JOURNAL OF APPLIED PHYSICS 107, 053715 共2010兲

Evidence of spin-density-wave transition and enhanced thermoelectric

properties in Ca3−xCexCo4O9+␦
G. D. Tang, Z. H. Wang,a兲 X. N. Xu, L. Qiu, and Y. W. Du
National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, China,
Department of Physics, Nanjing University, Nanjing 210093, China, and Jiangsu Provincial Laboratory for
NanoTechnology, Nanjing 210093, China
共Received 27 August 2009; accepted 18 January 2010; published online 9 March 2010兲
We have investigated the effect of Ce doping on the magnetic and low-temperature thermoelectric
properties of Ca3Co4O9+␦. A small shoulder occurring at about 23 K in the d␹−1 / dT curve indicates
an occurrence of spin-density-wave transition, which is confirmed by resistance characteristics.
With partial Ce substitution, the thermopower increases while the thermal conductivity decreases.
The magnetic measurements give a support to the concentration reduction in Co4+ ions, which
results in the enhancement of thermopower. The dimensionless figure of merit ZT= 0.016 is
achieved at 335 K for Ca2.9Ce0.1Co4O9+␦, demonstrating that heavy atoms Ce doping may promise
an effective way for improving thermoelectric properties of Ca3Co4O9+␦ system.
© 2010 American Institute of Physics. 关doi:10.1063/1.3313923兴

I. INTRODUCTION samples by Ce doping and investigated systematically their

Thermoelectric 共TE兲 materials as a clean energy-
conversion system have attracted renewed interest. The per-
formance of TE materials can be evaluated by the figure of
merit Z = S2 / ␳␬ with S, ␬, and ␳ as the thermopower, the
thermal conductivity, and the electrical resistivity, respec-
tively. Therefore, large thermopower 共an absolute value of
thermopower兲, low electrical resistivity, and thermal conduc-
tivity are required for an optimal TE material. In 1997,
Terasaki et al.1 reported a new layered cobalt oxide NaCo2O4
exhibiting a large thermopower of about 100 ␮V / K and a
low resistivity with 200 ␮⍀ cm at 300 K, which was sug-
gested as a potential TE material for application. Since then,
much attention has been focused on similar layer cobalt
oxides,2–7 among which cobaltite Ca3Co4O9+␦ system has
been considered to be a promising candidate of TE materials
due to its large room-temperature thermopower, low resistiv-
ity, and thermal conductivity.4 However, for practical appli-
cation, its TE performance needs to be further improved.8,9
So far, various rare earths 共Dy, Gd, Eu, La, and Nd兲, alkali
metals, or transition metals have been used to substitute for
Ca or Co for this system and these results show that the
doping is an effective way to improve the TE properties.8–15
Ce element doping inspires our interest for holding that dop-
ing with heavy atoms can enhance phonon scattering and
further suppress the lattice contribution to the thermal con-
ductivity. This will contribute to the improvement of TE ef-
ficiency for this system. In addition, Ca3Co4O9+␦ system ex-
hibits very complicated magnetic properties, such as
ferrimagnetic transition, spin-state transition, and spin-
density-wave 共SDW兲 transition due to its complex crystal
structure; moreover, the effect of doping on magnetic prop-
erties is evident.2,4,16 In order to improve its TE performance
and to understand the unusual magnetic properties of the
system, we obtained a new series of Ca3−xCexCo4O9+␦
a兲
Electronic mail: zhwang@nju.edu.cn.
TE and magnetic properties in this work. Our investigation
discloses an occurrence of SDW transition, which also dem-
onstrates that heavy atom Ce doping is an effective way for
improving TE properties of Ca3Co4O9+␦ system.
II. EXPERIMENT
The starting materials were standard reagents and used
as commercially obtained. Ca3−xCexCo4O9+␦ powders were
prepared using sol-gel method as follows: The stoichiometric
CaCO3, Co共NO3兲2 · 6H2O, Ce共NO3兲3 · 6H2O, and citric acid
monohydrate were dissolved in distilled water. Citrate solu-
tion was dehydrated at 353 K. The resulted uniform was
crushed and heated to 473 K for 2 h to remove the moisture
of gel. The obtained carbonaceous xerogel was calcined at
823 K for 3 h in air. After being cooled to room temperature,
the obtained powders were ground and sintered at 1173 K for
12 h, then pressed into pellets. Finally these pellets were
annealed at 1173 K for 24 h under O2 atmosphere.
The phase purify of samples was examined by x-ray dif-
fraction 共XRD兲 with Cu K␣ radiation. The magnetic mea-
surements were performed with a superconducting quantum
interference device measurement system. All the TE proper-
ties 共thermopower, thermal conductivity, and electrical resis-
tivity兲 were measured using a physical property measure-
ment system from 4 to 350 K.
III. RESULTS AND DISCUSSION
Figure 1 shows the XRD patterns for Ca3−xCexCo4O9+␦
samples. All the diffraction peaks can be indexed as
Ca3Co4O9+␦ phase with monoclinic symmetry.4 Clearly Ce
atoms are doped into Ca sites and a single phase is identified.
The magnetic measurements were performed in the
field-cooling mode under a magnetic field of 2000 Oe. The
susceptibility 共␹兲 as a function of temperature for
Ca3−xCexCo4O9+␦ samples with x = 0 – 0.5 is shown in Fig. 2.
It is found that ␹ increases slowly with decreasing tempera-

0021-8979/2010/107共5兲/053715/4/$30.00 107, 053715-1 © 2010 American Institute of Physics

053715-2 Tang et al.
FIG. 1. XRD patterns of Ca3−xCexCo4O9+␦.
ture until 25 K, then abruptly below 25 K. For all doped
samples, ␹ is unanimously suppressed with increasing Ce
doping content. The inset in Fig. 2 shows the curves of in-
verse susceptibility 共1 / ␹兲. It is obvious that the magnetic
behaviors of Ca3−xCexCo4O9+␦ with x = 0.1, 0.3, and 0.5
above 100 K are paramagnetism and obey the Curie–Weiss
law. The negative Weiss constant values obtained indicate
the presence of strong antiferromagnetic interaction at low
temperatures. It is found that the samples with x = 0.1, 0.3,
and 0.5 do not exhibit a clear ferrimagnetic transition, which
was observed in Ca3Co4O9+␦.2 Our results are consistent with
previous reports that the ferrimagnetic transition is sup-
pressed by M 共M represents Sr, Y, Bi, and Ti兲 doping into Ca
sites for a Ca3−xMxCo4O9+␦ system.2,10 As discussed in
literatures,16 the ferrimagnetic transition in Ca3Co4O9+␦ is
caused by the interlayer coupling between the 关Ca2CoO3兴
and 关CoO2兴 subsystems. In this respect, Ce doping into the
关Ca2CoO3兴 subsystem may enlarge the distance and weaken
the magnetic coupling between two subsystems. Therefore,
no ferrimagnetic transition is found down to 5 K in the doped
Ca3−xCexCo4O9+␦ samples. In order to look into more de-
tailed magnetic structure, we plot the d␹−1 / dT versus T for
all materials in Fig. 3. Interestingly, there exists a shoulder in
the d␹−1 / dT curves at about 23 K for x = 0.1, 0.3, and 0.5
samples while the free doped polycrystalline Ca3Co4O9+␦
FIG. 2. Susceptibility 共␹兲 in the Ca3−xCexCo4O9+␦ samples with x = 0 – 0.5 as
a function of temperature. The inset shows the temperature dependence of
the reciprocal of the susceptibility for these samples.
J. Appl. Phys. 107, 053715 共2010兲
FIG. 3. d␹−1 / dT vs T curves for Ca3−xCexCo4O9+␦.
sample exhibits no clear shoulder. We ascribe this anomaly
to the occurrence of SDW transition. Sugiyama et al.16 ob-
served a similar shoulder in Ca3Co4O9+␦ single crystal. They
suggested that this shoulder indicates the occurrence of SDW
transition, which was detected by muon spin rotation.2 SDW
transition was also observed in similar Ca3Co4−xTixO9+␦
system.17 For Ca3Co4O9+␦ polycrystalline sample, the change
in ␹ at the SDW transition temperature TSDW is expected to
be small and anisotropic due to its broad transition width and
two dimensional structure. Therefore, such a shoulder will be
difficult to detect.2 We notice that TSDW of Ce-substituted
samples is very close to that of Ca3Co4O9+␦ single crystal.
The SDW state exists in the CoO2 layers and propagates
within the CoO2 ab plane,18 while the substituted Ce ions
enter into the 关Ca2CoO3兴 rather than the 关CoO2兴 subsystem.
Therefore it is plausible that the Ce doping has little influ-
ences on the SDW transition.
Also we studied the TE properties in Ce-substituted
samples. The temperature dependence of thermopower 共S兲
for Ca3−xCexCo4O9+␦ is shown in Fig. 4. The positive values
of the thermopower suggest that holes are the major charge
carriers in Ca3−xCexCo4O9+␦ ceramics. The thermopower S
increases monotonically with temperature elevation in the
studied temperature range. We also find, as shown in Fig. 4,
that the thermopower is enhanced gradually with increasing
Ce doping level. For material with x = 0.5, the S value
reaches up to 128 ␮V / K at 336 K.
FIG. 4. Temperature dependence of thermopower for Ca3−xCexCo4O9+␦.
053715-3 Tang et al.
FIG. 5. Temperature dependence of the thermal conductivity 共␬兲 for
Ca3−xCexCo4O9+␦.
To clarify the enhancement of thermopower, we start
from the definition of thermopower. The thermopower in a
strong-correlation system can be expressed as19,20
1 M12 ␮
S=− + , 共1兲
eT M11 eT
where e is the absolute value of electron charge and ␮ is the
chemical potential. The meaning of M1i共i = 1 , 2兲 is given in
Refs. 19 and 20. We studied thermopower within room tem-
perature, but our results may stand well if extrapolated to-
ward high temperature. In the high temperature limit, M1i
becomes constant and thus the first term in Eq. 共1兲 decreases
to zero.19 Therefore, in this limit the thermopower is deter-
mined by the second term, which comes from spin entropy
contribution. The spin entropy contribution to the ther-
mopower can be expressed by the modified Heikes
formula,19,20
S=−
kB
e
ln冋 冉 冊册
g3 c
g4 1 − c
, 共2兲
where g3 and g4 are the spin orbital degeneracies for Co3+
and Co4+ ions, respectively, c is the concentration of Co4+
holes on the Co sites, and kB is the Boltzmann constant.
From Fig. 2, the susceptibility of all samples decreases with
increasing Ce doping content in the whole studied tempera-
ture range. Previous x-ray absorption and x-ray photoemis-
sion spectroscopy studies of Ca3Co4O9+␦ showed that Co4+
and Co3+ ions were in low-spin states t2g 5
and t2g6
, on the assumption that ␮共T兲 is independent of temperature,
7,21
respectively. Based on the studies of other substituted
layer cobalt oxides,22,23 one can believe that substitution of
Ce does not change the spin states of both Co3+ and Co4+
ions. Therefore, we think that the reduction in the suscepti-
bility by Ce doping is related to the reduced concentration of
the magnetic Co4+ 共S = 1 / 2 , ␮eff = 1.73 ␮B兲 ions. The spin
orbital degeneracies g3 = 1 and g4 = 6 are determined accord-
ing to the low-spin states of both Co3+ and Co4+ ions. Using
Eq. 共2兲 and considering that the first term in Eq. 共1兲 will
counteract the thermopower enhancement at room tempera-
ture, we think that the thermopower enhancement by Ce dop-
ing results from the decrease in Co4+ ions concentration. It is
consistent with the results of Ref. 24.
Figure 5 displays the temperature dependence of total
thermal conductivity 共␬兲 for Ca3−xCexCo4O9+␦ series. It is
J. Appl. Phys. 107, 053715 共2010兲
FIG. 6. Electric resistivity as a function of temperature for
Ca3−xCexCo4O9+␦. The inset shows the fitting plot of resistivity for
Ca3−xCexCo4O9+␦ at low temperature.
shown that the thermal conductivity for all materials in-
creases with elevated temperature. From Fig. 5, we can see
that the ␬ values of all Ce substitutions studied are lower
than Ca3Co4O9+␦. Among these series, Ca2.9Ce0.1Co4O9+␦ has
the lowest ␬ values. Our results suggest that heavy element
doping is an effective way to reduce thermal conductivity.
The decrease in total thermal conductivity can be explained
by that the heavy element Ce dopant makes scattering
phonons more effective, and therefore reduces the phonon
thermal conductivity.
The temperature dependence of electrical resistivity ␳
for Ca3−xCexCo4O9+␦ materials is presented in Fig. 6. We can
see that the resistivity increases with increasing Ce doping
content, possibly due to the substitution of Ce for Ca that
decreases the concentration of holes. Below 50 K, the resis-
tivity for all samples increases abruptly as the temperature
decreases, showing a semiconductor behavior. In a SDW
state, the resistivity is expected to take the form2,10,16,18,25
1
␳
= ␮共T兲exp − 冉 冊
E0
k BT
, 共3兲
where ␮共T兲 is the mobility of carriers and E0 is the activation
energy. To check if the SDW transition occurs, our experi-
mental data and fitting lines are both plotted in the inset of
Fig. 6. Our experimental data from 25 to 55 K follow Eq. 共3兲
and therefore is consistent with a SDW state. The fitting
parameters E0 are 1.61, 2.95, 4.01, and 4.50 meV for the
samples with x = 0, 0.1, 0.3, and 0.5, respectively. E0 in-
creases gradually with increasing Ce doping level.
Finally, we calculated the dimensionless TE figure of
merit ZT according to the equation of ZT= S2T / ␳␬. ZT value
as a function of temperature for Ca3−xCexCo4O9+␦ series is
shown in Fig. 7. It is clear that the ZT values increase with
increasing temperature. The ZT values of all Ce doped ma-
terials studied here are higher than that of Ca3Co4O9+␦ over
the whole studied temperature range. Ca2.9Ce0.1Co4O9+␦, in
particular, has the highest ZT value among these materials. A
ZT= 0.016 is achieved at 335 K and much larger than that of
Ca3Co4O9+␦. A further increase in Ce doping content from
x = 0.1 to 0.5 will result in a decrease in ZT values. In short,
053715-4 Tang et al. J. Appl. Phys. 107, 053715 共2010兲

2009CB929501兲 and the State Key Program for Basic Re-

search of China 共Grant No. 2010CB923403兲.
1
I. Terasaki, Y. Sasago, and K. Uchinokura, Phys. Rev. B 56, R12685
共1997兲.
2
J. Sugiyama, H. Itahara, T. Tani, J. H. Brewer, and E. J. Ansaldo, Phys.
Rev. B 66, 134413 共2002兲.
3
P. Limelette, S. Hébert, V. Hardy, R. Frésard, C. Simon, and A. Maignan,
Phys. Rev. Lett. 97, 046601 共2006兲.
4
A. C. Masset, C. Michel, A. Maignan, M. Hervieu, O. Toulemonde, F.
Studer, B. Raveau, and J. Hejtmanek, Phys. Rev. B 62, 166 共2000兲.
5
Y. Wang, N. S. Rogado, R. J. Cava, and N. P. Ong, Nature 共London兲 423,
425 共2003兲.
6
A. A. Taskin, A. N. Lavrov, and Y. Ando, Phys. Rev. B 73, 121101共R兲
共2006兲.
7
Y. Wakisaka, S. Hirata, T. Mizokawa, Y. Suzuki, Y. Miyazaki, and T.
FIG. 7. Temperature dependence of ZT for Ca3−xCexCo4O9+␦. Kajitani, Phys. Rev. B 78, 235107 共2008兲.
8
C. J. Liu, L. C. Huang, and J. S. Wang, Appl. Phys. Lett. 89, 204102
this investigation reveals that heavy atom Ce doping is an 共2006兲.
9
H. Q. Liu, X. B. Zhao, F. Liu, Y. Song, Q. Sun, T. J. Zhu, and F. P. Wang,
effective way for improving TE properties of Ca3Co4O9+␦ J. Mater. Sci. 43, 4933 共2008兲.
system. 10
B. C. Zhao, Y. P. Sun, and W. H. Song, J. Appl. Phys. 99, 073906 共2006兲.
11
D. L. Wang, L. D. Chen, Q. Yao, and J. G. Li, Solid State Commun. 129,
615 共2004兲.
IV. CONCLUSION 12
D. L. Wang, L. D. Chen, Q. Yao, and J. G. Li, J. Alloys Compd. 376, 58
共2004兲.
The magnetic properties of Ce doped Ca3−xCexCo4O9+␦ 13
J. Pei, G. Chen, D. Q. Lu, P. S. Liu, and N. Zhou, Solid State Commun.
共x = 0, 0.1, 0.3, and 0.5兲 have been studied. Small shoulders 146, 283 共2008兲.
14
in the d␹−1 / dT curves of Ca3−xCexCo4O9+␦ series indicate Y. H. Lin, J. L. Lan, Z. J. Shen, Y. H. Liu, C. W. Nan, and J. F. Li, Appl.
Phys. Lett. 94, 072107 共2009兲.
the occurrence of SDW transition, which is confirmed by the 15
Y. Wang, Y. Sui, J. G. Cheng, X. J. Wang, J. P. Miao, Z. G. Liu, Z. N.
resistance characteristics. We also investigated TE properties Qian, and W. H. Su, J. Alloys Compd. 448, 1 共2008兲.
16
of these samples and found that Ce doping leads to both the W. Chen, K. Hida, and B. C. Sanctuary, Phys. Rev. B 67, 104401 共2003兲.
17
thermopower enhancement and the thermal conductivity re- B. C. Zhao, Y. P. Sun, W. J. Lu, X. B. Zhu, and W. H. Song, Phys. Rev. B
74, 144417 共2006兲.
duction. As a result, the TE performance can be and has been 18
J. Sugiyama, J. H. Brewer, E. J. Ansaldo, H. Itahara, K. Dohmae, Y. Seno,
improved remarkably by Ce doping. A ZT= 0.016 is achieved C. Xia, and T. Tani, Phys. Rev. B 68, 134423 共2003兲.
19
at 335 K for Ca2.9Ce0.1Co4O9+␦. This investigation suggests W. Koshibae, K. Tsutsui, and S. Maekawa, Phys. Rev. B 62, 6869 共2000兲.
20
that heavy atom Ce doping may promise an effective way for W. Koshibae and S. Maekawa, Phys. Rev. Lett. 87, 236603 共2001兲.
21
T. Mizokawa, L. H. Tjeng, H.-J. Lin, C. T. Chen, R. Kitawaki, I. Terasaki,
searching for improved TE materials. S. Lambert, and C. Michel, Phys. Rev. B 71, 193107 共2005兲.
22
T. Mizokawa, L. H. Tjeng, P. G. Steeneken, N. B. Brookes, I. Tsukada, T.
Yamamoto, and K. Uchinokura, Phys. Rev. B 64, 115104 共2001兲.
ACKNOWLEDGMENTS 23
S. Hébert, S. Lambert, D. Pelloquin, and A. Maignan, Phys. Rev. B 64,
172101 共2001兲.
We would like to thank Teng Yang and Malcome Biggs 24
R. Asahi, J. Sugiyama, and T. Tani, Phys. Rev. B 66, 155103 共2002兲.
from IMR of CAS for useful discussions. This work was 25
A. Georges, G. Kotliar, W. Krauth, and M. J. Rozenberg, Rev. Mod. Phys.
supported by the MOST 973 Program of China 共Grant No. 68, 13 共1996兲.
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