APPLIED PHYSICS LETTERS 98, 214101 共2011兲

High-temperature transport properties of Ca0.98RE0.02MnO3−␦

„RE= Sm, Gd, and Dy…
Chia-Jyi Liu,a兲 Ankam Bhaskar, and J. J. Yuan
Department of Physics, National Changhua University of Education, Changhua 500, Taiwan
共Received 19 March 2011; accepted 2 May 2011; published online 24 May 2011兲
We report measurements of electrical resistivity and thermopower on CaMnO3−␦ and
Ca0.98RE0.02MnO3−␦ 共RE= Sm, Gd, and Dy兲 prepared by solid state reaction. CaMnO3−␦ exhibits
nonmetal-like temperature dependence of resistivity while metal-like temperature dependence of
thermopower. This inconsistency can be explained by the extrinsic carriers arising from oxygen
defects using two-band model. Ca0.98RE0.02MnO3−␦ exhibits metal-like temperature dependence in
both resistivity and thermopower. The transition to metal-like behavior resembles the case in
degenerate semiconductors and can be attributed to an impurity band formation with characteristic
of hybridized Mn 3d eg and O 2p states due to electron doping via partial substitution of
lanthanides for Ca2+ and oxygen defects. © 2011 American Institute of Physics.
关doi:10.1063/1.3593962兴

Thermoelectric energy conversion can be used to gener- Sm2O3, Gd2O3, and Dy2O3 powders. The powders were
ate electricity from waste heat. The efficiency of thermoelec- heated at 900 ° C for 10 h and at 1200 ° C for 20 h in air with
tric materials in this process is determined by their dimen- intermediate grinding. The resulting powders were then
sionless thermoelectric figure of merit, ZT = S2␴T / ␬, where pressed into pellets and sintered in air at 1200 ° C. The phase
S, ␴, T, and ␬ are the thermopower, the electrical conductiv- purity of the samples was examined by a Shimadzu x-ray
ity, the absolute temperature, and the thermal conductivity, diffraction 共XRD兲-6000 powder x-ray diffractometer
respectively.1,2 Thermoelectric bulk oxides have attracted equipped with Fe K␣ radiation. Electrical resistivity mea-
considerable attention because they are environmentally surements were carried out using standard four-probe tech-
friendly and stable at high temperatures in air.3–7 niques. Thermopower measurements were performed be-
There are relatively few n-type oxide materials. Among tween 300 and 700 K using steady-state techniques with
the n-type oxide materials, CaMnO3−␦ is one of the most a temperature gradient of 0.5–2 K across the sample. The
promising materials and has attracted attention as a possible temperature gradient was measured using a type E differen-
n-type oxide thermoelectric material for use in generators. tial thermocouple.14 Average valence of Co and oxygen con-
Oxygen deficiency 共␦ ⫽ 0兲 would create an electron in the tent were determined by iodometric titration.15 The valence
Co eg band due to creation of Mn3+. As a result, the electri- of Mn and oxygen content are 3.90共8兲 and 0.04共4兲 for
cal resistivity decreases due to the increase in electron carrier CaMnO3−␦; 3.94共4兲 and 0.01共2兲, 3.92共8兲 and 0.02共4兲,
3.91共9兲, and 0.03共4兲 for RE= Sm, Gd, and Dy in
concentration. In the same vein, increasing the electron car-
Ca0.98RE0.02MnO3−␦, respectively.
rier concentration of CaMnO3−␦ can be achieved by partial
Figure 1 shows the XRD patterns of CaMnO3−␦ and
replacement of Ca2+ by trivalent metal ions. Ohtaki et al.8
Ca0.98RE0.02MnO3−␦ 共Re= Sm, Gd, and Dy兲. The diffraction
and Funahashi et al.9 studied the effects on the thermoelec-
peaks of all the samples can be indexed based on an ortho-
tric properties of CaMnO3 by substituting Bi, Y, La, Ce and
rhombic lattice in space group Pnma 共No. 62兲 without any
rare earth ions of Nd, Tb, Ho, Yb, Lu for Ca. They reported measurable impurity phase, indicating that a single phase of
that the electrical conductivity increased significantly, while
the Seebeck coefficient decreased slightly. Wang et al.10 in-
vestigated high temperature transport of a series of electron-
doped Ca0.9R0.1MnO3 共R = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy,
Ho, Er, and Tb兲 and concluded that the size matching be-
tween Ca2+ and R3+ is the key to achieve a low resistivity.
Small polaron conduction model11,12 has often been
invoked to explain the electronic transport of doped perov-
skite manganites.8,10,13 We have carried out electrical resis-
tivity and thermopower measurements on CaMnO3−␦ and
Ca0.98RE0.02MnO3−␦ 共RE= Sm, Gd, and Dy兲 with the purpose
to better understand the transport properties of n-type ther-
moelectric oxides.
Polycrystalline samples of CaMnO3−␦ and
Ca0.98RE0.02MnO3−␦ 共RE= Sm, Gd, and Dy兲 were synthe-
sized by the solid state reaction from CaCO3, Mn2O3,
FIG. 1. 共Color online兲 XRD patterns of CaMnO3−␦ and Ca0.98RE0.02MnO3−␦
a兲
Electronic mail: liucj@cc.ncue.edu.tw. 共RE= Sm, Gd, and Dy兲.

0003-6951/2011/98共21兲/214101/3/$30.00 98, 214101-1 © 2011 American Institute of Physics

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 214101-2 Liu, Bhaskar, and Yuan
FIG. 2. 共Color online兲 Temperature dependence of electrical resistivity for
CaMnO3−␦ and Ca0.98RE0.02MnO3−␦ 共RE= Sm, Gd, and Dy兲.
orthorhombic Ca0.98RE0.02MnO3−␦ 共Re= Sm, Gd, and Dy兲 are
obtained in each sample.
Figures 2 and 3 show the temperature dependence of
electrical resistivity and thermopower for CaMnO3−␦ and
Ca0.98RE0.02MnO3−␦ 共RE= Sm, Gd, and Dy兲. Several features
can be clearly seen: 共1兲 electrical resistivity for CaMnO3−␦
decreases with increasing temperature, typical characteristic
of nonmetal-like temperature dependence. On the other hand,
the absolute value of thermopower increases with increasing
temperature, a characteristic of metal-like temperature de-
pendence; 共2兲 both electrical resistivity and absolute value of
thermopower for all doped samples Ca0.98RE0.02MnO3−␦ in-
crease with increasing temperature, typical characteristic of
metal-like temperature dependence; 共3兲 both resistivity and
absolute value of thermopower for all the doped samples
show significant decreases as compared to CaMnO3−␦; 共4兲
the relative size of the electrical resistivity for doped samples
Ca0.98RE0.02MnO3−␦ has the same trend as reported by Wang
et al.10 with regard to the size of lanthanides; 共5兲 both elec-
trical resistivity and absolute value of thermopower for
CaMnO3−␦ show significant decreases as compared to those
reported by Ohtaki et al.8 In sharp contrast to our CaMnO3−␦,
the absolute value of thermopower of Ohtaki’s sample de-
creases with increasing temperature, typical characteristic of
FIG. 3. 共Color online兲 Temperature dependence of thermopower for
CaMnO3−␦ and Ca0.98RE0.02MnO3−␦ 共RE= Sm, Gd, and Dy兲.
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Appl. Phys. Lett. 98, 214101 共2011兲
nonmetal-like temperature dependence. This difference
should be attributed to the contribution of the oxygen defi-
ciency, which will be discussed in the following.
Thermopower measurements are a complementary tool
to the resistivity measurements for studying the transport
properties of materials. Simultaneous increase in the electri-
cal conductivity and absolute value of thermopower with in-
creasing temperature is puzzling for CaMnO3−␦. In general,
materials either with activated or polaronic conduction, the
absolute value of thermopower is expected to decrease with
increasing temperature, namely, inversely proportional to
temperature. Oxygen defect in CaMnO3−␦ creates two Mn3+
five coordinate sites for each O vacancy according to the
x-ray absorption near-edge spectra results.16 Moreover, the
electrical resistivity of CaMnO3−␦ decreases with the oxygen
deficiency ␦, indicating an increase in charge carriers due to
the mixed valence of Mn4+ and Mn3+ arising from ␦. A pos-
sible scenario to explain the above puzzling results is as fol-
lows. For materials with more than one type of charge car-
rier, the diffusion thermopower can be expressed as
冉冊
␴i
S=兺 Si , 共1兲
i ␴
where ␴i and Si are respectively the partial electrical conduc-
tivity and partial thermopower associated with the ith group
of carriers. We can rewrite thermopower of CaMnO3−␦ as
␴in ␴ex,defect
S= Sin + Sex,defect , 共2兲
␴in + ␴ex,defect ␴in + ␴ex,defect
where ␴in and Sin are the contribution from intrinsic carriers;
␴ex,defect and Sex,defect are the contribution from extrinsic car-
riers due to oxygen defects. Since the increase in electrical
conductivity 共⬃e−共Ea/kBT兲兲 is faster than the decrease in S
共⬃Ea / kBT兲 for semiconductors, one could expect the second
term in Eq. 共2兲 would increase and, therefore, the absolute
value of thermopower for CaMnO3−␦ would increase, which
should be responsible for the simultaneous increase in the
electrical conductivity and absolute value of thermopower
with increasing temperature.
Since the experimental activation energies derived from
electrical resistivity and thermopower measurements are
distinguishable for the title system, the adiabatic small po-
laron conduction model11 has often been invoked to account
for the transport mechanism even though it shows metal-like
temperature dependence in both electrical resistivity and
thermopower.8,10,17 Figure 4 shows similar fitting for doped
Ca0.98RE0.02MnO3−␦ in the present study using the following
forms ␳ = ␳0T exp共Ea / kBT兲 and S = 共kB / e兲共WH / kBT + B兲,
where Ea is one-half of the energy gap between the polaronic
bands, WH one-half of the polaron binding energy; B is as-
sociated with the spin and the mixing entropy and e the
electron charge with minus sign. One would expect a de-
crease in absolute value of thermopower with increasing
temperature, and obtain a negative WH when fitting ther-
mopower data for the polaronic transport. The former is on
the contrary to the observed data; the latter is unlikely. Since
electron doping via partial lanthanide substitution and oxy-
gen defect induces partial occupation of eg states, hybridiza-
tion between Mn 3d eg and O 2p orbitals could develop an
impurity band for the title system in a similar way as degen-
erate semiconductors. Therefore, the above scenario is more
 214101-3 Liu, Bhaskar, and Yuan Appl. Phys. Lett. 98, 214101 共2011兲

band formation with characteristic of hybridized Mn 3d eg

and O 2p states due to electron doping via partial substitu-
tion of lanthanides for Ca2+ and oxygen defects.

This work was supported by National Science Council of

Taiwan, R.O.C. under the Grant No. NSC 98-2112-M-018-
005-MY3. Ankam Bhaskar would like to express thanks to
the postdoctoral fellowship sponsored by National Science
Council of Taiwan.
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