Mat. Res. Soc. Symp. Proc. Vol.

691 © 2002 Materials Research Society

Electronic Structure and Thermoelectric Properties of Ytterbium-Filled Skutterudites

Hiroaki Anno,1 Kazuhiro Ashida,1 Kakuei Matsubara,1 George S. Nolas,2 Koji Akai,3 Mitsuru
Matsuura,3 and Jiro Nagao4
1
Department of Electronics and Computer Science, Science University of Tokyo in Yamaguchi,
1-1-1 Daigaku-dori, Onoda 756-0884, Japan
2
Department of Physics, University of South Florida, 4202 East Fowler Avenue, Tampa, Flor-
ida 33620, U.S.A.
3
Department of Advanced Materials Science and Engineering, Yamaguchi University, 2-16-1
Tokiwadai, Ube 755-8611, Japan
4
Institute for Energy Utilization, National Institute of Advanced Industrial Science and Tech-
nology (AIST), 2-17-2-1 Tsukisamu-Higashi, Toyohira, Sapporo 062-8517, Japan

ABSTRACT
The electronic structure and thermoelectric properties of Yb partially filled CoSb3 skutteru-
dite compounds have been investigated by x-ray photoelectron spectroscopy and band calcula-
tion in terms of an itinerant f electron model. In these materials, the significant effect of Yb filling
is the large reduction of lattice thermal conductivity, remaining relatively high electron mobility
and Seebeck coefficient, resulting in high thermoelectric figure of merit. We discuss the effects of
the valence fluctuation between Yb2+ and Yb3+ and the strong hybridization of Yb 4f states with
the valence band states on the electronic properties and their relation to thermoelectric properties
for Yb partially filled CoSb3 compounds.

INTRODUCTION
The filled skutterudite compounds are of interest for thermoelectric applications due to the
extremely low thermal conductivity comparable to that for amorphous materials [1]. The glass-
like thermal conductivity of these materials is attributed to the dynamic disorder, rattling m o-
tions, of the void-filling rare-earth ions that substantially affect the phonon propagation through
the lattice [2]. Recent works [3-5] reported the successful synthesis of a new filled skutterudite
YbFe4Sb12 and revealed the unique physical properties that are associated with heavy-fermion or
itinerant f electron behavior of the Yb ions. For example, an intermediate valence of Yb ions be-
tween divalent and trivalent in YbFe4Sb12 has been evident from magnetic susceptibility and x-ray
absorption [3, 4]. Recently, several researchers [6-10] have investigated the partially filling the
voids of CoSb3 skutterudites with Yb ions as a new approach for optimizing the thermoelectric
properties. Nolas et al. [8] suggested that the Yb valence fluctuation (the f electron hybridization
effect) play an important role for Yb-filled CoSb3 compounds as in the case for YbFe4Sb12. In or-
der to clarify this point, we have investigated the electronic structure of Yb partially filled CoSb3
compounds as well as YbFe4Sb12 by x-ray photoelectron spectroscopy (XPS). XPS study holds
great promise in elucidating the band structure of these materials and in answering the questions
regarding the nature of the f electron effects. The photoemission spectra are compared to the re-
sults of band calculation for Yb-filled skutterudites. We discuss the effects of Yb filling on the
band structure and electronic and thermoelectric properties of Yb partially filled CoSb3 com-
pounds. We also consider effects of Pd or Pt substitution for Co sites on the electronic and ther-
moelectric properties of Yb-filled CoSb3 compounds.

G2.4.1
EXPERIMENTAL DETAILS
Polycrystalline Yb partially filled CoSb3 compounds (nominal formula Yby Co4Sb12 with fill-
ing fraction y=0-0.25, and Ge-compensated Yby Co4Gex Sb12-x with y=0.42, 0.5, 0.65) and fully
filled YbFe4Sb12 were prepared by combination of melting and sintering techniques, as described
previously [8-10]. The maximum value of Yb filling fraction into CoSb3 lattice was reported to
about y=0.2 [6, 8]. Materials with high filling fractions were successfully obtained by Ge com-
pensation. Pd- and Pt-substituted compounds, nominal formula Yby Co4-x M x Sb12 (M=Pd, Pt)
with y=0.25 and x=0-0.4, were also prepared to study the effects of Co site substitution on the
thermoelectric properties. X-ray diffraction and electron-beam microprobe analyses were em-
ployed in the structural and chemical characterization of single-phase samples. X-ray structure
refinements by the Rietveld method were also performed on selected samples.
Two-probe electrical conductivity σ and steady-state Seebeck S measurements were made in
the temperature range of 300-900 K. Hall measurements were curried out by applying an external
magnetic field of 1 T using a van der Pauw technique. The Hall mobility µ was determined from
the electrical conductivity σ and the Hall coefficient RH using µ = σ RH. Hall and Seebeck meas-
urements at room temperature showed that the Yb-filled CoSb3 samples, including Ge-
compensated, and Pd- and Pt-substituted compounds, were n type and YbFe4Sb12 samples were
p type. Measurements of the thermal conductivity κ were performed by a laser flash method
using a Ni standard. XPS measurements were performed at room temperature by using the Mg Kα
line (1253.6 eV) and a 180O hemispherical analyzer in the constant-resolution mode (pass en-
ergy=40 eV), as described previously [11]. Prior to the analysis samples were cleaned by argon
ion sputtering in the ultra-high vacuum analyzer chamber until no traces of contamination (mainly
core lines of carbon and oxygen) were observed within XPS sensitivity. The electronic structures
for CoSb3, Yb0.5Co4Sb12, YbCo4Sb12, and YbFe4Sb12 were calculated by the full-potential line-
arized augmented-plane-wave (FLAPW) method with the local density approximation (LDA), as
described elsewhere [12].

RESULTS AND DISCUSSION

Figure 1 shows valence-band photoemission spectra for Yb partially filled CoSb3 compounds
(y=0, 0.075, 0.5) and fully filled YbFe4Sb12. The densities of states (DOS) are shown for CoSb3
and YbFe4Sb12, including the Yb f-derived component of the DOS. The Yb 4f12 final-state mul-
tiplets are also shown [13]. The valence-band spectra for Yb-filled CoSb3 and YbFe4Sb12 clearly
show the intermediate valence features (Yb2+ and Yb3+). These f photoemission structures agree
substantially with those observed in the typical mixed-valence material YbAl3 [14]. The struc-
tures at 1 and 2.2 eV can be identified as the 4f14 −> 4f13 transitions (divalent feature), and those
between 6 and 14 eV as the 4f13 −> 4f12 transitions (trivalent feature). The band calculation based
on an itinerant f electron model gives a good explanation for the divalent feature, as is evident
from Fig.1. On the other hand, the trivalent feature can be interpreted as the 4f12 final-state mul-
tiplet structures [13, 14]. Furthermore, in Yb 4p and 4d core-level spectra we also clearly ob-
served photoemission structures due to Yb2+ and Yb3+ states in Yb-filled CoSb3 compounds and
YbFe4Sb12. The core-level photoemission lines for Yb-filled CoSb3 compounds agree well with
those for Yb (divalent) metal and Yb2O3 (trivalent) oxide as standard materials. The positions of
Yb core-level peaks are almost independent of Yb filling. The valence fluctuation of Yb observed
in the photoemission spectra for Yb-filled CoSb3 compounds is consistent with the results of
magnetic susceptibility measurements [6, 8].
We also investigated the chemical shifts (Wagner plot analysis) of the core-levels and the
Auger electron peaks for cobalt and antimony of Yb-filled CoSb3 compounds to study the effect
of Yb filling on the chemical bonding states. We found that the Auger parameters for Yb-filled

G2.4.2
 Figure 2. Hall mobility at room tempera-
ture as a function of carrier concentration
for Lay Co4Sb12 [16], Cey Co4Sb12 [17],
Yby Co4Sb12, and Yby Co4-x M x Sb12 (M=Pd
and Pt).

Figure 1. Valence-band photoemission

spectra for Yb partially filled CoSb3
compounds and fully filled YbFe4Sb12.

CoSb3 compounds are in good agreement with those for unfilled CoSb3. This result suggests that
the bonding of Co-Sb is covalent in Yb-filled CoSb3 compounds, as is the case for CoSb3 [11],
and that the Coulomb interaction from Yb ions is screened through the strong f electron hybridi-
zation with the surrounding valence band states.
Since it was found that the valence-band spectra (divalent feature) agree well with the calcu-
lated DOS for Yby Co4Sb12 (y=0.5 and 1) and YbFe4Sb12, we discuss the effect of Yb filling on the
band structure and electronic properties in terms of an itinerant f electron model. We can find out
some important points in the band structure of Yb-filled skutterudite compounds. The narrow
spin-orbit split Yb 4f bands, which strongly hybridized with Fe (Co) 3d and Sb 5p states, domi-
nate the top of the valence band. From the Yb f-derived component of the DOS, we found that
there is no significant contribution from the Yb 4f states to the lowest lying conduction bands for
YbFe4Sb12. This is a striking difference from the case of CeFe4P12 and CeFe4Sb12, in which the f
electron hybridization is crucial for the formation of the band gaps around the Fermi levels [15].
The conduction bands near the bottom have characters of hybridization of Yb 6s and 5d states
with Fe (Co) 3d states. From the band calculations for Yby Co4Sb12 (y=0.5 and 1), we found that
for n-type Yb-filled CoSb3 the Yb filling causes the change in the conduction band structure (es-
pecially large at the N point) and the shift of the Fermi level due to the change of the electron
count. Consequently, Yb filling may have an influence on the electronic properties through these
effects.
Figures 2 and 3 show Hall mobility and electron effective mass m*/m0, where m0 is the free
electron mass, at room temperature as a function of carrier concentration for Lay Co4Sb12 [16],
Cey Co4Sb12 [17], Yby Co4Sb12, and Yby Co4-x M x Sb12 (M=Pd and Pt). The effective mass was de-
termined from the analysis of transport properties assuming the parabolic band and predomi-
nance of acoustic phonon scattering, as described elsewhere [18]. It can be clearly seen that

G2.4.3
 Figure 3. Electron effective mass at room
temperature as a function of carrier con-
centration for Lay Co4Sb12 [16],
Cey Co4Sb12 [17], Yby Co4Sb12, and Yby Co4-
x M x Sb12 (M=Pd and Pt).
Figure 4. Lattice thermal conductivity at
room temperature as a function of filling
fraction for Lay Co4Sb12 [16], Cey Co4Sb12
[17], and Yby Co4Sb12. The inset shows the
temperature dependence of lattice thermal
conductivity for Yby Co4Sb12, Yby Co4-
x M x Sb12 (M=Pd and Pt), and YbFe4Sb12.

the electron effective mass for Yb filling is comparable with that for unfilled n-type Co1-x M x Sb3
(M=Pd and Pt) while the electron effective mass for La and Ce filling increases rapidly with in-
creasing carrier concentration. As stated in Ref. 8, this suggests rigid-band behavior with varying
Yb concentration for the conduction band. For La and Ce filling the f electron hybridization seems
to be important for both the valence and conduction bands, as predicted from the band calcula-
tions [15]. On the other hand, we estimated the hole effective mass for p-type YbFe4Sb12 to be
about 5m0. This value is about two orders of magnitude larger than that of unfilled p-type CoSb3
(0.05m0) [19] and in excellent agreement with the calculated band mass (4.25m0) close to the
Fermi level. This seems to be closely related to the strong hybridization of Yb 4f states with va-
lence band states for Yb-filled skutterudite compounds. One of advantages for Yb filling is that
the Hall mobility for Yb filling is larger than that for La and Ce filling for the same carrier concen-
tration. In full accordance with the results of Ref. 8, it is interesting that one can reach the opti-
mum carrier concentration of n-type Yb-filled CoSb3 by Yb filling and Yb filling may lead to more
optimized electronic properties as compared to other rare-earth filling.
Figure 4 shows lattice thermal conductivity κ L at room temperature as a function of filling
fraction for Lay Co4Sb12 [16], Cey Co4Sb12 [17], and Yby Co4Sb12. The inset shows the temperature
dependence of the lattice thermal conductivity for Yby Co4Sb12, Yby Co4-x M x Sb12 (M=Pd and Pt),
and YbFe4Sb12. The lattice thermal conductivity decreases with increasing filling fraction, and the
values for Yb filling are smaller than those for La and Ce filling for the same filling fraction. The
large atomic displacement parameter ADP for Yb as compared to La and Ce suggests the ra t-
tling (dynamic) effect on phonon scattering. In inelastic electron tunneling experiments on
Yby Co4Sb12 with different filling fractions, Nagao et al. [20] have observed a strong peak at 7
meV due to a rattling phonon mode of Yb ions. The analysis of tunneling conductance spectra
indicates that the filled Yb ions strongly interact with the host framework Co atoms for n-type
Yby Co4Sb12. This result is consistent with the fact that the conduction bands near the bottom
have characters of hybridization of Yb 6s and 5d states with Co 3d states. This finding seems to

G2.4.4
 Figure 5. Thermoelectric figure of merit
(PFmax/κ RT) as a function of carrier concen-
tration for Yby Co4Sb12, Yby Co4-x M x Sb12
(M=Pd and Pt), and unfilled Co1-x M x Sb3
(M=Pd and Pt).
Figure 6. Dimensionless thermoelectric
figure of merit ZT as a function of tem-
perature for Yby Co4Sb12 and Yby Co4-
x Ptx Sb12 with nominal y=0.25. ZT for
Yb0.19Co4Sb12 [8] is also shown.

be related to the valence fluctuation of Yb ions (strong hybridization of Yb 4f states with the va-
lence band states) in Yb-filled CoSb3 compounds.
Figure 5 shows the thermoelectric figure of merit Z (estimated by PFmax/κ RT, PFmax: the
maximum power factor, κ RT: room temperature thermal conductivity) as a function of carrier con-
centration for Yby Co4Sb12, Yby Co4-x M x Sb12 (M=Pd and Pt), and unfilled Co1-x M x Sb3 (M=Pd and
Pt). The figure of merit for Yb filling is systematically larger than that for unfilled Co1-x M x Sb3.
This is due to the large reduction in the lattice thermal conductivity for Yb filling. From Fig.5, the
optimum carrier concentration seems to be around 4×1020 cm-3, which was obtained by Yb filling
or by combination of Yb filling with Pd and Pt substitution. Figure 6 shows the temperature de-
pendence of ZT for n-type Yby Co4Sb12 and Yby Co4-x Ptx Sb12 with nominal y=0.25. ZT for
Yb0.19Co4Sb12 [8] is also shown for comparison. High ZT values were accomplished when the Yb
fraction was about 0.1-0.25 for both Yby Co4Sb12 and Yby Co4-x Ptx Sb12. Therefore, as stated in Ref.
8, we believe that the intermediate valence of Yb, strong hybridization of Yb 4f states with the
valence band, may be important for the improvement of the electronic and thermoelectric proper-
ties as compared to other rare-earth filling.

CONCLUSIONS
We have investigated the electronic structure and electronic and thermoelectric properties of
Yb partially filled CoSb3 compounds. From x-ray photoelectron spectroscopy study, it was
found that the Yb ions have an intermediate valence between 2+ and 3+ and that the Yb f states
are strongly hybridized with the valence band states. The results of the photoemission spectro-
scopy study are consistent with those of band calculation in terms of an itinerant f electron model.
Partially filling the voids of CoSb3 with Yb ions resulted in an increase in ZT as compared to pre-
viously reported values for n-type CoSb3 compounds. This is due to the low lattice thermal con-
ductivity and relatively high electron mobility and Seebeck coefficient. We believe that the unique
electronic states of Yb ions, i.e. the valence fluctuation or the strong f electron hybridization ef-
fects in the valence band, are important for Yb-filled CoSb3 compounds and may be a reason for

G2.4.5
the improved electronic properties for thermoelectric materials as compared to other rare-earth
filling.

ACKNOWLEDGEMENTS
One of authors (H.A.) acknowledges the support from Japan Society for the Promotion of
Science (Grant-in-Aid for Encouragement of Young Scientists, #13750636).

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