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Reversible electronic & magnetic structures in epitaxial strontium cobaltites
Woo Seok ChoiDepartment of Physics, Sungkyunkwan UniversityMaterials Science & Technology Division,Oak Ridge National Laboratory
Acknowledgements
(Materials Science & Technology Division, Oak Ridge National Laboratory)
Prof. C. U. Jung (HUFS) Film growthDr. D. W. Shin (Oak Ridge Nat’l Lab.) Thermodynamic modelingDr. J. H. Lee (Princeton Univ.) First principles calculationsProf. S. S. A. Seo (Univ. Kentucky) Optical measurementsDr. J. W. Freeland (Argonne Nat’l Lab.) X‐ray absorption spectroscopyDr. M. F. Chisholm (Oak Ridge Nat’l Lab.) Scanning Transmission Electron MicroscopyProf. H. Ohta (Hokkaido Univ.) Transport measurementandmany others…
Dr. H. N. Lee Dr. H. Jeen
K. Vidyasagar et al., J. Chem. Soc. Chem. Comm. 1, 7-8 (1985)
PerovskiteABO3
ABO2.5 ABO2.5 ABO2.5
Topotactic phase transformation
A structural transformation within a crystal lattice, which may include loss or gain of material, so that the final phase has one or more crystallographically equivalent orientational relationships to the lattice of the parent phase.
Advantages• Systematic tailoring of new (meta‐)stable compounds
• Controlled modification of physical properties
• Many technological applicationse.g.) oxide electronics,ionic conductors,cathodes in SOFCs,catalytic converters.
Introduction
Ionic transport
Electrochemical reaction• Catalytic activity• Gas conversion• Cathodes for SOFCs and batteries• Redox of the host material
A. Vojvodic & J. K. Nørskov, Science 334, 1355 (2011)J. Suntivich et al., Science 334, 1383 (2011)
In search for catalytic descriptors
Fundamentalphysical properties
• Structural property• Crystal field
• Stoichiometry• Valence state or Oxidation state
• Electronic structure• Electronic and magnetic property
Topotacticphasereversal
A perfect model system for studying the correlation between fundamental physical properties
and electrochemical activities!i.e., physical signatures for electrochemical processes.
Introduction
Oxygen ion conduction Cathode for solid oxide fuel cells and rechargeable batteries Catalytic gas sensors Oxygen separation membranes
S. B. Adler, Chem. Rev. 104, 4791 (2004).
Oxygen (ion) movement in oxides – Energy materials
J. N. Reimers & J. R. Dahn,J. Electrochem. Soc. 139,
2091 (1992).
Introduction
Multivalencyin transition metal oxides
Multivalent Cobalt in transition metal oxides
8
7
6
5
4
3
2
1
0 Sc Ti V Cr Mn Fe Co Ni Cu Zn
3d Elements
Oxi
datio
n St
ates
Solid dots: the most commonly found states
27
Co3d74s2
27
Co3d74s2
• Multivalent transition metal• Common oxidation states: 2+ & 3+• Less common: 4+
d6: La3+Co3+O3d5: Sr2+Co4+O3d6: Sr2+Co3+O2.5
Multiple sources to control the valence & spin state: A-site ion & oxygen
t2g
eg
Low spin (LS) state Intermediate spin (IS) state High spin (HS) state
S = 0 S = 1 S = 2
t2g
eg
Low spin (LS) state Intermediate spin (IS) state High spin (HS) state
S = 1/2 S = 3/2 S = 5/2
Co3+ (3d6)
Co4+ (3d5)
octahedral crystal field
Introduction
SrCoOx (SCO)
d5: Sr2+Co4+O3 d6: Sr2+Co3+O2.5
Brownmillerite (BM) (110)Perovskite (PV) (110)
Perovskite BrownmilleriteCubic
FM-M
ac = 3.829 Å
Orthorhombic
AFI-I
a = 5.545 Å,
b = 15.738 Å,
c = 5.448 Å
Brownmillerite (BM) (1-10)
1D vacancy channel
27
Co3d74s2
27
Co3d74s2
• Multivalent transition metal• Common oxidation states: 2+ & 3+• Less common: 4+
Introduction
La1-xSrxCoO3-δ
J. Wu & C. Leighton. Phys. Rev. B 67, 174408 (2003)
M. A. Senaris-Rodriguez & J. B. Goodenough,J. Solid State Chem. 118, 323 (1995).
Phase diagram of La1‐xSrxCoO3‐δ
CubicPerovskite
SrCoO3δ = 0
FerromagneticMetallic
Metastable
in La1-xSrxCoO3-δ
RhombohedralPerovskiteFerroelastic
CubicPerovskiteFerromagneticMetallic
1.0
BrownmilleriteAntiferromagneticLocalized Insulator(Co2+/Co4+)
Sr6Co5O15AntiferromagneticSemiconductor
Co3+ Co4+
• Promising cathode for SOFC• Mixed ionic and electronic conductor• Good catalytic activities• Magnetic material
Introduction
Difficult to achieve Co4+
(or, Perovskite SrCoO3)
Attempts to stabilize Co4+
- Quenching : Yakel, Acta. Cryst., 8, 394 (1955) (Co4+ = 3.8 %) : Takeda & Watanabe, J. Phys. Soc. Jpn. 33, 973 (1972) (x = 2.5)
- Electrochemical approach : Bezdicka et al., Z. anorg. Allg. Chem. 619, 7 (1993) (x = 2.5 3.0): Le Toquin et al., J. Am. Chem. Soc. 128, 13161 (2006)
- High pressure/high temperature approach : Takeda & Watanabe, J. Phys. Soc. Jpn. 33, 973 (1972) (x = 2.75 ~ 2.95)
- Hybrid method (high pressure/high temperature + oxidant): Long & Tokura et al., J. Phys.: Condens. Matter 23, 245601 (2011)
First Single Crystal!
However, all of these bulk synthesis methods require post treatmentssuch as high temperature, high pressure, and long time annealing, or chemical treatments.
Epitaxial thin films
0.19 0.20
0.60
0.61
qx || [100](Å-1)
103LSAT
0.19 0.20
0.59
0.60
103P-SCO
q z || [00
1](Å-1
)
qx || [100](Å-1)
106BM-SCO
103STO
22.5 23.4
Inten
sity (
arb.
units
)
(degrees)23.4 24.3
FWHM= 0.04
FWHM = 0.05
(degrees)
SrCoO2.5 epitaxial thin film
• Stable SrCoO2.5 phase readily formed.• Direct synthesis of oxidized perovskite SrCoO3
phase by ozonized growth.
First Epitaxial Thin Film!
Epitaxial thin films
Defect‐free brownmillerite SrCoO2.5 thin film
STO
[110] BM-SCO [1-10] BM-SCO
STO
Epitaxial thin films
SrCoO2.5 near interface
CoO2(4)
CoO2(2)
0.5 nm
TiO2 (N = 0)SrO (0.5) CoO (1)SrO (1.5)
SrO (2.5)
SrO (3.5) CoO (3)
0.5 nm
ABF imageZ-contrast image
Epitaxial thin films
0.19 0.20
0.60
0.61
qx || [100](Å-1)
103LSAT
0.19 0.20
0.59
0.60
103P-SCO
q z || [00
1](Å-1
)
qx || [100](Å-1)
106BM-SCO
103STO
22.5 23.4
Inten
sity (
arb.
units
)
(degrees)23.4 24.3
FWHM= 0.04
FWHM = 0.05
(degrees)
First SrCoO3 epitaxial thin film, structural properties
• Stable SrCoO2.5 phase readily formed.• Direct synthesis of oxidized perovskite SrCoO3
phase by ozonized growth.
First Epitaxial Perovskite Thin Film!
Epitaxial thin films
Determination of oxidation state: XAS
780 790 800-0.4
-0.2
0.0
Bulk
XMCD
Energy (eV)
0.0
2.0
4.0Co L-edge
O K-edge
L2
Inten
sity (
arb.
units
)
L3
525 530 535 5400.0
1.0
2.0
BM-SCO P-SCO
Inten
sity (
arb.
units
)
Energy (eV)
Karvonen et al., Chem. Mater. 22, 70, (2010)
Bulk data
• Significant change in the pre-peak spectral shape with the increase of the oxidation state (Co 3d - O 2p hybridization).
• Shift of L-edge toward high energy upon introduction of Co4+.
Distinct contrast in physical properties
Electronic and magnetic phase transition in SrCoOx
-10 -5 0
-2
-1
0
-4 -2 0 2 4-2
-1
0
1
2
V (m
V)T (K)
0 100 200 3000.0
0.2
0.4
0.6
0.8
1.0
BM-SCO P-SCO
M (
B/Co)
T (K)
10 10010-410-310-210-1100101102103
(cm
)
T (K)
M
(B/C
o)
H (T)
254 μV/K
9.6 μV/K
H. Jeen & W. S. Choi et al. Nat. Mater. 12, 1057 (2013)
Distinct contrast in physical properties
• Metallic transport behavior for P-SCO• Clear demonstration of successful
stabilization of Co4+.• Four orders of magnitude change in
dc-conductivity already at 300 K.• Insulator-to-metal transition with
incorporation of oxygen in SrCoOx.• A large Seebeck coefficient from BM-SCO.• Positive Seebeck coefficient supports the
p-type conduction (holes), also confirmed by Hall Measurements.
• Ferromagnetic ordering below ~250 K for P-SCO.
Topotactic transformation induced electronic and magneticphase transitions.
Optical properties and electronic structure
PV SCO
O 2p
t2g
Drude
eg
EF
Co 3dCo 3d
O 2p
BM SCO
Coo
Cot
0.5 1.0 1.5 2.0 2.5 3.00
1
2
3
4
5
300 K 5 K
a
(105 cm
-1)
(eV)
• Insulator (BM) to metal (PV) transition is clearly shown.
• BM SCO: A low optical band gap insulator (~0.5 eV)
• Typical BM phase oxides have >2 eV of band gap.
• Advantageous for application: ionic (vacancy channel) + electronic conduction (in the vicinity of IMT)
• PV SCO: Metallic with Drude peak.
-6 -4 -2 0 2 4-6-3036
-6 -4 -2 0 2 4-6-3036
Energy (eV)
DOS
Energy (eV)
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.50
2
4
6
8
10
12
14
Theo
retic
al 2(
) (eV)
• Complicated electronic structure with both CoO6 octahedral and CoO4teterahedral crystal field.
• First principles calculation reproduced the experimental peak features.
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.50
2
4
6
8
BM SCO PV SCO 1
2
Expe
rimen
tal 1(
) & 2(
)
(eV)
W. S. Choi et al. Phys. Rev. Lett. 111, 097401 (2013)
Distinct contrast in physical properties
Topotactic transformation induced optical property change.
PV SrCoO3
+ Oxygen
– Oxygen
BM SrCoO2.5
Fast and reversible phase transformation in SCOTopotactic phase reversal
Real‐time observation of redox processes
Ep
Es
viewport viewport
gas inlet (P(O2) control)
CCD detector
photon source(193 ≤ λ ≤ 1000 nm)
to pump
O2
heater(T control)
vacuum chamber
sample
Spectroscopic ellipsometryfor the electronic structure evolution
during topotatic phase reversal
in collaboration with Prof. Seo of University of Kentucky
Co3+ Co4+
Topotactic phase reversal
@ 10 6 T
2 3 4 5
400
350
300
250
200
150
100
50T
(o C)
(eV)
2.0003.7605.500
2
heating@ 10-6 Torr
Electronic structure evolution
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.50
2
4
6
8
BM-SCO P-SCO 1
2
1() &
2()
(eV)
P. Pasierb et al., J. Phys. Chem. Solids 60, 1835 (1999)
OXIDATION REDUCTION
γ
β
(P)
(BM)
Topotactic phase reversal
2 3 4 5320
300
280
260
240
220
200
180heating@ P(O2) = 500 Torr
T (o C)
(eV)
2.0004.8007.500
2
2 3 4 5350
300
250
200
150
100
50reheating@ 10-6 Torr(after cooldown)
T (o C)
(eV)
Real‐time ellipsometry: BM ↔ PV
2 3 4 5
50
100
150
200
250
300
350 cooling@ 10-6 Torr
@ 10-6 Torr
T (o C)
(eV)
2 3 4 5
400
350
300
250
200
150
100
50
T
(o C)
(eV)
2.0003.7605.500
2
heating@ 10-6 Torr
W. S. Choi et al. Phys. Rev. Lett. 111, 097401 (2013)
γ (P)
β (BM)
β (BM)
β (BM)
β (BM)
β (BM)
γ (P)
γ (P)
Topotactic phase reversal
200 400 600 800
-0.2
-0.4
-0.6
-0.8
-1.0
G SrMn
O 3- -
G SrMn
O 2.5
(eV)
SrMnO3
T (C)
SrMnO2.8
SrMnO2.9
SrCoO2.8
SrCoO2.9
0.2
0.4
0.6
0.8
1.0SrCoO 3
G SrCo
O 3- -
G SrCo
O 2.5 (e
V)
Real‐time XRD: BM ↔ PV
45 46 47 48500
400
300
200
100
T (C
)
2 (degrees)
45 46 47 48400
300
200
100
T
(C)
2 (degrees)
P BM
BM P
Difference in Gibbs free energy between BM and P phase
• Fast and reversible redox reaction at relatively low temperatures for epitaxial SCO thin films.
• Sign and absolute value of the Gibbs energy differenceprovides crucial insight for custom tailoring of topotacticprocesses in multivalent oxides.
• Reduced energy difference at low temperatures was predicted for SCO.
in vacuum
in O2
Topotactic phase reversal
H. Jeen & W. S. Choi et al. Nat. Mater. 12, 1057 (2013)
Catalytic activity
P BM
BM P
• The redox reaction at relatively low temperatures seems to enhance the catalytic activity of epitaxial SCO thin films (BM in this case).
• First evidence of catalytic activity shown form BM-SCO at relatively low temperature.
in vacuum
in O2
Topotactic phase reversal
PV SrCoO3
+ Oxygen
– Oxygen
BM SrCoO2.5
Epitaxial oxygen sponge SrCoOx
• First PLE growth of epitaxial brownmillerite (BM) and perovskite (P) phases of SrCoOx single crystalline thin films!
• Fast, reversible redox reactions at low temperatures!•The topotactic phase transformation accompanies various physical property transitions!
Adv. Mater. Early View doi:10.1002/adma.201302919 (2013).Phys. Rev. Lett. 111, 097401 (2013).Nat. Mater. 12, 1057 (2013).Adv. Mater. 25, 3651 (2013).