nanoscopic Magnetic Phase Separation at the SrTiO3(001)/La1-xSrxCoO3 Interface journal April 2011
Electronic Properties of Doped Semiconductors book January 1984
Hall conductivity of amorphous semiconductors in the random phase model journal November 1971
Phase-sensitive specular neutron reflectometry for imaging the nanometer scale composition depth profile of thin-film materials journal February 2012
wannier90: A tool for obtaining maximally-localised Wannier functions journal May 2008
Strongly correlated crystal-field approach to Mott insulator journal April 2005
Electrostatic versus Electrochemical Doping and Control of Ferromagnetism in Ion-Gel-Gated Ultrathin La 0.5 Sr 0.5 CoO 3−δ journal July 2016
Epitaxial Strain-Induced Chemical Ordering in La 0.5 Sr 0.5 CoO 3−δ Films on SrTiO 3 journal February 2011
Strain-Induced Ferromagnetism and Magnetoresistance in Epitaxial Thin Films of LaCoO 3 Prepared by Polymer-Assisted Deposition journal December 2012
Nanoscale Spin-State Ordering in LaCoO 3 Epitaxial Thin Films journal April 2014
Strain-Induced Spin States in Atomically Ordered Cobaltites journal January 2012
Room-temperature ferroelectricity in strained SrTiO3 journal August 2004
A strong ferroelectric ferromagnet created by means of spin–lattice coupling journal August 2010
Emergent phenomena at oxide interfaces journal January 2012
Whither the oxide interface journal January 2012
Impact of stress on oxygen vacancy ordering in epitaxial (La0.5Sr0.5)CoO3−∂ thin films journal May 2003
Ferromagnetic spin-correlations in strained LaCoO3 thin films journal November 2008
Microscopic evidence of a strain-enhanced ferromagnetic state in LaCoO3 thin films journal August 2009
Rhombohedral distortion effects on electronic structure of LaCoO 3 journal May 2013
Lattice mismatch accommodation via oxygen vacancy ordering in epitaxial La 0.5 Sr 0.5 CoO 3-δ thin films journal July 2013
Electrical transport properties of La 1− x Sr x CoO 3 thin films journal October 2016
Hall effect and impurity conduction in substitutionally doped amorphous silicon journal May 1977
Neutron powder diffraction study of rhombohedral rare-earth aluminates and the rhombohedral to cubic phase transition journal December 1999
The unusual magnetism of nanoparticle LaCoO 3 journal April 2015
Phase separation and resistivity jumps in Co compounds and other materials with low-spin - high-spin transitions journal July 1996
First-Order Localized-Electron ⇆ Collective-Electron Transition in LaCo O 3 journal March 1967
Temperature-induced magnetism in LaCoO 3 journal December 1989
Neutron-scattering study of the spin-state transition and magnetic correlations in La 1 − x Sr x CoO 3 ( x =0 and 0.08) journal August 1994
Spin-state transition and high-spin polarons in LaCo O 3 journal February 1996
Intermediate-spin state and properties of LaCoO 3 journal August 1996
Local lattice distortion during the spin-state transition in LaCoO 3 journal April 1997
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal January 1998
Thermally induced insulator-metal transition in LaCoO 3 :   A view based on the Mott transition journal July 1998
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Thermally excited spin-disorder contribution to the resistivity of LaCoO 3 journal June 2002
Evidence for a low-spin to intermediate-spin state transition in LaCoO 3 journal June 2002
Structural phenomena associated with the spin-state transition in LaCoO 3 journal September 2002
5 D term origin of the excited triplet in LaCoO 3 journal May 2003
Glassy ferromagnetism and magnetic phase separation in La 1 − x Sr x CoO 3 journal May 2003
Ferromagnetism in La Co O 3 journal July 2004
Doping dependence of the anomalous Hall effect in La 1 − x Sr x Co O 3 journal May 2006
Ferromagnetic order in epitaxially strained La Co O 3 thin films journal April 2007
Tuning the magnetic properties of La Co O 3 thin films by epitaxial strain journal January 2008
Suppression of spin-state transition in epitaxially strained LaCoO 3 journal November 2008
Strain-driven magnetism in LaCoO 3 thin films journal January 2009
Suppression of the ferromagnetic state in LaCoO 3 films by rhombohedral distortion journal January 2009
Structural effects on the spin-state transition in epitaxially strained LaCoO 3 films journal February 2009
Low-temperature interactions of magnetic excitons in LaCoO 3 journal May 2009
Heat capacity study of magnetoelectronic phase separation in La 1 − x Sr x CoO 3 single crystals journal December 2009
Quantifying octahedral rotations in strained perovskite oxide films journal July 2010
X-ray absorption and magnetic circular dichroism of LaCoO 3 , La 0.7 Ce 0.3 CoO 3 , and La 0.7 Sr 0.3 CoO 3 films: Evidence for cobalt-valence-dependent magnetism journal November 2010
Local atomic and electronic structures of epitaxial strained LaCoO 3 thin films journal January 2012
Ferromagnetic insulating state in tensile-strained LaCoO 3 thin films from LDA + U calculations journal April 2012
Strain-driven spin-state transition and superexchange interaction in LaCoO 3 : A b initio study journal July 2012
Long-range ferromagnetic order in LaCoO 3 − δ epitaxial films due to the interplay of epitaxial strain and oxygen vacancy ordering journal April 2015
Neutron-scattering-based evidence for interacting magnetic excitons in LaCo O 3 journal August 2015
Strain-sensitive spin-state ordering in thin films of perovskite LaCoO 3 journal November 2015
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces journal April 2008
Spin-Orbital Superstructure in Strained Ferrimagnetic Perovskite Cobalt Oxide journal July 2013
Insulating Ferromagnetic LaCoO 3 − δ Films: A Phase Induced by Ordering of Oxygen Vacancies journal February 2014
Ferromagnetism and Charge Order from a Frozen Electron Configuration in Strained Epitaxial LaCoO 3 journal May 2018
Tensile-Strain-Dependent Spin States in Epitaxial LaCoO 3 Thin Films journal May 2018
Exploiting Symmetry Mismatch to Control Magnetism in a Ferroelastic Heterostructure journal May 2019
Spin State Transition in LaCoO 3 Studied Using Soft X-ray Absorption Spectroscopy and Magnetic Circular Dichroism journal October 2006
Spin-State Transition in LaCoO 3 : Direct Neutron Spectroscopic Evidence of Excited Magnetic States journal December 2006
Formation and Thickness Evolution of Periodic Twin Domains in Manganite Films Grown on SrTiO 3 ( 001 ) Substrates journal February 2007
Direct Measurement of the Low-Temperature Spin-State Transition in LaCoO 3 journal July 2007
Potential resolution to the doping puzzle in iron pyrite: Carrier type determination by Hall effect and thermopower journal June 2017
Role of entropy and structural parameters in the spin-state transition of LaCoO 3 journal November 2017
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 journal December 2017
Switchable orbital polarization and magnetization in strained LaCo O 3 films journal January 2019
Metal-insulator transitions journal October 1998
Maximally localized Wannier functions: Theory and applications journal October 2012
Simple ways of determining perovskite structures journal November 1975
Nanoscale ferroelastic twins formed in strained LaCoO 3 films journal March 2019
Structural Parameters of LaCoO 3 near the Spin State Transition journal November 2001
Correlated Oxide Physics and Electronics journal July 2014
Magnetic Oxide Heterostructures journal July 2014
Strain Tuning of Ferroelectric Thin Films journal August 2007
Metal-Insulator Transitions book January 1990
Observation of magnetic excitons in LaCoO 3 journal June 2005
Data files of work on LaCoO3 using VASP dataset January 2020
Whither Oxide Electronics? journal November 2008