Charge, Orbital and Spin

Ordering in RBaFe2O5+x
Perovskites
Patrick M. Woodward
Department of Chemistry
Ohio State University
Pavel Karen
Department of Chemistry
University of Oslo

Charge, Orbital and Spin Ordering

Charge Ordering (TCO)

T > TCO Delocalized Electrons Single oxidation state

T < TCO Localized Electrons Distinct oxidation states

Orbital Ordering (TOO)

Preferential (anisotropic) occupation of given d-orbitals

Cooperative Jahn-Teller distortion

Spin Ordering (TN or TC)

Long range magnetic ordering

Mixed Valency (Robin & Day Classification)

Type III Metallic e- transport Single oxidation state

Type II Activated e- transport Two oxidation states at
a given instant, but CO pattern is fluctional
Type I Insulating Two oxidation states, with a regular
(long range) CO pattern

Examples of Charge Ordering

Fe3+(Fe2.5+)2O4 Fe3+(Fe2+Fe3+)O4
Verwey (1939)
Double Exchange Ferromagnetism

LaCa(Mn3.5+)2O6 LaCa(Mn3+Mn4+)O6
Wollan, Koehler & Goodenough (1955)
Colossal Magnetoresistance (CMR)

Ba2(Bi4+)2O6 Ba2(Bi3+Bi5+)O6
Cox & Sleight (1976)
High Tc Superconductivity in Oxides

Charge Ordering in Nd0.5Sr0.5MnO3

350

350

160 K

300

50 K

300

Incipient CO Phase
250

Intensity

Intensity

250

200

150

200

150

100

100

50

50

0
19

21

23

25

27

29

2-Theta (Degrees)

T = 160 K
Valence Mixed State

31

19

21

23

25

27

29

31

2-Theta (Degrees)

T = 60 K
Charge Ordered State

Synchrotron X-ray Powder Diffraction Data (NSLS-X7A)

A series of weak superstructure reflections arise (1% intensity at
the strongest) that indicate doubling of the a -axis.
Woodward, Cox, Vogt, Rao, Cheetham, Chem. Mater. 11, 3528-38 (1999).

Examples of Orbital Ordering

21.91

Mn3+
22.07

Mn4+

21.94
22.18
41.90

LaMnO3 (298 K)

NdSrMn2O6 (50 K)

Rodriguez-Carvajal, et al. Phys.

Rev. B 57, R3189 (1998).

Woodward, et al. Chem.

Mater. 11, 3528-38 (1999).

Orbital Ordering & Cooperative

Jahn-Teller Distortions
Axially Elongated
Octahedron

Regular
Octahedron
d(x2-y2)
eg (*)

d(z2)

Mn3+
t2g (*)

Examples of Orbital Ordering

21.91

Mn3+
22.07

Mn4+

21.94
22.18
41.90

LaMnO3 (298 K)

NdSrMn2O6 (50 K)

Rodriguez-Carvajal, et al. Phys.

Rev. B 57, R3189 (1998).

Woodward, et al. Chem.

Mater. 11, 3528-38 (1999).

Orbital Ordering in Nd0.5Sr0.5MnO3

Cell Parameter (A)

5.55

(b)

5.50

5.45
a
5.40
b/sqrt(2)

5.35
5.30
0

100

200

300

Temperature (K)

Upon cooling below 150 K, the a & c-axes expand and the b-axis
contracts. This is the signature of orbital ordering
Woodward, Cox, Vogt, Rao, Cheetham, Chem. Mater. 11, 3528-38 (1999).

Oxygen Deficient Double Perovskites

RBaFe2O5+w
R = Trivalent Rare Earth Ion
Nd, Sm, Tb, Ho, Y
Changing the radius of the R ion,
controls the layer spacing

M = 1st row Transition Metal Ion

V, Mn, Fe, Co, Cu
Changing M, alters the electron count
and covalency of the M-O bonds.

0 w ~ 0.7

Excess oxygen resides in R layer

The upper limit of w is dictated by
the ionic radius of R
w=0 M+2.5, w=0.5 M+3
changes the local coordination of the
transition metal ion from 5 to 6

Synthesis REBaFe2O5
RE2O3 +
Citric Acid

Fe2O3 +
Nitric Acid

Heat

BaCO3
& Stir

Amorphous
OrganicInorganic
Precursor

The sample is dehydrated at ~180 C.

The sample is then heated at ~400 C to drive off the organic

content and produce an amorphous precursor.

The precursor is calcined (800-900 C) and then sintered at

high temperature (1000-1150 C) in a carefully controlled pO 2
atmosphere.

The sintered pellets are heated at a lower temperature (600860 C) in a controlled atmosphere to attain the desired
oxygen content.

Powder Diffraction Data Collection

Synchrotron X-ray Powder Diffraction

NSLS - X7A (Dave Cox, Tom Vogt)

NSLS X3B (Peter Stephens, Sylvina Pagola)
ESRF BM1B (Swiss-Norwegian Beamline)

Neutron Powder Diffraction

NIST BT1 (Brian Toby) - YBaFe2O5

ILL D2B (Emmanuel Suard) - HoBaFe2O5 & NdBaFe2O5
PSI - HRPT (Peter Fischer) - TbBaFe2O5
ANSTO MRPD (Andrew Studer) - TbBaFe2O5

Neutron Thermodiffractometry

ILL D20 (Emmanuel Suard) - HoBaFe2O5 & NdBaFe2O5

Mossbauer Spectroscopy

Abo Akademi (Johan Linden)

TbBaFe2O5+x

0.15

0.10

TCO

0.05

0.00

I
200

II
250

Tpm

III

300

DSC

Ho
Dy
Tb
Gd
Eu
Sm
R
Pm
Nd

Resistivity (ohm.cm)

Heat flow (mW/g)

1.E+06

x=0.046
x=0.016

1.E+04

x=0.030
x=0.249

1.E+02

x=0.095

SmBaFe2O5+x
1.E+00
150

200

250

300

Temperature (K)

T (K)

Electrical Resistivity

T>TPM Mssbauer shows one Fe2.5+ signal (Type III MV)

TPM >T>TCO Mssbauer signal begins to split Fe2.5+x + Fe2.5-x (Type II MV)
TCO > T Mssbauer shows Fe2+ + Fe3+ (Type I MV, Charge Ordered State)
Karen, Woodward, Santhosh, Vogt, Stephens, Pagola, J. Solid State Chem.
167, 480 (2002).

TbBaFe2O5 Type III MV Structure

Temperature
Space Group
a
b
c
Bond Valences
Ba
Tb
Fe
O(x)
O(y)
O(z)

350 K
Pmmm
3.94453(4)
3.93331(4)
7.58655(8)

1.98
2.88
2.52
1.94
1.95
2.05

Fe-O Distances
22.0002(6) [Oy]
22.0046(5) [Ox]
11.9977(7) [Oz]

Karen, Woodward, Linden, Vogt, Studer, Fisher, Phys. Rev. B 64, 214405 (2001).

TbBaFe2O5 Synchrotron X-ray

120

Superstructure
Reflections indicate a
doubled a-axis

Intensity (Arb. Units)

100

80

Space Group = Pmma

60

Superstructure
reflections are stronger
when R = Nd

40

20

15

17

19

21

2-Theta (Degrees)

23

25

Superstructure
reflections are very
difficult to observe in
neutron powder patterns.

Karen, Woodward, Linden, Vogt, Studer, Fisher, Phys. Rev. B 64, 214405 (2001).

TbBaFe2O5 Neutron Diffraction

Doubled a-axis
2 Fe Sites
Intensity (Arb. Units)

Intensity (Arb. Units)

Room Temp. Structure

1 Fe Site

110

120

130

140

150

2-Theta (Degrees)

Mixed Valence Model

110

120

130

140

150

2-Theta (Degrees)

Charge Ordered Model

Rietveld refinements of neutron powder diffraction data confirm

charge ordered structure, TbBaFe3+Fe2+O5.
Karen, Woodward, Linden, Vogt, Studer, Fisher, Phys. Rev. B 64, 214405 (2001).

TbBaFe2O5 Type I CO Structure

x2-y2
x2-y2
z2

z2

yz
1.962(1)

xy

xy

yz

xz

1.975(1)

2.134(4)

Temperature
Space Group
a
b
c

70 K
Pmma
8.0575(2)
3.85032(6)
7.5526(2)

1.965(4)

2.134(4)

2.046(5)

Fe2+ BVS=2.37

xz

1.965(4)
1.895(6)

Fe3+ BVS=2.76

TbBaFe2O5 Magnetic Scattering

350 K

Intensity (Arb. Units)

Intensity (Arb. Units)

70 K

10

20

30

2-Theta (Degrees)

40

50

10

20

30

40

2-Theta (Degrees)

T < Tco Magnetic Cell

T > Tco Magnetic Cell
2a 2b c
2a 2b 2c
8.05 7.70 7.55
7.88 7.87 15.17
The charge ordering induces a rearrangement of the
antiferromagnetic structure!

50

TbBaFe2O5 MV State (T>TCO)

Magnetic Structure
AFM
FM
AFM

Isostructural with YBaFeCuO5

AFM Coupling in ab Plane

Fe-O-Fe Superexchange AFM

Fe-Fe Direct Exchange FM

TbBaFe2O5 CO State (T<TCO)

Magnetic Structure
AFM
AFM
AFM

AFM Coupling in ab Plane

G-Type AFM Structure

Fe-O-Fe Superexchange AFM
Fe-Fe Direct Exchange AFM

Charge & Spin Ordering in YBaM2O5

YBaMn2O5

YBaFe2O5

YBaCo2O5

TCO > 300 K (CB)

P4/nmm
TC = 165 K (Ferri)

TCO > 308 K (ST)

Pmma
TN = 430, 308 K

TCO > 220 K (ST)

Pmma
TN = 330 K

Millange, et al. Mater.

Res. Bull. 1999, 34, 1.

Woodward, Karen Inorg.

Chem. 2003, 42, 1121.

Vogt, et al. PRL 2003,

84, 2969.

Orbital Ordering in YBaM2O5

x2-y2

Mn2+

xz

z2
xy

Mn3+

z2

xz

xy

Fe2+

yz
x2-y2

yz

YBaMn2O5
P4/nmm

x2-y2
z2

xz

xy

Fe3+

z2

xz

xy

Co2+

yz
x2-y2

yz

YBaFe2O5
Pmma

x2-y2
z2

xz

xy

yz
x2-y2

Co3+

z2

xz

xy

yz

YBaMn2O5
Pmma

Phase Transitions RBaFe2O5

Paramagnetic to Antiferromagnetic (430-450 K)
YBaFeCuO5 Type AFM Order
Small Magnetostrictive coupling leads to a subtle Tetragonal
to Orthorhombic Distortion

Premonitory Charge Ordering (290-330 K)

Subtle charge localization can be seen in DSC & Mossbauer,
but not in diffraction measurements
Mixed valency changes from Type I to Type II

Long Range Charge Ordering (240-290 K)

Induces a large orbital ordering transition
Orbital ordering stabilizes a stripe CO pattern
Stabilizes G-type Antiferromagnetic order (changes the sign
of the Fe-Fe direct exchange)

Structural Evolution: REBaFe2O5

Fe-Fe Dist.
Fe-Fe
Dist.

2.04

Nd
Nd

Fe-O Distance (Angstroms)

3.69
3.67
3.65

Sm

3.63
3.61

Tb

Ho

3.59
3.57

Ho

3.55
115

117

163

119

121

123

125

Fe-O-Fe

Dist.

161

Nd

160
159

Sm

Ho

Ho

158

157

Nd

Tb

156
115

Ave. Fe-O
Ave.
Fe-O Dist.
Dist.

2.02
2.01

Sm

Ho

2.00
1.99

Ho

Nd
Nd

Tb

1.98
1.97

120
R Radius (CN=8, pm)

115

117

119

121

R Radius (CN=8, pm)

Ave. Fe-O-Fe

162

2.03

1.96

R Radius (CN=8, pm)

Fe-O Distance (Angstroms)

Fe-Fe Distance (Angstroms)

3.71

125

Changing the
size of the RE
ion modifies
the Fe-Fe
distance.

123

125

Phase Transitions vs. R size

340

V (Cubic Angstroms)

320

Tpm

Ho

Type III
Mixed Valent

TCO (MV IIMV I)

decreases significantly.

Nd

300
280

As the radius of the R

ion increases

TCO

Type II

TCO

TPM (MV IIIMV II)

decreases more gradually.

260
240

Type I
Charge Ordered

220

TN1 changes very little.

200
114

116

118

120

122

R Radius (CN=8, pm)

124

126

Volume Change at TCO

0.33

Sm

V (Cubic Angstroms)

0.31
0.29
0.27
0.25

Pmma
Pmma

0.23

ma

ma

0.21

Nd

Ho

0.19

P2
P211ma
ma

0.17
0.15
114

116

118

120

122

124

126

R Radius (CN=8, pm)

Volume change at TCO (MV II MV I)

HoBaFe2O5

Pmmm

300

GG

400

400

100

NdBaFe2O5

300

Pmmm
P21ma

100

20

40

2-theta

60

020

200

400

T(K)

020

Pmma

200

200/02
0

T(K)

400

200/02
0

Thermodiffractometry (ILL-D20)

80

Woodward, Karen, Suard, J. Amer. Chem. Soc. 125, 8889 (2003).

HoBaFe2O5 Unit Cell Evolution

1 K Temperature grid, 1 min collection time

No noticeable
change at TPM

P4/mmm to
Pmmm at TN

Woodward, Karen, Suard, J. Amer. Chem. Soc. 125, 8889 (2003).

NdBaFe2O5 Unit Cell Evolution

1 K Temperature grid, 1 min collection time

Woodward, Karen, Suard, J. Amer. Chem. Soc. 125, 8889 (2003).

Orbital Ordering (RE = Nd, Ho)

Orthorhombic distortion increase at
TCO is much larger in HoBaFe2O5.

Orthorhombic distortion
saturates at Tpm for
NdBaFe2O5. Similar
behavior is not observed
for HoBaFe2O5

Magnetism vs.
Temperature

RBaFe2O5 (R=Tb, Y, Ho)

YBaFeCuO5 AFM Structure
Fe-Fe Coupling Ferromagnetic
@ TCO

TCO

G-Type AFM Structure

Fe-Fe Coupling Antiferromagnetic
TCO

NdBaFe2O5
YBaFeCuO5 AFM Structure
Fe-Fe Coupling Ferromagnetic
@ TCO
YBaFeCuO5 AFM Structure
Fe-Fe Coupling Ferromagnetic

Nd Magnetism in NdBaFe2O5

Nd moment is ~1.2 B at 2 K, TN (Nd) ~ 30 K

No rare-earth magnetic order for R = Ho.

Nd magnetism is induced by Fe magnetism.

Structural Tuning in RBaFe2O5

As the radius of the R ion increases (R = Ho-Sm)
The spacing across the R-layer increases
TCO decreases significantly, TPM decreases more gradually
TN1 changes very little
Patterns of charge, orbital and spin order remain constant

NdBaFe2O5 The large size of Nd has several effects

Disrupts the ideal pattern of orbital ordering
The CO structure has P21ma symmetry rather than Pmma
The volume change at TCO is anomalous
The orthorhombic distortion parameter saturates at T PM

Decouples the magnetic and charge order

There is no rearrangement of the magnetic structure at T CO

Destabilizes the long range charge order

TCO is much lower than other members of the series