Journal of ELECTRONIC MATERIALS, Vol. 40, No.

5, 2011
DOI: 10.1007/s11664-011-1514-3
 2011 TMS

High-Temperature Thermoelectric Properties of Co4Sb12-Based

Skutterudites with Multiple Filler Atoms: Ce0.1InxYbyCo4Sb12

JENNIFER GRAFF,1,4 SONG ZHU,2 TIM HOLGATE,1 JIANGYING PENG,3

JIAN HE,2 and TERRY M. TRITT2,5

1.—Department of Materials Science and Engineering, Clemson University, Clemson, SC 29634,

USA. 2.—Department of Physics and Astronomy, Clemson University, Clemson, SC 29634, USA.
3.—School of Mechanical Science and Engineering, Huazhong University of Science and
Technology, Wuhan 430074, People’s Republic of China. 4.—e-mail: jwhubba@g.clemson.edu.
5.—e-mail: ttritt@clemson.edu

Void-filling in the CoSb3 skutterudite lattice with different kinds of heavy

elements has proven to be an effective mechanism to enhance thermoelectric
performance due primarily to a reduction in lattice thermal conductivity.
Specifically, our findings on the series InxYbyCo4Sb12 [0 £ (x, y) £ 0.2] have
further motivated an attempt to form triple-filled skutterudites Ce0.1InxYby-
Co4Sb12 with In and Yb concentrations [0 £ (x, y) £ 0.2] and with the Ce con-
centration held constant (Ce0.1). All of these samples have been prepared via a
simplified melting–annealing–sintering procedure and were first character-
ized by means of x-ray powder diffraction and scanning electron microscopy,
followed by measurements of the Hall coefficient, electrical and thermal con-
ductivities, and Seebeck coefficient. Our aim is to further elucidate the roles of
the three elements (Ce, In, and Yb) in these materials. Compared with the
addition of just In or Yb, we found that simultaneous addition of both In and Yb
reduced the lattice thermal conductivity without significantly degrading the
power factor. Further addition of the third element (Ce), along with In and Yb,
also produced a similar result. However, we noticed that some of the In and Yb
were also observed in the form of secondary phases (InSb and Yb2O3), not
entering entirely as filler atoms. As a result of our investigation, several
compositions achieved increased sustainability and enhanced thermoelectric
performance, with maximum ZT values of about 1.3 to 1.4 obtained at around
800 K.

Key words: Cobalt triantimonide, triple-filled, skutterudites,

thermoelectrics, figure of merit, thermal conductivity

INTRODUCTION thermal to electrical energy conversion process.

In the 19th century, Thomas Johann Seebeck,
Jean Charles Peltier, and William Thomson (Lord
Kelvin), better known as the founding fathers of the
field of thermoelectrics (TE), discovered the funda-
mentals of converting thermal energy into electrical
energy and the use of electrical energy to move
heat.1 The theories of these founding fathers were
later translated into an efficiency description of the
(Received May 14, 2010; accepted January 6, 2011;
published online February 15, 2011)
This conversion efficiency is proportional to 2the
quantity known as the TE figure of merit, ZT ¼ a jrT,
which represents the various important electrical
and thermal properties of the given material. Thus,
the higher the ZT obtained, the higher the conver-
sion efficiency. Increasing interest in TE applica-
tions of power generation and refrigeration has
prompted significant advancements in obtaining an
ultimate efficiency value, or figure of merit, ZT. The
salient qualities of the dimensionless figure of merit
require us to maximize the Seebeck coefficient (a in
V K1) and electrical conductivity (r in X1 m1)

696
High-Temperature Thermoelectric Properties of Co4Sb12-Based Skutterudites
with Multiple Filler Atoms: Ce0.1InxYbyCo4Sb12
Co-Cobalt Atoms (Metals)
Sb-Antimony Atoms (Pnicogens)
X-Filler Atom/Holes
Fig. 1. Im3 space group, CoSb3.
while minimizing the thermal conductivity (j in
W m1 K1), where j = jE + jL, the electronic jE
and lattice jL contributions, respectively. Skutter-
udites, such as the CoSb3 structure, are being
investigated as potential state-of-the-art TE mate-
rials with the ability of achieving such increasingly
high efficiency values. These narrow-bandgap
semiconductors have been studied for their high
efficiency performance for over a decade and gained
increasing popularity through Slack’s (1995) postu-
lation of the phonon glass electron crystal (PGEC)
model.2–4
PGEC materials form a regular periodic cage-like
crystal lattice, by which electrons move rather
freely, characteristic of an ideal electron crystal,
enclosing a larger, heavier, and more loosely bound
‘‘guest’’ atom (Fig. 1). The guest atom, or ‘‘rattler,’’
causes disturbed oscillations through the cage of the
material due to large local anharmonic vibrations,
which reduces heat conduction in the material to a
value that is nearly characteristic of glasses.4,5
MX3 skutterudites (M representing transition-
metal elements such as Ir, Rh, and Co; X repre-
senting pnicogen atoms such as P, Ar, and Sb)
consists of 32 atoms with a cobalt cubic structure,
six occupied antimony rings, and two absent cells.
Taking a PGEC approach with the XCo4Sb12 atomic
lattice structure, the absent cells can be filled with
heavy elements (rattlers) to reduce the lattice
thermal conductivity, without significantly affecting
the electrical properties.
One of the major drawbacks for additional
improvement in the efficiency of these materials is
the ability to reduce their thermal conductivity.
Double filling and triple filling of various guest
atoms have since been used as methods of reducing
lattice thermal conductivity and are the inspiration
for the work presented herein.6–9 Progressions are
being investigated through a multiple filling process
of the skutterudite void spaces, introducing the
697
rattling atoms, or thermal vibrations, causing
increased phonon scattering. Single filling10–12 and
double filling of the void spaces in the skutterudite
material have been proven successful with the ele-
ments indium, ytterbium, and cerium (In, Yb, and
Ce) from the single filling of In by He et al., Yb
filling by Nolas et al., and Ce filling by Fluerial
et al. Motivation for the triple-filling approach of
Ce0.1InxYbyCo4Sb12 came from successful results by
Peng et al.9 Peng’s successful attempt at double
filling of Yb0.2InyCo4Sb12 yielded a reduction in
lattice thermal conductivity, due to Yb, in compar-
ison with the single-filled approach as well as an
enhancement of electrical conductivity because of
an increase in the In content. Because of a higher
solubility limit in these materials, the triple-filling
approach can be implemented to further increase
thermal vibrations without significantly deteriorat-
ing the material’s crystalline electrical properties.
The third filler element, Ce, used in the Ce0.1Inx-
YbyCo4Sb12 samples successfully improves effi-
ciency by enhancing the concentration of charge
carriers, thus improving the Seebeck coefficient.
Also, compared with the double-filled samples of
Peng et al., the lattice thermal conductivity is low-
ered further by thermal vibrations from the rare-
earth fillers, which in turn enhances ZT at high
temperatures. It is important to note that the
presence of the secondary phases Yb2O3 and InSb
may also be contributing to the increased scattering
of phonons and the increased number of charge
carriers, respectively. It is not entirely conclusive
that triple filling is being achieved, as the indium
may substitute on the Sb site and may also form the
InSb phase previously discussed. However, TE
improvement in the prepared Ce0.1InxYbyCo4Sb12
[0 £ (x, y) £ 0.2] samples is achieved, and the results
are discussed herein.
EXPERIMENTAL PROCEDURES
Preparation began by mixing, evacuating, and
sealing stoichiometric amounts of Co powder
(99.998%; Alfa Aesar), Sb shot (99.9999%; Alfa
Aesar), Yb powder (99.9%; Alfa Aesar), In ingot
(99.99%; Alfa Aesar), and Ce powder (99.99%; Alfa
Aesar). The sealed quartz tube was heated to 873 K
and held for 3 h, then heated to 1323 K and held for
about 30 min. The quartz was then cooled to 923 K
and held for 72 h; afterwards, furnace cooling
occurred. The resulting ingots were removed from
the furnace, pulverized using a mortar and pestle,
and examined by powder x-ray diffractometry
(XRD) using a Rigaku Miniflex diffractometer with
Cu Ka radiation. The resulting powders were then
made into pellet form (15 mm diameter, 3 mm
thick) using a spark plasma sintering (SPS) tech-
nique (Dr. Sinter Lab, SPS-515S) at 873 K for 15 min.
Densities (q*) were measured using dimensional
analysis (Table I). The pellets were then tested
for their thermal conductivity (j) properties by
698
Table I. Nominal composition, carrier concentration
(n), and density (q*) of all samples at room
temperature
Nominal Concentration
Composition
In0.2Yb0.2Co4Sb12
Ce0.1In0.15Yb0.15Co4Sb12
Ce0.1In0.1Yb0.2Co4Sb12
measurements of the thermal diffusivity (D) using a
Netzsch Microflash 457 transient technique and
heat capacity (Cp) using the Dulong–Petit high-
temperature limit. These measurements were used
to calculate thermal conductivity through the
equation j = q*CpD.
The pellets were then cut into measurable sam-
ples for high-temperature properties, low-tempera-
ture properties, carrier concentration/mobility, and
for microscopy purposes. Four sections of a 15-mm-
diameter pellet were cut into: (1) 10 mm 9 3 mm 9
2 mm rectangles for determination of their high-
temperature electrical resistivity (q = 1/r) and See-
beck coefficient (a) values using an Ulvac-Riko
ZEM-2 (300 K to 800 K); (2) 7 mm 9 2 mm 9 2 mm
rectangles for low-temperature resistivity, Seebeck
coefficient, and thermal conductivity measurements
within the temperature range of 2 K to 300 K
using a custom-designed four-probe measurement
system13 for resistivity and Seebeck coefficient
measurements and a custom-designed steady-state
Intensity (arb. units)
20 22
Fig. 2. Cu Ka radiation x-ray diffraction (XRD) pattern for all samples (Rigaku Miniflex diffractometer).
Graff, Zhu, Holgate, Peng, He, and Tritt
system for thermal conductivity measurements;14
and (3) 4 mm 9 3 mm 9 1 mm rectangles for
determination of carrier concentration (n) and car-
rier mobility (l) by a Quantum Design Hall system
Carrier using the van der Pauw method with a magnetic
Density field strength of 0.5 T (5 K to 300 K).
(cm23) (g cm23) Scanning electron microscopy (SEM) and energy-
dispersive x-ray spectroscopy (EDS) were performed
2.2 9 1020 7.564 using field-emission scanning electron microscopy
2.1 9 1020 7.633 (FESEM; Hitachi S4800) to understand the micro-
1.7 9 1020 7.616 morphology and topology of the fractured bulk
samples, as well as grain size and location of pos-
sible InSb nanoinclusions and Yb-rich nanoclusters
(believed to be Yb2O3).
RESULTS AND ANALYSIS
The first triple-filling approach utilized the element
Ce in the previous double-filled In0.2Yb0.2Co4Sb12
system to create Ce0.1In0.15Yb0.15Co4Sb12. Efforts
were then made to alter the In and Yb content with
the third filler element Ce remaining stable. High-
resolution x-ray diffraction (HRXRD) patterns of the
SPS pulverized powders showed single-phase skutt-
erudite structures along with traces of Yb2O3 and
InSb clusters (Fig. 2). The traces of Yb2O3 that are
present in the HRXRD patterns are a result of excess
Yb that was unable to fill all cages.15 In recent stud-
ies, InSb clusters have appeared as a second phase in
In-doped CoSb3, rather than entering the Sb-icosa-
hedral voids, illustrating improvements in electrical
performance and thus TE efficiencies.16–17 Li et al.
published images of InSb islands found evenly dis-
tributed on the grain boundaries of an In,Ce-doped
CoSb3
+ Yb2O3
InSb In0.2Yb0.2Co4Sb12
*
Ce0.1In0.15Yb0.15Co4Sb12
Ce0.1In0.1Yb0.2Co4Sb12
24 26 28 30 32 34 36 38 40 42 44
2θ (°)
High-Temperature Thermoelectric Properties of Co4Sb12-Based Skutterudites 699
with Multiple Filler Atoms: Ce0.1InxYbyCo4Sb12

Fig. 3. SEM and EDS results for the Ce0.1In0.1Yb0.2Co4Sb12 sample showing the presence of Yb-rich secondary phase.

Hall mobility scattering of the charge carriers. As plotted, lH

1000 decreases with increasing In concentration, and it is
In0.2Yb0.2Co4Sb12
900 important to note that lH also increases with
Ce0.1In0.1Yb0.2Co4Sb12
800 increasing filling concentration. For a given carrier
Hall mobility (cm2/ V-s)

700
600
500
400
300
200
100
0
0 50 100 150
Temperature (K)
Fig. 4. Temperature dependence of Hall mobility for Ce0.1InxYby-
Co4Sb12 samples.
skutterudite structure.16 Field-emission scanning
electron microscopy (FESEM Hitachi S4800) images
confirm Yb-rich sites on the grain boundaries of the
fractured bulk ranging from approximately 20 nm
to 400 nm in size (Fig. 3). To date, we have not veri-
fied the presence of InSb through SEM/EDS analy-
sis even though it is clearly visible in the HRXRD
analysis.
All of the samples discussed herein show n-type
heavily doped semiconductor behavior. As shown in
Table I, densities are all greater than 97% of their
theoretical value. Nominal composition, carrier
concentration (n), and density (q*) values at room
temperature are also listed in Table I. Mobility (lH)
versus temperature is plotted in Fig. 4 for the
various samples. All of the samples exhibit a T3/2
behavior that is consistent with acoustic phonon
Ce0.1In0.15Yb0.15Co4Sb12 density, an increase in the scattering parameter
T-1.5 may suggest enhancement of the Seebeck coefficient
as well.18 The temperature dependence of the See-
beck coefficient and electrical conductivity are
shown in Fig. 5a and b, respectively. An increase in
the Seebeck coefficient is evident in the Ce0.1I-
n0.1Yb0.2Co4Sb12 sample and is verified by lH. Also,
compared with the double-filled InxCeyCo4Sb12
samples of Li et al., as well as the Yb0.2InyCo4Sb12
200 250 300 samples of Peng et al., there is an increase in the
Seebeck coefficient from 210 lV K1 to about
240 lV K1 when the third filler is introduced. The
electrical conductivity, in Fig. 5b, is similar at high
temperatures. At low temperatures, however, there
is a decrease in electrical conductivity with respect
to the amount of In induced in the samples. The r
of Peng’s double-filled Yb0.2In0.2Co4Sb12 has a
maximum around 0.9 mX1 cm1, whereas the
Ce0.1In0.15Yb0.15Co4Sb12 sample (Fig. 5b) has a maxi-
mum r at 1.1 mX1 cm1. Thus, we can conclude
that introduction of Ce as the proposed third filler
has improved the skutterudite’s electrical perfor-
mance at low temperatures. This improvement,
therefore, may be partially attributed to the InSb
secondary nanophases formed due to the Ce filling
more of the voids. Further studies to investigate the
role and location of the InSb nanophases are cur-
rently in progress.
Figure 6a displays the temperature dependence
of the total thermal conductivity (jT) from 300 K to
850 K. Recall that jT is derived from measure-
ments of thermal diffusivity (D) using the equation
700 Graff, Zhu, Holgate, Peng, He, and Tritt

Seebeck Coefficient Lattice Thermal Conductivity

(a) 0 (a) Total Thermal Conductivity
7

Total Thermal Conductivity (W/m-K)

0 100 200 300 400 500 600 700 800

Lattice TC (W/m-K)
5
Seebeck Coefficient (microV/K)

In0.2Yb0.2Co Sb12 3.9 4

-50 3

2
Ce0.1In0.1Yb0.2Co4Sb12 3.7 1

0
Ce0.1In0.15Yb0.15Co4Sb12 0 200 400 600 800
-100 3.5 Temperature (K)

3.3
-150
3.1
In0.2Yb0.2Co4Sb12
2.9
-200 Ce0.1In0.1Yb0.2Co4Sb12
Ce0.1In0.15Yb0.15Co4Sb12
2.7
300 400 500 600 700 800
-250
Temperature (K) Temperature (K)

(b) Electrical Conductivity

(b) Figure of Merit ZT (24 minute program)
6 1.6
Electrical Conductivity (1/mohm-cm)

In0.2Yb0.2Co4Sb12 1.4
5
Ce0.1In0.1Yb0.2Co4Sb12
1.2
Ce0.1In0.15Yb0.15Co4Sb12
4 1

3 ZT 0.8
In0.2Yb0.2Co4Sb12
0.6
2 Ce0.1In0.1Yb0.2Co4Sb12
0.4
Ce0.1In0.15Yb0.15Co4Sb12
1 0.2

0
0 300 400 500 600 700 800 900
0 100 200 300 400 500 600 700 800 900
Temperature (K) Temperature (K)

Fig. 5. Temperature dependence of (a) Seebeck coefficient and (b) Fig. 6. Temperature dependence of (a) thermal conductivity (jT)
electrical conductivity for Ce0.1InxYbyCo4Sb12 samples. with inset of lattice thermal conductivity (jL = jT  jE) and (b)
dimensionless ZT for Ce0.1InxYbyCo4Sb12 samples.

jT = Dq*Cp, where Cp is the heat capacity. As shown

applicable over a broader temperature range. Thus,
in Fig. 6a, jT decreases with increasing doping
noting from Fig. 6b, the temperature regime for the
content and concentration of Yb. Furthermore, in
multiple-filled samples is increased from about
the inset to Fig. 6a, the lattice thermal conductivity
600 K > T > 800 K compared with Peng’s samples.
(jL) additionally proves that, as the amount of
ZT reaches a maximum value of 1.4 at 800 K.
doping increases from double filling to triple filling,
Therefore, we can conclude that an increase in the
the rattling effect is enhanced, thus lowering jT. jL
Seebeck coefficient coupled with the reduction in
is found through the equation jL = jT – jE, where
thermal conductivity yields an increase in ZT for
jE is the electronic contribution to the thermal
the entire temperature range above 600 K.
conductivity. jE is given by the Wiedemann–Franz
relation jE = L0rT, where the Lorenz constant is
CONCLUSIONS
given by L0 = 2 9 108 V2 K2, which is typical for
heavily doped semiconductors. jE should not be Synthesis of Ce0.1InxYbyCo4Sb12 samples was
ignored, however, because as the number of charge performed by a melt-anneal process followed by
carriers increases in each sample, so does jE. densification using spark plasma sintering, result-
Therefore, it can be concluded that phonon scatter- ing in electrical and thermal stability of all samples
ing by carriers is also occurring, as seen by Yang reported herein. Improvement with multiple filling
et al.19 Additionally, the Yb-rich nanophases seen in compared with double filling was found in both the
Fig. 3 may also play a role in further lowering the electrical and thermal performance of the materi-
thermal conductivity. The figure of merit, ZT, als. Introducing the third filler element Ce signifi-
from 300 K to 850 K (Fig. 6b) is enhanced by cantly reduced the total thermal conductivity.
the multiple filling in the Ce0.1In0.15Yb0.15Co4Sb12 The formation of possible InSb nanophases as well
and Ce0.1In0.1Yb0.2Co4Sb12 samples compared as the presence of Yb-rich (verified as Yb2O3 by
with the double-filled In0.2Yb0.2Co4Sb12 sample. HRXRD analysis) nanoclusters may also contribute
The multiple-filling approach ultimately enhances to the improved electrical and thermal performance
ZT by approximately 40%. It is equally important of the materials. Future work will attempt to
for ZT to be less temperature dependent and more understand the role and location of these secondary
High-Temperature Thermoelectric Properties of Co4Sb12-Based Skutterudites
with Multiple Filler Atoms: Ce0.1InxYbyCo4Sb12
phases to pinpoint their possible contributions to
the observed enhancements of thermoelectric
properties in these materials. The third filler ele-
ment Ce gives rise to further potential enhance-
ment of electrical and thermal performance in these
materials as compared with Peng’s reported double-
filled sample. The sustainability of a ZT >1 over a
broad temperature range allows for application of
these materials within the specific temperature
range of 590 K to 800 K. A state-of-the-art maxi-
mum ZT of 1.4 at about 800 K was found in the
triple-filled Ce0.1In0.1Yb0.2Co4Sb12.
ACKNOWLEDGEMENTS
The work at Clemson University is supported by
DOE/EPSCoR Implementation Grant (#DE-FG02-
04ER-46139), and the SC EPSCoR cost sharing
program. One of the authors (J.P.) would like to
acknowledge the financial support from the
National Natural Science Foundation of China
(Grant No. 50972047) and the Scientific Research
Foundation for the Returned Overseas Chinese
Scholars, State Education Ministry. We would also
like to acknowledge Sloan Lindsay and Wenjie Xie
for their time and support of the project.
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