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Experimental Procedure
The main chemicals used in this work were analytical-reagentgrade (99.9%). YFe1yMnyO3 specimens were prepared using
the Pechini method12 or solid-state method. A stoichiometric
mixture of Y(NO3)3, Fe(NO3)3, and MnCO3 was combined with
citric acid and ethylene glycol. The polymer solution was evaporated, dried, burned at 500C, and calcined at 900C for 10 h. The
product was milled using zirconia balls for 24 h and then was cold
isostatically pressed and sintered at 1350C for 15 h. If the
solid-state method was applied, mixtures of corresponding metal
oxides or carbonates in the proper ratios were directly used for
calcination and sintering; the remainder of the preparation procedure was similar to the above. Samples that were prepared using
the Pechini method usually had a slightly higher electrical conductivity (20%) than those prepared using the solid-state method
because of the high homogeneity and good contact of the particles.
Phase impurity and crystal structure of each composition were
examined using powder X-ray diffractometry (XRD; Model XRD2000, Scintag, Inc., Santa Clara, CA) using CuK1 radiation.
Lattice parameters were calibrated using an internal standard of
silicon single crystal with a scanning rate of 1/min. Fouriertransform infrared spectra (FT-IR) were recorded using KBr
pellets and a spectrophotometer (Model 1725X8700, Perkin
Elmer Co., Norwalk, CT) from 10 000 to 400 cm1. Direct-current
electrical conductivity measurement was performed using a fourprobe technique programmable current source (Model 200,
Keithley Instruments, Inc., Cleveland, OH) and a multimeter
(Model 2000, Keithley Instruments). The Seebeck coefficient was
determined using a temperature gradient of maximum 10 K along
the length of the specimen and repeated measurements of the
temperature difference and the corresponding Seebeck voltage. At
least 20 points were measured, and the slope of the resulting line
was the Seebeck coefficient. The PO2 was controlled using a gas
mixture of N2/O2 or CO2/CO and monitored using a YSZ oxygen
sensor. The specimen size was 1.8 mm 1.8 mm 20 mm.
Introduction
H. U. Andersoncontributing editor
III.
Manuscript No. 189224. Received July 15, 1999; approved March 13, 2000.
Supported by the New and Renewable Energy Development Center, Korea Energy
Management Corporation.
*Member, American Ceramic Society.
To whom all correspondence should be addressed. Temporary address: Forschungszentrum Julich, D-52425 Julich, Germany.
1266
0
0
0
0
0
0
0
0.1
LaFeO3
LaMnO3
0
0.1
0.2
0.3
0.35
0.4
1
0.4
a ()
( 0.003)
b ()
( 0.006)
c ()
( 0.005)
V (3)
( 0.4)
D (%)
5.282
5.279
5.280
5.276
5.270
5.271
5.24
5.271
5.567
5.537
5.598
5.599
5.604
5.612
5.643
5.651
5.84
5.569
5.553
5.741
7.602
7.589
7.585
7.548
7.534
7.517
7.36
7.537
7.855
7.694
224.8
224.3
224.4
223.5
224.0
223.9
225.2
221.2
242.8
244.6
11.51
11.51
11.52
11.50
11.64
11.65
12.33
11.33
9.83
8.00
Fig. 1.
Fig. 2.
June 2001
Effect of Substitution of Mn for Fe on the Structure and Electrical Properties of Yttrium Ferrite
cubic perovskite structure belongs to the O1h space group. According to group theory, the optically active lattice vibrations are given
by 3F1u F2u,16 of which the F2u mode is inactive in the IR
region. Therefore, the IR spectra of the perovskite structure should
show three absorption bands. These can be attributed to the BO
bond stretching vibration of BO6 octahedra (1:F1u), the bending
vibration of the BO bond (2:F1u), and the lattice vibration
(3:F1u). The expected energy order is usually 1 2 3. Any
deviation from the cubic symmetry causes splitting of these three
bands. Under our experimental condition, we can observe only the
former two bands. Figure 2 shows that the substitution of manganese for iron makes the absorption peak shift toward the higherenergy side, implying that the covalence of the BO bond is
increased and the ionicity is decreased. On the other hand, the
substitution of manganese for iron also splits band 2 in two peaks.
Especially for YFe0.6Mn0.4O3, two absorption peaks in the 2 band
can be distinguished clearly, indicating that the structure deviates
more and more from the cubic symmetry, as proved by XRD
results.
(2) Electrical Properties
(A) YFeO3: Figure 3 shows the electrical conductivity ()
and Seebeck coefficient () of YFeO3 measured in an air atmosphere. In the entire experimental temperature range, YFeO3 has the
n-type conduction character. The Seebeck coefficient and electrical conductivity can be calculated using the following equations:1,8
k
21 C
ln
S0
e
C
(1)
a 2 e 2 N mC1 C
expEa/kT
kT
(2)
Fig. 3.
1267
2FeFe
k
21 2c
k
ln
ln
e
e
c
FeFe
a 2 e 2 N mc1 2c
expEa/kT
kT
(3)
(4)
FeFeFeFe
are charge carriers. In Eqs. (3) and (4), c is the
concentration of FeFe and (1 2c) is the available sites for the
jumping of charge carriers, and it is equal to the concentration of
FeFe, which can be easily obtained from the disproportionation
equation, 2FeFe
FeFe FeFe
.
As calculated using the above equations, at 1000C, c 0.03
and (5.7 5.6) 1014 Hz, which is slightly dependent on the
temperature.
The electrical conductivity of YFeO3 versus PO2 is shown in
Fig. 4. At 1000C, YFeO3 is stable until log PO2 13.5. The
conductivity behavior of YFeO3 in this study is somewhat different from the former work,1,4 but the Ca-doped YFeO3 has the same
electrical property as the former. In this study, YFeO3 does not
show a conductivity minimum. This difference is possibly induced
by different specimen preparation conditions, such as contamination and nonstoichiometric composition. Because the undoped
YFeO3 of this work shows the n-type conduction, it is possible that
the formation of FeFe is electronically compensated by the existence of impurities with valence 4, such as Zr4 and Si4, which
might be obtained during ball-milling. This possibility has been
checked using inductively coupled plasma spectrometry (ICP).
1268
Fig. 4.
However, the result has proved that impurity levels of Zr4 and
Si4 were below the sensitivity limit of the ICP instrument
( 0.01 wt%, approximately equal to 0.02 mol% for Zr4 and
0.07 mol% for Si4). These values are dramatically lower than the
charge-carrier concentration, 3 mol%. Therefore, the possibility of
contamination to make the undoped YFeO3 exhibit n-type conduction can be eliminated. On the other hand, a minor deviation in the
stoichiometry, if it exists, should not affect the conduction type
because Y3 and Fe3 have the same valence, and no electronic
compensation occurs. It has been observed that a trace of garnet
Y3Fe5O12 exists in the system Y1xCaxFeO3 (x 0 0.1), but
YFeO3 exhibits p-type conduction,1 implying that stoichiometry
deviation does not determine the conduction type. Therefore, it is
more reasonable to suppose the n-type conduction of YFeO3 to be
intrinsic than to be extrinsic.
(B) YFe1yMnyO3: Figure 5 shows the electrical conductivity of YFe1yMnyO3 versus temperature in an air atmosphere.
These curves are best fitted with s 1 in the equation
(C/T s) exp(-Ea/kT) for other than s 0 or s 3/2, implying that
electrical conduction occurs through the adiabatic small-polaron
hopping mechanism. The dotted lines in Fig. 5 are a theoretical
fitting to the experimental data according to this equation. The
conductivity of YFe1yMnyO3 at selected temperatures from 700
to 1200C is shown in Fig. 6. At 1000C, the conductivity of
YFe0.6Mn0.4O3 is 2.16 1cm1, 1 order of magnitude higher
than that of YFeO3 (0.10 1cm1). The activation energy of
YFe1yMnyO3 is shown in Fig. 7.
Figure 6 shows that the electrical conductivity of YFe1yMnyO3
can be clearly distinguished into two regimes with y 0.2 as the
crossover point. In the range y 0.2, the conductivity decreases
first and then increases with y 0.05 as the minimum point. When
y 0.2, the conductivity increases in linear proportion to the
manganese content, and, in this range, the activation energy is
almost constant. The conductivity behavior of YFe1yMnyO3 is
similar to that of La(Cr,Mn)O3, whose conductivity minimum also
occurs at Mn 0.05, and can be well described with the
random-well and random-barrier models.7,8 Despite the comparatively higher intrinsic conductivity of YMnO3, a small substitution
of manganese for iron in YFeO3 results in a decrease of conductivity below 900C. This decrease becomes larger as temperature
decreases. In the system YFe1yMnO3, the manganese site is
supposed to be energetically lower than the iron site. The activation energy of YFe0.95Mn0.05O3 (Ea 1.02 eV) must represent the
energy for a small polaron at a manganese site to hop to a
neighbored iron site (YFeO3, Ea 0.82 eV). The energy difference between the manganese site and the iron site makes the
manganese sites (y 0.05) act as traps for polarons migrating
among the iron sites. The trapping mechanism can be expressed
as FeFe MnFe
3 FeFe
MnFe. Small polarons (FeFe
FeFe
)
are supposed to be the main charge carrier in the systems
June 2001
Effect of Substitution of Mn for Fe on the Structure and Electrical Properties of Yttrium Ferrite
1269
2Mn3
c
0.42c
Mn2
0.20.5c
c
Mn4
0.20.5c
c
T 950C
T 950C
(5)
2Mn4
k
20.20.5c
k
ln
ln
e
Mn3
e
c
T 950C
Fig. 7.
electrons (FeFeFeFe
), as discussed above, are charge carriers, and,
Fig. 8.
k
e
ln
2Mn3
k
20.42c
ln
Mn4
e
c
a 2e 2N m
c0.20.5c expEa/kT
kT
a 2e 2N m
c0.42c expEa/kT
kT
(6)
T 950C
(7)
T 950C
T 950C
(8)
(9)
1270
HD 1 SD
GD
ln KD
RT
R T
R
(10)
YFe0.6Mn0.4O3
YFe0.6Mn0.4O3
Y0.9Ca0.1Fe0.6Mn0.4O3
Y0.9Ca0.1Fe0.6Mn0.4O3
T (C)
950
950
920
920
HD (kJmol
66 4
97.1 0.9
24 1
19.6 0.2
SD (Jmol
42.3 0.1
91.8 0.6
4.62 0.03
22.5 0.1
) 17.46 Jmol1K1.22
and (SD
Because the electrical conduction occurs only among the
manganese sites, and the function of iron sites can be neglected
when 0.4 y 0.2, we have two reasonable assumptions in
the conductivity calculation of compositions other than
YFe0.6Mn0.4O3: (i) (HD) and (SD) are independent of composition;
and (ii) compositions with 0.4 y 0.2 have similar activation
energy and similar vibrational frequency.
The theoretical fitting of conductivity is shown in Fig. 6. There
is a good agreement between the theoretical values and experimental results, further proving that the conduction occurs directly
among manganese sites when y 0.2.
The electrical conductivity of YFe0.6Mn0.4O3 as a function of
PO2 at 900, 1000, and 1100C is shown in Fig. 10. For all these
isotherms, conductivities are almost constant within a certain range
of PO2 depending on the temperature. These isotherms do not
exhibit the oxygen-activity-dependence behavior. The same phenomenon has been observed in the system Y1xCaxMnO3 by
Stevensen et al.5 The low phase stability of Y-Mn-O oxides can be
attributed to the small size of Y3, which apparently decreases the
stability of yttrium-containing perovskite structures, so that they
dissociate as soon as the loss of oxygen begins. Lanthanum
compounds with perovskite structures, such as LaMnO324 and
LaFeO3,25 have much higher stability than that of yttriumcontaining compounds, and the dependence of conductivity on PO2
can be observed clearly.5,19,26 When YFe0.6Mn0.4O3 begins to
dissociate, its conductivity increases sharply. As proved by XRD
experiment and indicated by Stevensen et al.,5 Mn3O4 is the stable
manganese oxide under the PO2 range where Y1xCaxMnO3 begins
Table III. Gibbs Free Energies for the Formation of
YFe0.6Mn0.4O3 and Y0.9Ca0.1Fe0.6Mn0.4O3
Gibbs free energy, Gf (kJmol1)
900C
1000C
1100C
Composition
June 2001
Fig. 11.
phere.
Effect of Substitution of Mn for Fe on the Structure and Electrical Properties of Yttrium Ferrite
Fig. 12.
1271
(C) Y0.9Ca0.1Fe0.6Mn0.4O3: The conductivity of calciumdoped samples is shown in Fig. 11. The conductivity increases
with the addition of calcium, as expected. Y0.8Ca0.2Fe0.6Mn0.4O3
has almost the same conductivity as Y0.9Ca0.1Fe0.6Mn0.4O3. The
former is not a single phase, and it should have similar chargecarrier concentration to Y0.9Ca0.1Fe0.6Mn0.4O3, because Ca 0.1
is the doping limit, as proved by XRD experiment. However, the
most curious phenomenon is that the conductivity of
Y0.9Ca0.1Fe0.6Mn0.4O3 (5.6 1cm1, 1000C) is much lower
than that of Y0.9Ca0.1FeO3 (18.0 1cm1, 1000C). It is
supposed that the electronic compensation of calcium doping in
Y0.9Ca0.1FeO3 is the formation of Fe4 and that the sample has
p-type conduction. In Y0.9Ca0.1Fe0.6Mn0.4O3, the electronic compensation must be the formation of Mn4. In CaMn1xFexO3y
and SrMn1xFexO3, all iron sites are in valence Fe3, and most
of the manganese sites are in Mn4.27,28
The thermopower of Y0.9Ca0.1Fe0.6Mn0.4O3 in an air atmosphere is shown in Fig. 12. Below 920C, it has p-type conduction,
and, above 920C, it changes to n-type. Its Seebeck coefficient is
in a good linear proportion with inverse temperature, but there is
a curvature at the change of the conduction mechanism, the same
as YFe0.6Mn0.4O3. On the other hand, this change coincides with
the curvature of the electrical conductivity plot. The n-type
conduction has a slightly higher activation energy (0.422 0.004
eV) than that of p-type conduction (0.326 0.003 eV). The
conductivity calculation of Y0.9Ca0.1Fe0.6Mn0.4O3 is similar to
that of YFe1-yMnyO3, and c 0.24, 1.3 1014 (1000C). The
equilibrium constant of Mn3 disproportionation in the calciumdoped sample is shown in Fig. 9. (HD) and (SD) obtained from the
plot of ln KD vs 1/T are listed in Table II.
The electrical conductivity of Y0.9Ca0.1Fe0.6Mn0.4O3 as a function of PO2 is shown in Fig. 13, which also indicates its lower phase
stability than that of YFe0.6Mn0.4O3 because of the addition of
Ca2. These isotherms are very similar to those of YFe0.6Mn0.4O3,
and the Gibbs free energy of formation is also listed in Table III.
The reason for conduction-type change is not clear at this time.
One possible reason is the change of crystal structure at high
1272
Conclusion
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