Journal of ELECTRONIC MATERIALS, Vol. 48, No.

8, 2019
https://doi.org/10.1007/s11664-019-07321-4
Ó 2019 The Minerals, Metals & Materials Society

Fabrication of Thermoelectric Module Consisting of Rare-Earth-

Filled Skutterudite Compounds and Evaluation of Its Power
Generation Performance in Air

SHIGERU KATSUYAMA ,1,3 WAKANA YAMAKAWA,1

YOKO MATSUMURA,2 and RYOJI FUNAHASHI2

1.—Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka

University, Yamadaoka, Suita, Osaka 565-0871, Japan. 2.—Research Institute for Ubiquitous
Energy Devices, National Institute of Advanced Industrial Science and Technology, Midorigaoka,
Ikeda, Osaka 563-8577, Japan. 3.—e-mail: katsuyama@mat.eng.osaka-u.ac.jp

Thermoelectric generation modules consisting of pairs of p-type CeFe3CoSb12

and n-type Yb0.15Co4Sb12 have been fabricated using Ag sheets as electrodes
and metal paste as bonding material. In the module using Ag-23mass%Pd
paste as the bonding material, the electric resistance was low and the diffusion
of atoms between the electrode and device material was the smallest. A 14-
pair thermoelectric module was fabricated using Ag-23mass%Pd as the
bonding material, and a power generation experiment of the module was
carried out in air. When the temperatures at the cold side and the hot side of
the module were kept at 293 K and 573 K, respectively, a maximum power
density of 0.70 kW/m2 was obtained in air, and, during a long priod of oper-
ation of 336 h (2 weeks), little change was seen in the electric resistance, open
circuit voltage and maximum electric power of the module. In an experiment
where the temperature at the hot side of the module was set to 673 K, an
increase of electric resistance and a decrease of maximum power of the module
were observed around 50 h or more, which was caused by the oxidation and
decomposition of the device material.

Key words: Thermoelectric generation, rare-earth- filled skutterudite

compound, metal paste, module, durability

strongest candidates for the generation of electricity

INTRODUCTION
Currently, human society has many environmen-
tal and energy problems. A great deal of fossil
energy is consumed by industrial activities, but
most of it is lost to the atmosphere as waste heat
without being effectively used. If a large amount of
this waste heat can be localized, electricity can be
generated by the use of mechanical conversion
systems, for example, the steam turbine or Stirling
engine. Unfortunately, most waste heat sources are
widely dispersed. Thermoelectric conversion has
attracted much attention because it is one of the
(Received April 1, 2019; accepted May 22, 2019;
published online June 11, 2019)
from dilute waste heat.
Skutterudite compounds are known as potential
thermoelectric materials1–3 and are represented by
MX3, where M is Co, Rh or Ir and X is P, As or Sb.
Most binary skutterudite compounds possess a
reasonably large Seebeck coefficient, S, and low
electrical resistivity, q, resulting in large power
factor S2/q. However, their thermal conductivity, j,
especially the lattice thermal conductivity, is too
large to make these materials efficiently thermo-
electric.3 One approach for the achievement of the
reduction of j for a skutterudite compound is to
prepare filled skutterudite compounds.4–6 The com-
position of the filled skutterudite compounds can be
represented by the formula, RM4X12, where R is La,
Ce, Pr, Nd, Eu or Yb. In these compounds, the

5257
5258
empty octants of the skutterudite structure which
are formed in the MX3 frameworks are filled with a
rare-earth element. X-ray and neutron structure
refinements indicate that the R atoms tend to
exhibit exceptionally large thermal parameters,
corresponding to the ‘‘rattling’’ of these atoms in
an oversized atomic cage.6 The rattling markedly
reduces the thermal conductivity of these filled
skutterudite compounds, resulting in the achieve-
ment of high dimensionless figure of merits, ZT
(= S2T/(qj)).
In power applications for thermoelectric materi-
als, good chemical stability under the operating
conditions is important. To fulfill these require-
ments, some oxide materials have been reported as
candidates for power applications. Thermoelectric
modules composed of oxide devices have been
developed and been shown to be durable at high
temperatures in air.7,8 We have fabricated thermo-
electric modules consisting of silicide legs of p-type
MnSi1.75 and n-type Mn2.7Cr0.3Si4Al2 and tested the
durability of these modules in air.9 In these silicide
modules, the use of Ni–B plating and Ag-Pt or Ag-
Pd paste improved the durability at the heat-source
temperature of 773 K.
The thermoelectric conversion performance of
skutterudite compounds is generally superior to
those of oxides or silicides. The thermoelectric
conversion modules consisting of skutterudite com-
pound legs have been assumed to be used in vacuum
or in an inert gas, but if we can develop modules
consisting of skutterudite compound legs that can
be used in air, wide applications of thermoelectric
conversion can be expected. In this study, we have
fabricated a thermoelectric module consisting of
rare-earth-filled skutterudite legs and have investi-
gated its thermoelectric power generation perfor-
mance at high temperature in air.
EXPERIMENTAL
CeFe3CoSb12 and Yb0.15CoSb12 sintered bodies
were used as the p- and n-type legs, respectively. To
prepare CeFe3CoSb12, Ce (purity 99.9%), Fe (purity
99.9%), Co (purity 99.9%) and Sb (purity 99.999%)
powders with a stoichiometric composition were
mixed and evacuated in a quartz ampoule. The
ampoule was heated at 1273 K for 30 h via holding
at 873 K for 3 h, then quenched in ice-water, and
then the ampoule was again annealed at 973 K for
30 h. After the reaction was completed, the ampoule
was opened and the product was ground by a mortar
and pestle into fine powder. The obtained product
was packed into graphite dies (40 mm in diameter)
and sintered by hot-pressing at 973 K for 2 h at a
pressure of 35 MPa under a vacuum of 10 3 Pa. The
Yb0.15Co4Sb12 sintered bodies were also prepared in
a similar way from Yb (purity 99.9%), Co and Sb
powders.
The Seebeck coefficient, S, and the electrical
resistivity, q, for the sintered bodies were
Katsuyama, Yamakawa, Matsumura, and Funahashi
simultaneously measured by the standard DC (di-
rect current) four-probe method under a vacuum of
10 3 Pa in the temperature range from room tem-
perature to 873 K. The thermal diffusion coefficient,
D, of the samples was measured by the laser flash
method using a thermal constant analyzer (ULVAC
TC-7000). The specific heat, Cp, of the samples was
measured by a differential scanning calorimeter.
The density, d, of the samples was measured by the
Archimedes method. The thermal conductivity, j,
was calculated from the measured D, Cp and d using
the relationship, j = DCpd.
The phase identification of the obtained samples
was made by x-ray diffraction using Cu Ka radiation
at room temperature. The stability of the samples at
high temperature was evaluated by a thermogravi-
metric differential thermal analyzer (TG-DTA). The
sample was placed in a platinum container and
Al2O3 powder was used as a reference. The mea-
surement was carried out in air at the heating rate
of 10 K/min. The microstructures and atomic com-
positions near the junctions between the skutteru-
dite devices and the Ag sheets were investigated by
scanning electron microscopy (SEM) and energy-
dispersive x-ray spectrometry (EDX).
Both p- and n-type sintered pellets were cut into
rectangular bars with dimensions of 3.5 mm 9 3.5
mm in cross-section and 5 mm in length. A module
with 14 pairs of the p- and n-type legs was prepared.
Ag sheets of 0.1 mm thickness were used as the
electrodes of the module. The junctions between the
skutterudite legs and the Ag electrodes were formed
by use of a commercially available metal paste (Pt,
Ag or Ag-Pd paste). An Al2O3 substrate with a
thickness of about 0.8 mm was attached to the
bottom side of the module. The organic binders in
the pastes were decomposed at 573 K for 20 h in air
under the uniaxial pressure of 3.19 MPa. Finally,
the electrodes and the skutterudite devices were
bonded by sintering at 723 K for 7 h in vacuum
under the uniaxial pressure of 14.7 MPa by hot-
pressing.
The output electric power generated by the mod-
ules was measured by use of a DC four-terminal
method by scanning the output load. The Al2O3
substrate of the module was heated up to a maxi-
mum of 873 K by use of a plate-shaped electrical
furnace. The other side of the module was cooled by
circulating water at 293 K through a copper jacket.
These measurements were performed in air.
RESULTS AND DISCUSSION
Thermoelectric Properties
The thermoelectric properties of the p-type
CeFe3Co4Sb12 and n-type Yb0.15Co4Sb12 skutteru-
dite compounds are shown in Fig. 1. The ZT values
of these samples, especially of the n-type
Yb0.15Co4Sb12, were lower than the ZT values
previously reported4,10,11; the Seebeck coefficients
of these samples were smaller and the electrical
Fabrication of Thermoelectric Module Consisting of Rare Earth Filled Skutterudite
Compounds and Evaluation of Its Power Generation Performance in Air
Fig. 1. (a) Seebeck coefficient, (b) electrical resistivity, (c) thermal
conductivity and (d) ZT for the p-type CeFe3CoSb12 and n-type
Yb0.15Co4Sb12.
resistivity was larger in n-type Yb0.15Co4Sb12. The
rare-earth-filled skutterudite compounds contain
rare-earth elements, which are easily oxidised in
air, making the synthesis generally difficult, and
the elemental composition of samples is apt to be
inhomogeneous. Further, both the p- and n-type
skutterudite compounds were sintered by the hot-
pressing method to prepare large sintered bodies.
Small pieces were cut out from the sintered bodies
for the measurement of their thermoelectric prop-
erties. The amount and homogeneity of rare-earth
elements in the samples greatly affect their ther-
moelectric properties. It is necessary to investigate
the optimization of the fabrication method.
Selection of the Metal Paste
In this study, Ag sheets were used as the elec-
trode of the module, and a metal paste was used for
the junction between the thermoelectric device and
the electrode. We have tested three kinds of metal
pastes, Pt, Ag or Ag-Pd (Ag-23mass%Pd) paste, and
investigated how the addition of these metal pastes
affects the durability of the skutterudite module at
high temperature in air. Prior to fabricating the 14-
5259
Fig. 2. Schematic drawing for a pair of p- and n-type devices.
pair module, we prepared a module consisting of a
pair of p- and n-type devices. Metal paste was
applied to the top and bottom surfaces of the devices
with dimensions of 3.5 mm 9 3.5 mm 9 5 mm,
which were cut from the sintered discs prepared
by hot-pressing, and Ag sheets with dimensions of
5 mm 9 50 mm 9 0.1 mm and 5 mm 9 70 mm 9
0.1 mm were connected with to devices so that
the p- and n-type devices were in series, as shown in
Fig. 2. The decomposition of the organic binders in
the pastes and the bonding of the electrodes and
devices by sintering were carried out in a similar
manner to that mentioned in the ‘‘Experimental’’
sectiuon.
In order to evaluate the bonding state of these
modules, the electric resistance of the modules was
measured by the dc four-probe method. The electric
resistances of the modules bonded using Pt, Ag or
Ag-23 mass%Pd paste were 18.3 mX, 15.1 mX and
15.9 mX, respectively. The electric resistance of the
module using the Pt paste was the largest, and the
electric resistances of the module using Ag or Ag-
23mass%Pd paste were almost the same.
In order to investigate the state of the junction
interface between the Ag electrodes and the
devices, the microscopic structure of the cross-
section was observed by SEM and the elemental
analysis by EDX was carried out. Figure 3a, b, and
c shows the SEM photographs for the cross-section
near the junction interface on the p-type CeFe3-
Co4Sb12 side of the 1-pair module fabricated using
Pt, Ag or Ag-23mass%Pd paste, respectively. The
results of the elemental analysis by EDX per-
formed on points A, B, C, D, E and F in the images
are shown in Table I. Here, point C is a point
located at the interface between the Ag electrode
and the device material. For all the modules,
mutual diffusion of elements between the Ag
electrode and the devices near the interface was
observed. It is considered that this diffusion has
occurred during the bonding process between the
electrode and the devices at 723 K. In the module
using the Pt paste, the mutual diffusion of ele-
ments between the Ag electrode and the devices
5260 Katsuyama, Yamakawa, Matsumura, and Funahashi

Fig. 3. SEM images for the cross-section near the junction interface on the p-type CeFe3CoSb12 side of the 1-pair module fabricated using (a) Pt,
(b) Ag and (c) Ag-23mass%Pd pastes.

Table I. Elemental analysis results of each point in Fig. 3 by EDX

EDX

Paste Point Ag (at%) Pd (at%) Pt (at%) Ce (at%) Fe (at%) Co (at%) Sb (at%)

Pt A 93 7
B 85 2 13
C 47 44 9
D 6 5 15 7 67
E 8 8 16 7 61
F 1 7 2 23 4 65
Ag A 91 9
B 86 14
C 59 2 13 5 21
D 50 10 7 3 30
E 6 7 4 19 64
F 14 8 5 17 56
Ag-23mass%Pd A 97 3
B 87 1 12
C 64 4 3 18 2 10
D 3 3 4 16 8 66
E 1 1 4 20 7 67
F 1 1 6 17 7 68

was small, while the electrical resistance of this
module is the largest. In the module using the Ag
paste, the diffusion of Ag to the device and the
diffusion of Sb to the Ag electrode were noticeable,
while in the module using the Ag-23mass%Pd
paste, such diffusion between the Ag electrode
and the device was suppressed. This is probably
because Ag and Pd are solid-solved in all ratios,12
and the alloy of Ag and Pd is more stable so that
the formation of alloying with other elements is
suppressed. The low electric resistance of the
module and the small change of thermoelectric
properties of the device material due to the alloy-
ing at the bonding interface are desirable for good
thermoelectric modules. In addition, in the module
using the Ag-23mass%Pd paste, sufficient bonding
strength to the extent that there is no problem in
handling was obtained. Thus, from the above
results we decided to use the Ag-23mass%Pd paste
for the fabrication of the 14-pair module.
Fabrication of Thermoelectric Module Consisting of Rare Earth Filled Skutterudite 5261
Compounds and Evaluation of Its Power Generation Performance in Air

Fig. 4. The 14-pair module.

Fabrication of the 14-Pair Module

Figure 4 illustrates the 14-pair module. This
module consists of 14 pairs of thermoelectric devices
connected in series, where each pair is composed of
two p- and n-type devices with dimensions of
3.5 mm 9 3.5 mm 9 5 mm connected in parallel. Fig. 5. TG-DTA curves for (a) p-type CeFe3CoSb12 and (b) n-type
An aluminum substrate was used on the bottom Yb0.15Co4Sb12.
side of the module, namely this module is of a half-
skeleton type. The electric resistance of this module
is 113.4 mX. As already mentioned, the electric
resistance of the 1-pair module is 15.9 mX, and so
the calculated electric resistance of the 14-pair
module is 111.3 mX, which is slightly smaller than
the measured value of 113.4 mX. This result shows
that the bonding state between the electrode and
the device in the fabricated module is good.

Evaluation of Power Generation Characteris-

tics for the 14-Pair Module
One of purposes of this study is to develop a
thermoelectric power generation module that can be
stably used for a long time at high temperature in
air. It is considered that the durability of the module
depends on the durability of the device material
itself and the durability of the joining section of the
module. Therefore, the durability of the device
materials at high temperature in air were investi-
gated by TG–DTA. Figure 5a and b shows the TG–
DTA curves for p-type CeFe3CoSb12 and n-type
Yb0.15Co4Sb12, respectively. In each sample,
exothermic peaks appear in the DTA curve, and a
weight increase is observed in the TG curve. It is
considered that these peaks and weight increases
correspond to the oxidation and decomposition of
the samples. From this result, Yb0.15Co4Sb12 has a
higher durability in the atmosphere at high tem-
perature in air than CeFe3CoSb12, and that neither
material will be oxidized and decomposed at 573 K
or less.
The generation power was measured in air by
equipment arranged by us. In this equipment, the
hot side of the module is heated by an electronic
plate heater and the cold side is cooled by
Fig. 6. I–V curve for the module when the temperatures at the cold
side and hot side were kept at 293 K and 573 K, respectively. The
electric power generated in the module is also shown.
circulating cooling water. During the measure-
ments, both sides of the module are kept at a
constant temperature difference and a pressure of
5.9 MPa was applied to both sides of the module.
When the temperatures at the cold side and the hot
side were kept at 293 K and 573 K, respectively,
and the electric current, I, flowing through the
module was changed from 0 to 1.5 A, the electric
voltage, V, generated in the module was measured.
The obtained I–V curve is shown in Fig. 6 and
shows a substantially straight line. Here, the slope
of the straight line is the electric resistance, R, of
the module, and the intercept of the voltage axis is
5262
the open circuit voltage, V0, generated in the
module due to the temperature difference between
both sides of the module. The electric power gener-
ated in the module is also shown in Fig. 6 and shows
a maximum value at the current of V0/(2R).
Figure 7 shows the electric resistance, open cir-
cuit voltage and maximum electric power of the
module at each hot side temperature. Both electric
resistance and open circuit voltage increase almost
linearly with the hot side temperature, which
indicates that the module is operating without
damage within the measuring time. As the hot side
temperature becomes higher, the maximum electric
power tends to be larger and the rate of an increase
also becomes larger. Table II shows the maximum
electric power and power density of the module at
each hot side temperature.
Garcı́a-Cañadas et al. also fabricated a module
composed of 9 pairs of p-type Ce0.8Fe3CoSb12 and n-
type Yb0.36Co4Sb12 using commercially available
solder alloys (Zn78Al22) and metal barriers.11 Their
module provided more than 1.5 W cm 3 volume
power density at a temperature difference of
365 K between the cold and hot sides. This value
is much larger than the value of our module,
0.3 W cm 3, at a temperature diference of 380 K.
The main reason for this difference in the power
generation performance seems to be the difference
Fig. 7. Electric resistance, open circuit voltage and maximum
electric power for the module as a function of the hot side
temperature
Table II. Maximum electric power and power density at each hot side temperature
373
Maximum electric power (W) 0.03
Maximum power density (kW/m2) 0.04
Katsuyama, Yamakawa, Matsumura, and Funahashi
in the performance of the device material. Further-
more, it is considered to be due to the difference in
contact resistance between the device material and
electrode: an average specific contact resistivity
value of their module is 4.77 9 10 4 X cm2, while
that of our module can be estimated to be
2.6 9 10 2 X cm2 from values of the measured and
calculated electric resistance of the module.
Next, a power generation test of the module over a
long period in air was carried out. The time
dependence of the I–V curve of the module was
measured by keeping the hot side temperature at
573 K. Figure 8 shows the elapsed time dependence
of the electric resistance, open circuit voltage and
maximum electric power of the module obtained
from the I–V curve. Until an elapsed time of 100 h
from the start of the measurement, the electric
resistance decreased slightly with the increase of
time, and the open circuit voltage and maximum
electric power tended to increase; however, after
100 h, they became almost constant up to 336 h
(2 weeks). The fact that the module can withstand
power generation testing for a long time at 573 K is
consistent with the result of TG–DTA shown in
Fig. 5. Neither an exothermic peak nor a weight
increase was observed in the TG–DTA curves for the
device materials at 573 K or less.
Then, the hot side temperature was set at 673 K
and a similar measurement was carried out. Fig-
ure 9 shows the elapsed time dependence of the
Fig. 8. Elapsed time dependence of the electric resistance, open
circuit voltage and maximum electric power of the module when the
hot side temperature is kept at 573 K.
Hot side temperature (K)
473 573 673 773 873
0.17 0.48 1.00 1.68 2.43
0.25 0.70 1.46 2.45 3.54
Fabrication of Thermoelectric Module Consisting of Rare Earth Filled Skutterudite
Compounds and Evaluation of Its Power Generation Performance in Air
Fig. 9. Elapsed time dependence of the electric resistance, open
circuit voltage and maximum electric power of the module when the
hot side temperature is kept at 673 K.
electric resistance, open circuit voltage and maxi-
mum electric power of the module. Until the elapse
of about 50 h from the start of the measurement, the
electric resistance, open circuit voltage and maxi-
mum electric power showed stable values, but then,
with the passage of time, the electric resistance
gradually increased and the maximum electric
power decreased.
For the module after the measurement, the cross-
section of the junction of the electrode and device
material was observed by SEM and elemental
analysis by EDX was carried out. As a result, no
remarkable change in the microstructure was
observed as compared with before the measure-
ment, and further progression of element diffusion
was not recognized. The x-ray diffraction pattern for
the surface of the device material after the mea-
surement was almost the same as that before the
measurement, and no diffraction peaks such as the
oxide phase were observed. When the Ag electrode
at the hot side was peeled off from the device
material and its joint surface was subjected to x-ray
diffraction analysis, diffraction peaks of Sb2O3 were
detected in the p-type CeFe3CoSb12 device. During
the measurement, oxygen may intrude through the
bonding interface to generate oxides. It is consid-
ered that the degradation of the power generation
performance of the module is caused by the oxida-
tion of the p-type device material at the hot side
with the temperature of 673 K, which is higher than
the oxidation and decomposition temperature of p-
type CeFe3CoSb12.
CONCLUSION
We have fabricated a thermoelectric module
consisting of p-type CeFe3CoSb12 and n-type
Yb0.15Co4Sb12 compounds using Ag-23mass%Pd
paste as the bonding material, and investigated its
5263
stability and power generation performance in air.
The module using Ag-23mass%Pd paste showed a
lower electric resistance than the module using Pt
paste, and the diffusion of elements at the bonding
interface was suppressed compared with the module
using the Ag paste without Pd. Since Ag and Pd are
solid-solved in all ratios and the alloy of Ag and Pd
is more stable, the formation of alloying with other
elements is suppressed. In the power generation
experiment at 573 K in air, the fabricated 14-pair
module showed a stable electric resistance, open
circuit voltage and maximum electric power over
336 h (2 weeks), but in the experiment at 673 K, the
deterioration of the performance was observed at
more than 50 h. The deterioration of the perfor-
mance is caused by the oxidation and decomposition
of the p-type device material. In this research, we
have focused on the development of elemental
technologies for fabricating modules using skut-
terudite compounds. The thermoelectric perfor-
mance of the rare-earth-filled skutterudite
compounds prepared this time has not been as
good, and it is necessary in the future to study the
optimization of the fabrication method. It is also
necessary to investigate the device materials, espe-
cially p-type materials, with high-temperature
durability and to improve the bonding property at
the interface between the electrode and the device
material.
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