Journal of ELECTRONIC MATERIALS, Vol. 40, No.

5, 2011
DOI: 10.1007/s11664-010-1446-3
Ó 2010 TMS

Thermoelectric Properties of the Ca1xRxMnO3 Perovskite

System (R: Pr, Nd, Sm) for High-Temperature Applications

SOON-MOK CHOI,1 CHANG-HYUN LIM,1 and WON-SEON SEO1,2

1.—Green Ceramic Division, Korea Institute of Ceramic Engineering and Technology (KICET),
Seoul 153-801, Korea. 2.—e-mail: wsseo@kicet.re.kr

Perovskite oxides have attracted considerable attention in the area of ther-

moelectrics owing to the advantages of their isotropic crystal structure and
straightforward control of their electrical properties. Among the many per-
ovskites, different types of polycrystalline Ca1xRxMnO3 (R: Pr, Nd, Sm) were
prepared by solid-state reaction in this study. Three different rare-earth
dopants were substituted at the Ca-ion site at various amounts. Considering
phase stability, rare-earth ions with nearly the same ionic radius as Ca2+ were
selected. To assess thermoelectric performance, the electrical conductivity,
Seebeck coefficient, and power factor were measured, and phase analysis was
conducted. The effects of ionic radius variation on single phase formation and
the effect of doping amount on carrier concentration are discussed.

Key words: Thermoelectric semiconductor, oxide, perovskite, CaMnO3,

dopant

INTRODUCTION thermoelectric performance, polycrystalline mate-

rial with a textured structure or a single crystal
Thermoelectric oxides have the advantage of long-
should be produced.3 To overcome the complexity
term use in air, even at high temperatures. More-
of manufacturing such material, new oxides with
over, their constituent components are abundant in
isotropic crystal structure and highly symmetric
the Earth’s crust, and they are less toxic than heavy-
unit cells are necessary. Several researchers have
metal compounds. Therefore, thermoelectric oxides
investigated perovskite-type oxides, for example,
are regarded as promising materials for power gen-
CaMnO34 and LaNiO3.5 Among these perovskites,
eration, especially at high temperatures. Terasaki
CaMnO3 has received attention as an alternative
reported an oxide material, NaxCoO2, with a high
thermoelectric oxide. Flahaut et al. indicated that
Seebeck coefficient (100 lV/K at 300 K) and low
CaMnO3 was essential to overcome the lack of
resistivity (0.2 mX at 300 K).1 Calcium cobalt oxide,
n-type thermoelectric oxides.4
Ca3Co4O9, was also reported to exhibit excellent
Electronic ceramic perovskite structures have
conductivity with an extraordinarily large Seebeck
attracted attention owing to the advantages of their
coefficient.2 These results show that the thermo-
isotropic crystal structure and easy control of
electric performance of oxides is comparable to that
their electrical properties. Their first advantage is
of intermetallic compounds. However, these cobalt
their isotropic crystal structure, as mentioned
oxide systems have anisotropic crystal structures,
above. Therefore, in this system, there is no need for
hence polycrystalline material produced by a con-
a complex manufacturing process to produce a tex-
ventional sintering process has a layered structure in
tured structure. As a second advantage of this sys-
this system. If these layered structures of the grains
tem, various types of perovskites can be created
are not well controlled in polycrystalline material,
from many constituent atoms with various ionic
these systems may show relatively low thermo-
radii and charge valences, to the extent that geo-
electric performance. Therefore, to improve their
metric factors allow. An ideal perovskite structure is
represented as having the ABO3 cubic structure.
(Received May 5, 2010; accepted November 12, 2010; The A-site ion has a relatively large ionic radius
published online December 15, 2010) that is nearly identical to the radius of the O2 ion.

551
552
The B-site ion has a relatively small ionic radius.
Many types of perovskite structures have been dis-
covered; examples include A3+B3+O3, A2+B4+O3, and
A2+B3+ 5+
1/2B1/2O3.
Another advantage is the range of possibilities
when seeking to control the electrical properties of
these materials. In general, the electrical conduc-
tivity of an oxide depends on the carrier concen-
tration and carrier mobility. In the perovskite
structure, these two factors can be controlled
simultaneously by substitution of dopants. In the
case of pure CaMnO3, the charge valence for all of
the Mn ions is 4+. If some donors produce effectively
positive defects in this perovskite, the charge
valence of Mn4+ can be changed to 3+ in proportion
to the amount of donors. As a result, this mixed
valence between the Mn4+ and Mn3+ states can
increase the carrier concentration in accordance
with the Verwey controlled ionic valence principle.6,7
These electrons create the Ca1xRxMnO3 perovskite
n-type semiconductor. Moreover, in this ABO3
perovskite system, it is possible to substitute dopant
ions at the A site and B site simultaneously to
control the carrier concentration of the system. It is
also possible to control the mobility of these perov-
skite oxides by controlling the tolerance factor of the
perovskite structure. Specifically, controlling the
ratio of the ionic radius between the A-site ion and
B-site ion can have an effect on the carrier mobility
of this perovskite system. As the last advantage,
perovskite structures are more stable than any
other electronic ceramic. Above all, they have been
researched for more than 60 years;8 hence, a con-
siderable amount of data exists regarding the
phase stability of these materials as well as methods
to enhance their electrical properties. However,
research concerning the thermoelectric properties of
these types of perovskite systems is in its infancy at
present.
Thus, in this study, to control the carrier con-
centration, three different rare-earth dopants, Pr3+,
Nd3+, and Sm3+, were substituted into the Ca-ion
site at different amounts of 0.01 mol%, 0.05 mol%,
and 0.1 mol%. Considering phase stability, rare-
earth ions with nearly the same ionic radius as Ca2+
were selected. The effects of doping on the formation
characteristics of the single phase and on the
change of the mobility and the carrier concentration
were investigated in the Ca1xRxMnO3 perovskite
system. In addition, the thermoelectric properties at
high temperature for Ca1xRxMnO3 doped with
the rare-earth ions Pr3+, Nd3+, and Sm3+ were
compared.
EXPERIMENTAL PROCEDURES
Ca1xRxMnO3 (R = Pr, Nd, Sm; x = 0, 0.01, 0.05,
0.1) samples were prepared by conventional solid-
state reaction. CaCO3 (99.99%, High-Purity Chem-
ical), Mn2O3 (99.9%, High-Purity Chemical), Nd2O3
(99.9%, High-Purity Chemical), Sm2O3 (99.9%,
Choi, Lim, and Seo
High-Purity Chemical), and Pr2O3 (99.9%, High-
Purity Chemical) powders were used as the starting
materials. They were weighed stoichiometrically
and mixed for 20 h with ethanol and yttria-
stabilized zirconia (YSZ) balls in a ball-milling pro-
cess. The mixture was dried, and then calcined at
900°C for 15 h in air after compaction. The grinding
and calcination processes were repeated at 1000°C,
1100°C, and 1200°C for 15 h with the same powders
for the formation of a single phase. The powders
calcined at 1200°C were pressed using a CIP at
200 MPa for 5 min after sieving (325 mesh). The
pressed compacts were sintered at 1300°C for 15 h
in air. The sintered samples were cut into rectangular
bars with dimensions of 2 mm 9 2 mm 9 15 mm to
measure the thermoelectric properties.
The phases of the sintered Ca1xRxMnO3 samples
were analyzed by x-ray diffraction (XRD) with a
Rigaku D/MAX-2500/PC diffractometer (Rigaku,
Japan, Cu Ka radiation). The thermoelectric prop-
erties were measured by a thermoelectric property
measurement system (Ozawa Science, model
RZ2001i). The electrical conductivity was measured
by a four-probe method, and the Seebeck coefficient
was obtained from the slope of the linear relation-
ship between DV and DT, where DV is the thermo-
electromotive force produced by the temperature
difference DT.
RESULTS AND DISCUSSION
Pure CaMnO3 samples can be indexed as a single
phase with orthorhombic symmetry of Pnma.4,9 The
XRD patterns presented in Fig. 1 indicate that it
was very difficult to build a single phase in the
doped CaMnO3 perovskite system, especially in the
Sm3+-doped case. Even after four calcinations
(900°C, 1000°C, 1100°C, and 1200°C) for the for-
mation of a single phase, the XRD results did not
show a single phase. The second phase detected was
indexed as another perovskite structure; in this case
it was Ca0.5Sm0.5MnO3.10 This difficulty regarding
the formation of a single phase can be explained in
terms of the difference in the ionic radius between
the Sm3+ and Ca2+ ions at the A site. Unlike the
CaMnO3 perovskite system with a large Ca2+ ion, in
case of a small A-site ion such as in YbMnO3, the
perovskite structure is indexed as rhombohedral.4
The difference in the ionic radius between the A-site
ions can cause a difference in the crystal structure,
which can disturb the formation of a single-phase
solid solution in this system. Instead of forming a
single phase, substituted dopants are considered to
prefer the formation of a new second phase, specif-
ically an ordered perovskite structure. In this or-
dered perovskite structure, large and small ions at
the A site can alternately occupy the A sites of the
A0.5A0.5BO3 perovskite structure.11
This phenomenon can also be explained by the
conventional parameter of the perovskite tolerance
factor, which describes the geometric distortion of
Thermoelectric Properties of the Ca1xRxMnO3 Perovskite System (R: Pr, Nd, Sm) for High-Temperature
Applications
Fig. 1. XRD analysis results for the Ca0.9Sm0.1MnO3 samples after:
(a) first calcination at 900°C for 15 h, (b) second calcination at
1000°C for 15 h, (c) third calcination at 1100°C for 15 h, (d) fourth
calcination at 1200°C for 15 h, and (e) subsequent sintering at
1300°C for 15 h.
ABO3-type perovskites. This conventional parame-
ter is defined as
pffiffiffi
t ¼ ðrA þ rO Þ= 2ðrB þ rO Þ; (1)
where rA, rB, and rO are the ionic radii of each ion.
An ionic radius in a crystal structure can have
various values depending on both the coordination
number and the charge valence of each ion. In the
perovskite structure, t falls within the range of 0.75
to 1.1. For the cubic perovskite structure, t is close
to 1. In this case, the oxygen octahedra around the
Mn ions are located exactly at the corners of the
cubic perovskite structure. Hence, these octahedra
need not be distorted. However, in the event of a
smaller rA, in other words as t decreases from 1, the
geometric distortion gradually increases. Therefore,
the decrease in rA confirms the enhancement of the
orthorhombic distortion. As a result, the oxygen
octahedra around the Mn ions become more dis-
torted, appearing as tilted structures that lean
against each other, similar to zigzag chains.12 The
tolerance factors calculated in this study were
0.996, 0.995, and 0.994 for the cases of Pr3+ (1.30 Å,
12-coordinated), Nd3+ (1.27 Å, 12-coordinated), and
Sm3+ (1.24 Å, 12-coordinated) doping, respectively.
553
Fig. 2. XRD analysis results for Ca0.9R0.1MnO3 (RE : Pr, Nd, Sm):
(a) pure CaMnO3 sintered at 1300°C, (b) Ca0.9Sm0.1MnO3 sintered
at 1300°C, (c) Ca0.9Nd0.1MnO3 sintered at 1300°C,
(d) Ca0.9Pr0.1MnO3 sintered at 1300°C, (e) Ca0.9Sm0.1MnO3 calcined
at 1200°C, (f) Ca0.9Nd0.1MnO3 calcined at 1200°C, and
(g) Ca0.9Pr0.1MnO3 calcined at 1200°C.
To calculate the tolerance factor values in the
present study, the coordination numbers of the
A-site ion, B-site ion, and O ion (1.40 Å, 6-coordinated)
were set to 12, 6, and 6, respectively. In addition,
Shannon’s ionic radii were used in this study for the
calculation of the tolerance factors.13 As a result, it
can also be expected that, in the Sm3+-doped case, it
will be more difficult to build a single-phase solid
solution compared with the other cases doped with
large ions, as the Sm3+-doped case has a low toler-
ance factor due to the smaller ionic radius of Sm3+.
After five mixings and firings (1300°C), the XRD
patterns shown in Fig. 2 indicate that all of the
samples are single-phase samples with orthorhom-
bic symmetry. However, a small amount of a second
phase undetected by XRD may exist, especially
when doping with the smaller-sized Sm3+ ion. The
existence of the second phase is suspected because a
smaller Sm3+ ion makes it more difficult to build a
single-phase solid solution due to the distortion of
oxygen octahedra around the Mn ions. This
assumption can be deduced given that the largest
amount of the second phase remained after calci-
nation at 1200°C, as shown in Fig. 2e. In fact, this
was proved by the decrease in the electrical con-
ductivity in this Sm3+-doped system.
554 Choi, Lim, and Seo

Another important factor that should be consid-

ered in the donor-doped CaMnO3 system is that the
charge valence of the Mn ion is changed owing to
the donor doping. The charge valence of Mn4+
(0.53 Å, 6-coordinated) becomes Mn3+ (0.645 Å,
6-coordinated) in proportion to the donor amount.
This change in charge valence from Mn4+ to Mn3+
has two types of effects on the CaMnO3 perovskite
structure. The first is an increase in the ionic radius
of the Mn, from the small Mn4+ to the large Mn3+.
Thus, when calculating the tolerance factor of this
donor-doped CaMnO3 system, the average radius
value for the Mn ion should be calculated after
considering the change of the charge valences due to
the dopant amount. The second effect is Jahn–Teller
distortion. The structural distortion in the CaMnO3
perovskite is associated not only with a decrease in
the tolerance factor but also with the presence of a
Jahn–Teller-type Mn3+ cation on the B site with
octahedral coordination. Such a cation promotes
anisotropic deformation, which induces a change of
symmetry.14 In eg electron systems such as Mn3+
compounds, the electronic configuration is t32ge1g,
hence the eg electron occupies an orbital. The Jahn–
Teller effect removes the degeneracy of the eg orbi-
tal by causing large deformation of the MnO6 octa-
hedra. Therefore, the distortion of the structure can
increase with the doping amount.
In addition, the electrical conductivity increased Fig. 3. Thermoelectric properties for Ca0.9Nd0.1MnO3 samples
with the doping amount. Figure 3a shows the within a temperature range of 333 K to 1132 K: (a) variation of
increase of the electrical conductivity with doping electrical conductivity with doping amount, and (b) variation of See-
beck coefficient with doping amount.
amount for the Ca1xNdxMnO3 system. This is evi-
dence of an increase in the electron concentration
due to the change in the charge valence from Mn4+
to Mn3+ in accordance with the Verwey controlled
ionic valence principle.6,7 Figure 3b shows the
decrease of the Seebeck coefficient with the doping
amount for the Ca1xNdxMnO3 system. In general,
the Seebeck coefficient is inversely proportional to
the electrical conductivity in thermoelectric mate-
rials.15 Therefore, the decreasing Seebeck coeffi-
cient in this system can also be evidence of an
increase in the electron concentration due to the
change of the charge valence in accordance with the
Verwey controlled ionic valence principle.6,7 In
addition, while the electrical conductivity of the
Ca0.9Nd0.1MnO3 specimen was much higher than
that of the Ca0.95Nd0.05MnO3 specimen, the Seebeck
coefficient of the Ca0.9Nd0.1MnO3 specimen was not
much lower than that of the Ca0.95Nd0.05MnO3
specimen. This result can also be explained in terms Fig. 4. Variation of the power factor for Ca1xNdxMnO3 samples
of the Jahn–Teller effect for this donor-doped from 333 K to 1132 K with doping amount.
CaMnO3. As Jahn–Teller distortion removes the
degeneracy of the eg orbital, the Seebeck coefficient
could be enhanced in proportion to the increase of
the Mn3+ ion. More detailed investigation of this expressed as rS2, increases as the carrier concen-
effect, including the measurement reliability, will tration increases due to the increase in electrical
be done as a follow-up study. conductivity. Thus, in a high-carrier-concentration
The change in the power factor with doping region, the power factor decreases as the carrier
amount is presented in Fig. 4. Generally, in a concentration increases due to the decreasing
low-carrier-concentration region, the power factor, Seebeck coefficient. Therefore, the power factor has
Thermoelectric Properties of the Ca1xRxMnO3 Perovskite System (R: Pr, Nd, Sm) for High-Temperature
Applications
Fig. 5. Variation of thermoelectric properties for Ca0.9R0.1MnO3 (RE:
Pr, Nd, Sm) samples with tolerance factor for the perovskite structure
(in other words, with dopant ionic radius): (a) variation of electrical
conductivity and Seebeck coefficient at 1080 K, (b) variation of
power factor within the temperature range 877 K to 1132 K.
a maximum at the intermediate region of carrier
concentration in general. However, as shown in
Fig. 4, the power factor increased with doping
amount over the entire range in this work. This
result indicates that the carrier concentration,
explicitly the doping amount, is not yet optimized
in this work. Thus, there is the possibility to
increase the power factor further with additional
doping.
The effect of the change in the tolerance factor on
the electrical conductivity is shown in Fig. 5a. As
mentioned above, in the case of a dopant smaller
than the host ion Ca2+, it is difficult to build a
single-phase solid solution owing to the distortion of
the oxygen octahedra around the Mn ions. This
implies that doping with a large ion at the A site,
specifically in the event of a large tolerance factor,
would effectively increase the electrical conductiv-
ity. For this reason, the electrical conductivity of the
Pr-doped specimen was higher than any of the other
cases. Moreover, the Sm-doped case showed a lower
electrical conductivity compared with the other
specimens. However, Flahaut et al. pointed out that
a small-sized dopant can increase the electron con-
ductivity by narrowing the eg electron’s conduction
bandwidth.4 The reason for this discord is not yet
clear. It should be noted here, however, that a
555
possibility exists for a negative effect of the distor-
tion of the oxygen octahedra around the Mn ions on
the mobility of the electrons. Moreover, as men-
tioned above, the second phase can also have a
negative effect.
As a result, the maximum power factor for a rare-
earth-doped Ca1xRxMnO3 system was 3.98 9 104
W/m K2 for 10 mol% Pr-doped composition at
1132 K, as presented in Fig. 5b. This value is com-
parable to the value for Ca3Co4O9, the most prom-
ising oxide thermoelectric material.16 The reason for
the highest Seebeck coefficient for the Pr-doped
case, even with high electrical conductivity, is not
yet clear, as shown in Fig. 5a. However, it should be
noted that the Pr ion has a complex electronic
structure; for example, the possibility exists for a
change of the charge valence from Pr3+ to Pr4+ in
oxides. Therefore, this complex electronic structure
can enhance the entropy and the Seebeck coefficient
for this Pr-doped system. More detailed research
into the Pr-doped system will be conducted in sub-
sequent work.
The efficiency of a thermoelectric material is
determined by its dimensionless figure of merit,
ZT = S2rT/j, where S2r, j, and T are the power
factor, the thermal conductivity, and absolute tem-
perature, respectively. The thermal conductivity
for this doped CaMnO3 system was reported as
1.7 W/m K to 1.5 W/m K at 1100 K.17 So, the dimen-
sionless figure of merit (ZT) can be calculated to be
as high as about 0.28 at 1132 K, being comparable
to the value for Ca3Co4O9, the most promising oxide
thermoelectric. For a follow-up study, we can
increase the power factor slightly by increasing the
doping amount. In addition, if we build a pure solid
solution for the Sm3+-doped case via additional
grinding and calcination, this may lead to an
increase in the power factor of the system.
CONCLUSIONS
The effects of donor doping at the Ca site of
perovskite CaMnO3 on the electrical conductivity
were investigated. The effects are discussed from
two viewpoints: the effect of ionic radius variation
on the formation of a single phase, and the effect of
varying the doping amount on the carrier concen-
tration. Doping with a smaller ion led to greater
difficulty in building a single-phase solid solution,
due to distortion of the oxygen octahedra around the
Mn ions. Therefore, with increasing ionic radius of
the donor at the Ca site, the power factor increased.
The power factor also increased with doping amount
due to the increase in carrier concentration. This
implies that the doping amount is not yet optimized
in this work.
As a result, the maximum power factor (3.98 9
104 W/m K2) was achieved for a 10 mol% Pr-doped
composition at 1123 K. As a subsequent step, we
can increase the power factor slightly by increasing
the doping amount.
556
ACKNOWLEDGEMENTS
This work was supported by Energy Efficiency
and Resources (2008EID11P060000) of KETEP
R&D Program and by a Fundamental R&D Pro-
gram for Core Technology of Materials (K0006007)
Grant funded by the Ministry of Knowledge Econ-
omy, Republic of Korea.
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