Thermelectric Ceramics For Energy Harvesting

See
discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/235346287
Thermoelectric Ceramics for Energy Harvesting

Article in Journal of the American Ceramic Society January 2012
DOI: 10.1111/jace.12076
CITATIONS
READS
78
203
7 authors, including:
Emmanuel Guilmeau
Yuzuru Miyazaki
Laboratoire CRISMAT
Tohoku University
142 PUBLICATIONS 1,594 CITATIONS
SEE PROFILE
SEE PROFILE
Anke Weidenkaff
Yifeng Wang
Universitt Stuttgart
Nanjing Tech University
80 PUBLICATIONS 802 CITATIONS
SEE PROFILE
SEE PROFILE
All content following this page was uploaded by Emmanuel Guilmeau on 23 January 2015.
The user has requested enhancement of the downloaded file.
J. Am. Ceram. Soc., 96 [1] 123 (2013)

DOI: 10.1111/jace.12076
2012 The American Ceramic Society
Journal
Thermoelectric Ceramics for Energy Harvesting

Kunihito Koumoto, Ryoji Funahashi, Emmanuel Guilmeau, Yuzuru Miyazaki,k
Anke Weidenka, Yifeng Wang,, and Chunlei Wan,
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
National Institute of Advanced Industrial Science & Technology, Osaka 563-8577, Japan
CRISMAT Laboratory, 14050 Caen Cedex, France
Department of Applied Physics, Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan
Solid State Chemistry and Catalysis Laboratory, Empa Swiss Federal Laboratories for Materials Testing and Research,
Uberlandstrasse 129, 8600 Dubendorf, Switzerland
College of Material Science and Engineering, Nanjing University of Technology, Nanjing 210009,China
Metal oxides (Ca3Co4O9, CaMnO3, SrTiO3, In2O3), Ti sulfides, and Mn silicides are promising thermoelectric (TE) material candidates for cascade-type modules that are usable in a
temperature range of 3001200 K in air. In this paper, we
review previous studies in the field of TE materials development and make recommendations for each material regarding
future research. Furthermore, the R&D of TE modules
composed of metal oxide materials and the prospect of their
commercialization for energy harvesting is demonstrated.
I.
Introduction
(TE) power generation is based on the

Seebeck eect, the phenomenon that an electromotive
force (voltage) develops when a material is exposed to a temperature gradient. When the TE material is integrated in an
electric circuit a current ows, thus, resulting in the conversion of heat into electricity. Accordingly, this is an energy
conversion device which is characterized by its energy conversion eciency. The maximum energy conversion eciency, gmax, can be expressed by
HERMOELECTRIC
gmax
M
Th Tc
M1

Th
M Tc =Th
p
1 ZTh Tc =2
(1)
(2)
X.-D. Zhoucontributing editor
Manuscript No. 31451. Received May 08, 2012; approved October 02, 2012.
Author to whom correspondence should be addressed. e-mail: chunlei.wan@gmail.com
where ZT (= Z(Th + Tc)/2) is the dimensionless thermoelectric

gure of merit
ZT rS2 T=j
(3)
where r is the electrical conductivity, S is the Seebeck coecient, j is the thermal conductivity, and T is the absolute
temperature. It can be seen that the higher the ZT the larger
the conversion eciency, implying that a good TE material
is characterized by a high r, large S and low j.
To harvest electric energy from various heat sources, both
p-type and n-type solid materials with high ZT in a wide
temperature range are required. However, we have no such
materials now, so either cascade-type or segment-type modules composed of several dierent TE materials are usually
designed (Fig. 1). A number of high ZT materials, such as
Te-based and/or Se-based compounds, skutterudite and the
related compounds, and intermetallic compounds have been
discovered and developed in the last 1015 years, but most
of them show high ZT only in mid-to high-temperature
ranges, and moreover, these materials are composed of toxic,
naturally rare, and heavy elements, and can be melted or oxidized at high temperatures in air.1,2 Accordingly, these conventional TE materials cannot be employed to harvest
electricity from renewable energy sources, such as solar
heat,310 as well as waste heat discharged from various systems, such as industrial furnaces, incinerators, vehicles, etc.11
To overcome these problems novel TE materials with high
ZT composed of non-toxic, naturally abundant, light, and
cheap elements usable in air should be developed.
Figure 1 shows new TE materials that have been
developed or are under investigation to be described in the
following sections. As p-type materials, calcium cobaltite
(CCO; Ca3Co4O9) for high-temperature (>700 K) and
higher manganese silicide (HMS; MnSix) for mid-temperature
Feature
Vol. 96, No. 1
Journal of the American Ceramic SocietyKoumoto et al.
Fig. 1. Schematic illustrations of cascade-type TE modules (above)

and the specic materials described in the manuscript.
(500700 K) modules have been developed by Funahashi and

Miyazaki, respectively, and their basic characteristics, processing, and TE properties will be discussed in Section II. As
n-type materials, manganate (CaMnO3) and In2O3-based
compounds for high-temperature, TiS2-based natural superlattice (TiS2 NSL) for mid-temperature, and 3D superlattice
SrTiO3 (3D SL STO) for low-temperature (300500 K) modules have been developed or studied by Weidenka, Guilmeau, Wan+Koumoto, and Wang+Koumoto, respectively,
and their structure-property relations will be discussed in
detail in Section III.
These materials are all composed of non-toxic and naturally abundant elements except In2O3, and stable in an air in
the corresponding temperature ranges. It should also be
noted that competitive low-temperature p-type materials to
replace bismuth telluride-based compounds are yet to be discovered representing a challenging topic of research.
In Section IV the current status of thermoelectric modules
containing novel TE materials will be presented and in Section V nal conclusions will be drawn.
marginally metallic situation may be realized if the Fermi

level falls in a steep declining slope of a pseudogap. Thus, we
consider compounds having a deep pseudogap at the Fermi
level to be a good candidate as thermoelectric material.
Chemical stability of the material without involving harmful elements is also important to develop practical thermoelectric devices. At present, materials possessing a high
thermoelectric performance are found among intermetallic
compounds similar to Bi2Te3, CoSb3, and Si-Ge alloys.1218
However, practical applications have been restricted because
of their low melting points or decomposition temperatures,
the content of harmful or scarce elements, and/or their insufcient conversion eciency. Oxide compounds have been
recently considered as an alternative candidate for thermoelectric device materials. Some oxides commencing with
NaCo2O419 and Ca3Co4O9,2022 (generally called Co-349
phase) have been demonstrated to exhibit high thermoelectric
performances. The Bi- and Sr-doped (Ca, Sr, Bi)3Co4O9
compound has a Seebeck coecient higher than 100 lV/K
while q is decreased to below ~1.6 9 105 m above
~200 K.21
The Co-349 phase constitutes a layered structure, in which
two dierent layers are alternately stacked in the direction of
the c-axis, as shown in Fig. 2(a).20,21 In the CoO2 layer, each
Co atom is surrounded by six O atoms in an octahedral
conguration and the neighboring octahedra are edge-shared.
On the other hand, Ca, substituted by Sr and Bi, Co and O
atoms forms a triple rock-salt layer Ca2CoO3. The alternately
layered structure can be studied using transmission electron
microscopy (TEM) [Fig. 2(b)]. According to the X-ray and
electron diraction measurements, [Ca2CoO3]xCoO2 is characterized by the so-called hybrid crystal in which a monoclinic [Ca2CoO3] sub-lattice and a monoclinic [CoO2]
sub-lattice interleave with each other.12 Here both sublattices
are found to possess a common a-cell parameter, but dierent
b-cell parameters of 0.28 and 0.45 nm for [CoO2] and
[Ca2CoO3], respectively.21 [(Ca, Sr, Bi)2CoO3]xCoO2 with
x = 0.821.1 crystallizes into the layered rock salt type structure with monoclinic symmetry and the average cationic com-
(a)
II.
(b)
Promising p-Type Materials
(1) Calcium Cobaltite, Ca3Co4O9

(A) Thermoelectric Properties of a Whisker Crystal:
In the framework of the Boltzmann transport equation the
Seebeck coecient is expressed in the following form:
S p2 k2 T@De=@ee eF =3eDeF
(4)
where k, e, and D(e) represent the Boltzmann constant, the

elemental charge, and the density of states at the energy e,
respectively. We see that the Seebeck coecient takes either
a positive or negative sign, depending on whether holes or
electrons serve as dominant carriers, respectively. In the freeelectron model, Eq. (4) is reduced to
Sfree p2 kT=2eTF
(c)
(5)
where TF is the Fermi temperature dened as TF = eF/k.

Thus, the value of S may be enhanced as high as we wish by
reducing TF or the carrier concentration in a degenerate
semiconductor. However, the reduction in TF along this line
concomitantly results in a signicant increase in resistivity
and, hence, the reduction in ZT. According to Eq. (4), however, the value of S may be increased to a high value while
suppressing an increase in resistivity. This is in principle possible, provided that the derivative of D(e) at the Fermi level
is increased but the value of D(e) itself is kept nite. Such a
Fig. 2. Schematic crystallographic structure (a) and transmission

electron microscopic image (b) of [Ca2CoO3]xCoO2.20
January 2013
Energy Harvesting
position of the whiskers determined by electron micro-probe

analysis is Ca:Sr:Bi:Co = 2.56:0.66:0.56:4.0.
The temperature dependence of S and q is shown in
Fig. 3. It is found that q remains lower than 1.6 9 105 m
while S is higher than 100 lVK1 over the temperature
range 2001000 K. Both q-T and S-T curves may be divided
into four regions (I) to (IV), as marked in Fig. 3. Generally
speaking, S decreases with increasing T in semiconductors.
In the Co-349 whiskers, however, S increases almost linearly
with increasing T in region (I), where the q-T dependence is
apparently typical of a semiconductor. In region (II) where
the q-T slope becomes slightly positive, S continues to
increase with T as in ordinary metals. The q-T slope becomes
negative again in region (III) but reverses its sign in region
(IV). Nevertheless, S still continues to increase with increasing temperature up to region (IV).
The Co-349 whiskers show strong anisotropic electrical
behavior because of the two-dimensional layered structure.
Temperature dependence of q measured in the directions
parallel (a) and perpendicular (b) to the ab-plane shows that
the former is lower than the latter by a factor of 5001000.
This two-dimensional characteristic becomes a serious problem for the production of polycrystalline devices as will be
shown later.
Figure 4 depicts the temperature dependence of RH in the
temperature range of 5300 K, which corresponds to region
(I) in Fig. 3. RH becomes almost independent of T at
T > 100 K. The carrier density deduced from RH was found
to be as high as 3 9 1027 m3 in this temperature range. The
Hall mobility is also estimated from the quotient of the RH
and q to be 1.52.3 9 104 m2 V1 s1 at T > 100 K in
region (I). Comparison shows that this value is about seven
times lower than that of NaCo2O420 due to its seven times
higher q while the carrier density deduced from RH of both
compounds is comparable. TEM studies reveal that the
respective Co-349 whisker is essentially free from defects and
impurity phases and its crystallinity is fairly high [Fig. 2(b)].
Thus, we believe that carriers at the Fermi level are rather
immobile presumably due to its large eective mass.
The Seebeck coecient of a classical semiconductor is
known to be inversely proportional to temperature.23 However, the Seebeck coecient of the studied Co-349 whiskers
is almost linearly proportional to temperature. Judging from
a sharp increase in RH below 100 K coupled with an almost
linearly increasing Seebeck coecient in region (I) we believe
that a small pseudogap rather than a real gap exists in this
system and that lowering the temperature below 100 K
makes thermal excitations of electrons across the gap more
dicult. The evidence for the pseudogap has been obtained
using high-resolution ultraviolet photoemission spectroscopy

(UPS) and Co 2p-3d resonant photoemission spectroscopy
(RPES).24 The width of the pseudogap may be roughly estimated from the q-T curve at 1050 K to be a few meV or a
few tens K.
The inset of Fig. 4 shows the both the transverse and
longitudinal
magnetoresistance,
Dq(H)/q(0T) = [q (5T)
q (0T)]/q (0T), measured in the geometry shown in the gure.
Below 30 K both longitudinal and transverse magnetoresistance is negative. A decrease in resistivity with increasing
magnetic eld may be interpreted as the suppression of thermal uctuations of magnetic moments. Furthermore, the
occurrence of a positive transverse magnetoresistance at 100
K is interesting. A positive transverse magnetoresistance is
expected to occur when both electrons and holes coexist at
the Fermi level and their numbers are unequal.25 We believe
therefore that the positive transverse magnetoresistance
observed at high temperatures is due to the presence of an
unequal number of electrons and holes in the pseudogap at
the Fermi level and that the number of holes exceeds that of
the electrons owing to the positive Seebeck coecient.
Finally, a hysteresis of the transverse magnetoresistance at
100 K is observed. The origin of the hysteresis is still unclear
and might be based on thermodynamic phenomena.
(B) Processing of Bulk Textured Calcium Cobaltite:
The discoveries of large thermopower coexisting with low
electrical resistivity in layered cobaltite single crystals, as
NaxCoO2,19 Ca3Co4O9 (Co-349)20,21 and Bi2M2Co1.67Ox
(M = Ca, Sr or Ba),26 opened the way to the exploration of
new oxide thermoelectric materials and the development of
polycrystalline bulk materials for potential applications.
While single crystals have shown ZT values close to 0.5 and
1 at 1000 K (extrapolated value),27 polycrystalline ceramics
present lower ZT values between 0.1 and 0.3 at 1000 K
mainly due to their larger resistivity, which depends greatly
on grain size, electrical properties of grain boundary, bulk
density, and grain orientation. The volatility of sodium at
high temperatures and the hygroscopicity of NaxCoO2 in air
have limited its application for power generation. Nevertheless, due to their relatively good TE performance and resistance to humidity, the layered cobaltites Ca3Co4O9 and
Bi2M2Co1.67Ox have attracted the interest of many researchers to improve the TE properties of ceramics in various ways.
A well-known way to enhance transport properties is the
(a)
(b)
(a)
(a)
(b)
(b)
Fig. 3. Seebeck coecient and electrical resistivity of a Co-349

whisker.20
Fig. 4. Temperature dependence of the Hall coecient RH (a) and

the carrier density (b) of a Co-349 whisker.20 Inset: relative change
in resistance [q(5T) q(0T)]/q(0T) by applying a transverse (a) and
longitudinal (b) magnetic eld to the electrical current owing
parallel to the ab-plane (magnetoresistance).
alignment of plate-like grains in the bulk materials owing to

the anisotropic properties of these layered structures. Investigation of Ca3Co4O9 has been aimed to replace Bi-based compounds suering from low temperature stability28 and weak
mechanical properties. It must be mentioned that the texture
of Bi2M2Co1.7Ox has been varied using diverse techniques
like hot-pressing or the laser oating zone method.2831 However, the reported ZT values remain low compared to those
of the Ca3Co4O9 phase.
Guilmeau et al.32 for example, studied Ca3Co4O9 textured
specimens in detail using neutron diraction. These samples
were processed by slip-casting in a magnetic eld. The
inverse pole gure in Fig. 5 calculated along the ber direction (sample normal direction) reveals that the crystallographic direction most likely parallel to the sample plane is
the (001) plane. According to the monoclinic structure, the
001 pole is rotated at 98 based on the 100 plane. The
degree of texture is ~30 m.r.d. (multiple of a random distribution) which is relatively high for bulk polycrystalline materials.
Several research groups have developed preparation techniques for layered cobaltite ceramics aiming to improve the
grain alignment of this typical ber texture and with that the
thermoelectric properties. It is indeed well known that the
best properties are observed in the in-plane direction, as the
ratio of the in-plane to the out-of-plane electrical conductivity (approximately ve to six) is higher than the ratio related
to the thermal conductivity (approximately two to three;
Fig. 6).3335
Tani et al.36 proposed the reactive-templated grain growth
(RTGG) technique using b-Co(OH)2 templates for the fabrication of Co-349 textured ceramics. Thanks to a high degree
of orientation and a precise control of the grain alignment
(Fig. 7),37 high electrical conductivity has been obtained
leading to average ZT values of 0.15 at 1000 K.30 Enhanced
grain alignment led to an improved power factor (0.73 mW/
mK2) and higher ZT values close to 0.25.38 Although a very
high degree of orientation can be obtained, the small thickness (along the out-of-plane direction) of the as-prepared
textured sheets remains the most signicant limitation of the
RTGG technique.
Zhou et al.39 developed an eective magnetic grain-alignment method for texturing layered cobaltites. Although this
technique has been mostly used for ferromagnetic materials,
it can also serve the texturation of non magnetic materials
with high anisotropic magnetic susceptibility. In the case
of layered cobaltites, high texture strength and ZT values of
0.2 at 1000 K have been obtained in Ca3Co4O9 bulk
compounds.
Hot-pressing and sinter-forging are also currently demonstrated as reliable techniques to produce large samples with
high preferential orientation.4043 Most of the studies reveal
a correlation between electrical resistivity, texture strength
and TE properties and the applied stress and its dwell-time.
Fig. 5. Inverse pole gure of Ca3Co4O9 calculated along the ber

direction (sample normal direction) based on neutron diraction
data. Logarithmic density scale, equal area projection.32
Vol. 96, No. 1
More recently, spark plasma sintering (SPS) was also

reported as a fast and reliable technique for densifying and
texturing layered cobaltites.4446 It allows the elaboration of
highly dense (98%) compounds with uniform grain morphology at lower temperature and with shorter sintering time
than conventional or hot pressing sintering techniques.
Noudem et al.46 recently reported high bulk density, low
electrical resistivity, and enhanced thermoelectric power factor of Ca3Co4O9 samples prepared this way. As shown in
(a)
(b)
(c)
Fig. 6. Temperature dependence of (a) the Seebeck coecient and

(b) electrical conductivity for the preferentially oriented specimens:
x-axis denotes the direction perpendicular to the pressing for
compaction (presumably ab-plane) and z-axis is parallel to the
pressing direction (presumably c-axis), and (c) temperature
dependences of thermal conductivity j (solid lines) and the electronic
thermal conductivity je estimated by the WiedermanFranz law
(dotted lines).35
January 2013
Energy Harvesting
Fig. 7. SEM micrograph of a textured Co-349 sample prepared by

reactive-templated grain growth (RTGG) using b-Co(OH)2
templates.37
Fig. 8, the magnitude of the electrical resistivity is drastically

decreased as compared to conventional sintering samples,
even after a very short dwell time of 2 min at 750C.
For the last 10 years, layered cobaltites appeared as the
best p-type oxide thermoelectric materials. Their chemical
stability in air and under high temperature gradient has been
proven by the conception of reliable thermoelectric
generators.47 However, ZT values are still lower than those
predicted for single crystals even though noticeable improvements have been demonstrated using these grain orientation
techniques.
A second route to improve ZT values is cationic substitutions. Most studied in this eld are replacements of calcium
by heavier atoms such as strontium,48,49 bismuth,50,51 rare
earth elements,52,53 or yttrium.45 Finally, the best ZT ever
reported for a polycrystalline Ca3Co4O9 sample has been
obtained by Ag-substituted and doped samples Ca2.7Ag0.3Co4O9/Ag-10 wt%, which exhibit a ZT value of 0.5 at
1000 K.54 However, the thermal conductivity of these doped
mist layered compounds must be carefully studied. Indeed,
considering some low reported thermal conductivity values
we can speculate that the calculation of the ZT values was
based on the out-of-plane thermal conductivity leading to a
signicant overestimation.
(2) Higher Manganese Silicides

(A) Chemical Formula and Crystal Structure: Higher
manganese silicides (HMSs) have been extensively studied as
p-type thermoelectric materials since the 1960s, in particular
by groups from Russia and Japan.5557 The compounds are
known to exhibit ZT values of 0.30.7 at ~800 K.58 However, several structure formulas, e.g., Mn4Si7,59 Mn11Si19,60,61
Fig. 8. Temperature dependence of electrical resistivity (open

symbols) and Seebeck coecient (lled symbols) state the respective
compound.45
Mn15Si26,62,63 and Mn27Si46,64 were proposed as HMS phases

and there had been a controversy as to whether the compounds are an identical phase or a series of phases with different structures. The existence of Mn7Si12, Mn19Si33 and
Mn39Si68 was also reported but these phases were only
observed in a microscopic domain using transmission microscopy.65 Among many mixed phases the MnSi binary phase
diagram displays only one line compound, Mn11Si19.66
Based on electron diraction patterns, Ye and Amelinckx65 proposed that the HMS phases consist of two tetragonal Mn- and Si-subunits with an identical a-axis but
dierent c-axes. Taking two dierent c-axis lengths of the
subunits, cMn and cSi as a basis, a variety of complicated
superlattice reections can be well indexed. Yamamoto67
introduced the concept of superspace group to appropriately
describe the detailed crystal structure of HMSs. He proposed
that the HMSs belong to a family of composite crystals,
consisting of two tetragonal subsystems of [Mn] and [Si]. The
[Mn] subsystem has the three dimensional (3D) space group
I41/amd isostructural with b-Sn, while the [Si] subsystem has
the 3D space group P4/nnc. By combining these space
groups, the most suitable (3+1)D superspace group is represented as I41/amd(00c)00ss, with the modulation vector component (00c). c is dened as c = cMn/cSi, i.e., the c-axis ratio
of the two subsystems, and also denotes the stoichiometry
MnSic of the HMSs. Miyazaki et al.68 determined the
detailed modulated structure based on the I41/amd(00c)00ss
superspace group by means of the neutron diraction data
[Fig. 9(a)]. According to their structure model, the helical
arrangement of the Si atoms, i.e., the structural modulation,
can be well described by the universal curves plotted against
the fourth coordinate in the superspace group m = (zSi 1/
4)/c, as shown in Fig. 9(b). Similarly, the positional modulation of the Mn atoms can also be accurately described using
m. They demonstrated that the atomic positions of all HMS
phases regardless of the stoichiometry can be coherently
described using the superspace group approach and the six
universal lines.
(B) Electronic Structure of HMS: The electronic
structure of HMSs was rst computed by Imai et al.69 and
Imai and Watanabe70 by means of the rst-principle pseudopotential method based on the density-functional theory.
Later, Migas et al.71 calculated the density-of-states (DOS)
and band structure of HMSs using the full potential linearized augmented plane-wave method (FLAPW). They
obtained similar DOS curves for all four phases, Mn4Si7,
Mn11Si19, Mn15Si26, and Mn27Si46. Figure 10 shows the DOS
of Mn4Si7 reported by Migas et al.71 The DOS near the
Fermi level consists of a broad band with the bonding character of Mn d and Si p, ranging from 4 to 0.5 eV, and a
sharp band with the nonbonding character of Mn d, between
0.5 and 0 eV. The latter sharp band is responsible for the
good p-type TE performance, because the Fermi level is
located at the top of the valence band. As a large DOS can
be also observed at the conduction band bottom separated
from the valence band by an energy gap of Eg ~ 0.8 eV, a
good n-type TE material can be prepared by an appropriate
electron doping. Except for Mn4Si7, the other three HMSs
were identied as metals, due to the fact that the Fermi level
is located slightly below the valence band top. The revealed
cigar-shaped Fermi surface is elongated along the -Z direction of the tetragonal Brillouin zone suggesting the
two-dimensional electronic transport perpendicular to the
crystallographic c-axis. In fact, in-plane conductivity
rab ~ 800 S/cm of a single crystal is almost one order of
magnitude larger than that of out-of-plane rc ~ 100 S/cm at
300800 K.73 Currently, it is not possible to calculate the
electronic structures of incommensurate HMSs because the
3D unit cell cannot be dened.
In contrast to the calculated electronic structures, experimentally observed Eg values range from 0.4 to 1 eV. The
values of 0.650.8 eV are a direct transition either from or
Vol. 96, No. 1

(a)
Mn
Si
cMn
b
a
cMn
c
cSi
cSi
b
a
Fig. 10. The total and projected density of states (states/eV/cell) of

Mn4Si7. Zero at the energy scale corresponds to the Fermi level. D.
B. Migas, V. L. Shaposhnikov, A. B. Filonov, V. E. Borisenko, and
N. N. Dorozhkin, Phys. Rev. B, 77, (2008) 075205. Copyright (2008)
by the American Physical Society.71
b
a
(b)
0.2
200
-0.2
0.25
0
-0.1
0.20
-0.2
Si
0.6
0.35
0.3
0
0.25
-0.3
0.15
-0.6
0
0.2
0.4
0.6
0.8
1.0
Fig. 9. (a) Modulated composite crystal structure of MnSic with a

length of 4 9 9 cMn (left). The unit cells of the [Mn] (upper right)
and the [Si] subsystem (lower right). (b) Revealed positional
modulations of the Mn and Si atoms plotted as a function of the
fourth superspace coordinate, m. The right vertical axes are rescaled
to illustrate the displacement for each atom.
Z point to the corresponding points in the conduction band.

Several experimental techniques were used, including optical
absorption (0.66 eV),74 high temperature electrical conductivity (0.70 eV),75 tunneling spectroscopy (0.70.8 eV),76 and
ellipsometry (0.96 eV).77 By contrast, transitions at around
0.458,75,76 are indirect. The origin of these indirect transition
is yet unclear, but they might be attributed to a stacking
fault of Si layers, since Migas et al.71 calculated an indirect
bandgap of Eg ~ 0.4 eV when a kind of stacking fault of the
Si layers was introduced into the structure model.
(C) Thermoelectric Properties: Figure 11 represents
the temperature dependence of S, r, j and ZT of a polycrystalline sample prepared via an arc-melting route.77 A typical
100
600
(S/cm)
0.1
ZT
0.5
0.4
0.3
0.2
400
0.1
200
(W/Km)
0.2
Si
0.30
150
displacement ()
-0.05
position
ZT
x,y
(V/K)
250
Mn
0.05
3
2
1
300
500
700
900
T (K)
Fig. 11. Temperature dependence of the Seebeck coecient S, the
electrical conductivity r, the thermal conductivity j and the
dimensionless gure-of-merit ZT of a polycrystalline sample
prepared via an arc-melting route.77
sample exhibits S ~ 120130 lV/K, r ~ 500600 S/cm and

j ~ 2.53.0 W/Km at room temperature, resulting in
ZT ~ 0.1. With increasing temperature the sample shows
metallic behavior until S reaches its maximum of ~220 lV/K
at ~800 K although r monotonically decreases to ~250 S/cm.
Above 800 K, the bipolar diusion of carriers becomes dominant and j value starts to increase. The maximum ZT of a
typical polycrystalline HMSs is ~0.30.4 at 800 K.
The presence of MnSi is believed to deteriorate the thermoelectric properties.58 The MnSi phase itself is a highly
conducting metal, but a large dierence in thermal expansion
coecients between the HMS and MnSi causes a microcrack
at grain boundaries during heat cycles, and results in a significant decrease in r and a resultant low ZT. The formation of
platelike MnSi precipitates with a typical thickness of ~1 lm,
is thermodynamically inevitable because it is formed as a
primary phase from a eutectic reaction according to the binary Mn-Si phase diagram66 To avoid such a MnSi precipitation, a solid-state reaction, e.g., pulse discharge sintering
(PDS), would be a potential alternative to obtain HMSs.
Yoshikura and Itoh have obtained Si-rich samples of the
nominal composition MnSi1.84 that exhibit a ZT ~ 0.83 at
818 K.78
January 2013
Energy Harvesting
A further increase in TE performance has been expected

by a partial substitution of the constituent elements. At the
Mn-site Cr, Fe and Co and at the Si-site B, C, Al and Ge
can be introduced.58
A Ge-substituted sample has a
ZT > 0.7 at ~800 K. A 30% increase in ZT has been
achieved
with the solid solution (Mn1xCrx)Sic with
x = 0.20.79 By combining the optimum substitution and
appropriate solid state reactions, it would be possible to
obtain samples with ZT exceeding unity in the near future.
Aoyama et al.80 designed an eight-pair TE module using
partially substituted HMS as p-legs and Mg2(Si,Sn) as n-legs.
The module has the conversion eciency of g = 7.3% at
DT = 520 K (303823 K). As the materials have the advantage of less toxicity and high chemical stability, silicide-based
materials are promising as components of mid-temperature
range TE modules. In order to obtain durable TE modules,
p- and n-type materials should have an identical crystal
structure, because a considerable dierence in the thermal
expansion coecients could seriously damage the leg materials after repeated thermal cycles. Consequently, the next step
will be to prepare comparable HMS n-type materials. For
that, the partial substitution of Fe for Mn is a reasonable
approach. However, further research appears to be required
to optimize the TE properties of these n-type materials.77,8183
III.
n-Type Material Candidates
(1) Perovskite-type Manganates

Manganese oxides are chemically stable even at temperatures
as high as 1200 K. In complex transition metal oxides with
correlated electrons such as manganates and cobaltates, the
spin of electrons can become an additional source of entropy
resulting in the large thermopower found in these systems.84
The amount of localized and mobile charge carriers and thus
the electrical conductivity and thermoelectric properties in
this system can be tuned by suitable substitution reactions.
The heat transfer in solids is governed by the lattice contribution (phonons) and the electronic component corresponding to the mobile charge carriers. For oxides the
phonon contribution remains the predominant component of
the total thermal conductivity. Strategies to lower the lattice
heat conduction, i.e., enhance the phonon scattering, include
the nanostructuring of crystallites, substitution with heavy
elements, or application of complex crystal structures.85 The
interface scattering of phonons can dominate the heat conduction in oxide nanostructures.
Promising n-type thermoelectric oxides with strongly
correlated electrons are perovskite-type calcium manganese
oxides. CaMnO3 is an insulator with a Seebeck coecient of
350 lV/K86 at room temperature. Electrical and thermal
transport properties of substituted CaMnO3 have been studied by several groups up to T 1000 K.8794 The conductivity can be enhanced by partial substitutions of e.g., niobium,
tantalum or tungsten for manganese. If the substitution level
is low, most promising n-type thermoelectric materials can
result presenting an additional spin-orbit entropy factor
thereby enhancing the thermopower.9597 A microstructure
with twinned domains decreases the thermal conductivity
under conservation of a good electronic transport property
at high temperature. CaMn0.08Nb0.02O3 samples produced
with a soft chemistry procedure show ZT values of 0.3 at
1070 K.98
A series of manganates, with Ca on the A-site position
and Mn and Nb or W on the B-site position of a ABO3
lattice were successfully synthesized using classic solid-state
methods (SSR), a polymeric precursor method (Soft Chemistry)99 and ultrasonic spray combustion (USC).98 All samples
are single phase and crystallize in perovskite-type crystal
structures (Fig. 12). The particles from the ceramic synthesis
process are several micrometer in diameter, while ne powders result from the chimie douce synthesis route at
T < 873 K with a uniform particle size of ~50 nm diameter.
The particles from the USC process reveal a mean crystallite

size of less than 20 nm diameter.
After further annealing to 1273 K, sintering processes lead
to an increase in the particle size by a factor of 8. The
pressed sintered bodies reveal a density of ~85% and a
porosity which is considered in the thermoelectric property
measurements by applying the Maxwell formula. The EDX
and XRF analyses show a homogeneous composition in
agreement with the nominal composition. The oxygen content measurements indicate fully oxidized manganates.
Single crystals and nearly 100% dense resolidied polycrystalline ingots with diameters of up to several mm were
obtained from the oat-zone experiments (Fig. 13). Laue diffraction reveals millimeter-sized single crystalline domains.
Single crystal diraction shows a heavily twinned crystal
structure.
CaMn1-xNbxO3-d phases (x = 0.02, 0.05, and 0.08) exhibit
large absolute Seebeck coecients and low electrical resistivity (q ~ 20 m cm) at high temperatures (T > 500 K). The
values correlate well with the theoretically determined values.
The phases from dierent synthesis processes and after dierent thermal treatments reveal equal S for the same Nb substitution as the thermopower depends solely on the electronic
band structure (Fig. 14).
With aliovalent substitutions the amount of charge carriers
(localized and itinerant) and thus the transport and thermoelectric properties can be tuned. The electrical resistivity can
be reduced with suitable hexavalent W or pentavalent Nb
substitution for Mn.
The eects of the strongly interacting or correlated electrons in these systems are substantial and lead to exciting
related properties.100 Important factors aecting the thermopower of manganates are not only the valence of the manganese atoms, the spin of the charge carriers, the symmetry of
the structure, and the strengths of the crystal eld, but also
the interplay of these properties.
Generally, the eect of increasing spin and orbital degrees
of freedom in systems with transition metals in dierent
oxidation states dominates the intrinsic transport and has a
positive inuence on the thermopower in lightly doped systems. The thermopower can be interpreted with the modied
Heikes formula.101,102
(a)
(b)
(c)
Fig. 12. Transmission electron microscopic view of a typical

particle (a), electron diraction result (b) and powder pattern (c) of
particles from the ultrasonic spray combustion process.
Fig. 13. Result of a oat-zone recrystallization experiment of

CaMn0.97W0.03O3.

j
g3 x
S ln
g4 1 x
e
(6)
where x is the carrier concentration and g3 and g4 are the

degeneracy of congurations of manganese in octahedral
coordination. Applying this formula, large thermopower is
expected for low level substituted compounds.
Thus, the absolute value of the thermopower depends on
the carrier concentration. Accordingly, as Nb substitution
increases the carrier concentration, a reduction in the
absolute thermopower value at room temperature results in
agreement with Heikes formula.103
The thermal conductivity can be reduced by lowering the
particle dimensions. In chimie douce and USC synthesis
methods the crystallite size of the product particles ranges
from 5 to 200 nm diameter. The individual crystallites are
more or less agglomerated depending on the precursor and
synthesis process. In ceramic solid state reaction processes
the average crystallite size of the product powders typically
ranges from 1 to 10 lm diameter.
The total thermal conductivity of the sub-microcrystalline
compounds is very low compared to values reported for similar compounds.104 This observation can be related to the
small crystallite size and microstructure of the powders leading to a reduction in the lattice conductivity.105 The typical
microstructure of the compounds reveals twinned domains,
which are frequently observed in orthorhombic perovskite-type
structures. Twinning phenomena occur when orthorhombic unit
Fig. 14. Seebeck coecient values versus T of CaMn1xNbxO3 of

samples with the same composition (color code) but dierent
synthesis processes and thermal treatment (closed and half-open
symbols).
Vol. 96, No. 1
cells can grow in dierent directions accommodating slight

discrepancy between lattice parameters.
The lattice thermal conductivity is calculated using the
Wiedemann-Franz-Lorenz relation. The obtained value for
the lattice thermal conductivity (phononic part) accounts for
90% of the total thermal conductivity in these materials.
This leads to the assumption that the heat is carried predominantly by phonons.
The manganate samples show total thermal conductivities
between 1.0 and 1.5 W(mK)1 depending strongly on the
crystallite size106 (see Fig. 15).
The CaMn1xNbxO3d phases (x = 0.02, 0.05, and 0.08)
crystallize in orthorhombic symmetry with Pnma space group
(S.G.) and cell parameters 2ap ~ 2ap ~ 2ap (ap refers to the
cubic perovskite structure). Nano-sized twinned domains
characterize the microstructure of the polycrystalline manganates [Figs. 16(a) and (b)].
Electron diraction (ED) patterns of each domain were
simulated in fast Fourier transform (FFT) mode. The FFTs
from areas A and B correspond to rotation twins oriented
along perpendicular b axis directions: [101]o and [010]o.
The FFT from the region C is the superposition of the
twinned domains. Fig. 16(b) highlights the twin direction,
where the b axis is either oriented in the plane (region A) or
out of the plane (region B). The combination of close lattice
parameters, i.e., ao ~ co and low octahedra tilt angles is a
prerequisite for the formation of twins in orthorhombic crystal structures.
Unusually
low
thermal
conductivity
values
(j < 1 W (mK)1) are achieved for the CaMn1xNbxO3d
phases synthesized by chimie douce compared to the compounds obtained by solid state reactions, as shown in
Fig. 15. Also in these compounds the major contribution to
the thermal conductivity originates from the lattice component (jlattice > 95% jtotal). Introduction of nano-sized twins
in chimie douce phases can act as additional scattering centers aecting the phonons but not the charge carriers. Thus,
rotation twins decrease j due to phonon scattering under
conservation of the electronic transport properties. The chimie douce -series lead to ZT = 0.32 at 1060 K for the 2%
Nb-containing CaMnO3 and represent one of the best perovskite-type oxides as n-type polycrystalline TE materials operating in air at high temperatures. The ZT values for the
same composition synthesized using classical ceramic synthesis reveal only values around ZT = 0.15.
This promising n-type TE material is implemented in a
thermoelectric oxide module together with a suitable p-type
material for the direct conversion of high temperature heat
into electricity. The thermoelectric materials with p-type
conductivity as well as compounds with n-type conductivity
have been used to produce thermoelectric oxide modules
(TOM)cascades of thermoelectric oxide thermocouples- to
convert the applied temperature gradient of geothermal and/
or solar heat exchanger systems into electric power.107
(2) SrTiO3
Perovskite-type strontium titanate, SrTiO3 (STO) is one of
the most important electronic oxides, showing various interesting properties, such as dielectricity,108 paraelectricity,109
ferroelectricity,110 piezoelectricity,111 superconductivity,112
etc. and has been widely used as substrate material for
preparing a variety of electronic thin lms as well.113
Above ~105 K,114 STO adopts a cubic crystal structure,
the usual form known for STO (space group: pm3m, lattice
parameter: a ~ 0.3905 nm at room temperature, melting
point: 2080C). The structure tolerance factor of STO is calculated to be ~1.02, almost ideal for perfect cubic perovskite
symmetry, thus allowing a high level doping or substitution.
The basic band structure of STO consists of a valence band
of O2p orbitals (Fig. 17), a conduction band of Ti 3d with
three t2g orbitals (i.e., 3dxy, 3dyz, and 3dxz), and a band gap
January 2013
Energy Harvesting
(a)
(b)
Fig. 15. Thermal conductivity versus T of CaMn1xNbxO3 solid state reaction- and chimie douce-series (closed and half-open symbols,
respectively).
Eg ~ 3.2 eV.115 Although pure stoichiometric STO is a band

insulator, free carriers of controlled density (here: electrons)
can be generated by introduction of oxygen vacancies (Vo)
or precisely trivalent cations, A3+ (e.g., La3+) at the Sr
site or penta-valent cations, B5+ (e.g., Nb5+) at the Ti site,
preferentially in reducing atmosphere, leading to a STO ntype semiconductor as follows:
! Vo 12 O
Reduced
OO
_
Sr
! B
_
Ti
Tisite

k
Nc T
S ln
Ae
e
n
Nc T 2
! A
Srsite
2 2e
mo), for which the large DOS of the triply degenerate 3dt2g
orbitals at the conduction band bottom is considered to be
responsible. This characteristic should be benecial for a
large |S|, as can be seen from the relationship between S and
density of states Nc(T) and m* for non-degenerate broad
band semiconductors as follows:
The exploration of TE properties of STO has covered a

wide scope, from single crystals to polycrystalline ceramics,
epitaxial lms, superlattice lms, nanostructured ceramics,
and a recently proposed three-dimensional superlattice bulk
material. As a matter of fact, the electrical and heat transport properties of various STO materials are inuenced by a
series of parameters including stoichiometry, crystallographic
orientation of the crystallites, defects in the grains and at the
grain boundaries etc., which will be involved but not emphasized in the examination of the TE properties.
(A) SrTiO3 Single Crystals: Actually, long before the
report on excellent TE properties of NaxCoO2,18 the thermopower |S| of slightly reduced STO single crystals and
Sr1xLaxTiO3 (x = 0.1 ~ 0.5) ceramics was investigated by
Frederikse et al.116 and Moos et al.117 Their results demonstrated a rather heavy DOS eective mass, m*, in both STO
single crystals (613 mo) and polycrystalline ceramics (~4.3
(a)

2pm kT 3=2
h2
(7)
(8)
where h is the Planck constant.118

Indeed, unusually large power factors (S2r) were observed
in Sr1-xLaxTiO3 (x = 00.1) and reduced single crystals due
to the large |S| along with high S2r (1.23.6 mW(mK2)1
at 300 K) favored by a high m*. Moreover, Nb-doping at
the T-site position was observed to be more favorable to
enhance m* [7.37.7 mo, n ~ (1.63.3) 9 1020 cm3] compared
with
La-doping
[6.06.6
mo ,
n ~ (0.84
7.9) 9 1020 cm3] by Ohta et al.122 This was considered to
be mainly related to a decrease in the overlapping of Ti 3d
t2g orbitals as a result of TiTi distance expansion by Nbdoping. This emphasizes the potential of Nb-doping.
(b)
Fig. 16. (a) and (b) High-resolution TEM image of twins in the
SC-derived CaMn0.95Nb0.05O3. The inset gures present FFTs of the
regions A, B and C.
Fig. 17. Illustration of the density of states (left) and the band
structure (right) of cubic phase of SrTiO3, demonstrating a triply
degenerate conduction band bottom consisting of Ti 3dxy, 3dyz, 3dzx
orbitals, and a valence bandtop of O 2p orbital.
10
As is well known for semiconductors, the total thermal

conductivity, j or jtotal, is mainly contributed by the lattice
component or phonons jph, and electronic component je
that can be estimated by the Wiedemann-Franz law using the
equation, je = LrT (L: Lorentz number), i.e., jtotal = jph +
je. As a matter of fact for STO single crystals either reduced
or doped, the j values are rather high (711 W(mK)1 at
300 K),120122 where the lattice component dominates,
accounting for more than 70%80% of the total. Roughly, j
drops proportionally to T1 from 300 K to ~700 K,122 characteristic of Umklapp-type phononphonon interaction. It is
considered primarily related to the nature of STO crystal
structure: consisting of strongly bonded lightweight atoms
with highly symmetric structure. As a result, the ZT values
for these single crystals are rather low (below 0.27), and the
reduction in j is critical to improve the ZT, whereas introduction of point defects alone, e.g., by solubility-limited doping, is insucient to suppress the heat transport of STO.
In short, researches on the STO single crystals revealed a
promising potential as an excellent n-type TE oxide that is
non-toxic and naturally abundant while showing a high
power factor comparable to that of conventional Bi2Te3
alloy.123 Moreover, it shows, as the high j and the low solubility of dopants (e.g., La and Nb) in STO single crystals are
concerned, further eorts should be focused not only on
reduction in j but also on searching other STO materials
which can accommodate more dopants to reach the optimal
carrier concentration.
(B) STO Epitaxial Films: In 2005, Ohta et al. studied
systematically the TE properties of a series of heavily doped
SrTi1xNbxO3 (x = 0.050.4) epitaxial lms prepared using a
pulsed-laser-deposition (PLD) technique, which allowed a
high Ti-site-Nb-doping up to 40% for further optimization.124 The record ZT of ~0.37 at 1000 K was achieved in
20 at.% Nb-doped STO with n ~ 4 9 1021 cm3 (Fig. 18),
which is primarily beneted from the large S2r
(~1.3 mW m1 K2 at 1000 K).
Iso-valent substitution attempting to further reduce j was
done by partially replacing Sr with Eu in Sr1xEuxTi0.8Nb0.2O3 (x = 0 ~ 0.8) epitaxial lms by Kato et al.125 It
was found that Eu substitution almost did not change the
electrical properties much although it suppressed heat transport by shortening the low temperature phonon mean free
path by 12% at 300 K but very little at high temperatures,
suggesting Eu-substitution should be favorable only at low
temperatures. By contrast, Yu et al. demonstrated a signicant reduction in j in oxygen-decient La-doped STO lms
prepared by PLD under a high vacuum of ~107 Torr at 650C
(j = 3.88 W(mK)1 at 300 K) and 450C (j = 2.55 W(mK)1
at 300 K). As the authors explained, oxygen vacancies are much
more eective in suppressing the heat transfer than
La doping, whereas the low-temperature (450C) growth should
have introduced larger sized defects such as dislocations and
low-angle grain boundarieswhose characteristic length could
be longer than that of the oxygen vacanciesthat would be
responsible for scattering mid- and/or long wavelength
phonons.126,127 Recently, epitaxial thin lms of STO doped
with both La and oxygen vacancies synthesized at 850C by
PLD have been characterized from 300 to 900 K. The |S|
values of double-doped lms are comparable to previous
studies of La-doped single crystals at similar carrier concentrations, and the j values, although increased a little compared to the above oxygen decient lms, are also rather low
at 300 K (45 W(mK)1), but similar to that of bulk crystal
at high temperatures (~3 W(mK)1 at 873 K) due to weakened phonon scattering by the defects that dominates only
around room temperature. As a result, the ZT values for the
oxygen-decient
5 at.%
La-doped
lm
(n = 2.5 9
1021 cm3), were ~0.23 and 0.28 at 300 and 873 K,
respectively.127
Thus, despite the decreased j, the epitaxial lms grown at
low temperatures fail to reach a ZT higher than 0.37,
Vol. 96, No. 1
Fig. 18. Typical values of ZT and thermal conductivity of STO

single crystal, epitaxial lm, and polycrystalline ceramics.
because of the sacrice in electrical transport properties as a

result of limited solubility of the dopants. Besides, oxygen
vacancies are not so stable at high temperatures. Moreover,
from the cost and the productivity points of view, polycrystalline ceramics are preferred.
(C) STO Polycrystalline Ceramics: Polycrystalline TE
ceramics are important both for practical applications,
because of being low-cost ones and having the potential to
reduce j due to phonon scattering at the grain boundaries.
First, Sr-site-rare earth-doped STO ceramics were investigated
by Muta et al. Although the j values (3.56 W(mK)1 at
300 K) were observed to be signicantly smaller than those of
single crystals and epitaxial lms, the S2r values were fairly
lower than those obtained in STO single crystals.128130 Ohta
et al. reported that, although the 20 at.% Nb-doped STO
ceramics maintained a high S2r close to those of epitaxial
lms of the same composite, the j could not be lowered
eectively, especially at high temperatures.128 Consequently,
its highest ZT (0.35 at 1000 K) is similar to that of the epitaxial lms (Fig. 18). Thus, the additional phonon scattering
eects due to grain boundaries is still not eective enough,
because the grain size in these ceramics are too large (several
micrometers) to introduce a suciently large amount of grain
boundaries for phonon scattering although the phonon mean
free path is ~2 nm.129
Muta et al.129 suggested that Sr-site substitution of STO
with Ca or Ba as a good way to improve ZT of Nb-doped
STO because these substitutions eciently reduce the lattice
thermal conductivity due to the fact that alloying enhances
phonon scattering without aecting much the electron transport properties. However, Yamamoto et al.130 evidenced the
negative eect of this Ca-Ba-Sr ternary substitution, primarily because: Ca and/or Ba-substitution for Sr in Sr
(Ti0.8Nb0.2)O3 results in an asymmetrical distortion of the
TiO6 octahedra, which, in turn, reduces the linearity of the
electron conduction paths and consequently the r, and
nally, the eect of j reduction would be largely oset by
the deterioration of power factor S2r.
(D) SrO(SrTiO3)n
Ceramics: Ruddlesden-Popper
type SrO(SrTiO3)n (n = integral) compounds are a family of
STO-based Ruddlesden-Popper phase,131,132 whose crystal
structures can be viewed as a natural superlattice repeating
alternatively one SrO layer with every n layer of STO along
the c-axis, and therefore are expectable to show electrical
properties similar to STO while suppressing j by enhanced
phonon scattering at the SrO/STO interfaces. Researches on
doped SrO(SrTiO3)n (n = 1, 2)with Nb at Ti-site and rare
earth metals at Sr-siteas new TE oxides demonstrated low
j (35 W(mK)1 at 300 K, 22.5 W(mK)1 at 1000 K),
which is decreased by 50%60% at 300 K and 30%40% at
1000 K as compared to that of STO, with major reduction in
jlatt.133 Nevertheless, due to the crystal eld splitting in the
inherently distorted TiO6, the m* for Nb-, La-, Nd-doped
January 2013
11
Energy Harvesting
compounds are all decreased (~2 mo), leading to a relatively

smaller |S| than that of STO with similar carrier density ne.
Correspondingly, the largest ZT ~ 0.15 at 1000 K was
obtained in n = 2 compounds. By contrast, when doped with
smaller cations (Gd3+ and Sm3+) at Sr-site, the distorted
TiO6 octahedra in n = 2 compounds restore gradually with
increasing temperature to a symmetrical conguration.133
Consequently, the m* (~7.5 mo for 5%Gd-doped SrO
(SrTiO3)2 at 1000 K) and |S| values (350 lVK1 for 5%
Gd-doped SrO(SrTiO3)2 at 1000 K) in these samples increase
with temperature at a higher rate than do those of Nb-, La-,
and Nd-doped counterparts. These ndings emphasized the
signicance of TiO6 symmetry for achieving a large m* in the
STO-based TE materials. Finally, the ZTmax ~ 0.25 at
1000 K was achieved in a 5% Gd-doped SrO(SrTiO3)2,
which is ~70% larger than the corresponding maximum in
Nb-, La, and Nd-doped samples, and even slightly larger
than 5%Nb-doped STO.124 Due to the solubility limitation
of the dopants and the insulation of innumerable SrO layers
in the ceramic matrix, further eorts to improve the ZT values should be made on texturing of the ceramics or epitaxial
lms of these compounds.
(E) STO Composite Ceramics: Thermoelectric composites have been reported to oer more possibilities to
enhance the performance by intensication of phonon scattering and to manipulate the electrical transport properties,
and thus TE nanocomposites have become a new direction
for development of TE materials.
Recently, Wang et al. fabricated STO composite ceramics
where some low j oxides (YSZ, K2Ti6O13, mesoporous
SiO2)134136 were introduced into the matrix of 15 at.%
Nb-doped STO by sintering the mechanically milled mixtures. They observed that the addition of these oxides could
eectively reduce thermal conductivity. For instance, in a
3 wt% K2Ti6O13 (KTO)-added sample, j values calculated
for the fully dense composites of ~3.5 and ~2.2 W(mK)1 at
300 and 900 K, respectively, were achieved, which is
decreased by ~65% and 30% as compared to that of the
non-KTO-added, possibly due to a strong phonon scattering
in the KTO inhomogeneities and at the grain boundaries
where KTO seems to enrich as evidenced by EDX analysis
(Fig. 19). Meanwhile, it is interesting that the r values
seemed to be little aected despite the insulation of the additives, which actually may be favored by additive-promoted
densication enhancing electron transport, as the average
grain size of KTO added samples (~10 lm) is perceivably larger than that of those non-added (~2 lm). The |S| values
were independent of KTO addition, as these samples contain
an almost same carrier concentration, as explained in the
article. Similar results were also observed in YSZ- and mesoporous SiO2-added composites. Finally, a maximum
ZT ~ 0.34 at 900 K was obtained in the 3 wt% KTO-added
sample.134
(F) Nanostructured STO Ceramics: Nanostructuring
is a general and promising approach to suppress heat transport, as it introduces into the bulk a large amount of grain
boundaries where the phonon propagation will be interrupted inevitably due to perturbed lattice vibration modes,
on the other hand, if the grains are ne enough to be comparable with or even smaller than the phonon mean free path,
the phonon scattering will be even more vigorous by the
so-called phonon connement, leading to a signicant
decrease in jph.137
Recently, Wang et al. investigated the eective thermal
conductivity dependence on the average grain size (from
20 lm to 55 nm) of non-doped STO ceramics.138 The j
values (~8 and ~5.2 W(mK)1 for 20 lm- and 55 nmgrained samples at 300 K, respectively) decrease with the
grain size gradually, most at low- and mid-temperatures
(~300700 K). The heat capacity and the phonon speed are
not perceivably aected by the grain size in the studied
range, although the phonon mean free path (1.81.3 nm at
(a)
(b)
(c)
(d)
Fig. 19. The FE-SEM comparison of cross section between (a) nonK2Ti6O13(KTO)-added and (b) 1 wt%, (c) 5 wt%, (d) 3 wt% KTOadded SrTi0.9Nb0.1O3 ceramics, showing the signicant grain growth
related to KTO addition. The EDX proles from (d) (right) indicate
an enrichment of Ti, i.e., a segregation of KTO at the grain
boundaries.
300 K and ~0.7 nm at 1000 K) was observed to decrease

with decreasing grain size, although substantially shorter
than the average grain size. Thereby, the reduction in j is
thought to be caused primarily by the enhanced interfacial
thermal resistance due to the increased amount of grain
boundaries as grains get smaller. By using a Kapitza model,
the interfacial resistance of STO was estimated to be
4.98 9 109 m2(WK)1 (300 K) to 3.41 9 109 m2(WK)1
(1000 K).134 Based on this result, the established grain size
dependence of j on grain size d shows that at d ~ 10 nm, a
low j would be obtained close to the theoretical minimum
value (1.4 W(mK)1 at 300 K, and 1.7 W(mK)1 at
1000 K) which is calculated from the Cahill model.139
Moreover, besides the primary role of nanostructuring as
suppressing the heat transport, its eect on electrical transport properties can be pronounced when the grain size is
small enough to present the change in band structure of STO
and the enhancement of electron scattering (possibly cause
the energy ltering) at the interfaces. In a recent report by
Wang et al. for a 60 nm-grained 2 at.% La-doped STO ceramic sample, the value of |S| (~360 lVK1) was found to be
increased by 38%, the r (~105 S cm1) was almost 80%
lowered as compared with those of bulk crystal
(S ~ 260 lV K1, r ~ 500 Scm1, j ~ 12 W(mK)1 at
300 K) with the same composition.140 Meanwhile, the j
(~3.5 W(mK)1) was decreased by a factor of ~3.5. The
resulting ZT300K was ~0.12, 30% larger than that in the bulk
crystal. The behavior of electrical properties was interpreted
as a result of expanded lattice parameter (a = 3.976 and
3.958 A for the 60 and 100 nm particles, respectively)146

which could possibly have caused the enlargement of m*. As
for the further mechanism, it remains a disputation that
whether the energy ltering instead of the growth of m* has
played a dominant role, as no further results for the grain
boundaries were presented in the research.
(G) Two-Dimensional Electron Gas (2DEG): As theoretically predicted by Dresselhaus et al.,141 and experimentally evidenced partially by the work for PbTe (1.5 nm)/
Pb0.927Eu0.073Te (45 nm) multiple quantum well (MQW),142
S2 for quantum-well (QW) structures increases linearly with
decreasing QW thickness when the thickness becomes less
than a few nanometers, based on the assumption that the
enhancement of S2 arises mainly from an increase in the
12
density of states near the conduction band edge when the

carrier electrons are conned in such a narrow space.
Two-dimensional superlattice lms were grown using a
PLD technique by Ohta et al.,143 with several-unit-cell-thick
20% Nb-doped STO QW layers (n = 2.4 9 1021 cm3) sandwiched in undoped STO barrier layers (n 1015 cm3).
A drastic increase in |S| from the bulk ceramic data
(|S|3D ~ 61 lV K1) occurred when the thickness of the
SrTi0.8Nb0.2O3 layer is less than four unit cells of STO, with
the barrier layers nine unit cells thick. In the best case, the
|S| at room temperature is ~480 lV K1, which is ~4.4 times
larger than that of SrTi0.8Nb0.2O3 bulk ceramic (Fig. 20).
The slope of |S|300K against log n is about 1000 lV K1,
about ve times of that for SrTi0.8Nb0.2O3 bulk ceramic.
However, the n and Hall mobility, lHall, in the 2DEG layers
are almost unchanged as compared to those of bulk counterpart. As a result, the ZT value estimated using the j of bulk
single crystal for the SrTi0.8Nb0.2O3 QW reached an extremely large value of ~2.4, about ve times larger than that of
SrTi0.8Nb0.2O3 ceramic. Successive work, revealed the critical
thickness of STO barrier should be 16 unit cells at least (i.e.,
6.3 nm),144 and the 2DEG in the superlattice lms should be
stable even up to ~900 K.145
(H) 3D Superlattice Ceramics: Inspired by the attracting properties of 2DEG in the STO superlattices, as a
pioneering and challenging eort, Koumoto et al. proposed a
3D superlattice (3DSL) bulk STO ceramics with 2DEG grain
boundaries,146 as shown in Fig. 21. The 3DSL structure is
built up by <001> stacked nanocube grains (with size
>6.3 nm) of 10 at.% La-doped STO, with the grain boundaries (GBs) with thickness within four unit cells consisting of
20 at.% Nb-doped STO. The GBs are considered to synergistically function in three ways: (1) acting as 2DEG layers
with a lowered conduction band minimum (CBM) relative to
the unchanged CBM in La-doped STO grain interior147; (2)
giving rise to the energy ltering eect by the potential barriers formed in the space charge region near GBs,148 and (3)
scattering phonons to reduce jlatt even in a highly ordered
nanostructure149 where phonon connement should be considered with the grain size as small as a few nanometers.150
Theoretical simulations by Zhang et al. have shown that
ZT value increases either when the GB thickness is small
(2DEG quantum connement eect) or the GB barrier
height is optimized (energy ltering eect). In the best case
with one-unit-cell-thick GBs and 16-unit-cell-sized grains and
calculated j300K ~ 2.2 ~ 2.4 W(mK)1, a strikingly high ZT
~0.8 at 300 K is predicted, comparable to that of conven-
(a)
Vol. 96, No. 1
tional Bi2Te3 materials. Furthermore, based on the theoretical minimum lattice thermal conductivity jmin ~ 1.4
W(mK)1,138 even higher ZT300K ~ 1.2 was predicted for
this 3D superlattice bulk STO.148
The 3DSL STO material would be a revolutionary eort
to develop practical TEs beyond the conventional toxic and
naturally-scarce compounds, despite the diculties on the
way to realize this encouraging goal, for instance, in the control over the synthesis of La-doped STO nanograins and the
precise Nb-doping at the grain boundaries, and the grain
growth during the densication process.
(3) In2O3-Based Oxides

Indium oxide is a wide band gap semiconductor which has
attracted considerable attention due to its great potential for
gas sensing,151 optical transparency152 and optoelectronics.153
Numerous studies have been carried out on thin lms of this
material as a transparent conducting oxide (TCO).154 They
show that doping with tin increases dramatically the electrical conductivity as illustrated by the well-known indium tin
oxide (ITO). More recently, the doping of In2O3 with titanium and zirconium,155,156 with molybdenum157,158 and with
tungsten159 has shown the possibility to reach exceptionally
high carrier mobility with carrier density higher than
1020 cm3 on thin lms. However, very few attempts have
been made to study the transport properties of bulk ceramics
of In2O3 in view of other applications. Doped In2O3 based
uorite derivative structures have been then investigated as
thermoelectric oxides, such as electron-doped In2O3,160162
Ga3xIn5+xSn2O16,163 and In4Sn3O12.164 In those systems,
fairly good thermoelectric performances with ZT ~ 0.3 at
1000 K have been reached.
At rst, metal-doped In2O3 bulk ceramics160162 have
shown a great potential as n-type elements. To optimize the
thermoelectric properties of such bulk ceramics, the inuence
of the nature and concentration of the doping element
(Ge4+, Ti4+, Zr4+, Sn4+, Ta5+, and Nb5+) upon the transport
properties of this material has been carefully studied.
The evolution of the electrical conductivity at room temperature versus the titanium doping level x [Fig. 22(a)] shows
that the electrical conductivity increases abruptly for very
low x values. Importantly, beyond a certain limit value x,
the increase is suddenly stopped and the conductivity tends
to decrease with x. This shows that below x, titanium
substitutes for indium, increasing the carrier concentration
by valency eect [Fig. 22(b)]. In contrast, it suggests that
(b)
(c)
Fig. 20. (a) HAADF-STEM image of the SrTiO3/SrTi0.8Nb0.2O3/SrTiO3 multi-quantum well (MQW). (b) high-resolution HAADF-STEM
image, Ti-L2,3 edge EELS prole, and integrated intensity prole of the Ti-L2,3 edge EELS across a SrTiO3/SrTi0.8Nb0.2O3/SrTiO3 QW, showing
that Ti in the SrTi0.8Nb0.2O3 layer exhibits a +3/+4 mixed valence state. (c) |S|300K versus well thickness for the SrTiO3/SrTi0.8Nb0.2O3/SrTiO3
MQWs. A dramatic increase in |S|300K is seen when the thickness of the SrTi0.8Nb0.2O3 layer is smaller than 1.56 nm (4 unit cell).
January 2013
13
Energy Harvesting
(a)
Fig. 21. 3D superlattice STO ceramics.
beyond x, the substitution does not take place anymore,

leading to the formation of a secondary phase. This statement is strongly supported by X-ray analysis, which
conrms in all cases the appearance of a secondary phase
for x > x, as illustrated in the series In2xTixO3. The XRD
patterns of this series (Fig. 23) show that for x 0.02 no
impurity can be detected, whereas an additional Bragg peak
at 2h = 31.7, characteristic of In2TiO5 is observed as soon
as x
0.04, whose intensity increases with x. For all the
other In2O3 series with M = Ge4+, Zr4+, Sn4+, Ta5+, and
Nb5+, impurity phases such as In2Ge2O7, ZrO2, In4Sn3O12,
InTaO4, and InNbO4 are observed when the doping
level exceeds the solubility limit, and the solubility limit
well matches the ones determined using the transport
properties.
To conclude on the thermoelectric performances of these
doped In2O3 compounds at high temperature, electrical conductivity, Seebeck coecient, power factor, thermal conductivity, and ZT values at 1000 K are given in Fig. 24 in the
series In2xTixO3. As a representative trend for the dierent
studied cationic substitutions, minima values of q and |S|
around their solubility limit is observed (x = 0.02 for
Ti-doped system). According to the Seebeck and electrical
resistivity values, the highest value of the power factor,
~0.9 mW/mK2, is reached for intermediate doping levels, i.e.,
below the solubility limit. At these doping levels, high mobilities, moderate carrier concentrations associated with high
thermopower give the best electrical performances.152 The
doping fraction dependence of the thermal conductivity follows the same behavior as the electrical conductivity. Highest
values of j are found around the solubility limits. As
expected, the increase in the thermal conductivity (mainly the
electronic contribution) is correlated with a decrease in the
electrical resistivity. Further additions of dopant above their
solubility limits lead to a slow decrease in the thermal conductivity due to the slow increase in the electrical resistivity.
The highest ZT values close to 0.3 for all the series are
reached for the low doping levels where high power factors
are combined with low thermal conductivities.
One of the concerns in developing indium-based oxides,
especially doped In2O3, is the scarcity of indium, and consequently its rather high cost. Its content must be then reduced
for the sake of applications. In this respect, the indium-based
oxide In4Sn3O12, a uorite-related oxide containing much less
indium,165 appears as a potential material for high-temperature thermoelectric applications. It has been reported with a
relatively low resistivity of 0.03 cm at room temperature.165 However, the study of this oxide by Pitschke et al.166
has claimed this system as a poor thermoelectric with
ZT ~ 0.03 (1000 K) and attributed the poor performance to
high porosity. The following studies have also emphasized
the diculty of achieving well sintered products, with the
maximum relative density obtained at only 60%. The sintering and TE properties of In4Sn3O12 have been then improved
through reactive sintering with addition of small amounts of
Ga2O3.163
(b)
Fig. 22. Inuence of the titanium fraction In2xTixO3 on

electrical resistivity (open symbols) and the thermopower
lled symbols) and (b) the carrier concentration measured
The dotted line in the n(x) plot corresponds to the doping
electron per Ti cation.162
(a) the
(square
at RT.
by one
Fig. 23. XRD patterns for the series In2xTixO3.162
As shown previously in Ga3xIn5+xSn2O16 phase164 and

described in the next paragraph, the origin of the rather low
thermal conductivity of In4Sn3O12, as compared to doped
In2O3, may be due to the structural change that generates
enhanced defect scattering. It is conrmed by the linear temperature-independent thermal conductivity (inset of Fig. 25),
which was also observed in Ga3xIn5+xSn2O16 compounds.
The observed increase in the total thermal conductivity with
increasing x, implies that the dominating inuence is from
the electronic thermal conductivity, which enhances as the
porosity decreases.
The gure of merit ZT as a function of temperature for
the dierent samples is evaluated based on the above discussed transport data and shown in Fig. 25. A maximum ZT
value of 0.23 at 1000 K is obtained at x = 0.05. This maximum originates from the combination of moderately high
density ~83% and signicantly low electrical resistivity and
thermal conductivity as compared to the parent composition.
14
Vol. 96, No. 1
Fig. 25. Temperature dependence of ZT for In4xGaxSn3O12

compounds. Inset shows the temperature dependence of the thermal
conductivity.163
Fig. 24. Inuence of the titanium fraction in the In2xTixO3 series

on (a) the electrical resistivity, Seebeck coecient, power factor and
(b) the thermal conductivity and ZT values at 1000 K. Note the
break in the x-coordinate.162
At the origin of good TCO materials are the In2O3-based

uorite derivative type structure and the peculiar 5d10 electronic conguration of In3+ as well as the promising thermoelectric performances in doped In2O3 and In4Sn3O12. It
suggests that any system composed especially of InO6 edgeshared octahedra may lead to improved TE properties. For
example, the oxide Ga3xIn5+xSn2O16, synthesized more
than 10 years ago,167,168 is of great interest due to its oxygen-decient uorite structure, closely related to bixbyite
structure having space group I41/a. Like the doped In2O3
phase, it was shown to be an excellent TCO,168 with a rather
high room temperature conductivity of 375 S/cm. The thermoelectric properties of this phase have been then recently
studied.176
The temperature dependence of the electrical resistivity
[Fig. 26(a)] in the series Ga3xIn5+xSn2O16 shows a linear
increase with temperature, characteristic of a metal-like
behavior in the range 3501000 K. Moreover, for a given
temperature, resistivity drops with x, e.g., from ~4 mcm
for x = 0.30.9 mcm for x = 1.60 at room temperature.
The Hall eect measurements show a linear increase in the
carrier concentration with x (Table I), consistent with the
electrical conductivity evolution.
The temperature dependence of the Seebeck coecient
[Fig. 26(b)] reveals that |S| drops monotonically with x, in
agreement with the decrease in electrical resistivity. A maximum absolute value of 145 lV/K is observed for x = 0.3 at
1000 K. The negative sign of the Seebeck coecient indicates
that electrons are the majority carriers in the system. The
magnitude of the thermopower increases almost linearly with
temperature for all the compositions. The maximum power
factor value of 0.55 mW m1 K2 is observed for x = 1.6 at
1000 K as compared to the value of 0.36 mW m1 K2 for
x = 0.3 [Fig. 26(c)]. It should be noted that these values are
slightly lower than those observed in the Ge-doped In2O3.
The measured thermal conductivity values (Table I) ranging from 1.36 to 1.91 W(mK)1, are signicantly lower than
those reported in other indium based oxides with optimized
thermoelectric properties. For instance, the thermal conductivity of doped In2O3 compounds was found to be higher
(a)
(c)
(b)
(d)
Fig. 26. Temperature dependence of (a) electrical resistivity, (b)

Seebeck coecient, (c) power factor, and (d) ZT in the series
Ga3xIn5+xSn2O16.164
than 3 W(mK)1. It is speculated164 that the complex structure associated with highly disordered Ga3+, In3+ and Sn4+
cations and also the large mass dierence between Ga3+ and
In3+/Sn4+ are possible reasons for the enhanced defect scattering. Such behavior leads to the nearly temperature-independent thermal conductivity for Ga3xIn5+xSn2O16, as
shown in Fig. 27. Finally, as the thermal conductivity is
almost compensating the power factor, ZT value does not
vary signicantly with the Ga/In ratio. We obtain a maximum ZT value of 0.28 for x = 0.6 at 1000 K [Table I,
Fig. 26(d)], comparable to those reported on doped In2O3.
In conclusion, the investigation carried out on In2O3 based
oxides demonstrates that the derivative uorite type
January 2013
Table I.
x
0.3
0.6
1.0
1.3
1.6
15
Energy Harvesting
Summary of Thermoelectric Properties for Compositions in the Ga3xIn5+xSn2O16 Series at 1000 K164
q (mcm)
S (lV/K)
PF (mW/mK2)
j (W(mK)1)
5.8
3.5
2.8
2.5
1.5
145
127
111
108
92
0.36
0.45
0.44
0.46
0.55
1.36
1.74
1.91
1.69
1.85
structures and the peculiar 5d10 electronic conguration of

In3+ are at the origin of good thermoelectric performances.
It suggests that combining dierent sublattices in the same
framework, similar to that in In4Sn3O12 and Ga3xIn5
+xSn2O16 with complex structrures, cation disordering and/
or mass uctuation for enhancing phonon scattering, is the
clue for the realization of the large ZT values. Other systems
based on the uorite structure or replacing Ga by other
cheaper tetrahedral cations must be explored in the future.
(4) TiS2-based Misfit-layer Compounds

The concept of phonon-glass electron-crystal (PGEC) has
now become a general guideline for developing new thermoelectric materials.169 To obtain a PGEC material, the idea of
complex structure was put forward which imagines a material with distinct regions providing dierent functions.170 It is
believed that the ideal thermoelectric material would have
regions of the structure composed of a high-mobility
semiconductor that provides the electron-crystal electronic
structure, interwoven with a phonon-glass. The phonon-glass
region would be ideal for housing dopants and disordered structures without disrupting the carrier mobility in the electroncrystal region.170 On the basis of the above idea, we intercalate a
layer of MS (M = Pb, Bi, Sn) into the van der Waals gap of
layered TiS2, forming a series of mist layer compounds
(MS)1+x(TiS2)2.171173 They consist of an alternative stacking of
CdI2-type TiS2 trigonal anti-prismatic layers and rock-salt-type
MS slabs, which could be viewed as a natural superlattice.174
The TiS2 layer can provide thermopower as well as electron
pathway according to Imais research on TiS2 single crystal.175
The MS layer was intercalated into the gap of the TiS2 layers to
form a modulated structure, which would suppress the transport
of phonons by the interaction between the MS layer and TiS2
Fig. 27. Temperature dependence of thermal conductivity. In the

inset, the thermal conductivity of phonon deduced from WiedemannFranz low and the tted curves based on the Callaway model are
shown for Ga3xIn5+xSn2O16 and doped In2O3.
ZT
0.26
0.28
0.23
0.25
0.27
n 9 1020 (cm3)
0.27
0.83
1.11
1.48
1.82
layer and/or disruption of the periodicity of TiS2 in the direction

perpendicular to the layers.
Moreover, the structure of these natural superlattice materials can be varied to some extent, including the species of
the host material, the intercalated material as well as the
ratio of these two components, thus constituting the large
family of chalcogenide mist layer compounds, (MX)1+x
(TX2)n (M = Pb, Bi, Sn, Sb, Rare earth elements; T = Ti, V,
Cr, Nb, Ta, X = S, Se; n = 1, 2, 3).6 The structure and physical properties of mist layer compounds have been intensively investigated in the 1990s.174,176,177 By now, only a few
studies have been performed on the thermoelectric properties
of these compounds. Miyazaki et al.178 prepared polycrystalline samples of (Yb1.90S2)0.62NbS2 and obtained a ZT value
of 0.1 at 300 K. A modulated elemental reactants method
was developed to make thin lms of the mist layer compounds with designed composition. Low thermal conductivities were found and an ability of tuning the carrier
concentration was also demonstrated, but a ZT below 0.02
was reported for the (PbSe)0.99(WSe2)x superlattice thin lms
because of the low in-plane electrical conductivity.179182
(A) Crystal Structure: The crystal structure of
(SnS)1.2(TiS2)2 is analyzed as an example.183 The stage-2
compound (SnS)1.2(TiS2)2 consists of alternative stacks of
one SnS layer and paired TiS2 layers (Fig. 28). Its crystal
structure can be analyzed by analogy with the available data
of stage-1 compound (SnS)1.2TiS2, because the subsystem of
SnS and TiS2 are more or less identical in these two types
of compositions.183,184 Both subsystems, SnS and TiS2, of
(SnS)1.2(TiS2)2 are triclinic. The space groups are C-1 for SnS
and F-1 for TiS2. The SnS layer consists of deformed slices
of SnS with a thickness of half the cell edge of the distorted
NaCl-type SnS. Each Sn atom is coordinated by ve S atoms
within the same layer and two or three S atoms of the TiS2
layers. The Sn atoms are slightly pushed out of the a-b plane
with respect to the sulfur atoms in the same plane. The structure of the TiS2 part is hardly distorted compared to the
crystal structure of 1T-TiS2, in which Ti is octahedrally
coordinated. The Ti atoms have a trigonally antiprismatic
coordination by six S atoms. In (SnS)1.2(TiS2)2, the van der
Waals gap still exists between the paired TiS2 layers as in
1T-TiS2. The SnS layer and the paired TiS2 layers stack in
the direction of the c axis, although the two c axes of the
two subsystems slightly diverge. Inside the layers, the b axes
are parallel and of equal length while the a axes, being also
parallel, have dierent lengths and the ratio is ~3:5. Therefore, the value of 1.2 in the chemical formula of
(SnS)1.2(TiS2)2 is obtained by taking account of the ratio of
lattice parameters and number of atoms contained in one
unit cell.
(B) Electrical Properties: In the in-plane direction,
all the (MS)1+x(TiS2)2 compounds show higher electrical
conductivity than TiS2 and it increases in the sequence of Sn,
Pb, and Bi in the whole temperature range (Fig. 29). It was
found that all the (MS)1+x(TiS2)2 compositions have higher
carrier concentration than that of TiS2.171,173 A general viewpoint has been accepted that there exists electron transfer
from the MX layer to the TX2 layers in the mist layer
compounds (MX)1+x(TX2)n, which also accounts for its stability.6 From the carrier concentrations and the lattice
parameters, we can estimate the number of electrons received
16
Vol. 96, No. 1
(a)
(b)
Fig. 28. HRTEM image of (SnS)1.2(TiS2)2 along the [130] zone

axis.171
per Ti atom for (BiS)1.2(TiS2)2, (SnS)1.2(TiS2)2, and

(PbS)1.18(TiS2)2 is 0.45, 0.16, and 0.2, respectively. In the
in-plane direction, the electron mobility of TiS2 is almost
maintained after the intercalation of SnS or PbS layers.
However, the BiS intercalation has much lower mobility. The
electron transfer from the MS layers to the TiS2 layers may
also change the eective mass, resulting in dierent mobilities. An estimation of the eective mass will be shown below.
The Seebeck coecients of (MS)1+x(TiS2)2 are decreased
compared with those of TiS2 [Fig. 29(a)]. It has generally
been accepted that 1T-TiS2 is a semiconductor with an indirect gap of 0.20.3 eV, with its conduction and valence bands
consisting of Ti 3d and S 3p states, respectively.185,186 In stoichiometric TiS2, the Fermi level lies at the bottom of Ti 3d
band, making multi-valley structure with six small electron
pockets around the L-point in the hexagonal Brillouin
zone.175 Large Seebeck coecient was observed due to high
density of states just above the Fermi level as well as phonon-mediated inter-valley. In (MS)1+x(TiS2)2, a rigid band
model can hold and the band structure is a superposition of
those of MS and TiS2 subsystem, as in the case of
(SnS)1.2TiS2.183,187,188 It is realized that the d orbitals of Ti play
an important role in determining the physical properties of TiS2based materials and the degree of band lling, their energy levels
and the width of the d-band signicantly aect their thermoelectric properties.187 In (MS)1+x(TiS2)2, the position of the Fermi
level in the 3d orbital of Ti atom can be shifted upward due
to band lling by those electrons transferred from the MS
layer, Therefore, the Seebeck coecient was decreased as the
density of states decreased. The density of states eective
mass m* values for (BiS)1.2(TiS2)2, (SnS)1.2(TiS2)2 and
(PbS)1.18(TiS2)2 were calculated to be 6.3m0, 4.8m0 and
4.5m0, respectively, where m0 is the bare electron mass.
The power factors of the (MS)1+x(TiS2)2 compositions
were found to be lower than that of TiS2.171173 At lower
temperatures, the power factors almost increase in the order
of Bi < Pb < Sn, indicative of increased carrier concentration. Although the carrier concentration in (MS)1+x(TiS2)2 is
not yet optimized, it can be expected that further reduction
in carrier concentration would increase the power factor. In
fact, an optimum carrier concentration for the highest power
factor of a typical thermoelectric material is of the order of
1020 cm3,170 which is one order of magnitude lower than
the corresponding values for the (MS)1+x(TiS2)2 compositions (>1021 cm3).
(c)
(d)
Fig. 29. Seebeck coecients (a), electrical conductivities (b),

lattice thermal conductivities (c), and ZT values (d) of TiS2 and
(MS)1+x(TiS2)2.171,172
To control this overdoping, Guilmeau et al. have recently

intercalated copper into the TiS2 layers.189 The Cu content in
the structure can be accurately tuned leading to smaller
carrier concentration than in mist layered suldes. Power
factor values of 1.5 and 1.1 mW/mK2 were obtained at,
respectively, RT and 700 K for Cu0.02TiS2.
(C) Thermal Conductivity: It was found that the
(MS)1+x(TiS2)2 compositions have lower thermal conductivities than TiS2 in the in-plane directions in the whole temperature range and the main reason of the reduction in thermal
conductivity is the reduction in lattice thermal conductivity.171173 It can be noticed in Fig. 29(c) that the
(MS)1+x(TiS2)2 has much lower lattice thermal conductivities
than TiS2 in the in-plane directions. Same behavior has been
reported in CuxTiS2 compounds189 (Fig. 30). To analyze the
low thermal conductivities, the kinetic theory of thermal
conductivity was used;
January 2013
k 1=3Cv Vl
(9)
where Cv, V, and l represent the heat capacity, speed of

sound, and phonon mean free path, respectively.
The sound velocity is determined by the density and the
elastic constants of a solid. The sound velocity has three
polarization modes, including one longitudinal mode and
two transverse modes. In the in-plane direction, the two
transverse velocities are not equal because of the layered
structure. The measured values are listed in Table II. Compared with pure TiS2, the longitudinal velocities of the mist
layer compounds are a little decreased, which can be attributed to the increase in density. In contrast, the transverse
sound velocities, especially VT1, apparently decreased, which
arise from the softening of atomic bonding. The transverse
polarization is a kind of shear movement, and the velocity is
determined by shear modulus as follows:
s
G
VT
q
17
Energy Harvesting
(10)
performances. In CuxTiS2 compounds, ZT values of 0.41

have been obtained at 700 K.189
Evidently, a signicant improvement of the thermoelectric
properties in layered TiS2 compounds requires two combined
eects: (1) a high power factor through a tuning in the carrier concentration, and (2) a substantial decrease in the total
thermal conductivity. Although the thermal conductivity of
layered TiS2 compounds is relatively large compared to other
PGEC thermoelectrics, most of it comes from the reducible
lattice component especially when the carrier concentration
remains small or moderate. Thus, two-dimensional metallic
TiS2 compounds could be a good thermoelectric if the 2D
structure would scatter more eciently the heat-carrying
phonons.
A large family of mist layer (MX)1+x(TX2)n (M = Pb,
Bi, Sn, Sb, Rare earth elements; T = Ti, V, Cr, Nb, Ta,
X = S, Se; n = 1, 2, 3) or metal intercalated TX2 compounds
with natural superlattice structures can be proposed as possible candidates for high-performance thermoelectric materials,
including both n-type and p-type.
IV.
where G is the shear modulus and q is the density. The shear
modulus is calculated by the above equation and shown in
Table II. The shear moduli of the mist layer compounds
are much lower than those of pure TiS2 due to the intercalation of the MS layers into the TiS2 layers. It can also be seen
that the velocities of the two transverse waves (VT1 and VT2)
are dierent, as VT1 is mainly determined by the interlayer
bonding while VT2 is determined by the intralayer bonding.
For VT1, the weak interlayer bonding between the MS layer
and TiS2 layer arises either from the electrostatic interaction
due to the electron transfer between these layers or weak
covalent bonds between the M atom and the sulfur atoms in
the TiS2 layers.183,190 For VT2, the intralayer bonding is
weakened by intercalating MS layers, possibly due to
the incommensurate structure or disruption of
periodicity of TiS2 layers in the direction perpendicular
to the layers.
(D) Dimensionless Figure of Merit, ZT: It has been
found that all the mist layer compounds show relatively
high ZT values in the in-plane direction [Fig. 29(d)]. However, compared with pure TiS2, only (SnS)1.2(TiS2)2 shows a
higher ZT value (0.37 at 700 K). The intercalation of MS
layer does reduce the lattice thermal conductivity signicantly, but the electron transfer eect in (PbS)1.18(TiS2)2 and
(BiS)1.2(TiS2)2 is too strong, leading to a reduction in the
power factor and an increase in the electronic thermal conductivity. It is required to reduce the carrier concentrations
of the mist layer compounds to optimize the thermoelectric
Fig. 30. Temperature dependence of the thermal conductivity and

its lattice component in CuxTiS2.189
Applications
(1) Waste Heat Recovery

Strong points and advantages of thermoelectric generation
are shown in Table III. The conversion eciency is dependent on the temperature gradient, but independent scale of
heat energy. Maintenance is not necessary because of the
absence of moving parts in this generator. This was successfully demonstrated in the Voyager and Pioneer Programs by
NASA.
Temperature dependence of ZT values are indicated in
Fig. 31 for several thermoelectric materials.85 Bi2Te3, Si-Ge,
and Pb-Te alloys have been used for Peltier cooler or radioisotope generators for spaceships. Recently, Mg2Si and skutterudite are promising materials because of high ZT values at
700800 K. ZT values for all materials greatly depend on
temperature. The materials should use in temperature region,
in which ZT values reach maximum. But most materials
except Bi2Te3 oxidize at temperatures lower than that of their
maximum ZT when operated in air. In Fig. 31, the symbol
indicates the oxidation temperature as measure by thermogravimetric (TG) analysis. Sealing thermoelectric devices in
inert gas atmosphere is required for many of these materials
and can limit their wide spread application. Oxide materials
have recently drawn signicant attention because of their
strong durability against oxidation at high temperature in air.
(2) Oxide Thermoelectric Generator
As mentioned above, oxides are one of the strongest candidates for recovery of high temperature waste heat. Recently,
CoO2 layered materials are paid attention because of their
excellent p-type thermoelectric properties at high temperature
in air.19,20 The authors reported high ZT values of p-type
Ca3Co4O9 (Co-349)20 and are developing thermoelectric generation system using Co-349 and n-type CaMnO3 (Mn-113).
Not only are thermoelectric materials with high ZT values
required, but also modules possessing high conversion eciency are necessary for thermoelectric generation. Junction
between the thermoelectric materials and high temperature
electrodes with high bond strength, and low contact electric
resistance is essential to obtain high performance modules.
Such a good junction can be formed by developing commercially available silver paste incorporated into oxide powder.191
Thermoelectric modules composed of 108 pairs of p-type
Ca2.7Bi0.3Co4O9 and n-type Ca0.9Yb0.1MnO3 legs were constructed using silver electrodes and silver paste including the
p-type powder.192 Dimensions of both oxide legs were 7 mm
wide and 3.5 mm thick and 5 mm high. There was no
substrate on either side of the module, namely a skeleton type
module. The module can generate up to 13 V and 12 W of
18
Vol. 96, No. 1

Table II.
Material
TiS2
(BiS)1.2(TiS2)2
(PbS)1.18(TiS2)2
(SnS)1.2(TiS2)2
Densities, Longitudinal and Transverse Sound Velocities, and Shear Moduli of TiS2, and (MS)1+x(TiS2)2171173
q g/cm3
VL m/s
VT1 m/s
VT2 m/s
G1 GPa
G2 GPa
3.21
4.57
4.69
3.87
5284
3662
3834
4111
2799
1350
1120
1578
3295
1688
1837
2352
25.0
8.3
5.9
9.6
34.7
13.0
15.8
21.4
Table III.
Strong Points and Advantages of Thermoelectric Conversion
Strong points
Advantages
Independence of heat amount

No moving parts
Power generation by temperature dierence
High power density (W/cm2, W/kg)
Recovery of dilute waste heat

No maintenance, long life-time, low cost, silence, no vibration
Solar energy, geothermal energy, body heat etc. no emission
Automobile, ship, portable devices
open circuit voltage and maximum power, respectively, at

873 K of the hot end temperature of the oxide device, which
was measured using a thermocouple xed on an alumina plate
attaching the oxide devices and a temperature dierential
between the hot and cold ends of devices of 400 K in air. The
maximum density of generation power reaches 4.2 kW/m2.
Pmax and density of Pmax increase with increasing hot side

temperature. At 1273 K for the plate heater temperature, the
density of Pmax reaches 8 kW/m2, which is twice that of the
monolithic oxide module. The temperature at the interface
between oxide and Bi2Te3 modules must be held at 453 K or
lower to prevent damages to the Bi2Te3 module.
A thermoelectric unit has been produced by stacking a
heat collection n, oxide and Bi2Te3 modules, and water
jacket for cooling (Inset of Fig. 33). The unit includes four
pieces of oxide/Bi2Te3 cascade modules. The surface area of
the unit is 140 9 140 mm. A thermoelectric power generation test was carried out using a pilot incinerator with natural gas burner. Temperature around the top of heat
collection n and at the hot end of the oxide device (a thermocouple was xed on the alumina substrate of the oxide
module) reached ~1373 and 943 K, respectively. Testing was
carried out 21 h and no deterioration was observed. After
6 h from ignition, open circuit voltage became constant
(Fig. 33). In this condition, maximum power was 49 W.
(3) Oxide/Bi2Te3 Cascade System

As mentioned above, the Co-349/Mn-113 modules show
power densities of 4.2 kW/m2 at high temperature in air. The
conversion eciency of the oxide thermoelectric generators,
however, is evaluated as low as 3% from the properties of
Co-349 and Mn-113 materials. To enhance the conversion
eciency in the low temperature region (300473 K), a
cascade structure was invented consisting of an oxide thermoelectric generator on top of a Bi2Te3 module.
The oxide modules including 14 pairs of p and n-type
devices were fabricated. The dimensions of the devices were
5.0 9 5.0 mm and 5.0 mm height and an alumina substrate
was used on the hot side of the modules, namely half-skeleton module (33 9 34.5 9 6.2 (in thick) mm). A commercially
available Bi2Te3 module with dimensions of 30 9 30 9 3.6
(in thick) mm was used for the cooler region of the cascade
structure (Inset of Fig. 32). Generation power from the cascade module was measured using an electric plate heater to
maintain the hot side temperature and by circulating cooling
water for the cold side.
Temperature dependence of maximum generation power
Pmax and power density for the surface area of the substrate
of the oxide module (30 9 30 mm) are shown in Fig. 32.
Fig. 31. Temperature dependence of ZT for Bi2Te3, Mg2Si, and

skutterudite materials. indicates the oxidation temperature of the
indicted materials as measured using TG analysis.
V.
Conclusions
Metal oxides, Ti suldes, and Mn silicides are proposed as

candidate thermoelectric (TE) materials, which are usable in
air atmosphere at 3001200 K, for cascade-type modules.
Calcium cobaltite (Ca3Co4O9) basically shows good TE
performance at high temperatures in air and appears to be
the best p-type material at the moment. It is already installed
in a commercial TE module for high-temperature energy harvesting.
Fig. 32. Plate heater temperature dependence of maximum

generation of oxide/Bi2Te3 cascade module. Inset: photograph of
cascade module.
January 2013
Energy Harvesting
Fig. 33. Open circuit voltage of the Bi2Te3 modules and oxide of
thermoelectric unit. Inset: photograph of thermoelectric unit
composed of a heat collection, cascade modules, and a water jacket.
Calcium manganate (CaMnO3) seems to be the best n-type

material for high-temperature energy harvesting, while
indium oxide-based compounds are another candidate n-type
materials, although they are somewhat inferior to calcium
manganate due to high vapor pressure of indium oxide at
high temperatures. Calcium manganate is chosen for n-type
TE elements in a commercial module.
Strontium titanate (SrTiO3) also shows good TE performance at high temperatures in a reducing atmosphere, but it
degrades rapidly above 700 K in air. Accordingly, nanostructured ceramics of STO, especially 3D superlattice ceramics
with 2DEG GBs, are proposed for low-temperature applications, and the simulation work has shown its possibility to
exceed TE performance of the conventional bulk bismuthtelluride material at room temperature. Development of a
new process to realize 3D superlattice with millimeter order
size is urgently required.
Higher manganese silicide (MnSix) as p-type and titanium
sulde (TiS2)-related compounds as n-type materials for
mid-temperature energy harvesting are proposed to be good
candidates for the future.
References
1
K. Koumoto, Thermoelectric Materials, co-edited by The Ceramic Society

of Japan and The Thermoelectrics Society of Japan, Nikkan-Kogyo-Shinbun,
Tokyo, 2005. (in Japanese)
2
K. Koumoto, Handbook of Thermoelectrics for Energy Harvesting, edited
by D. M. Rowe, CRC Press, USA, 2012.
3
M. Telkes, Solar Thermoelectric Generators, J. Appl. Phys., 25, 76577
(1954).
4
H. Scherrer, L. Vikhor, B. Lenoir, A. Dauscher, and P. Poinas, Solar Thermolectric Generator Based on Skutterudites, J. Power Sources, 115, 1418
(2003).
5
Y. Lan, A. J. Minnich, G. Chen, and Z. Ren, Enhancement of Thermoelectric Figure-of-Merit by a Bulk Nanostructuring Approach, Adv. Funct.
Mater., 20, 35776 (2010).
6
A. Weidenka, R. Robert, M. H. Aguirre, L. Bocher, T. Lippert, and S.
Canulescu, Development of Thermoelectric Oxides for Renewable Energy
Conversion Technologies, Renewable Energy, 33, 3427 (2008).
7
C. Suter, P. Tomes, A. Weidenka, and A. Steinfeld, Heat Transfer and
Geometrical Analysis of Thermoelectric Converters Driven by Concentrated
Solar Radiation, Materials, 3, 273552 (2010).
8
P. Li, L. L. Cai, P. C. Zhai, X. F. Tang, Q. J. Zhang, and M. Niino,
Design of a Concentration Solar Thermoelectric Generator, J. Electron.
Mater., 39, 152230 (2010).
9
D. Kraemer, B. Poudel, H. P. Feng, J. C. Caylor, B. Yu, X. Yan, Y. Ma,
X. Wang, D. Wang, A. Muto, K. McEnaney, M. Chiesa, Z. Ren, and G.
Chen, High-performance Flat-panel Solar Thermoelectric Generators With
High Thermal Concentration, Nat. Mater., 10, 532 (2011).
10
N. Wang, L. Han, H. C. He, N. H. Park, and K. Koumoto, A Novel
High-performance PhotovoltaicThermoelectric Hybrid Device, Energy
Environ. Sci., 4, 36769 (2011).
11
K. Koumoto, Y. F. Wang, R. Z. Zhang, A. Kosuga, and R. Funahashi,
Oxide Thermoelectric Materials: A Nanostructuring Approach, Annu. Rev.
Mater. Res., 40, 36394 (2010).
19
12
C. B. Satterthwaite and R. W. Ure Jr, Electrical and Thermal Properties
of Bi2Te3, Phys. Rev., 108, 116470 (1957).
13
F. D. Rosi, B. Abeles, and R. V. Jensen, Materials for Thermoelectric
Refrigeration, J. Phys. Chem. Solids, 10, 191200 (1959).
14
Y. Nagamoto, K. Tanaka, and T. Koyanagi, Transport Properties of
Heavily Doped N-type CoSb3, Proc. 17th Int. Conf. on Thermoelectrics,
(Nagoya, Japan, May 1998) 302 pp.
15
J. P. Dismukes, L. Ekstrom, E. F. Steigmeier, I. Kuman, and D. S. Beers,
Thermal + Electrical Properties of Heavily Doped Ge-Si Alloys up to 1300
Degrees K, J. Appl. Phys., 35, 2899 (1964).
16
H. R. Meddins and J. E. Parrott, Thermal and Thermoelectric Properties
of Sintered Germanium-silicon Alloys, J. Phys. C Solid State Phys., 9, 1263
76 (1976).
17
D. M. Rowe and V. S. Shukla, The Eect of Phonon-grain Boundary
Scattering on the Lattice Thermal-conductivity and Thermoelectric Conversion
Eciency of Heavily Doped Fine-grained, Hot-pressed Silicon Germanium
Alloy, J. Appl. Phys., 52, 74216 (1981).
18
C. B. Vining, W. Laskow, J. O. Hanson, R. R. Van der Beck, and P. D.
Gorsuch, Thermoelectric Properties of Pressure-sintered Si0.8Ge0.2 Thermoelectric Alloys, J. Appl. Phys., 69, 433340 (1991).
19
I. Terasaki, Y. Sasago, and K. Uchinokura, Large Thermoelectric Power
in NaCo2O4 Single Crystals, Phys. Rev. B, 56, R126857 (1997).
20
R. Funahashi, I. Matsubara, H. Ikuta, T. Takeuchi, U. Mizutani, and S.
Sodeoka, An Oxide Single Crystal With High Thermoelectric Performance in
Air, Jpn. J. Appl. Phys., 39, L11279 (2000).
21
A. C. Masset, C. Michel, A. Maignan, M. Hervieu, O. Toulemonde, F.
Studer, B. Raveau, and J. Hejtmanek, Mist-layered Cobaltite With an
Anisotropic Giant Magnetoresistance: Ca3Co4O9, Phys. Rev. B, 62, 16675
(2000).
22
Y. Miyazaki, K. Kudo, M. Akoshima, Y. Ono, Y. Koike, and T. Kajitani,
Low-temperature Thermoelectric Properties of the Composite Crystal
[Ca2CoO3.34](0.614)[CoO2], Jpn. J. Appl. Phys., 39, L5313 (2000).
23
N. F. Mott, and E. A. Davis, Electronic Processes in Non-Crystalline
Materials. Clarendon Press, Oxford, 1971.
24
T. Takeuchi, T. Kondo, T. Takami, H. Takahashi, H. Ikuta, U. Mizutani,
K. Soda, R. Funahashi, M. Shikano, M. Mikami, S. Tsuda, T. Yokoya, S. Shin,
and T. Muro, Contribution of Electronic Structure to the Large Thermoelectric
Power in Layered Cobalt Oxides, Phys. Rev. B, 69, 125410, 9pp (2004).
25
J. M. Ziman, Principles of the Theory of Solids. Cambridge University
Press, Cambridge, 1972.
26
R. Funahashi, I. Matsubara, and S. Sodeoka, Thermoelectric Properties
of Bi2Sr2Co2Ox Polycrystalline Materials, Appl. Phys. Lett., 76, 23857
(2000).
27
M. Shikano and R. Funahashi, Electrical and Thermal Properties of Single-crystalline (Ca2CoO3)(0.7)CoO2 With a Ca3Co4O9 Structure, Appl. Phys.
Lett., 82, 18513 (2003).
28
E. Guilmeau, M. Mikami, R. Funahashi, and D. Chateigner, Synthesis
and Thermoelectric Properties of Bi2.5Ca2.5Co2Ox Layered Cobaltites, J.
Mater. Res., 20, 10028 (2005).
29
T. Kumagai, S. Horii, T. Uchikoshi, T. S. Suzuki, Y. Sakka, T. Okamoto,
J. Shimoyama, and K. Kishio, Development of Thermoelectric Bi-Based Cobaltites with an Easy Axis of Magnetization Parallel to the C-Axis for Magnetic Alignment, Jpn. J. Appl. Phys., 44, 12636 (2005).
30
H. Itahara, C. Xia, J. Sugiyama, and T. Tani, Fabrication of Textured
Thermoelectric Layered Cobaltites with Various Rock Salt-type Layers by
Using b-Co(OH)2 Platelets as Reactive Templates, J. Mater. Chem., 14, 616
(2004).
31
A. Sotelo, E. Guilmeau, S. Rasekh, M. A. Madre, S. Marinel, and J. C.
Diez, Enhancement of the Thermoelectric Properties of Directionally Grown
Bi-Ca-Co-O Through Pb for Bi Substitution, J. Euro. Ceram. Soc., 30, 1815
20 (2010).
32
E. Guilmeau, D. Chateigner, J. Noudem, R. Funahashi, S. Horii, and B.
Ouladdiaf, Rietveld Texture Analysis of Complex Oxides: Examples of
Polyphased Bi2223 Superconducting and Co349 Thermoelectric Textured
Ceramics Characterization Using Neutron and X-ray Diraction, J. App.
Crystallography, 38, 199210 (2005).
33
H. Itahara and T. Tani, Highly-textured Thermoelectric Oxide Polycrystals Synthesized by the Reactive Templated Grain Growth (RTGG) Method,
Toyota R&D Review of Toyota CRDL, 39 [1] 6370 (2004).
34
H. Itahara, C. Xia, Y. seno, J. Sugiyama, T. Tani, and K. Koumoto,
Synthesis of Textured Thermoelectric Layered Cobaltites by Reactive Templated Grain Growth; pp. 18891 in Proceedings of 22nd International conference on Thermoelectrics (ICT2003), La Grande Motte, 2003.
35
J.-W. Moon, D. Nagahama, Y. Masuda, W.-S. Seo, and K. Koumoto,
Anisotropic Thermoelectric Properties of Crystal-Axis Oriented Ceramics of
Layer-Structured Oxide in the Ca-Co-O System, J. Ceram. Soc. Jpn., 109,
64750 (2001).
36
T. Tani, H. Itahara, C. Xia, and J. Sugiyama, Topotactic Synthesis of
Highly-textured Thermoelectric Cobaltites, J. Mater. Chem., 13, 18657
(2003).
37
H. Itahara, W. S. Seo, S. Lee, H. Nozaki, T. Tani, and K. Koumoto,
The Formation Mechanism of a Textured Ceramic of Thermoelectric
[Ca2CoO3]0.62[CoO2] on a-Co(OH)2 Templates Through In Situ Topotactic
Conversion, J. Am. Chem. Soc., 127, 636773 (2005).
38
H. Itahara, J. Sugiyama, and T. Tani, Enhancement of Electrical Conductivity in Thermoelectric [Ca2CoO3]0.62[CoO2] Ceramics by Texture
Improvement, J. J. Appl. Phys., 43, 51349 (2004).
39
Y. Zhou, I. Matsubara, S. Horii, T. Takeuchi, R. Funahashi, M. Shikano,
J. Shimoyama, K. Kishio, W. Shin, N. Izu, and N. Murayama, Thermoelec-
20
tric Properties of Highly Grain-aligned and Densied Co-based Oxide Ceramics, J. Appl. Phys., 93, 26538 (2003).
40
R. Funahashi, S. Urata, T. Sano, and M. Kitawaki, Enhancement of
Thermoelectric Figure of Merit by Incorporation of Large Single Crystals in
Ca3Co4O9 Bulk Materials, J. Mater. Res., 18, 164651 (2003).
41
E. Guilmeau, H. Itahara, D. Chateigner, D. Grebille, and T. Tani,
Quantitative Texture Analysis of Grain-aligned Ca2CoO3.0.62.CoO2. Ceramics Processed by the Reactive-templated Grain Growth Method, J. Appl.
Phys., 97, 064902 (2005).
42
M. Prevel, S. Lemonnier, Y. Klein, S. Hebert, D. Chateigner, B. Ouladdiaf, and J. G. Noudem, Textured Ca3Co4O9 Thermoelectric Oxides by Thermoforging Process, J. Appl. Phys., 98, 093706 (2005).
43
E. Guilmeau, R. Funahashi, M. Mikami, K. Chong, and D. Chateigner,
Thermoelectric Propertiestexture Relationship in Highly Oriented Ca3Co4O9
Composites, Appl. Phys. Lett., 85, 14902 (2004).
44
Y. H. Liu, Y. H. Lin, Z. Shi, C. W. Nan, and Z. J. Shen, Preparation of
Ca3Co4O9 and Improvement of its Thermoelectric Properties by Spark Plasma
Sintering, J. Am. Ceram. Soc., 88, 133740 (2005).
45
H. Q. Liu, Y. Song, S. N. Zhang, X. B. Zhao, and F. R. Wang, Thermoelectric Properties of Ca3xYxCo4O9+d Ceramics, J. Phys. Chem. Solids, 70,
6003 (2009).
46
J. G. Noudem, D. Kenfaui, D. Chateigner, and M. Gomina, Granular
and Lamellar Thermoelectric Oxides Consolidated by Spark Plasma Sintering, J. Electron. Mater., 40, 11006 (2011).
47
R. Funahashi, Waste Heat Recovery Using Thermoelectric Oxide Materials, Sci. Adv. Mater., 3, 6826 (2011).
48
S. Li, R. Funahashi, I. Matsubara, H. Yamada, K. Ueno, and S. Sodeoka,
Synthesis and Thermoelectric Properties of the New Oxide Ceramics
Ca3xSrxCo4O9+d (x=0.01.0), Ceram. Int., 27, 3214 (2001).
49
L. B. Wang, A. Maignan, D. Pelloquin, S. Hebert, and B. Raveau,
Transport and Magnetic Properties of Ca3xSrxCo4O9, J. Appl. Phys., 92,
1248 (2002).
50
M. Mikami, K. Chong, Y. Miyazaki, T. Kajitani, T. Inoue, S. Sodeoka,
and R. Funahashi, Bi-Substitution Eects on Crystal Structure and Thermoelectric Properties of Ca3Co4O9 Single Crystals, J. J. Appl. Phys., 45, 41316
(2006).
51
Y. Miyazaki, Y. Suzuki, M. Onada, Y. Ishii, Y. Morii, and T. Kajitani,
Modulated Structure of Mist Layered Cobalt Oxide [(Ca0.90Bi0.10)2(Co0.95Bi0.05)O3]pCoO2, J. J. Appl. Phys., 43, 62528 (2004).
52
I. Matsubara, R. Funahashi, T. Takeuchi, and S. Sodeoka, Thermoelectric Properties of Spark Plasma Sintered Ca2.75Gd0.25Co4O9 Ceramics,
J. Appl. Phys., 90, 4625 (2001).
53
J. Pei, G. Chen, N. Zhou, D. Q. Lu, and F. Xiao, High Temperature
Transport and Thermoelectric Properties of Ca3xErxCo4O9+d, Phys. B, 406,
5714 (2011).
54
Y. Wang, Y. Sui, J. Cheng, X. Wang, and W. Su, Comparison of the
High Temperature Thermoelectric Properties for Ag-doped and Ag-added
Ca3Co4O9, J. Alloys Compounds, 477, 81721 (2009).
55
E. N. Nikitin, V. I. Tarasov, and P. V. Tamarin, Thermal and Electrical
Properties of the Higher Manganese Silicide from 4.2 to 1300K and its Structure, Sov. Phys. Solid State, 11, 1879 (1969).
56
E. N. Nikitin, V. I. Tarasov, A. A. Andreev, and P. V. Tamarin, Electrical Properties of the Single-Crytsal Highest Silicide of Manganese, Sov. Phys.
Solid State, 11, 27578 (1970).
57
I. Nishida, Semiconducting Properties of Nonstoichiometric Manganese
Silicides, J. Mater. Sci., 7, 43540 (1970).
58
M. I. Fedorov and V. K. Zaitsev, Thermoelectrics of Transition Metal
Silicides; pp. 110, chapter 31 in Thermoelectrics Handbook, Edited by D. M.
Rowe. CRC Press, Boca Raton, FL, 2006.
59
U. Gottlieb, A. Sulpice, B. Lambert-Andron, and O. Laborde, Magnetic
Properties of Single Crystalline Mn4Si7, J. Alloys Compd., 361 [1] 38
(2003).
60
O. Schwomma, H. Nowotny, and A. Wittmann, Die Kristallarten
RuSi1.5, RuGe1.5 und MnSi~1.7, Monatsh. Chem., 94 [68] 15 (1963).
61
O. Schwomma, A. Preisinger, H. Nowotny, and A. Wittmann, Die
Kristallstruktur von Mn11Si19 und deren Zusammenhang mit Disilicid-Typen,
Monatsh. Chem., 95 [152] 737 (1964).
62
H. W. Knott, M. H. Mueller, and L. Heaton, The Crystal Structure of
Mn15Si26, Acta Cryst., 23 [54] 955 (1967).
63
G. Flieher, H. Vollenkle, and H. Nowotny, Die Kristallstruktur von
Mn15Si26, Monatsh. Chem., 98 [217] 39 (1967).
64
G. Zwilling and H. Nowotny, Zur Struktur der Defekt-Mangansilicide,
Monatsh. Chem., 104 [66] 875 (1973).
65
H. Q. Ye and S. Amelinckx, High-Resolution Electron Microscopic
Study of Manganese Silicides MnSi2-x, J. Solid State Chem., 61, 839 (1986).
66
H. Okamoto, Mn-Si (Manganese-Silicon), J. Phase Equilibria., 12 [4]
5057 (1991).
67
A. Yamamoto, Determination of Composite Crystal Structures and
Superspace Groups, Acta Cryst. A, 49 [83] 146 (1993).
68
Y. Miyazaki, D. Igarashi, K. Hayashi, T. Kajitani, and K. Yubuta,
Modulated Crystal Structure of Chimney-Ladder Higher Manganese Silicides
MnSic (c~ 1.74), Phys. Rev. B, 78, 214104, 8pp (2008).
69
Y. Imai, M. Mukaida, and T. Tsunoda, Comparison of Density of States
of Transition Metal Disilicides and Their Related Compounds Systematically
Calculated by a First-Principle Pseudopotential Method Using Plane-Wave
Basis, Intermetallics, 8, 38190 (2000).
70
Y. Imai and A. Watanabe, Consideration of the Validity of the 14
Valence Electron Rule for Semiconducting Chimney-Ladder Phase
Compounds, Intermetallics, 13, 23341 (2005).
Vol. 96, No. 1
71
D. B. Migas, V. L. Shaposhnikov, A. B. Filonov, V. E. Borisenko, and N.
N. Dorozhkin, Ab Initio Study of the Band Structures of Dierent Phases of
Higher Manganese Silicides, Phys. Rev. B, 77, 075205, 9pp (2008).
72
V. K. Zaitsev, S. V. Ordin, V. I. Tarasov, and M. I. Fedorov, Optical
Properties of Higher Manganese Silicide, Sov. Phys. Solid State, 21, 14546
(1979).
73
I. Kawasumi, M. Sakata, I. Nishida, and K. Masumoto, Crystal Growth
of Manganese Silicide, MnSi~1.73 and Semiconducting Properties of Mn15Si26,
J. Mater. Sci., 16, 35566 (1981).
74
M. Tanaka, Q. Zhang, M. Takeguchi, and K. Furuya, In Situ Characterization of Mn and Fe Silicide Islands on Silicon, Surf. Sci., 532-535, 94651
(2003).
75
M. Rebien, W. Henrion, H. Angermann, and S. Teichert, Interband
Optical Properties of Higher manganese Silicide Thin Films, Appl. Phys.
Lett., 81, 64951 (2002).
76
C. Krontiras, K. Pomoni, and M. Roilos, Resistivity and the Hall Eect
for Thin MnSi1.73 Films, J. Phys. D Appl. Phys., 21, 50912 (1988).
77
Y. Miyazaki, Y. Saito, K. Hayashi, K. Yubuta, and T. Kajitani, Preparation and Thermoelectric Properties of a Chimney-Ladder (Mn1-xFex)Sic (c~1.7)
Solid Solution, Jpn. J. Appl. Phys., 50, 035804, 5pp (2011).
78
M. Yoshikura and T. Itoh, Thermoelectric Properties of Higher Manganese Silicide Compounds Synthesized by MG-PDS Method, J. Jpn. Soc.
Powder Powder Metallurgy., 57, 2426 (2010) [in Japanese].
79
Y. Kikuchi, Y. Miyazaki, Y. Saito, K. Hayashi, K. Yubuta, and T. Kajitani, Enhanced Thermoelectric Performance of a Chimney-Ladder (Mn1-xCrx)
Sic (c ~1.7) Solid Solution, Jpn. J. Appl. Phys.,, 51, 085801, 5pp (2012).
80
I. Aoyama, H. Kaibe, L. Rauscher, T. Kanda, M. Mukoujima, S. Sano,
and T. Tsuji, Doping Eects on Thermoelectric Properties of Higher
Manganese Silicides (HMSs, MnSi1.74) and Characterization of Thermoelectric
Generating Module using p-Type (Al, Ge and Mo)-doped HMSs and n-Type
Mg2Si0.4Sn0.6 Legs, Jpn. J. Appl. Phys., 44, 427581 (2005).
81
E. N. Nikitin and V. I. Trasov, Electrical Properties of Solid Solutions
Based on Higher Silicides of Manganese, Sov. Phys. Solid State, 13, 29389
(1971).
82
V. I. Tarasov, E. N. Nikitin, and L. N. Shumilova, Conductivity of the
Solid Solution System Mn1-xFexSi1.7, Izv. Akad. Nauk SSSR Neorg. Mater.,
11, 103840 (1975) [in Russian].
83
V. K. Zaitsev, V. I. Tarasov, and A. A. Adilbekov, Metal-Nonmetal
Tarnsition in Compensated Manganese Silicide, Sov. Phys. Solid State, 17,
3701 (1975).
84
Y. Wang, N. S. Rogado, R. J. Cava, and N. P. Ong, Spin entropy as the
likely source of enhanced thermopower in NaxCo2O4, Nature, 423, 4258
(2003).
85
G. Chen, G. Dresselhaus, M. S. Dresselhaus, J. P. Fleural, and T. Caillat,
Recent Developments in Thermoelectric Materials, Int. Mater. Rev., 48, 45
66 (2003).
86
B. C. Raveau, C. Martin, and A. Maignan, What About the Role of B
Elements in the CMR Properties of ABO3 Perovskites?, J. Alloys and Compds., 275-277, 461467 (1998).
87
T. Kobayashi, H. Takizawa, T. Endo, T. Sato, and M. Shimada, MetalInsulator-Transition and Thermoelectric Properties in the System (R1-XCax)
MnO3-Delta(R-Tb, Ho, Y)., J. Solid State Chem., 92 [1] 116129 (1991).
88
W. Kobayashi, I. Terasaki, M. Mikami, R. Funahashi, T. Nomura, and
T. Katsufuji, Universal Charge Transport of the Mn Oxides in the High
Temperature Limit., J. Appl. Phys., 95 [11] 68256827 (2004).
89
M. Ohtaki, H. Koga, T. Tokunaga, K. Eguchi, and H. Arai, Electrical
Transport Properties and High-Temperature Thermoelectric Performance of
(Ca0.9M0.1)MnO3 (M = Y, La, Ce, Sm, In, Sn, Sb, Pb, Bi)., J. Solid State
Chem., 120, 105111 (1995).
90
L. Pi, S. Hebert, C. Martin, A. Maignan, and B. Raveau, Comparison of
CaMn1-xRuxO3 and CaMn1-yMoyO3 perovskites., Phys. Rev. B, 67, 024430
024437 (2003).
91
P. X. Thao, T. Tsuji, H. Masamichi, and Y. Yamagura, High Temperature Thermoelectric Properties of Ca1-xDyxMnO2.98, J. Ceram. Soc. Jpn., 111,
544547 (2003).
92
G. Xu, R. Funahashi, Q. Pu, B. Liu, R. Tao, G. Wang, and Z. Ding,
High-Temperature Transport Properties of Nb and Ta Substituted CaMnO3
System, Solid State Ion, 171, 147151 (2004).
93
M. Miclau, S. Hebert, R. Retoux, and C. Martin, Inuence of A-site
Cation Size on Structural and Physical Properties in Ca1-xSrxMn0.96Mo0.04O3:
A Comparison of the x=0.3 and 0.6 Compounds, J. Solid State Chem., 178
[4] 11041111 (2005).
94
D. Flahaut, T. Mihara, R. Funahashi, N. Nabeshima, K. Lee, H. Ohta,
and K. Koumoto, Thermoelectrical Properties of A-site Substituted Ca1xRexMnO3 system, J. Appl. Phys., 100, 084911, 4pp (2006).
95
R. Robert, D. Logvinovich, M. H. Aguirre, S. G. Ebbinghaus, L. Bocher,
P. Tomes, and A. Weidenka, Crystal Structure, Morphology and Physical
Properties of LaCo1xTixO3d Perovskites Prepared by a Citric Acid Assisted
Soft Chemistry Synthesis, Acta Mater., 58, 68091 (2010).
96
A. Weidenka, R. Robert, M. H. Aguirre, T. Lippert, and S. Canulescu,
Development of Thermoelectric Oxides Forrenewable Energy Conversion
Technologies, Renewable Energy, 33, 3427 (2008).
97
E. Krupicka, A. Reller, and A. Weidenka, Morphology of Nanoscaled
LaMO3-particles (M=Mn, Fe, Co, Ni) Derived by Citrate Precursors in Aqueous and Alcoholic Solvents, Cryst. Eng., 5, 195202 (2002).
98
L. Bocher, R. Robert, M. H. Aguirre, S. Malo, S. Hebert, A. Maignan,
and A. Weidenka, Thermoelectric and Magnetic Properties of Perovskitetype Manganate Phases Synthesised by Ultrasonic Spray Combustion (USC),
Solid State Sci., 10 [4] 496501 (2008).
January 2013
Energy Harvesting
99
A. Weidenka, Preparation and Application of Nanostructured Perovskite Phases, Adv. Eng. Mater., 6, 70914 (2004).
100
G. Kotliar and D. Vollhardt, Strongly Correlated Materials: Insights
From Dynamical Mean-Field Theory, Phys. Today, 57, 539 (2004).
101
W. Koshibae and S. Maekawa, Eect of Spin and Orbital on
Thermopower in Strongly Correlated Electron Systems, J. Mag. Mag.
Mater., 258259 21618 (2003).
102
W. Koshibae, K. Tsutsui, and S. Maekawa, Thermopower in Cobalt
Oxides, Phys.Rev. B, 62, 686972 (2000).
103
R. R. Heikes, R. C. Miller, and R. Mazelsky, Magnetic and Electrical
Anomalies in LaCoO3, Physica B Condensed Matter., 30, 16008 (1964).
104
P. Migiakis, J. Androulakis, and J. Giapintzakis, Thermoelectric Properties of LaNi1xCoxO3 Solid Solution, J. Appl. Phys., 94, 761620 (2005).
105
G. Chen, Phonon Heat Conduction in Nanostructures, Int. J. Thermal
Sci., 39, 471 (2000).
106
L. Bocher, R. Robert, M. H. Aguirre, and A. Weidenka, Thermoelectric Perovskite-Type Oxides for Geothermal and Solar Energy Conversion;
pp. 12430 in Proceedings of the 4th European Conference on Thermoelectrics,
ECT Cardi Wales, 2006.
107
P. Tomes, R. Robert, M. Trottmann, L. Bocher, M. Aguirre, J. Hejtmanek, and A. Weidenka, Synthesis and Characterization of New Ceramic
Thermoelectrics Implemented in a Thermoelectric Oxide Module, A. J. Electron. Mater., 39, 1696 (2010).
108
H. E. Weaver, Dielectric Properties of Single Crystals of SrTiO3 at Low
Temperatures, J. Phys. Chem. Sol., 11, 2747 (1959).
109
J. E. Geusic, S. K. Kurtz, L. G. Vanuitert, and S. H. Wemple, Electrooptic Properties of Some ABO3 Perovskites in the Paraelectric Phase, Appl.
Phys. Lett., 4, 1413 (1964).
110
H. Uwe and T. Sakudo, Stress-induced Ferroelectricity and Soft Phonon
Modes in SrTiO3, Phys. Rev. B, 13, 27186 (1976).
111
Y. P. Guo, K. Kakimoto, and H. Ohsato, Dielectric and Piezoelectric
Properties of Lead-free (Na0.5K0.5)NbO3-SrTiO3 Ceramics, Solid State Commun., 129, 27984 (2004).
112
J. F. Schooley, W. R. Hosler, and M. L. Cohen, Superconductivity in
Semiconducting SrTiO3, Phys. Rev. Lett., 12, 4745 (1964).
113
X. D. Wu, D. Dijkkamp, S. B. Ogale, A. Inam, E. W. Chase, P. F. Miceli,
C. C. Chang, J. M. Tarascon, and T. Venkatesan, Laser Induced Deposition
of YBa2Cu3O7-x Thin Films, Appl. Phys. Lett., 51, 8613 (1987).
114
T. Riste, S. Ej, K. Otnes, and J. Feder, Critical Behavior of SrTiO3 near
the 105 K Phase Transition, Solid State Commun., 9, 14558 (1971).
115
K. Uchida, S. Tsuneyuki, and T. Schimizu, First-principles Calculations
of Carrier-doping Eects in SrTiO3, Phys. Rev. B, 68, 17410712 (2003).
116
H. P. R. Frederikse, W. R. Thurber, and W. R. Hosler, Electronic
Transport in Strontium Titanate, Phys. Rev., 134, A4425 (1964).
117
R. Moos, A. Gnudi, and K. H. Hardtl, Thermopower of Sr1-xLaxTiO3
Ceramics, J. Appl. Phys., 78, 50427 (1995).
118
A. F. Joe, Physik der Halbleiter (Physics of Semiconductors). AkademieVerlag, Berlin, Germany, 1958, pp. 292 (in German).
119
M. Onoda and S. Tsukahara, The Upper Limit of Thermoelectric Power
Factors in the MetalBand-insulator Crossover of the Perovskite-type Oxygen
Decient System SrTiO3-d/2, J. Phys. Condens. Matter., 23, 045604, 7pp
(2011).
120
T. Okuda, K. Nakanishi, S. Miyasaka, and Y. Tokura, Large Thermoelectric Response of Metallic Perovskites: Sr1-xLaxTiO3(0 x 0.1), Phys.
Rev. B, 63, 113104, 4pp (2001).
121
H. Muta, K. Kurosaki, and S. Yamanaka, Thermoelectric Properties of
Reduced and La-doped Single-crystalline SrTiO3, J. Alloy. Compd., 392, 306
9 (2005).
122
S. Ohta, T. Nomura, H. Ohta, and K. Koumoto, High-temperature Carrier Transport and Thermoelectric Properties of Heavily La- or Nb-doped
SrTiO3 Single Crystals, J. Appl. Phys., 97, 034106, 4pp (2005).
123
Z. H. Dughaish, Lead Telluride as a Thermoelectric Material for
Thermoelectric Power Generation, Phys. B Condens. Matter., 322, 20523
(2002).
124
S. Ohta, T. Nomura, H. Ohta, M. Hirano, H. Hosono, and K. Koumoto,
Large Thermoelectric Performance of Heavily Nb-doped SrTiO3 Epitaxial
Film at High Temperature, Appl. Phys. Lett., 87, 092108, 3pp (2005).
125
K. Kato, M. Yamamoto, S. Ohta, H. Muta, K. Kurosaki, S. Yamanaka, H.
Iwasaki, H. Ohta, and K. Koumoto, The Eect of Eu Substitution on Thermoelectric Properties of SrTi0.8Nb0.2O3, J. Appl. Phys., 102, 116107, 3pp (2007).
126
C. Yu, M. L. Scullin, M. Huijben, R. Ramesh, and A. Majumdar,
Thermal Conductivity Reduction in Oxygen-decient Strontium Titanates,
Appl. Phys. Lett., 92, 191911, 3pp (2008).
127
J. Ravichandran, W. Siemons, D. W. Oh, J. T. Kardel, A. Chari, H.
Heijmerikx, M. L. Scullin, A. Majumdar, R. Ramesh, and D. G. Cahill,
High-temperature Thermoelectric Response of Double-doped SrTiO3 Epitaxial Films, Phys. Rev. B, 82, 165126, 5pp (2010).
128
S. Ohta, H. Ohta, and K. Koumoto, Grain Size Dependence of Thermoelectric Performance of Nb-doped SrTiO3 Polycrystals, Jpn. J. Ceram. Soc.,
114 [1] 1025 (2006).
129
H. Muta, K. Kurosaki, and S. Yamanaka, Thermoelectric Properties of
Doped BaTiO3-SrTiO3 Solid Solution, J. Alloys Compd., 368, 224 (2004).
130
M. Yamamoto, H. Ohta, and K. Koumoto, Thermoelectric Phase
Diagram in a CaTiO3-SrTiO3-BaTiO3 System, Appl. Phys. Lett., 90, 072101,
3pp (2007).
131
S. N. Ruddlesden and P. Popper, New compounds of the K2NiF4
Type, Acta Cryst allogr., 10, 5389 (1957).
132
S. N. Ruddlesden and P. Popper, The Compound Sr3Ti2O7 and its
Structure, Acta Cryst allogr., 11, 545 (1958).
21
133
Y. Wang, K. Hyoung Lee, H. Ohta, and K. Koumoto, Thermoelectric
Properties of Electron-doped SrO(SrTiO3)n (n=1,2) Ceramics, J. Appl. Phys.,
105, 103701, 6pp (2009).
134
N. Wang, H. C. He, Y. S. Ba, C. L. Wan, and K. Koumoto,
Thermoelectric Properties of Nb-doped SrTiO3 Ceramics Enhanced by Potassium Titanate Nanowires Addition, Jpn. J. Ceram. Soc., 118, 1098101
(2010).
135
N. Wang, H. Li, Y. Ba, Y. Wang, C. Wan, K. Fujinami, and K. Koumoto, Eects of YSZ Additions on Thermoelectric Properties of Nb-doped
Strontium Titanate, J. Electro. Mater., 39, 177781 (2010).
136
N. Wang, L. Han, H. C. He, Y. S. Ba, and K. Koumoto, Eects of
Mesoporous Silica Addition on Thermoelectric Properties of Nb-doped
SrTiO3, J. Alloys Compd., 497, 30811 (2010).
137
A. I. Hochbaum, R. Chen, R. D. Delgado, W. Liang, E. C. Garnett, M.
Najarian, A. Majumdar, and P. Yang, Enhanced Thermoelectric Performance
of Rough Silicon Nanowires, Nature, 451, 1637 (2008).
138
Y. F. Wang, K. Fujinami, R. Z. Zhang, C. L. Wan, N. Wang, Y. S. Ba,
and K. Koumoto, Interfacial Thermal Resistance and Thermal Conductivity
in Nanograined SrTiO3, Appl. Phys. Exp., 3, 031101, 3pp (2010).
139
D. G. Cahill, S. K. Watson, and R. O. Pohl, Lower Limit to the Thermal
Conductivity of Disordered Crystals, Phys. Rev. B, 46, 613140 (1992).
140
Y. Wang and H. Fan, Sr1xLaxTiO3 Nanoparticles: Synthesis, Characterization and Enhanced Thermoelectric Response, Scripta Materia, 65, 190
3 (2011).
141
L. D. Hicks and M. S. Dresselhaus, Thermoelectric Figure of Merit of a
One-dimensional Conductor, Phys. Rev. B, 47, 166314 (1993).
142
L. D. Hicks, T. C. Harman, X. Sun, and M. S. Dresselhaus, Experimental Study of the Eect of Quantum-well Structures on the Thermoelectric
Figure of Merit, Phys. Rev. B, 53, R104936 (1996).
143
H. Ohta, S. Kim, Y. Mune, T. Mizoguchi, K. Nomura, S. Ohta, T. Nomura, Y. Nakanishi, Y. Ikuhara, M. Hirano, H. Hosono, and K. Koumoto,
Giant Thermoelectric Seebeck Coecient of a Two-dimensional Electron Gas
in SrTiO3, Nat. Mater., 6, 12934 (2007).
144
Y. Mune, H. Ohta, K. Koumoto, T. Mizoguchi, and Y. Ikuhara,
Enhanced Seebeck Coecient of Quantum-Conned Electrons in SrTiO3/
SrTi0.8Nb0.2O3 Superlattices, Appl. Phys. Lett., 91, 192105, 3pp (2007).
145
K. H. Lee, Y. Mune, H. Ohta, and K. Koumoto, Thermal Stability of
Giant Thermoelectric Seebeck Coecient for SrTiO3/SrTi0.8Nb0.2O3 Superlattices at 900 K, Appl. Phys. Exp., 1, 015007, 3pp (2008).
146
R. Zhang, C. Wang, J. Li, and K. Koumoto, Simulation of Thermoelectric Performance of Bulk SrTiO3 with Two-Dimensional Electron Gas Grain
Boundaries, J. Am.Ceram. Soc., 93, 167781 (2010).
147
N. Shanthi and D. D. Sarma, Electronic Structure of Electron-doped
SrTiO3: SrTiO3-d and Sr1-xLaxTiO3, Phys. Rev. B, 57, 21538 (1998).
148
M. S. Dresselhaus, G. Chen, M. Y. Tang, R. G. Yang, H. Lee, D. Z.
Wang, Z. F. Ren, J. P. Fleurial, and P. Gogna, New Directions for
Low-Dimensional Thermoelectric Materials, Adv. Mater., 19, 104353
(2007).
149
W. Kim, R. Wang, and A. Majumdar, Nanostructuring Expands Thermal Limits, Nano Today, 2, 407 (2007).
150
J. N. Gillet, Y. Chalopin, and S. Volz, Atomic-Scale Three-Dimensional
Phononic Crystals With a Very Low Thermal Conductivity to Design Crystalline Thermoelectric Devices, J. Heat Transfer., 131, 043206, 10pp (2009).
151
T. Takada and K. Komatsu, O3 gas sensor of thin lm semiconductor
In2O3; pp. 6939 in Proceedings of the Fourth International Conference on
Solid State Sensors and Actuators, Tokyo, 1987.
152
I. Hamberg and C. G. Granqvist, Band-gap Widening in Heavily Sndoped In2O3, Phys. Rev. B, 30, 32409 (1984).
153
I. Hamberg and G. C. Granquist, Evaporated Sn-doped In2O3 Films:
Basic Optical Properties and Applications to Energy-ecient Windows,
J. Appl. Phys., 60, R12360 (1986).
154
K. L. Chopra, S. Major, and D. K. Pandia, Transparent Conductors
A Status Review, Thin Solid Films, 102, 146 (1983).
155
M. F. A. M. van Hest, M. S. Dabney, J. D. Perkins, D. S. Ginley, and
M. P. Taylor, Titanium-doped Indium Oxide: A High-mobility Transparent
Conductor, Appl. Phys. Lett., 87, 032111 (2005).
156
T. Koida and M. Kondo, Comparative Studies of Transparent Conductive Ti-, Zr-, and Sn-doped In2O3 Using a Combinatorial Approach, J. Appl.
Phys., 101, 063713 (2007).
157
M. F. A. M. van Hest, M. S. Dabney, J. D. Perkins, and D. S. Ginley, Highmobility Molybdenum Doped Indium Oxide, Thin Solid Films, 496, 704 (2006).
158
Y. Meng, X. L. Yang, H. X. Chen, J. Shen, Y. M. Jiang, Z. J. Zhang,
and Z. Y. Hua, A New Transparent Conductive Thin Film In2O3:Mo, Thin
Solid Films, 394, 21822 (2001).
159
X. Li, Q. Zhang, W. Miao, L. Huang, and Z. Zhang, Transparent
Conductive Oxide Thin Films of Tungsten-doped Indium Oxide, Thin Solid
Films, 515, 24714 (2006).
160
D. Berardan, E. Guilmeau, A. Maignan, and B. Raveau, In2O3:Ge, a
Promising n-type Thermoelectric Oxide Composite, Solid State Commun.,
146, 97101 (2008).
161
D. Berardan, E. Guilmeau, A. Maignan, and B. Raveau, Enhancement
of the Thermoelectric Performances of In2O3 by the Coupled Substitution of
M2+/Sn4+ for In3+, J. Appl. Phys., 104, 064918 (2008).
162
E. Guilmeau, D. Berardan, Ch. Simon, A. Maignan, and B. Raveau,
Tuning the Transport and Thermoelectric Properties of In2O3 Bulk Ceramics
Through Doping at In-Site, J. Appl. Phys., 106, 053715 (2009).
163
S. D. Bhame, T. Zhou, E. Guilmeau, Y. Kinemuchi, F. Delorme, and B.
Raveau, Synthesis and Thermoelectric Properties of Oxygen Decient
Fluorite Derivative Ga3xIn5+xSn2O16, J. Appl. Phys., 108, 093708 (2010).
22
Vol. 96, No. 1
164
T. Zhou, S. D. Bhame, E. Guilmeau, S. Marinel, and B. Raveau, Enhanced
Densication and Thermoelectric Performance of In4Sn3O12 by Reactive Sintering
in the In-Sn-Ga-O System, J. Am. Ceram. Soc., 94, 37337 (2011).
165
J. Choisnet, L. Bizo, R. Retoux, S. Hebert, and B. Raveau, New transparent conductors with the M7O12 ordered decient uorite structure: From
In4Sn3O12 to In5.5Sb1.5O12, J. Solid State Chem., 177, 374851 (2004).
166
W. Pitschke, J. Werner, G. Behr, and K. Koumoto, Structure and Thermoelectric Properties of Me-substituted In4Sn3O12, Me = Y and Ti, J. Solid
State Chem., 153, 34956 (2000).
167
D. D. Edwards, T. O. Mason, W. Sinlker, L. D. Marks, F. Goutenoire,
and K. R. Poeppelmeier, A Structural Investigation of Ga3-xIn5+xSn2O16,
J. Solid State Chem., 140, 24250 (1998).
168
D. D. Edwards, T. O. Mason, F. Goutenoire, and K. R. Poeppelmeier,
A New Transparent Conducting Oxide in the Ga2O3In2O3SnO2 System,
Appl. Phys. Lett., 70, 17068 (1997).
169
G. A. Slack, CRC Handbook of Thermoelectrics. CRC, Boca Raton, 1995.
170
G. J. Snyder and E. S. Toberer, Complex Thermoelectric Materials,
Nat. Mater., 7 [2] 105114 (2008).
171
C. Wan, Y. Wang, N. Wang, and K. Koumoto, Low-Thermal-Conductivity (MS)1+x(TiS2)2 (M = Pb, Bi, Sn) Mist Layer Compounds for Bulk
Thermoelectric Materials, Materials, 3 [4] 26062617 (2010).
172
C. Wan, Y. Wang, N. Wang, and K. Koumoto, Development of Novel
Thermoelectric Materials by Reduction of Lattice Thermal Conductivity, Sci.
Tech. Adv. Mater., 11 [4] 044306, 7pp (2010).
173
C. Wan, Y. F. Wang, N. Wang, W. Norimatsu, M. Kusunoki, and K.
Koumoto, Intercalation: Building a Natural Superlattice for Better Thermoelectric Performance in Layered Chalcogenides, J. Electron. Mater., 40 [5]
127180 (2011).
174
G. A. Wiegers, Mist Layer Compounds: Structures and Physical Properties, Prog. Solid State Chem., 24 [12] 1139 (1996).
175
H. Imai, Y. Shimakawa, and Y. Kubo, Large Thermoelectric Power
Factor in TiS2 Crystal With Nearly Stoichiometric Composition, Phys. Rev.
B, 64 [24] 241104, 4pp (2001).
176
G. A. Wiegers and A. Meerschaut, Structures of Mist Layer Compounds (MS)nTS2 (M=Sn, Pb, Bi, Rare Earth Metals; T=Nb, Ta, Ti, V, Cr;
1.08<n<1.23), J. Alloy. Compd., 178, 351368 (1992).
177
J. Rouxel, A. Meerschaut, and G. A. Wiegers, Chalcogenide Mist
Layer Compounds, J. Alloy. Compd., 229, 144157 (1995).
178
Y. Miyazaki, H. Ogawa, and T. Kajitani, Preparation and Thermoelectric Properties of Mist-layered Sulde [Yb1.90S2]0.62NbS2, J. J. Appl. Phys.,
43 [9AB] L1202L1204 (2004).
179
C. Chiritescu, D. G. Cahill, C. Heideman, Q. Y. Lin, C. Mortensen, N.
T. Nguyen, D. Johnson, R. Rostek, and H. Bottner, Low Thermal
Conductivity in Nanoscale Layered Materials Synthesized by the Method of
Modulated Elemental Reactants, J. Appl. Phys., 104 [3] 033533, 5pp (2008).
180
C. Heideman, N. Nyugen, J. Hanni, Q. Lin, S. Duncombe, D. C. Johnson, and P. Zschack, The Synthesis and Characterization of New
[(BiSe)(1.10)](m)[NbSe2](n), [(PbSe)(1.10)](m)[NbSe2](n), [(CeSe)(1.14)](m)[NbSe2](n)
and [(PbSe)(1.12)](m)[TaSe2](n) Mist Layered Compounds, J. Solid State
Chem., 181 [7] 17016 (2008).
181
Q. Lin, C. L. Heideman, N. Nguyen, P. Zschack, C. Chiritescu, D. G.
Cahill, and D. C. Johnson, Designed Synthesis of Families of Mistlayered Compounds, Euro. J. Solid State Inorg. Chem., 15, 23822385
(2008).
182
A. Mavrokefalos, Q. Y. Lin, M. Beekman, J. H. Seol, Y. J. Lee, H. J.
Kong, M. T. Pettes, D. C. Johnson, and L. Shi, In-plane Thermal and Thermoelectric Properties of Mist-layered [(PbSe)(0.99)](x)(WSe2)(x) Superlattice
Thin Films, Appl. Phys. Lett., 96 [18] 181908, 3pp (2010).
183
C. M. Fang, R. A. deGroot, G. A. Wiegers, and C. Haas, Electronic
Structure of the Mist Layer Compound (SnS)(1.20)TiS2: Band Structure
Calculations and Photoelectron Spectra, J. Phys. Condens. Mater., 8 [11]
16631676 (1996).
184
G. A. Wiegers, A. Meetsma, J. L. Deboer, S. Vansmaalen, and R. J.
Haange, X-Ray Crystal-Structure Determination of the Triclinic Mist
Layer Compound (SnS)1.20TiS2, J. Phys. Condens. Mater., 3 [16] 26032612
(1991).
185
J. A. Wilson, Modeling Contrasting Semimetallic Characters of TiS2 and
TiSe2, Phys. Status Solidi B, 86 [1] 1136 (1978).
186
J. J. Barry, H. P. Hughes, P. C. Klipstein, and R. H. Friend, Stoichiometry Eects in Angle-Resolved Photoemission and Transport Studies of Ti1
+xS2, J. Phys. C Solid State, 16 [2] 393402 (1983).
187
A. Meerschaut, Mist Layer Compounds, Curr. Opin. Solid State
Mater. Sci., 1 [2] 250259 (1996).
188
H. Martinez, C. Auriel, D. Gonbeau, G. Pster-Guillouzo, and A. Meerschaut, Electronic Structure of two Mist Layer Compounds: (PbS)(1.18)(TiS2)
and (PbS)(1.18)(TiS2)(2), J. Electron Spectrosc. Relat. Phenom., 95 [23] 145
158 (1998).
189
E. Guilmeau, Y. Breard, and A. Maignan, Transport and Thermoelectric Properties in Copper Intercalated TiS2 chalcogenide, Appl. Phys. Lett.,
99, 052107, 2pp (2011).
190
Y. Ohno, Electronic-Structure of the Mist-Layer Compounds PbTiS3
and SnNbS3, Phys. Rev. B, 44 [3] 12811291 (1991).
191
R. Funahashi, S. Urata, K. Mizuno, T. Kouuchi, and M. Mikami,
Ca2.7Bi0.3Co4O9/La0.9Bi0.1NiO3 Thermoelectric Devices with High Output
Power Density, Appl. Phys. Lett., 85, 1036 (2004).
192
R. Funahashi, S. Urata, T. Mihara, N. Nabeshima, and K. Iwasaki,
Power Generation Using Oxide Thermoelectric Modules, Industrial Ceram.,
28, 22733 (2008).
h
Kunihito Koumoto, He received

BS, MS, PhD, all from the University of Tokyo and served as Assist.
Prof., Lecturer, Assoc. Prof. at UT
before joining the faculty as a full
professor of School of Eng., Nagoya University in 1992. He is now
the director of Research Center for
Materials Backcasting Technology.
His research interest lies in inorganic materials chemistry, especially bioinspired processing of ceramics and thermoelectric
materials. He served as the president of the International Thermoelectric Society in 20032005 and was awarded the Fellow of
the American Ceramic Society in 2005. He has published over
350 scientic papers, 90 review articles, 50 book chapters and 50
patents.
received his Ph.D. degree by a thesis entitled in Recrystallization mechanism and superconducting property of Bi-based
superconducting oxide. He switched his research to thermoelectric oxides in 1999. Articles about p-type layered cobaltites have been reported from his group in 2000. In 2002
2007, he explored new thermoelectric oxides as a member of
JST CREST lead by Prof. Koumoto, Nagoya University. He
also started development of thermoelectric modules from
2002 and demonstrated thermoelectric generation using oxide
thermoelectric modules. In May 2010, he established a startup company (TES Newenergy) for producing and selling
thermoelectric systems. He was awarded excellent paper ward
from Journal of Japan Applied Physics and Thermoelectric
Society of Japan in 2001.
Ryoji Funahashi, Ryoji Funahashi

is a Senior Researcher of National
Institute of Advanced Industrial
Science and Technology, Kansai.
He received his B.S. and M.S.
degrees in Faculty of Science from
Nagoya University and Ph.D.
degrees in Graduate school of
engineering from Nagoya University. He got a researching post in
Osaka National Research Institute
(National Institute of Advanced Industrial Science and Technology, Kansai from 2001). The main topic of his works was
processing of Bi-Sr-Ca-Cu-O superconducting material. He
Emmanuel Guilmeau, Dr Emmanuel Guilmeau is currently a CNRS

permanent researcher in CRISMAT Laboratory (Caen, France).
After receiving his Ph.D. in Materials Science in 2003 from the University of Caen, he spent a year as
postdoctoral researcher in the
group of Dr. Ryoji Funahashi in
Osaka (Japan). In 2004, he was a
postdoc at LCIS laboratory in
Lie`ge (Belgium) and then moved to CRISMAT laboratory in
2005. His main research interests focus on the synthesis and
characterization of bulk thermoelectric materials, such as
oxides and chalcogenides.
January 2013
Energy Harvesting
Yuzuru Miyazaki graduated from

Tohoku University in 1987 with a
Bachelor degree in Materials Science. After received an M.S.
degree in Materials Science, he
joined to a research division of
Honda R&D Co. Ltd. In 1994, he
received a Ph. D. degree in Materials Science and moved to the
department of Applied Physics in
Tohoku University as a research
associate. He was honoured a JSPS post doctoral fellowship
to study abroad and worked for two years at the School of
Chemistry in the University of Birmingham under Professor
Peter P. Edwards, FRS. He was promoted to an Associate
Professor in 2004 and a Professor in 2012, both at the
department of Applied Physics in Tohoku University. His
research group has been devoted to discover new potential
thermoelectric materials, such as layered cobalt oxides,
organic compounds and transition metal silicides.
Anke Weidenka, Prof. Dr. Anke
Weidenka completed her PhD
degree in Chemistry at ETH Zurich in 2000 and received the Venia Legendi for Solid State
Chemistry and Materials Sciences
from the University of Augsburg
in 2006. She published more than
150 scientic articles on materials
research in energy conversion
technologies and was appointed
Senior Lecturer at the University of Augsburg in 2007 and
Professor at the Department for Chemistry und Bio-chemistry, University of Berne in 2008. As head of the Laboratory for Solid State Chemistry and Catalysis and member
of the steering committee for the research programme
Energy she coordinates the research on Solid State Chemistry and Catalysis, and Materials for Energy Converter
Technologies at Empa, Swiss Federal Laboratories for
Materials Science and Technology. Her research interests
comprise the development, synthesis and characterisation of
novel advanced functional materials (perovskite-type oxides
and oxynitrides, halfheuseler compounds and carbon
nanotube composite materials) for energy conversion and
storage,
i.e.
solar water
splitting,
photocatalysis,
photoelectrocatalysis, thermoelectric converters, fuels cells,
batteries and exhaust gas catalysis.
23
Yifeng Wang received his Doctors

degree of Engineering from
Nagoya University (Japan) in
2008 under the supervision of
Kunihito Koumoto. From there,
he became a post-doctor research
fellow in the eld of oxide thermoelectrics in Koumotos Lab till
2011. Currently, he is working as
an associate professor in the College of Material Science and Engineering, and the State Key Laboratory of Materials-Oriented
Chemical Engineering, Nanjing University of Technology
(China). His research interests focus on the energy-related
materials including thermoelectrics, photovoltaics, and
lithium-ion batteries.
Chunlei Wan, Chunlei Wan is
now an assistant professor in the
Graduate School of Engineering at
Nagoya University in Japan. He
received his BS and PhD degree
from Department of Materials Science and Engineering of Tsinghua
University in 2003 and 2008.
Then, he moved to Nagoya University of Japan, working as a
postdoctoral researcher, where he
became an assistant professor in April of 2012. His research
interests cover both phonon and electron-transport phenomena in solid-state materials. He has extensively worked on
novel thermal-barrier coating materials and thermoelectric
materials with low thermal conductivity. Wan has coauthored more than 30 peer-reviewed publications and two
book chapters.

Thermelectric Ceramics For Energy Harvesting

Transféré par

Informations du document

Titre original

Copyright

Formats disponibles

Partager ce document

Partager ou intégrer le document

Options de partage

Avez-vous trouvé ce document utile ?

Ce contenu est-il inapproprié ?

Droits d'auteur :

Formats disponibles

Thermelectric Ceramics For Energy Harvesting

Transféré par

Droits d'auteur :

Formats disponibles

See

Thermoelectric Ceramics for Energy Harvesting

142 PUBLICATIONS 1,594 CITATIONS

132 PUBLICATIONS 1,763 CITATIONS

Nanjing Tech University

314 PUBLICATIONS 4,059 CITATIONS

80 PUBLICATIONS 802 CITATIONS

J. Am. Ceram. Soc., 96 [1] 123 (2013)

Thermoelectric Ceramics for Energy Harvesting

CRISMAT Laboratory, 14050 Caen Cedex, France

(TE) power generation is based on the

X.-D. Zhoucontributing editor

Author to whom correspondence should be addressed. e-mail: chunlei.wan@gmail.com

where ZT (= Z(Th + Tc)/2) is the dimensionless thermoelectric

Vol. 96, No. 1

Journal of the American Ceramic SocietyKoumoto et al.

Fig. 1. Schematic illustrations of cascade-type TE modules (above)

(500700 K) modules have been developed by Funahashi and

marginally metallic situation may be realized if the Fermi

Promising p-Type Materials

(1) Calcium Cobaltite, Ca3Co4O9

where k, e, and D(e) represent the Boltzmann constant, the

where TF is the Fermi temperature dened as TF = eF/k.

Fig. 2. Schematic crystallographic structure (a) and transmission

position of the whiskers determined by electron micro-probe

using high-resolution ultraviolet photoemission spectroscopy

Fig. 3. Seebeck coecient and electrical resistivity of a Co-349

Fig. 4. Temperature dependence of the Hall coecient RH (a) and

Journal of the American Ceramic SocietyKoumoto et al.

alignment of plate-like grains in the bulk materials owing to

Fig. 5. Inverse pole gure of Ca3Co4O9 calculated along the ber

Vol. 96, No. 1

More recently, spark plasma sintering (SPS) was also

Fig. 6. Temperature dependence of (a) the Seebeck coecient and

Fig. 7. SEM micrograph of a textured Co-349 sample prepared by

Fig. 8, the magnitude of the electrical resistivity is drastically

(2) Higher Manganese Silicides

Fig. 8. Temperature dependence of electrical resistivity (open

Mn15Si26,62,63 and Mn27Si46,64 were proposed as HMS phases

Vol. 96, No. 1

Journal of the American Ceramic SocietyKoumoto et al.

Fig. 10. The total and projected density of states (states/eV/cell) of

Fig. 9. (a) Modulated composite crystal structure of MnSic with a

Z point to the corresponding points in the conduction band.

sample exhibits S ~ 120130 lV/K, r ~ 500600 S/cm and

A further increase in TE performance has been expected

n-Type Material Candidates

(1) Perovskite-type Manganates

The particles from the USC process reveal a mean crystallite

Fig. 12. Transmission electron microscopic view of a typical

Journal of the American Ceramic SocietyKoumoto et al.

Fig. 13. Result of a oat-zone recrystallization experiment of

where x is the carrier concentration and g3 and g4 are the

Fig. 14. Seebeck coecient values versus T of CaMn1xNbxO3 of

Vol. 96, No. 1

cells can grow in dierent directions accommodating slight

Eg ~ 3.2 eV.115 Although pure stoichiometric STO is a band

The exploration of TE properties of STO has covered a

where h is the Planck constant.118

Journal of the American Ceramic SocietyKoumoto et al.

As is well known for semiconductors, the total thermal

Vol. 96, No. 1

Fig. 18. Typical values of ZT and thermal conductivity of STO