Journal of the Korean Physical Society, Vol. 63, No. 9, November 2013, pp.

1764∼1767

Effects of Heat Treatment on the Thermoelectric Properties of Yb-filled

Skutterudites

Kwan-Ho Park, Young Soo Lim and Won-Seon Seo

Energy and Environmental Materials Division, Korea Institute of Ceramic Engineering and Technology, Seoul 153-801, Korea

Il-Ho Kim∗
Department of Materials Science and Engineering,
Korea National University of Transportation, Chungju 380-702, Korea

(Received 2 April 2013, in final form 4 June 2013)

The p-type Yb-filled skutterudites Yb0.9 Fe3 CoSb12 were prepared by encapsulated melting and
hot pressing, and the effects of heat treatment on the phase transformation, microstructure, and
thermoelectric properties were examined. The ingots were melted at 1323 K, cooled in a furnace or
in a water bath, and then annealed at 873 K for 24 to 100 h. The ingots were ground into powders
and consolidated by hot pressing at 873 K for 1 h. According to the X-ray diffraction analysis and
the Rietveld refinement, the water-quenched specimen had more Yb-filled skutterudites and fewer
YbSb2 phases compared to the furnace-cooled sample. All the specimens were transformed into the
skutterudite phases by annealing. The dimensionless figure-of-merit value (ZT) was increased by
about 50% by a subsequent annealing after water quenching. The water quenching suppressed the
formation of secondary phases due to the sluggish peritectic reaction for the skutterudite phase.

PACS numbers: 72.15.Jf, 72.20.Pa

Keywords: Thermoelectric, Skutterudite, Heat treatment
DOI: 10.3938/jkps.63.1764

I. INTRODUCTION charge compensation is needed for RFe4 Sb12 compounds

Thermoelectric research on skutterudites has been car-
ried out since the mid-nineteenth century [1–3], and
many studies are still in progress for thermoelectric
power generation from industrial waste heat and exhaust
gas from automotive vehicles [4–8]. Skutterudites ex-
hibit superior thermoelectric properties in the tempera-
ture ranges from 500 K to 900 K than chalcogenides at
lower temperature and silicides/oxides at higher temper-
ature. Ry Co4 Sb12 -based skutterudites (R: filler atom, y:
filling fraction) exhibit excellent n-type thermoelectric
properties [9–12] whereas RFe4 Sb12 -based skutterudites
are known as good p-type thermoelectric counterparts
[13–16].
The skutterudite has eight tilted octahedral frame-
works with two voids in the crystal lattice of the cu-
bic structure. A stable [Co4 Sb12 ] has 72 outermost elec-
trons. However, [Fe4 Sb12 ]4− has 68 outermost electrons,
and it is unstable due to a lack of electrons. The in-
corporation of the filler ion R4+ into the void can make
R4+ [Fe4 Sb12 ]4− stable [17]. Because of the limitation of
R+ ions, R2+ or R3+ ions are usually used for fillers, and
like Ry Fe4−x Tx Sb12 , where T is a transition element [13,
16,18,19]. The synthesis of skutterudites by using a sin-
gle process is difficult due to the sluggish peritectic re-
action. They have generally been prepared by using me-
chanical alloying [20,21], a solid-state reaction [22], melt-
ing/annealing [15, 19], and other methods. Mechanical
alloying forms metastable phases by applying mechani-
cal energy to constituent elements, and the metastable
phases are then stabilized through heat treatment. A
solid-state reaction provides stable phases through an
inter-elemental diffusion of heated solid-state constituent
elements. The melting/annealing process stabilizes a
sample through annealing after a high-temperature re-
action of constituent elements [15, 19]. In general, the
focus has been on the effects of filling and doping on the
thermoelectric properties and the electrical conduction
type of a material, but it is also important to control the
process parameters for the synthesis of a material with
the desired performance. In this study, p-type Yb-filled
skutterudite Yb0.9 Fe3 CoSb12 obtained from a previous
study [18] is used, and the effects of heat treatment on
the phase transition, microstructure, and thermoelectric
properties are examined.

∗ E-mail: ihkim@ut.ac.kr; Fax: +82-43-841-5380

-1764-
Effects of Heat Treatment on the Thermoelectric Properties· · · – Kwan-Ho Park et al. -1765-

Table 1. Sample preparation conditions for Yb0.9 Fe3 CoSb12 skutterudites.

Specimen Heating Melting Cooling Annealing Hot pressing

FC furnace cooling • •
WQ 873 K water quenching • •
FCANN100 @ 3 K/mim furnace cooling 873 K, 100 h •
WQANN100 water quenching 873 K, 100 h •
+ 1323 K, 10 h
WQANN24 water quenching 873 K, 24 h •
FCANN100HP 1323 K furnace cooling 873 K, 100 h
WQANN100HP @ 1 K/min water quenching 873 K, 100 h 873 K, 1 h, 70 MPa
WQANN24HP water quenching 873 K, 24 h

II. EXPERIMENTS AND DISCUSSION

The Yb0.9 Fe3 CoSb12 skutterudite is a Yb-filled and

Co-substituted (charge-compensated) skutterudite. The
experimental conditions are summarized in Table 1. Yb
(purity 99.9%), Co (purity 99.95%), Fe (purity 99.95%),
and Sb (purity 99.999%) were melted at 1323 K for 10
h with 2-step heating, to 873 K from room temperature
at 3 K/min, and to 1323 K from 873 K at 1 K/min,
for reaction control of the constituent elements. Evacu-
ated and sealed quartz tubes, internally coated with car-
bon, were used for melting and annealing. Two types
of cooling were adopted after melting: furnace cool-
ing (FC) and water quenching (WQ). Ingots were an-
nealed for the peritectic transformation to the skutteru-
dite at 873 K for 100 h (FCANN100, WQANN100) or
24 h (WQANN24). Annealed ingots were ground into
<75 µm powders, which were subjected to hot press-
ing (FCANN100HP, WQANN100HP, WQANN24HP) in
a graphite die with an internal diameter of 10 mm at 873
K under a pressure of 70 MPa for 1 h in a vacuum.
Phases were analyzed by using X-ray diffraction
(XRD: Bruker D8 Advance) with Cu Kα radiation (40
kV, 40 mA). The diffraction patterns were measured in
the θ-2θ mode (10 to 90◦ 2θ) with a step size of 0.02
degrees, a scan speed of 3 ◦ /min, and a wavelength of
0.15405 nm. The Rietveld refinement was performed
by using the TOPAS program. After the constituent
phases had been identified by using X-ray diffraction,
phases fractions were calculated by using the Rietveld
analysis. Then, the microstructure was observed us-
ing an optical microscope (OM) and a scanning electron
microscope (BSE-SEM) in the back-scattered electron
mode, and elemental distributions (compositions) were
analyzed by an energy dispersive spectrometer. After all
analysis results had been evaluated, the phases were es-
timated. The compact subjected to hot pressing was cut
into rectangular pieces of 3 × 3 × 10 mm3 to measure
the Seebeck coefficient and the electrical conductivity,
and cut into cylindrical pieces of 10 mm (diameter) × 1
mm (length) to measure the thermal conductivity. The
Seebeck coefficient and the electrical conductivity were
Fig. 1. (Color online) XRD patterns of Yb0.9 Fe3 CoSb12
skutterudites: (a) FC, (b) WQ, (c) FCANN100, (d)
WQANN100, (e) WQANN24 and (f) WQANN24HP speci-
mens.
measured using the temperature differential and 4-probe
methods (Ulvac-Riko ZEM3), respectively. The ther-
mal conductivity was evaluated by using the laser flash
method (Ulvac-Riko TC9000) from the measurements of
the thermal diffusivity, specific heat, and density.
Figure 1 shows the XRD patterns of Yb0.9 Fe3 CoSb12
for various heat treatment conditions. The diffraction
patterns of annealed samples matched the reference data
(ICDD PDF No. 00-056-1123) well. The FC and the WQ
specimens had many secondary phases (YbSb2 , FeSb2 ,
Sb), as well as the skutterudite phase. This confirmed
that the skutterudite phase is difficult to form through
a single melting process. FC and WQ were fully trans-
formed to the skutterudite phase by annealing at 873 K.
However, a small amount of Yb2 O3 was produced when
annealing for 100 h. Therefore, the heat treatment at
873 K for 24 h was sufficient and practical for the phase
transformation to the skutterudite.
Figure 2 shows the constituent phase fractions for the
WQ and the FC specimens after melting, which were an-
alyzed by using an XRD Rietveld refinement. The WQ
-1766-
Fig. 2. (Color online) Phase fractions analyzed by using
the Rietveld refinement: (a) FC and (b) WQ specimens.
Fig. 3. (Color online) Microstructure variations with heat-
treatment conditions.
specimen showed a slightly higher phase fraction of the
skutterudite and a much lower phase fraction of YbSb2
than the FC specimen. Because YbSb2 is not produced
if every Yb fills a void of the skutterudite structure, the
WQ specimen with a smaller amount of YbSb2 is ex-
pected to be transformed to the skutterudite more easily
by a subsequent heat treatment.
Figure 3 illustrates the microstructural and atomic
distribution for different heat-treatment conditions, and
Fig. 4 presents the microstructures of the FC and the
WQ specimens in detail. In addition to the skutterudite
phase, YbSb2 , FeSb2 , and Sb existed in the FC and the
WQ specimens. This is in good agreement with the XRD
analysis results in Figs. 1 and 2. The WQ specimen had
fine grains with a typical microstructure due to solidifi-
cation by rapid cooling. The FC and the WQ specimens
could be homogenized and transformed to the skutteru-
dite phases by annealing, but many pores existed. The
annealed specimen (transformed to the skutterudite) was
hot pressed, and a sound compact with a single-phase
skutterudite was obtained for WQANN24HP.
Figure 5 compares the thermoelectric properties
of hot-pressed Yb0.9 Fe3 CoSb12 skutterudites prepared
by using three kinds of heat-treatment conditions:
Journal of the Korean Physical Society, Vol. 63, No. 9, November 2013
Fig. 4. (Color online) BSE-SEM images after cooling of
melted Yb0.9 Fe3 CoSb12 : (a) FC and (b) WQ specimens.
Fig. 5. Changes in the thermoelectric properties of
Yb0.9 Fe3 CoSb12 skutterudites with heat-treatment condi-
tions: (a) electrical conductivity, (b) Seebeck coefficient, (c)
thermal conductivity and (d) dimensionless figure of merit.
FCANN100HP, WQANN100HP, and WQANN24HP. All
samples showed high electrical conductivities ranging
from 1.7 × 105 S/m to 2.0 × 105 S/m at room tem-
perature, which slightly decreased with increasing tem-
perature, indicating a degenerate semiconductor behav-
ior. These three samples had no significant differences in
the electrical conductivity, but the WQANN100HP indi-
cated a slightly higher electrical conductivity, probably
due to the grain growth caused by the longer annealing
time. All samples showed positive Seebeck coefficients,
indicating p-type conduction. The Seebeck coefficient in-
creased with increasing temperature and saturated above
723 K. This was caused by bipolar conduction due to in-
trinsic excitation. The highest Seebeck coefficient was
obtained in the WQANN24HP. The Seebeck coefficient
can be increased by a decrease in the carrier concentra-
tion and/or an increase in the charge carrier scattering.
This was attributed to the grain boundary scattering ef-
fect caused by the grain refinement of water quenching
rather than to the decreased carrier concentration.
Effects of Heat Treatment on the Thermoelectric Properties· · · – Kwan-Ho Park et al.
The thermal conductivity ranged from 2.6 W/mK to
3.1 W/mK at temperatures from room temperature to
723 K and then increased at temperatures above 723 K,
which are caused by an increase in the electronic ther-
mal conduction due to the intrinsic conduction. The
lowest thermal conductivity was obtained under the
WQANN100HP heat-treatment condition, which was at-
tributed to phonon scattering by grain refinement. Fig-
ure 5(d) presents the dimensionless thermoelectric figure
of merit ZT = σα2 Tκ−1 , where σ is the electrical conduc-
tivity, α is the Seebeck coefficient, κ is the thermal con-
ductivity, and T is the absolute temperature in Kelvin.
The FCANN100HP exhibited ZTmax = 0.4 at 723 K to
823 K, and that of the WQANN24HP was ZTmax =
0.62 at 723 K to 823 K, an improvement by over 50%.
This ZT value is higher than those of Yb0.8 Fe3 CoSb12
reported by Zhou et al. [23] and Yb0.95 Fe3 NiSb12 re-
ported by Cho et al. [24], as shown in Fig. 5(d). Water
quenching is preferred after the melting of rare-earth-
filled RFe4 Sb12 -based skutterudites because of suppres-
sion in the formation of the secondary phase, and the
subsequent annealing time of 24 h is sufficient for skut-
terudite transformation for water-quenched specimens.
III. CONCLUSION
The effects of heat treatment on the phase, mi-
crostructure and the thermoelectric properties of
Yb0.9 Fe3 CoSb12 skutterudite were examined. Sound
compacts with a single-phase skutterudite were obtained
from melting, subsequent annealing, and hot pressing.
The FC and the WQ specimens had many secondary
phases (YbSb2 , FeSb2 , Sb), as well as the skutterudite
phase. This confirmed that the skutterudite phase is
difficult to form through a single process. The water-
quenched specimen had more Yb-filled skutterudites and
fewer YbSb2 phases compared with the furnace-cooled
sample. Annealing at 873 K for 24 h was enough for a
phase transformation to the Yb-filled skutterudite phase.
The specimen quenched with water followed by anneal-
ing for 24 h showed a higher thermoelectric performance,
with ZTmax = 0.62 at 723 K to 823 K, which was at-
tributed to the inhibition of the secondary phases dur-
ing melting (synthesis). Water quenching of the melt is
a useful and practical process for rare-earth-filled skut-
terudites with respect to the suppression of secondary
phases, the shortening of the subsequent annealing, and
improvements of the thermoelectric properties.
ACKNOWLEDGMENTS
This work was supported by the Defense Acquisition
Program Administration (DAPA) and the Agency for
-1767-
Defense Development (ADD) under the contract No.
UC120037GD.
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