1 s2.0 S0042207X17300544 Main

Vacuum 146 (2017) 356e374
Contents lists available at ScienceDirect
Vacuum
journal homepage: www.elsevier.com/locate/vacuum
Recent advances in oxide thermoelectric materials and modules

Yinong Yin, Bharati Tudu 1, Ashutosh Tiwari*
Department of Materials Science and Engineering, University of Utah, Salt Lake City, UT 84102, USA
a r t i c l e i n f o a b s t r a c t
Article history: Due to the growing concern on depletion of non-renewable resources, waste heat harvesting has become
Received 13 January 2017 one of the effective approaches for solving the energy shortage issue. Oxide thermoelectric materials
Received in revised form have the advantages of low cost, environment-friendly manufacturing and chemical stability at high
4 April 2017
temperatures. However, compared to traditional thermoelectric materials, they exhibit only modest
Accepted 6 April 2017
thermoelectric properties due to their low electrical- and high thermal conductivity. Numerous studies
Available online 8 April 2017
have been done to improve their thermoelectric response by doping. These oxide materials mainly
include the p-type Ca3Co4O9 and n-type ZnO, SrTiO3, and CaMnO3. By connecting these both types of
Keywords:
Thermoelectricity
thermoelectric oxides in series, a module which is capable of generating considerable power can be
Oxides obtained. In this review, we present the progress made on p-type and n-type thermoelectric oxides in
Figure of merit recent years. We discuss the electronic structure of these oxides as it plays an important role in deter-
Thermal conductivity mining the thermoelectric properties. We also discuss the advanced modules which have been fabricated
Thermoelectric modules using these thermoelectric oxide couples.
© 2017 Elsevier Ltd. All rights reserved.
1. Introduction " pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi #

Th Tc 1 þ ZTm 1
h¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi Tc ; (1)
Energy demand is one of the major concerns to the whole world. Th 1 þ ZTm þ Th
Depletion of natural energy resources, as well as negative envi-
ronmental impacts of pollution and global warming, has stimulated where ZT is the dimensionless figure of merit which is further
researchers to look for alternative and sustainable energy har- related to the Seebeck coefficient (S), electrical conductivity (s), and
vesting methods. One of the eco-friendly though straightforward thermal conductivity (k) by Refs. [3,4]
approach is the conversion of waste heat or environmental heat
into energy. The basis of this approach is the Seebeck effect, a S2 sT S2 sT
phenomenon where a voltage is generated across a solid when ZT ¼ ¼ ; (2)
k ke þ kl
maintained under a temperature difference [1,2]. Thermoelectric
materials are thus promising candidates for solid-state energy where T is the absolute temperature, ke is the thermal conductivity
generators for converting the huge amount of industry and auto- contribution from the electrons and the holes, and kl is the corre-
mobile exhausted waste heat into electricity. sponding contribution from the phonons moving through the lat-
For thermal power generation, the energy conversion efficiency tice. The term S2 s represents the power factor which gives a
or the thermoelectric efficiency, h can be expressed in terms of the measure of the amount of energy generated at a particular tem-
temperatures of the hot side (Th ), cold side (Tc ) and their average perature. ZT plays an important role in the overall conversion ef-
(Tm ) as [3] ficiency. The dependence of conversion efficiency on the
temperature difference (Th-Tc) for different ZT values is shown in
Fig. 1a [3]. This indicates that the value of ZT for any thermoelectric
material should be at least 1 for its practical application [3]. As
evident from equation (2), the value of ZT can be improved by either
increasing the Seebeck coefficient and electrical conductivity or
* Corresponding author.
E-mail address: tiwari@eng.utah.edu (A. Tiwari).
lowering the thermal conductivity of the material. However,
1
Permanent address: Department of Physics, Jadavpur University, 700032 Kol- increasing electrical conductivity is accompanied by an increase in
kata, India. the heat transport by electrons and holes according to the
http://dx.doi.org/10.1016/j.vacuum.2017.04.015
0042-207X/© 2017 Elsevier Ltd. All rights reserved.
Y. Yin et al. / Vacuum 146 (2017) 356e374 357
Fig. 1. (a) Thermoelectric conversion efficiency as a function of temperature difference for different ZT values corresponding to the cold side temperature of 300 K. Reprinted from Z.
G. Chen, G. Han, L. Yang, L. Cheng and J. Zou, Nanostructured thermoelectric materials: Current research and future challenge, Chinese Materials Research Society. 22 (2012)
535e549, copyright (2012), with permission from Elsevier; (b) Carrier concentration dependence of Seebeck coefficient a, electrical conductivity s, thermal conductivity k and ZT.
Reprinted by permission from Macmillan Publishers Ltd: [NATURE] (G. J. Snyder and E. S. Toberer, Complex thermoelectric materials, Nat. Mater. 7 (2008) 105e114), copyright
(2008).
Wiedemann-Franz law concentration of typical broad-band materials is presented in

Fig. 1b [4]. It can be inferred that in order to obtain optimum
ke ¼ LT s; (3) thermoelectric property, a band gap of less than 10 kB T and a car-
rier concentration of ~10191021/cm3 are desired [3,16]. However,
where L is the Lorenz number, which is equal to for the non-parabolic band, the band effective mass becomes
2:44 108 W U=K 2 (neglecting the bipolar effect). This means that dependent on band gap and temperature, which consequently can
reducing the value of ke worsens the electrical conductivity which influence the temperature dependence of the Seebeck coefficient
is not desired, so the lattice thermal conductivity has to be reduced [9,17]. In the case of narrow-band materials such as transition metal
to get a lower thermal conductivity [4]. One of the most important oxides, the carriers are no longer itinerant and hopping conduction
approaches for reducing the value kl is to use the Phonon-Glass occurs. In ionic compounds, polarons (quasiparticles consisting of
Electron-Crystal (PGEC) approach [2,5,6]. PGEC is a concept charged carriers together with its surrounding lattice distortion)
where the material should have a lower thermal conductivity like are formed due to the strong interaction between carriers and
the amorphous materials such as glass, while good electronic lattices. When small polarons hop between the energetically
properties similar to the semiconductor crystals [1,6e8]. Typical inequivalent lattice sites with different vibrational energies, the
PGEC materials are skutterudites and clathrates, where oversized Seebeck coefficient is given as [18]:
voids can be filled with foreign atoms i.e. rattlers which have slower
vibrations and loose bonding energy [9e11]. The reduction of kl in DS* ET
these materials was known to be a result of the resonant phonon S ¼ þ ; (5)
e eT
scattering by vibrations of the rattlers which consequently decrease
the average phonon relaxation time [11,12]. However, recent where DS* is the average change of the material's entropy with the
studies on the clathrate, Ba8Ga16Ge30 show that the main mecha- injection of charge carriers, and ET is the average vibrational en-
nism for reduction of kl can be either a decrease in average sound ergy. The Seebeck coefficient consists of two parts: temperature-
velocity or due to the non-resonant phonon scattering [13,14]. independent (first term) and temperature-dependent (second
It has been discussed earlier that ZT can be improved by term). The first term is related to the entropy of materials, which
increasing the electrical conductivity and Seebeck coefficient. In means a disordered crystal structure contribute to high ZT. When
broad-band materials such as metals, the Seebeck coefficient in the the energies of crystal lattice are broadly distributed, the second
parabolic band model and energy-independent scattering approx- term becomes directly proportional to temperature, which means
imation can be expressed as [4,9]: the Seebeck coefficient increases linearly with temperature. It in-
dicates that the value of Z can be improved at higher temperatures
8p2 k2B * p 2=3 [18].
S¼ m T ; (4) Recently, a number of studies have been conducted on the
3eh2 3n
skutterudites, clathrates, Heusler alloys and bismuth/lead chalco-
where e is the electron charge, h is the Planck's constant, kB is the genides, most of which reported ZT value reaching 1 [6,9,10,19e23].
Boltzmann constant, n is the carrier concentration and With the development of nanostructure engineering, low-
2=3
m* ¼ NV m*b is the density-of-state effective mass (NV and m*b are dimensional thermoelectric materials have been explored which
valley degeneracy and band effective mass respectively) [15]. Thus, show better thermoelectric performance compared to their corre-
low carrier concentration, flat bands and symmetric crystal struc- sponding bulk materials due to their enhanced density of states and
ture with high degeneracy can contribute to the improvement of decreased thermal conductivity [3,23,24]. For instance, Bi2Te3/
Seebeck coefficient. However, flat bands with heavy band effective Sb2Te3 superlattices have an extraordinary ZT of 2.4 at 300 K [24].
mass and low carrier concentration are not advantageous for However, most of these thermoelectric materials are toxic and/or
electrical transport properties. The dependence of Seebeck coeffi- unstable at high temperatures [25]. In this context, metal oxides
cient, electrical conductivity and power factor on the carrier have good chemical stability and environment friendliness, which
358 Y. Yin et al. / Vacuum 146 (2017) 356e374
captivated many researchers to study their thermoelectric prop- b parameters, phonons can be scattered at the mismatched in-
erties. Initially, metal oxides were not considered good thermo- terfaces leading to a low thermal conductivity [38]. A high ther-
electric materials because of their low carrier mobility and high moelectric power is attributed to large electronic correlations and
thermal conductivity [16]. In early 90's, several works have been spin entropy [33,38]. The large contribution of the spin entropy in
reported showing good thermoelectric properties of transition the thermoelectric power can be expressed as [38]:
metal-based oxides such as NaCo2O4 and ZnO [25]. In principle,
transition metal oxides have strong electronic correlations and m k g x
¼ B ln 3 ; (6)
narrow d bands. Hence, strong spin and orbital fluctuations, as well eT e g4 1 x
as high degeneracy, can take place in these d-electron systems,
which are advantageous for improved thermoelectric performance where m is the chemical potential, g3 and g4 are respectively the
[26]. In these systems, if the t2g or eg orbitals are not fully occupied, spin-orbital degeneracy of Co3þ and Co4þand x is the
Jahn-Teller effects can be induced, which leads to lattice distortions Co4þconcentration. This contribution of spin entropy can be
producing small polarons [26,27]. Hence, some transition metal enhanced by increasing the Co4þ degeneracy and decreasing the
oxides, such as manganites and cobalt-based oxide, show a positive Co4þ concentration. The gg34 ratio is related to different spin states:
temperature dependence of electrical conductivity in the high- low-spin (LS), intermediate-spin (IS) and high-spin (HS) states of
temperature regime due to the Jahn-Teller polarons [28e31]. In the Co ions [33]. A high Seebeck coefficient, as well as high metallic
last two decades, both p-type and n-type metal oxide thermo- conductivity, occurs in Ca3Co4O9. This metallic conductivity results
electric materials have been widely investigated due to their sig- from the finite density of states at Fermi level situated at the edge of
nificant thermoelectric behavior [25]. In this review, we discuss the its narrow valence band [39,40].
progress made in the mostly studied metal oxide thermoelectrics: In 2003, M. Shikano et al. reported a high ZT of 0.87 at 973 K for
the p-type (Ca3Co4O9) and n-type (ZnO, SrTiO3, and CaMnO3) ma- single crystal Ca3Co4O9 grown by flux technique [41]. Later, Bi-
terials, during the last ten years. substituted single crystal Ca3Co4O9 was reported by M. Mikami
et al. showing the structural stress released and moderated misfit
2. P-type thermoelectric oxide: Ca3Co4O9 layers by the Bi which simultaneously increased the thermal and
electrical conductivity, leading to a slight improvement of ZT~
2.1. Thermoelectric properties of single crystal Ca3Co4O9 0.90 at 973 K [42]. Zhao et al. reported thermoelectric performance
of Ti-doped Ca3Co4O9 system [34]. They studied the in-plane and
The representatives of p-type thermoelectric oxides are layered out-of-plane thermoelectric properties of Ti- doped single crystals
cobalt oxides including NaCo2O4, Ca3Co4O9 and Bi2Sr3Co2O9 [16,25]. of Ca3Co4-xTixO9 and found a strong anisotropy in such systems,
Because of the volatility of Na and Bi at high temperatures [32,33], with much higher in-plane electrical conductivity, thermal con-
Ca3Co4O9 is the most prospective candidate for high-temperature ductivity and Seebeck coefficient compared to that of its corre-
thermoelectric applications. Generally, Ca3Co4O9 has anisotropic sponding out-of-plane values. They concluded that Ti induced spin
thermoelectric properties in the in-plane and out-of-plane di- fluctuations at low temperatures as they observed an upturn
rections, where its in-plane properties surpass the out-of-plane behavior of the out-of-plane Seebeck coefficient in the low-
properties [25,34]. The electrical conductivity in the temperature temperature regime and this behavior was impeded under a
range of 0e1000 K shows three main transitions, which include magnetic field. The decrease in carrier concentration with Ti-
short-range spin-density-wave (SDW) transition at about 63 K, doping was considered to be the cause of increase in the in-plane
Fermi-liquid to incoherent metal transition at about 140 K and electrical resistivity and Seebeck coefficient. Because of the struc-
metal-to-semiconductor transition due to formation of small po- tural distortions caused by Ti substitutions, both in-plane and out-
larons at about 510 K [35]. The single crystal of Ca3Co4O9 is of-plane thermal conductivity were decreased.
composed of CdI2-type CoO2 conduction layer and rocksalt-type
Ca2CoO3 layer (Fig. 2a [36]). Electrical transport takes place via 2.2. Thermoelectric properties of polycrystalline Ca3Co4O9 and its
the hopping of a hole from Co4þ to Co3þ, which is accompanied by a improvement
transfer of spins as seen in Fig. 2b [37]. The Ca2CoO3 layer however,
acts as a charge reservoir. Since these two sublattices have different The fabrication process for obtaining single crystals takes a long
Fig. 2. Schematic of the crystal structure of Ca3Co4O9 (blue balls represent Ca, red balls represent O and purple balls represent Co). Reproduced from T.Wu, T. A. Tyson, J. Bai, K.
Pandya, C. Jayed and D. Fischer, On the origin of enhanced thermoelectricity in Fe doped Ca3Co4O9, J. Mater. Chem. C. 1 (2013) 4114e4121 with permission of The Royal Society of
Chemistry; (b) Illustration of electrical conduction mechanism in Ca3Co4O9 (hopping of a hole from Co4þ to Co3þ takes place along with the transfer of a spin). Reprinted by
permission from Macmillan Publisher Ltd: [NATURE] (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 (2003) 425e428), copyright (2003).
time due to a slow cooling rate of ~1 K/h. Besides this, it is also

expensive to fabricate thermoelectric devices utilizing single crys-
talline materials [43]. Hence, polycrystalline Ca3Co4O9 has drawn
the attention of researchers, as it can be easily obtained by solid-
state reactions and quick fabrication technique. Pure poly-
crystalline bulk Ca3Co4O9 shows very low ZT, due to its poor out-of-
plane thermoelectric response compared to its in-plane thermo-
electric response and randomly oriented grains [44]. Therefore,
there is considerable interest in improving its thermoelectric per-
formance. High densifications, uniform grain alignment, decreasing
carrier concentration and enhanced electronic correlations can
contribute to the improvement of ZT [44e46]. Three main ap-
proaches to achieve these goals are discussed in the following.
2.2.1. Fabrication process

Initially, polycrystalline Ca3Co4O9 bulk materials or pellets were
fabricated by solid-state reactions combined with the conventional
sintering (CS) method [47]. This conventional sintering method,
however, resulted in high electrical resistivity and hence poor
thermoelectric performance [47]. Spark plasma sintering (SPS) was
therefore introduced to improve the electrical conductivity of
Ca3Co4O9. This sintering is much faster than CS because high me-
chanical pressure and pulsed heat both are applied together during
the sintering process [47]. Noudem et al. investigated the ther-
moelectric responses of Ca3Co4O9 pellets prepared by both CS and
SPS techniques [48]. The electrical resistivity values of CS samples
were almost five times higher than that of SPS samples and showed
abnormal insulating behavior below 600 K. This abnormal con-
duction was ascribed to the contributions from electrically insu-
lated inter-granular air medium which impeded the motion of the
carriers. Above 600 K, CS samples exhibited metallic transport
characteristics because grains started to connect with each other.
The Seebeck coefficient is not influenced by different fabrication
methods. The reason why SPS samples showed better electrical
properties can be figured out from the fact that SPS samples have
lamellar texture and high density as shown by their group later,
whereas a large number of pores existed in the CS samples [49]. The
scanning electron microscopy (SEM) images of the samples pre-
pared by CS and SPS techniques is shown in Fig. 3 a,b [49].
This SPS technique, however, failed to obtain high densification
in the outer region of pellets. Since the wall of the die exerts shear Fig. 3. Scanning Electron Microscopy (SEM) images of Ca3Co4O9 samples fabricated by
stress on samples, uncontrolled formation of microcrack takes (a) Conventional Sintering (CS), (b) Sparks Plasma Sintering (SPS) and (c) Sparks
place in the outer region resulting in unstable thermoelectric per- Plasma Texturing (SPT), showing different microstructures. Reprinted from J. G. Nou-
formance [49]. Therefore, sparks plasma texturing (SPT) was pro- dem, D. Kenfaui, D. Chateigner and M. Gomina, Toward the enhancement of thermo-
electric properties of lamellar Ca3Co4O9 by edge-free spark plasma texturing, Scripta
posed by Noudem's group to modify the traditional SPS technique Mater. 66 (2012) 258e260, with permission from Elsevier.
[49]. A die with a slightly larger diameter than that of samples
was utilized in the pressing process in order to get samples with
edge-free deformations. The microstructure of SPT samples is 2.2.2. Nanostructured Ca3Co4O9
shown in Fig. 3c. The SPT samples showed lamellar microstructure Thermoelectric responses of Ca3Co4O9 thin films have been
and uniform grain alignment. The value of S2 =r of SPT samples was extensively studied. Films with several-hundred-nanometer
found to be 400 mW/m-K2 at 550 C, which was 30% higher than thickness can be obtained by RF-planar magnetron sputtering or
that of SPS samples at the same temperature. pulse laser deposition [51e53]. Different types of substrates play an
Apart from SPS and SPT techniques, a high-magnetic field-sin- important role in determining the structure and epitaxial growth of
tering technique combined with cold pressing method was inves- Ca3Co4O9 films [54]. It is well established that grains of Ca3Co4O9
tigated by Huang et al. [50]. The electrical conductivity and Seebeck grow epitaxially along c-axis on the single crystal Al2O3 (0001) and
coefficient of samples sintered in the presence of 8 T magnetic field Si (100) substrate [55,56]. Kang et al. used polycrystalline Al2O3
were found to improve significantly. It was suggested that the substrate textured by SPS to control the grain sizes of Ca3Co4O9 thin
magnetic field weakened the electronic correlations and lowered films [53]. Owing to the local epitaxial growth of Ca3Co4O9, the
the effective mass leading to a higher carrier mobility. The magnetic grain size of Ca3Co4O9 was equivalent to the grain size of the sub-
field also provides additional energy to some electrons in Co4þ strate that simultaneously acted as a template. Because of the
which move to a higher energy level; thereby the average de- increased phonon scattering and uniform grain alignments, ther-
generacy of Co4þ and consequently the Seebeck coefficient value moelectric properties of those thin films were improved compared
was increased [38].
to that of the bulk materials. For the Ca3Co4O9 thin films deposited carrier mobility and spin entropy can also be modified by doping.
on polycrystalline Al2O3 substrate, they reported the S2 =r value of Substitutions at Ca-sites can modify the microstructures which can
514 mW/m-K2 at 700 C, which was higher than that of pure bulk indirectly affect the carrier mobility. Substitutions at Co-sites in
Ca3Co4O9. Additionally, Ca3Co4O9 thin films doped with metallic CoO2 layers disturb the conduction path, influence electronic cor-
elements or alkaline earth metals have also been investigated relations and change spin states. All these aforementioned changes
[51,52,57]. It has been shown that doping contributes to a decrease contribute to the enhanced thermoelectric performance of Bi or Na-
in electrical resistivity. The substitutions with aforementioned el- doped Ca3Co4O9 samples.
ements relieve internal stress of Ca3Co4O9 thin films and thus
improve their carrier mobility. The Seebeck coefficient is also re-
ported to improve by doping, which results from a decrease in
carrier concentration due to different valence states between the 2.2.5. Alkaline earth metal-doped Ca3Co4O9
dopants and the substituted elements [4]. Sr, Ba, and Mg belong to the alkaline earth metals, which possess
In addition, Ca3Co4O9 nanofibers have also been studied. two valence electrons. Their substitutions for Ca-sites can thus
Ceramic nanofibers with various diameters are effectively prepared barely change the carrier concentrations of Ca3Co4O9. Due to this
by sol-gel based electrospinning method. Yin et al. combined this isovalent character of the substitutions by alkaline earth metals, the
method with SPS technique to obtain Ca3Co4O9 ceramics composed Seebeck coefficient of Sr- or Ba-doped Ca3Co4O9 remains un-
of numerous nanofibers [58]. The average diameter of these changed at high temperatures [44,59]. Delorme et al. studied the
nanofibers was around 200 nm and each nanofiber consisted of thermoelectric properties of Ca3-xSrxCo4O9 over the temperature
randomly orientated nanocrystals whose grain sizes were around range of 650 Ke1000 K [44]. Despite any unnoticeable improve-
40 nm. Compared to the SPS samples synthesized by the conven- ment of the power factor, the value of ZT was enhanced reaching
tional sol-gel method, the thermal conductivity of SPS samples 0.22 at 1000 K owing to a significant reduction of the thermal
obtained by sol-gel based electrospinning synthesis was lower conductivity. Constantinescu et al. fabricated polycrystalline bulk
because of the increased phonon scattering at the grain boundaries. Ca2$99Ba0$01Co4O9 by the CS technique and studied its thermo-
Besides, both Seebeck coefficient and electrical conductivity of electric properties over the temperature range of 323 Ke1073 K
these samples were found to increase because of the refined [59]. According to them, substitutions of Ca by Ba improve electrical
texture. A high ZT of 0.40 was estimated at 975 K [58]. conductivity by moderating the microstructure and releasing the
internal stress. They reported a power factor of 280 mW/m-K2 at
2.2.3. Doped polycrystalline Ca3Co4O9 1073 K, which was 40% higher than that of the undoped samples
Doping can improve the thermoelectric properties of poly- fabricated by the same technique. Similarly, polycrystalline
crystalline Ca3Co4O9 by enhancing the electronic correlations, Ca2$95Mg0$05Co4O9 has been shown to exhibit lower electrical re-
tuning carrier concentrations and creating phonon-scattering sites. sistivity compared to undoped samples and therefore an improved
Doping the polycrystalline Ca3Co4O9 with substitutional elements power factor [60].
such as alkaline earth metals or rare-earth elements for Ca-site and
transition metal elements for Co-site have been widely studied
[36,44,45,59e73]. Other doping elements, such as Bi and Na have
also been reported for improving its thermoelectric response. 2.2.6. Transition-metal element-doped Ca3Co4O9
Additionally, co-doped compounds, such as Ca3Co4O9 co-doped Several studies have been done on the thermoelectric properties
with Ag and Lu have been investigated as well [74e77]. of Ca3Co4-xMxO9 (M ¼ Fe, Cu, Mn, Ni, Ti, Cr, Cd, Nb, Ag) [36,61e68].
The incorporation of transition metals into the crystal structure of
2.2.4. Bi- and Na-doped Ca3Co4O9 Ca3Co4O9 can not only tune the carrier concentration and modify
Bi-substituted Ca3Co4O9 have been reported to show improved the energy band structure to enhance the electrical transport
Seebeck coefficient and electrical conductivity [74,75]. It is because properties and Seebeck coefficient, but also shortens the average
substitutions of bivalent Ca2þ with trivalent Bi3þ not only improves mean free path of phonons to lower the thermal conductivity.
the Seebeck coefficient by reducing the hole concentrations but Amongst these transition metals, Ag, Cd and Fe are some of the
also enhances the carrier mobility by modifying the microstructure. most prospective dopant candidates for improving the thermo-
In addition to the substitution with Bi3þ at Ca-sites, substitution electric performance of polycrystalline Ca3Co4O9.
with Naþ has been investigated by Xu et al. [76]. They showed Wang et al. reported a remarkable improvement of ZT which
improved electrical conductivity (due to the augmentation of hole exceeded 0.3 at 1000 K for Ca3-xAgxCo4O9 (x ¼ 0e0.3) materials
concentration) and unexpectedly high thermal conductivity (due to [65]. Both Seebeck coefficient and electrical conductivity were
the weak phonon scattering) leading to a maximum ZT of 0.18 at found to increase at high temperatures. The electrical conductivity
1000 K. Similar kind of study was done by Huang et al. where they was enhanced by the augmentation of carrier concentration which
studied Na substitutions at Co-sites [77]. The electrical conductivity was caused by the different valencies of Agþ and Ca2þ. Seebeck
was improved by the variation of carrier density. However, they coefficient was found to increase with Ag content from 200 to
found that Na substitutions at Co-sites took place in the CoO2 230 mV/K at 1000 K. According to their study, the variation of carrier
layers, which weakened the electronic correlations and induced concentration is not the only factor which influences the Seebeck
some spin fluctuations. Therefore, there was no obvious change in coefficient. The carrier mobility is another important factor which
Seebeck coefficient for their Na-doped samples. The thermal con- influences the Seebeck coefficient. In case of Al-doped Ca3Co4O9,
ductivity was found to decrease, which was attributed to the lattice lattice expansion occurs due to the larger radius of Agþ than Ca2þ,
distortions due to the introduction of Na, since the radius of Naþ is which weakens the interaction between Co ions. Hence, the narrow
larger than the radii of Co3þ and Co4þ. The ZT value of energy band which restricts the itinerant behavior of carriers in-
Ca3Co3$9Na0$1O9 reached 0.0117 at room temperature, which was fluence the energy dependence of carrier mobility at the fermi
1.5 times higher than that of undoped samples. energy, EF . Seebeck coefficient is expressed in a more general way
In summary, substitutions by Bi are electron-doping processes by the energy dependence of both carrier concentration nðEÞ and
while substitutions by Na are hole-doping processes, both of which carrier mobility mðEÞ at EF , as shown in equation (7) (Mott expres-
lead to a change in carrier concentration. At the same time, the sion) [78]
substituted Ca3Co4O9 samples were observed to have the highest

ZT of 0.4 at 1000 K as shown in Fig. 4, which improved further with
ðpkB Þ2 T d½lnðsðEÞÞ
S¼ the Fe content. This was explained by the Fe-substitutions for Co in
3e dE E¼EF the CoO2 layer which increased the charge carriers since the
2
ðpkB Þ T 1 dnðEÞ 1 dmðEÞ average valency of Fe is lower than that of Co. At the same time,
¼ þ ; (7) addition of Fe induced lattice distortions which enhanced the
3e n dE m dE E¼EF
electronic correlations and hindered the propagation of phonons.
where sðEÞ is the energy-dependent electrical conductivity at EF . Therefore, both the electrical conductivity and Seebeck coefficient
On expressing the energy-dependent carrier concentration by the were increased, and the thermal conductivity was decreased which
effective mass, m* , this expression reduces to equation (4) for the resulted in considerable improvement of ZT. Recently T. Wu et al.
energy-independent carrier mobility. Thus, due to the strong reinvestigated the thermoelectric properties of Fe-doped Ca3Co4O9
energy-dependent scattering behavior of carriers, the energy samples [36]. However, they showed that Fe-substitutions occurred
dependence of carrier mobility and therefore Seebeck coefficient in Ca2CoO3 layers and not the CoO2 layers, where it introduces the
was enhanced. Besides, a decrease in thermal conductivity due to electrons thereby decreasing the hole concentration. Further, the
the lattice distortions in the Ag-doped samples was observed. incorporation of Fe made the structure of CoO2 layers well-ordered.
Therefore, Ag-doped Ca3Co4O9 showed improved thermoelectric Hence, the carrier mobility was increased, leading to improved
performance. They further studied Ca3Co4O9 including Ag pre- electrical transport properties.
cipitates which showed better thermoelectric performance
compared to the Ag-doped samples [66]. This was contributed by 2.2.7. Rare-earth element-doped Ca3Co4O9
the addition of the highly conductive Ag which improved the Rare-earth (R) elements consist of scandium, yttrium and the
electrical conductivity significantly. They reported a high ZT of lanthanides. The incorporation of heavy R elements into the crystal
0.5 at 1050 K for the Ca2$7Ag0$3Co4O9/Ag-10 wt% sample. structure of Ca3Co4O9 can enhance the thermoelectric properties of
Cd-doped polycrystalline Ca3Co4O9 (Ca3-xCdxCo4O9) pellets polycrystalline Ca3Co4O9. [69e71]. The substitution of trivalent
fabricated by sol-gel and SPS techniques were investigated by S. rare-earth ions (R3þ) for Ca2þ assists in improving the Seebeck
Butt et al. over the temperature range of 323 Ke1000 K [67]. With coefficient (due to a reduction in charge carriers) and suppressing
the increase in Cd contents, the electrical conductivity was the thermal conductivity (since they are heavier than Ca). Y. Wang
observed to increase first which then decreased. The maximum et al. showed that substitution by R3þ ions enhance the electronic
electrical conductivity obtained was 124.5 S/cm for the sample correlations of Ca3Co4O9 [45]. Such enhancement of electronic
Ca2$95Cd0$05Co4O9. Using Hall measurements, they showed an in- correlations was explained from the increase in the electron spe-
crease in carrier concentration with Cd content, thereby explaining cific heat coefficient g (g ¼ C/T, where C is the specific heat) ac-
the enhanced electrical conductivity in lightly doped samples. cording to Landau's Fermi liquid theory, where effective mass of
However, in heavily doped samples, increased scattering of the electrons, m* and g has the following relationship [45]:
carriers resulted in reduced carrier mobility and thus a reduction in

the electrical conductivity. Moreover, the addition of Cd suppressed p2 dNA kB m*

g ¼ ; (8)
the concentration of Co4þ existing in the CoO2 layers [38], which led 2 TF
to an enhancement of the spin entropy consequently improving the
Seebeck coefficient. The Cd also acts as a phonon scattering center, where d; NA and TF respectively denotes the doping level, Avogadro
which aids in lowering the thermal conductivity. The highest ZT number, and Fermi temperature. It is known that Ca3Co4O9 has the
they found for the Cd-substituted Ca3Co4O9 was 0.35 at 1000 K phase characteristics of fermi liquid in the low-temperature
compared to a ZT of only 0.15 for the undoped sample at the same regime. A higher value of g for the R3þ doped Ca3Co4O9 thus
temperature. means stronger electronic correlations. They also reported a
Wang et al. studied the effect of Fe, Mn and Cu doping on the noticeable improvement in Seebeck coefficient of R3þ doped
thermoelectric properties of polycrystalline Ca3Co4O9 [68]. By Ca3Co4O9 samples with the reduction in R3þ radius. The samples
fabricating samples using a cold high-pressure pressing technique, doped with Y3þ showed higher Seebeck coefficient compared to the
they found that the overall thermoelectric performance was samples doped with La3þ which was due to its enhanced electronic
improved compared to those fabricated by the CS method. Fe- correlations (Fig. 5). They attributed this to the doping-induced
Fig. 4. (a) The ZT values of undoped and Fe-, Mn- and Cu-doped Ca3Co4O9þd prepared by cold-pressed method as a function of temperature; (b) The ZT values of Mn-, Cu-doped
samples and two types of Fe-doped samples fabricated by two different methods as a function of dopants concentration. Reprinted from Y. Wang, Y. Sui, X. Wang, W. Su and X. Liu,
Enhanced high temperature thermoelectric characteristics of transition metals doped Ca3Co4O9þd by cold high-pressure fabrication, J. Appl. Phys. 107 (2010) 033708, with the
permission of AIP Publishing.
Fig. 5. (a) Seebeck coefficient of La- and Y-doped Ca3Co4O9 samples as a function of temperature. Y-doped samples show higher Seebeck coefficient than that of La-doped samples;
the inset shows decrease of carrier concentration of R-doped Ca3Co4O9 (R ¼ La, Pr, Dy and Y) with dopants concentration, (b) Plots of C/T vs T2 of sample Ca3Co4O9 and Ca3-xRxCo4O9
(R ¼ Y, x ¼ 0.2 and 0.3; R ¼ La, x ¼ 0.3). Reprinted from Y. Wang, L. Xu, Y. Sui, X. Wang, J. Cheng and W. Su, Enhanced electron correlation in rare-earth doped Ca3Co4O9, Appl. Phys.
Lett. 97 (2010) 062114, with the permission of AIP Publishing.
chemical pressure due to lattice mismatch at Ca-sites. Shanthi et al. studied the electronic structures of stoichiometric
SrTiO3, SrTiO2.875 and Sr0$875La0$125TiO3 by ab initio calculations
2.2.8. Dually doped Ca3Co4O9 [81]. According to their study, oxygen vacancy has a more signifi-
Further enhancements of ZT in polycrystalline Ca3Co4O9 have cant effect on the electronic structure at and near the fermi energy
been achieved by dual doping. Butt et al. studied Ca3Co4O9 pellets compared to the La-substitution in SrTiO3. When the distance be-
co-doped with both La and Fe which was fabricated using sol-gel tween adjacent vacancies reduces to a critical value, a small midgap
method followed by SPS technique [72]. The partial La- is formed in the bottom region of the conduction band (Fig. 6b).
substitutions at Ca-sites reduced the carrier concentration which Hence the total number of delocalized electrons decreases. A
together with the increased phonon scattering due to La and Fe similar study was done by Cuong et al. showing that oxygen va-
induced lattice distortions reduced the thermal conductivity in the cancies are inclined to form clusters reducing the density of free
La, Fe co-doped samples. Thus, they found a notable improvement electrons [83]. Therefore, substitutions of La and Nb become the
of ZT in the co-doped samples compared to the singly Fe-doped more effective approaches for improving the electrical conductivity
ones. Nong et al. investigated the thermoelectric properties of [84]. Ohta et al. showed that electrical conductivity and hence ZT
Ca3Co4O9 doubly doped with Ag and Lu into the Ca2CoO3 subsystem can be increased by increasing the carrier concentration in both La-
[73]. They found that Lu3þ completely substituted Ca2þ whereas and Nb-doped SrTiO3 (shown in Table 1) [84]. They reported a
Agþ agglomerated at the grain boundaries forming nano-sized in- maximum ZT of 0.27 at 1073 K for the heavily La-doped SrTiO3
clusions. This increased the electrical conductivity of this doubly single crystal (n ¼ 8.4 1020 cm3).
doped samples. Since the substitution of Lu3þ for Ca2þ reduced the
hole concentration, the Seebeck coefficient was enhanced. The 3.1.2. Thermoelectric properties of electron-doped SrTiO3
thermal conductivity was significantly suppressed in the heavily Due to the high degeneracy of Ti d states which are the main
Lu-doped sample Ca2$8Ag0.05Lu0.15Co4O9, which indicates that Lu3þ components of the conduction bands, electron-doped SrTiO3 sys-
has the capability to reduce thermal conductivity. So far, among all tems have large density-of-state effective mass. The strong
doubly doped Ca3Co4O9 samples, Ca2$8Ag0.05Lu0.15Co4O9 has shown electron-phonon coupling can also take place in the electron-doped
the highest ZT of 0.61 at 1118 K [73]. SrTiO3 resulting in an enhanced effective mass. Hence, electron-
doped SrTiO3 systems exhibit high Seebeck coefficient [85]. A po-
3. N-type thermoelectric oxides wer factor of 28e36 mW/cm-K at room temperature has been re-
ported for the La-doped SrTiO3 single crystal, which is comparable
3.1. SrTiO3 to the value of intermetallic Bi2Ti3 alloys [85,86]. However, because
of the high thermal conductivity of around 9e12 W/m-K at room
3.1.1. Electronic properties of stoichiometric and electron-doped temperature, the ZT of electron-doped SrTiO3 systems are very low.
SrTiO3 As seen in Table 1, the ZT of La- and Nb-doped SrTiO3 single crystals
Stoichiometric SrTiO3 has isotropic cubic perovskite structure, are less than 0.1 at room temperature [84]. To improve ZT, Wang
where oxygen anions form an octahedron with one Ti4þ ion lying at et al. made mesoporous silica (MS)-SrNb0.15Ti0$85O3 composites to
the center. The 3d t2g orbitals of Ti make a significant contribution significantly suppress the lattice thermal conductivity [87]. The
to the conduction band of SrTiO3. At G point, there are three empty addition of MS induced the formation of thermally insulating sec-
degenerate t2g subbands with different energy dispersions along ond phase at grain boundaries which improved the value of ZT in
the ky direction as shown in Fig. 6a [79]. Due to d0 configuration of Nb-doped samples to 0.165 at 900 K. They showed that the pre-
the Ti, the stoichiometric SrTiO3 with an experimental band gap of cipitates at grain boundaries effectively scatter phonons and
3.2 eV shows an insulating characteristic, with very low carrier therefore lower the lattice thermal conductivity. Inspired by this
concentration (≪1015 cm3) [80]. However, by doping electrons experiment, they subsequently prepared Nb-doped SrTiO3 with
into SrTiO3, the Fermi energy can be raised from the forbidden band yttria (Y2O3) stabilized zirconia (YSZ) nano-precipitates which
to the conduction band. Such electron-doped systems thereby showed an improved ZT of above 0.2 at the same temperature [88].
become highly conductive [81]. A strong phonon-electron coupling According to them, these nano-precipitates at grain boundaries not
can take place and induce the formation of polarons [82]. Till now, only acted as phonon-scattering centers and decreased the thermal
La, Nb-doped SrTiO3, and SrTiO3-d have been widely studied by conductivity but also promoted the growing progress of grains by
researchers aiming to improve the electrical conductivity. N. lowering the interfacial energy, which improved the carrier
Fig. 6. (a) The electronic band structure of SrTiO3 showing three unoccupied d bands at the symmetry point G along the ky direction. Reprinted by permission from Macmillan
Publishers: [NATURE] (A. Santander-Syro, O. Copie, T. Kondo, F. Fortuna, S. Pailhe, R. Weht, X. Qiu, F. Bertran, A. Nicolaou, A. Taleb-Ibrahimi, P. L. Fe'vre, G. Herranz, M. Bibes, N.
Reyren, Y. Apertet, P. Lecoeur, A. Barthe'lemy and M. J. Rozenberg, Two-dimensional electron gas with universal subbands at the surface of SrTiO3, Nature. 469 (2011) 189e194),
copyright (2011); (b) Plots of partial density of states of Ti d and O p states as a function of energy in electron-doped SrTiO3. The separation between oxygen vacancies gradually
decrease from panel A to G. Reprinted figure with permission from N. Shanthi and D. Sarma, Electronic structure of electron doped SrTiO3: SrTiO3-d and Sr1-xLaxTiO3, Phys. Rev. B. 57
(1998) 2153e2158, copyright (1998) by the American Physical Society.
Table 1
Room-temperature thermoelectric responses of La-doped and Nb-doped single crystal SrTiO3 (Reprinted from 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 (2005) 034106, with the permission of AIP Publishing).
STO s (S cm1) n (1020 cm3) m (cm2 V1 s1) S (mV K1) Ss2 (104 W m1 K2) k (W m1 K2) Z (105 K1) ZT ()
(a) La-doped (8.4 1019 cm3) 54 0.5 7.0 0.42 9.5 12 7.9 0.02
(b) La-doped (8.4 1020 cm3) 1000 6.8 9.2 0.15 23 9.1 25 0.08
(c) Nb-doped (1.6 1020 cm3) 95 1.5 6.2 0.33 10 11 9.3 0.03
(d) Nb-doped (3.3 1020 cm3) 353 3.7 6.0 0.24 20 9.6 21 0.06
mobility. Recently, their research on Nb-doped polycrystalline doping level showing a maximum of 0.37 at 973 K for the sample
SrTiO3 coated with surface modified nano-sized titania (TiO2) with highest doping (9.0 at%). Dehkordi et al. reported a significant
showed a high ZT of 0.33 at 900 K [89]. improvement of power factor in non-uniform Pr-doped SrTiO3
Apart from adding nano-precipitates in bulk electron-doped samples fabricated with solid-state reaction and SPS technique
SrTiO3, tuning the doping levels also enhances the thermoelectric [91]. Pr-rich boundaries were formed during the fabrication pro-
properties. By increasing the concentration of dopants, the carrier cess. Since, the grains of their samples were larger than the mean
concentration and effective mass increase leading to improved free path of phonons, they proposed a different phonon-scattering
power factor [84,90e92]. However, heavy doping results in the mechanism. According to them, the non-uniform distribution of
localization of electrons which in contrast impairs the electrical dopants induced structural transitions at the grain boundaries
transport properties of SrTiO3 [90e92]. Park et al. reported doping which assisted in extra phonon scatterings. The thermal conduc-
level effects of La-doped bulk SrTiO3 comprising of numerous nano- tivity was much lower compared to the previously reported values.
sized grains fabricated using chemical colloidal synthesis of nano- Along with the increase in power factor, a high ZT of 0.35 was ob-
crystals followed by SPS technique [90]. The large number of grain tained for the sample Sr0.85Pr0.15TiO3 at 773 K. A remarkable
boundaries assisted in reducing the lattice thermal conductivity. At improvement in ZT (~0.40) was achieved by Zhang et al. for the bulk
high temperatures, the ZT value increased with the increase in electron-doped SrTiO3 [92]. They prepared Nb-doped SrTiO3
samples with varying Nb concentration of 0e20 mol%. The elec- 3.1.3. Enhanced thermoelectric responses of SrTiO3 with two-
trical conductivity was enhanced due to the formation of appro- dimensional electron gas
priate amount of oxygen vacancies. Due to the trade-off between Two-dimensional electron gases (2DEG) can be created at the
Seebeck coefficient and electrical conductivity, the optimal Nb- interface between polar and non-polar surfaces [114]. The typical
doping range was 10e15 mol%. All these studies show that appro- examples of such interfaces are RTiO3/SrTiO3 (R3þ represents rare-
priate doping can contribute to a significant enhancement of ZT. earth metal ions) and LaAlO3/SrTiO3 [114]. In the case of RTiO3/
Thin films of electron-doped SrTiO3 have also been intensively SrTiO3, RTiO3 consists of alternative layers of positively charged
studied for their thermoelectric properties [82,93]. To deposit such R3þO2 and negatively charged Ti3þO4 2 , while SrTiO3 is composed
films, PLD is a powerful method. By controlling the deposition pa- of neutral Sr2þO2- and Ti4þO42 layers. 2DEG can form at the SrTiO3/
rameters, different amount of oxygen vacancies can be incorpo- RTiO3 interfaces to neutralize the positive charges of R3þO2- layer
rated into SrTiO3 thin films. In these thin films, the out-of-plane [114]. The 2DEG can also be created at the interface between
thermal conductivity can be measured by the 3u technique [93]. electron-doped wide-gap SrTiO3 and narrow-gap semiconductors
The effect of growth atmosphere on the thermoelectric properties [114]. In this case, the 2DEG is formed by a transfer of electrons into
of Nb-substituted SrTiO3 thin films has been reported by Kumar the conduction band of semiconductor across the interface, from
et al. [93]. They grew epitaxial stoichiometric Nb-doped SrTiO3 thin the donors with higher conduction band edge [114]. Since the
films on LaAlO3 (LAO) substrates under an oxygen pressure of electrons are separated from their donors, the ionized impurity
0.027 mbar. Oxygen vacancies were introduced into SrTiO3 and Nb- scattering decreases leading to higher electrical conductivity. In
doped SrTiO3 thin films by replacing oxygen with argon. For sam- addition, 2DEG formation has been reported to occur on the
ples with the same amount of Nb, the incorporation of oxygen vacuum-cleaved surfaces of SrTiO3 [79]. During the cleaving pro-
vacancies improved the carrier mobility and carrier density as cess, large amount of oxygen vacancies can form at the surface
shown in Table 2. The maximum ZT they found at 1000 K was 0.29. inducing a number of electrons. The positively charged oxygen
Choi et al. investigated the effect of oxygen partial pressure on the vacancies make the electrons to travel within SrTiO3 surface. Such
thermoelectric performance of La-doped SrTiO3 thin films [82]. quantum confinement can increase the DOS at Fermi energy, thus
They found polaron transport behavior in these films which influ- Seebeck coefficient can be improved significantly compared to bulk
enced the thermoelectric properties. Films grown at low oxygen SrTiO3. Ohta et al. demonstrated that 2DEG systems with very high-
pressure showed oxygen and strontium vacancies which resulted in density confined electrons are very effective in enhancing the
an increment of charge carriers. Increased oxygen pressure influ- Seebeck coefficient [80]. They showed very high ZT of 2.4 for the
enced the polaronic mass and consequently the Seebeck coefficient. strongly confined electrons at heterointerfaces of TiO2/SrTiO3. The
Instead of showing an increasing trend with the increased oxygen oxygen vacancies generated in TiO2 phase during the pulsed laser
pressure, the absolute value of Seebeck coefficient initially deposition made electrons strongly confined within the interfacial
increased to 260 mV/K and then decreased, which was explained by region. They fabricated bulk SrTi0$8Nb0$2O3/SrTiO3 superlattice
the dominant polaron conduction. Their research elucidated the structures whose band structure was composed of multiple quan-
polaronic effects on the thermoelectric performance of electron- tum wells where 2DEG were formed at SrTi0$8Nb0$2O3 (well).
doped SrTiO3. Recently, Abutaha et al. made a great progress in However, for this material consisting of alternating barrier and
improving the ZT of SrTiO3 thin films [94]. They fabricated Sr1- active 2DEG layers, they obtained a ZT of only 0.24. Different models
nPrnTiO3/SrTi1-mNbmO3 (SPTO/STNO) superlattices using PLD tech- have been proposed for SrTiO3 bulk materials with 2DEG regions,
nique. They deposited alternating layers of oxygen-deficient SPTO for instance, nanocrystalline grain boundaries with 2DEG [115,116].
and STNO (about 5e20 nm each), with the aim of increasing the In this case, combined quantum confinement and energy filtering
phonon scattering by the extrinsic dopants and oxygen vacancies. effects can improve the thermoelectric properties [115].
They observed a lower value of thermal conductivity for thin films
of SPTO compared to the STNO films. For the superlattices, they
found a descending trend of thermal conductivity with the increase 3.2. ZnO
of SPTO to STNO thickness ratio (a/b). For different films, the plot of
ZT values as a function of temperature with different thickness ratio 3.2.1. Electronic structure of ZnO
(a/b) is shown in Fig. 7a. Fig. 7b shows a comparison of the ZT values Single-crystal ZnO has a hexagonal wurtzite structure
of different SrTiO3-based thermoelectric materials that have been (a ¼ 3.25 Å, c ¼ 5.21 Å) at atmospheric pressure. Its crystal and
obtained over time, showing a maximum of 0.46 obtained by this band structures are shown in Fig. 8 [117,118]. Large ZnO single
group [80,83,85,86,90,94e113]. These studies show that nanocrystals can be easily obtained by several chemical methods
structuring can effectively decrease thermal conductivity and [119,120], which is one of the best advantages of ZnO over other
therefore enhance the thermoelectric properties. semiconductors. As shown in Fig. 8b, ZnO has a wide direct band
gap (3.44 eV at 2 K), which is a very important physical
Table 2
Room-temperature lattice parameters and electrical transport properties of Nb-doped SrTiO3 thin films fabricated under different growth conditions. (r denotes the scattering
parameter, r ¼ 0, 1, 2 respectively represent acoustic phonon scattering, mixed scattering and ionized impurity scattering) (Reprinted with permission from S. Kumar, A. Z.
Barasheed and H. Alshareef, High temperature thermoelectric properties of strontium titanate thin films with oxygen vacancy and niobium doping, ACS Appl. Mater. Interfaces.
5 (2013) 7268e7273. Copyright (2013) American Chemical Society).
Film Nb conc/ Lattice Carrier concentration Hall mobility (cm2 m*/m0 Electrical conductivity (S Seebeck coefficient
ambient constant (Å) ( 1021 cm3) V1 s1) cm1) (mV K1)
r¼0 r¼2 r¼1
SrTi0$80Nb0$20O2.75 20%/Ar 3.968 1.32 15.6 1.98 0.66 0.99 3294.7 56
SrTi0$88Nb0$12O2.75 12%/Ar 3.952 1.01 7.3 2.10 0.70 1.05 1182.3 70
SrTi0$80Nb0$20O3 20%/O2 3.962 0.92 3.1 2.68 0.89 1.34 453.0 86
SrTi0$88Nb0$12O3 12%/O2 3.949 0.83 1.4 3.16 1.05 1.58 188.2 131
SrTiO2.75 0%/Ar 3.928 0.05 0.3 2.2 338
Fig. 7. (a) Temperature dependence of ZT values of Sr1-nPrnTiO3 (SPTO)/SrTi1-mNbmO3 (STNO) superlattices with different thickness ratios (a/b); (b) Plots of various previously (year:
2000 to 2016) reported ZT values of bulk, thin films and superlattice of SrTiO3. The red star denotes the highest achieved ZT till date for the SPTO/STNO superlattice with a/b ratio of
1.6. Reprinted with permission from A. I. Abutaha, S. Kumar, K. Li, A. Dehkordi, T. M. Tritt and H. Alshareef, Enhanced thermoelectric figure-of-merit in thermally robust, nano-
structured superlattices based on SrTiO3, Chem. Mater. 27 (2015) 2165e2171. Copyright (2015) American Chemical Society. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)
Fig. 8. (a) Crystal structure of ZnO, which shows the hexagonal wurtzite characteristic [P. Samanta, P. Chaudhuri, Substrate effect on morphology and photoluminescence from ZnO
monopods and bipods, Front. Optoelectron. China. 4 (2011) 130e136, with permission of Springer]; (b) The band structure and density of states of ZnO. Reprinted figure with
permission from P. Schroer, P. Kriiger and J. Pollmann, First-principles calculation of the electronic structure of the wurtzite semiconductors Zno and ZnS, Phys. Rev. B. 47 (1993)
6971e6980, copyright (1997) by the American Chemical Society.
characteristic [118]. The energy difference between 2p state of conductivity [122]. Additionally, defects formed during the fabri-
isolated oxygen and 4s state of isolated zinc is around 3 eV. Hence, cation process can also provide inadvertent electrons [126]. For
such wide band gap originates from a strong repulsion between O example, during ZnO preparation, hydrogen from surrounding at-
2p (bonding) and Zn 4s (anti-bonding) states [118]. The non- mosphere can diffuse into ZnO and substitute the oxygen which
degenerate conduction band is mainly contributed by Zn 4s band. bonds to four Zn atoms. Hydrogen and its four surrounding zinc
The degenerate valence bands are mainly composed of O 2p states atoms form a five-center bond sharing three electrons. The in-
[118]. Therefore, ZnO has a very light electronic effective mass teractions between H 1s and Zn 4s orbitals generate two electronic
(~0.30 m0 ) resulting in high carrier mobility [121]. Nevertheless, states, of which one lies in the valence band and the other in the
undoped ZnO has a low carrier concentration and consequently low conduction band. With two electrons occupying the lower-energy
electrical conductivity. Through doping or band-gap engineering, state, the remaining one electron occupies the higher-energy
the electrical properties of ZnO can be improved significantly state and then moves to the bottom of conduction band. Hence,
[122e126]. Since the valence band has a high degeneracy, hole- unintentional substitution of H can produce n-type conduction
doped ZnO is expected to show high Seebeck coefficient [122]. [126].
However, it is challenging to obtain p-type ZnO because the dop-
ants, such as IA, VA and IB elements either behave as deep acceptors 3.2.2. Thermoelectric properties of bulk ZnO-based oxides
or become stable interstitials therefore failing to introduce holes Due to its wide band gap, ZnO has no bipolar conduction [127].
[122]. Compared to hole-doped process, it is more practical to dope Though a non-parabolic characteristic of its band structure has
electrons in ZnO. N-type ZnO can be obtained by the additions of been suggested, the effective mass behavior of ZnO is still unclear
donors like Al, Ni and In Refs. [123e125]. The incorporation of Al or [128]. ZnO shows high Seebeck coefficient due to its low carrier
In can reduce the band gap and therefore improve the electrical concentration. However, its low electrical and high thermal
conductivity (about 40 W/m-K) affects the ZT value and ZnO ex- a significant increase in electrical conductivity compared to the
hibits poor ZT of less than 0.01 [123]. decrease in Seebeck coefficient. Hence, the power factor increased
There are two major approaches to improve ZT of ZnO. The first from 0.081 mW/m-K2 to 0.39 mW/m-K2. They also found that the
approach is to increase the carrier density by doping [129e131]. So addition of Al reduced the grain size and increased the surface
far, extensive research on Al-doped ZnO has been performed, roughness of the thin films, which is shown in Fig. 9. Owing to this,
because Al-doped ZnO exhibits the best thermoelectric perfor- low thermal conductivity (1.19 W/m-K) was achieved in relatively
mance [129]. Tsubota et al. reported a noticeable improvement of heavily doped films. Table 3 shows a comparison of their result
ZT (~0.30 at 1273 K) in Al-doped ZnO bulk samples [129]. However, with previously reported results on thermoelectric properties of
there is limited solubility of Al (2 at%) in bulk ZnO. On heavy Al- ZnO, which indicates that RF magnetron sputtering is a promising
doping some secondary phases may form which hinders the elec- method for obtaining high thermoelectric performance of ZnO
trical transport properties. The same is true for other candidate [123,139e148]. Recently, another novel method of inkjet printing
dopants, such as Ga [130,131]. Jung et al. improved the solubility of has been applied to elaborate ZnO thin films. An inkjet printer was
Ga in ZnO from 1 at% to 1.5 at% by lowering the sintering temper- employed to print the precursors on a glass substrate [149]. A
ature [130]. Besides, dual doping also helps to improve the solu- subsequent heat treatment was carried out to form ZnO phase and
bility of dopants in ZnO [131]. Zhang et al. reported an increase in Al to remove impurities. By controlling the printing cycles, a homo-
solubility by doping ZnO with Al and Ti [131]. They fabricated the geneous thin film was obtained. The thermoelectric properties of
samples using hydrothermal method and SPS technique which the prepared thin films were consistent with previous reports.
favored the formation of Ti interstitials. The comparatively larger In addition, reducing the dimensionality can enhance the See-
radius of Ti expands the volume of the unit cell, thereby providing beck coefficient because of the quantum confinement. Most of the
extra free space for Al interstitials. Hence, the solubility of Al was studied ZnO thin films had 3D electronic structures, thereby failed
improved in ZnO. The maximum ZT found was 0.057 at 773 K. The to improve the Seebeck coefficient. Reducing the thickness of ZnO
second promising approach to optimize the thermoelectric prop- thin films or creating 2DEG regions in bulk ZnO can generate
erties of ZnO is defect engineering [132]. Recently Tian et al. quantum confinement effects [150]. However, it is still elusive
demonstrated the important role of defects in determining ther- whether such 2D density of states can directly enhance the Seebeck
moelectric properties of ZnO [132]. The native defects (i.e. Zn va- coefficient. For example, the enhancement of Seebeck coefficient in
cancies) have a tendency to aggregate in grain boundaries and trap 2D SrTiO3 can only be realized when the carrier concentration is
electrons due to the formation of the Schottky barrier. Thus, quite high [116]. However, Shimizu et al. recently reported signifi-
removal of grain boundary defects can amend electrical conduc- cantly enhanced Seebeck coefficient of ZnO with 2DEG for a wide
tivity. Besides, introducing defects in grain interiors can reduce the range of carrier concentrations, which was ascribed to the single 2D
thermal conductivity without affecting the electrical properties. It sub-band in ZnO [150]. They fabricated ZnO-based ion-gated field
has been reported earlier that the oxygen pressure during fabri- effect transistor to create high density 2DEG in the presence of an
cation process and doping can influence the formation of defects. electric field. By tuning the gate voltage, maximum power factor
Tian et al. showed that ZnO fabrication in reduced atmosphere can was obtained at a carrier concentration of 1020 cm3. Lee et al.
decrease the number of boundary defects and at the same time can fabricated Al2O3/ZnO superlattices using atomic layer deposition
introduce oxygen vacancies in the grains. Multiple doping with Al, (ALD) [151]. The concurrence of increased Seebeck coefficient and
Mg, and Ti can further improve the electrical conductivity of ZnO. reduced thermal conductivity yielded a high ZT of 0.14. Tynell et al.
The highest ZT reported in multi-doped ZnO is 0.09 at 973 K [132]. proposed an organic/ZnO superlattice to improve the thermoelec-
In addition to doping and defect engineering, there are other tric properties [152]. Since organic materials have significantly low
promising approaches for improving the value of ZT in ZnO thermal conductivity, the overall thermal conductivity of inorganic/
[133,134]. Roy et al. proposed that amorphous bulk ZnO should organic hybrid was expected to decrease. They prepared super-
exhibit better thermoelectric properties than crystalline ZnO ac- lattices of hydroquinone/Al-doped ZnO by alternatively depositing
cording to their theoretical calculations [133]. They showed the Al-doped ZnO by ALD and hydroquinone by molecular layer
similar value of power factor for both amorphous and crystalline deposition (MLD). Despite the reduced carrier concentration due to
ZnO, whereas the thermal conductivity of amorphous ZnO was hydroquinone, they found enhanced electrical conductivity which
found to be much lower than that of crystalline ZnO. The ZT of was attributed to the inclusion of electrons due to Al. They expected
amorphous ZnO was calculated to be above 0.2 at 600 K. Tang et al. the improved value of ZT for this system since hydroquinone layers
made Zn4Sb2$94In0.06/1 wt% ZnO composites observing a remark- were expected to block the transport of phonons. To prove this
ably high ZT of 1.16 at 700 K [134]. However, they only had small enhancement, their group further calculated the lattice thermal
amount of ZnO in their samples. conductivity as a function of the maximum mean free path of
phonons using first-principles [153]. They found the thermal con-
3.2.3. Thermoelectric properties of nanostructured ZnO ductivity to decrease considerably with the decrease in phonon's
Nanometric ZnO thin films doped with other elements (Al, Ga, maximum mean free path. This study shows that, if such super-
In) have been widely studied [135,136]. Most of the novel thin films lattices can be made where the organic layers can scatter phonons
still show a much lower ZT (below 0.1) compared to the bulk n-type effectively, the thermal conductivity of nano-scale ZnO films can be
ZnO [137,138]. However, thin films have an advantage over bulk significantly reduced compared to the bulk ZnO.
materials due to their possible application in transparent thermo- As of yet, a highest ZT of 0.44 at 1000 K has been achieved in Al-
electric devices. In recent years, some advances in thermoelectric doped ZnO nanocomposites prepared by Jood et al. [154]. They
performance of n-type ZnO thin films have been accomplished. prepared Al-doped ZnO nanocrystals by a quick microwave-
Loureiro et al. reported significant improvement in ZT of Al-doped activated solvothermal method as shown in Fig. 10. Subsequent
ZnO thin films up to a value of 0.1 at room temperature [139]. cold pressing and sintering were carried out to fabricate bulk pel-
They fabricated these thin films using RF magnetron sputtering. lets. Due to the limited solubility of Al, a co-existing secondary
They sintered the targets which were composed of Al-doped ZnO phase, ZnAl2O4 was found in their ZnO samples. The nano-sized
nanopowders with different doping levels. Increasing the Al con- ZnAl2O4 clusters and the large number of grain boundaries played
centration caused an increase in carrier density. Despite the conflict an important role in impeding phonon transport. The thermal
between Seebeck coefficient and electrical conductivity, there was conductivity was appreciably lower than that of non-
Fig. 9. SEM images showing the morphology of ZnO samples with a doping of (a) 0.5 wt % and (b) 2.0 wt % Al, which indicates that the addition of Al could increase surface
roughness and decrease grain sizes. Reproduced from J. Loureiro, N. Neves, R. Barros, T. Mateus, R. Santos, S. Filonovich, S. Reparaz, C. M. Sotomay, F. Wyczisk, L. Divay, R. Martinsa
and I. Ferreira, Transparent aluminium zinc oxide thin films with enhanced thermoelectric properties, J. Mater. Chem. A. 2 (2014) 6649, with permission of The Royal Society of
Chemistry.
Table 3
Thermoelectric properties of Al-doped ZnO bulks and thin films fabricated by different methods (Reproduced from J. Loureiro, N. Neves, R. Barros, T. Mateus, R. Santos, S.
Filonovich, S. Reparaz, C. M. Sotomay, F. Wyczisk, L. Divay, R. Martinsa and I. Ferreira, Transparent aluminium zinc oxide thin films with enhanced thermoelectric properties, J.
Mater. Chem. A. 2 (2014) 6649, with permission of The Royal Society of Chemistry).
ZnO: Al2O3 wt% Dep. method d (nm) Twork (K) s (U m)1 k (W mK1) jSj (mV K1) PF (W mK1) ZT Ref
98: 2 RF (St-AZO target) 240 RT 4 10 4

<1.19 98 3.9 104 >0.1 Loureiro et al. [139]
98.5: 1.5 DC 120 RT 104 _ 62 1.3 104 ~0.03* [140]
98.5: 1.5 DC 103 RT 104 to 105 _ 68 1.5 104 ~0.04* [141]
97.3: 2.7 DC 716 RT 104 _ 99 1.5 104 ~0.04* [142]
98: 2 PLD 500 RT 104 _ 65 1.3 104 ~0.03* [143]
98: 2 Solid-state reaction (pressure) Bulk RT 104 to 105 40.2 100e150 8 103 6 103 [144]
98: 2 Solid-state reaction (pressure) Bulk RT 105 _ 62.5 3.8 104 103** [145]
99: 1 RF plasma and hot pressed Bulk RT 104 28 37 1.3 104 2 103 [123]
97: 3 Chemical co-deposition and pressed Bulk 373 104 14 200 5 104 ~0.02 [146]
96: 4 Spark plasma sintering Bulk 675 104 2 88 3.2 104 0.085 [147]
98: 2 Spark plasma sintering Bulk 1173 104 5.15 120 8 104 0.17 [148]
nanostructured Al-doped ZnO (Fig. 10). However, since these de-

fects and boundaries inhibit the motion of electrons, the authors
compensated it by increasing the carrier concentration through Al-
doping. The electrical conductivity increased exponentially with
temperature, which was attributed to the augmented thermally
activated electrons provided by Al donors. The Seebeck coefficient
was also improved compared to that of non-nanostructured ZnO
because of quantum confinement effect. Their research demon-
strates that nanostructuring can considerably contribute to the
improvement of thermoelectric properties of ZnO.
3.3. CaMnO3
3.3.1. Electronic structures of CaMnO3

CaMnO3 has an orthorhombic perovskite structure consisting of
oxygen octahedron, as shown in Fig. 11a [155]. Generally, it shows
G-type anti-ferromagnetic properties (The Mn atom has opposite
spin alignment with respect to its six nearest adjacent Mn atoms)
and large magnetoresistance [155,156]. Mn4þ (t32ge0g) is located at
the center of the oxygen octahedron structure with negligible Jahn-
Teller distortions [26,157]. The energy gap between Mn t2g and eg
Fig. 10. Illustration of fabrication process of ZnO nanocomposites using microwave-
aided solvothermal synthesis. The ZnAl2O4 nanoprecipitates formed at grain bound- levels is above 1 eV due to the crystal field effect [158]. Owing to the
aries can effectively scatter phonons. Reprinted with permission from P. Jood, R. J. e0g configuration, pure CaMnO3 shows insulating character
Mehta, Y. Zhang, G. Peleckis, X. Wang, R. W. Siegel, T. Borca-Tasciuc, S. Dou and G. [158,159]. Its electronic structure is shown in Fig. 11b [155]. CaMnO3
Ramanath, Al-doped zinc oxide nanocomposites with enhanced thermoelectric prop-
has an indirect band gap, whose theoretical value is around 0.7 eV.
erties, Nano Lett. 11 (2011) 4337e4342. Copyright (2011) American Chemical Society.
Mn 3d states and O p states are responsible for the electrical
properties of CaMnO3. There are two types of oxygen, O1 and O2, in
Fig. 11. (a) Schematic of oxygen octahedron of CaMnO3 containing two types of oxygen and one Mn atom at the center. Since O1 and Mn have a higher hybridization magnitude,
Mn-O1 is the main conduction path; (b) Band structure of CaMnO3. Reprinted F. Zhang, Q. Lu, X. Zhang and J. Zhang, First principle investigation of electronic structure of CaMnO3
thermoelectric compound oxide, J. Alloys. Compd. 509 (2011) 542e545, copyright (2011), with permission from Elsevier.
terms of the degree of hybridization (Fig. 11a). Since Mn-O1 has a 3.3.2. Thermoelectric properties of CaMnO3
higher hybridization degree than Mn-O2, major carrier transport CaMnO3 exhibits high Seebeck coefficient (~350 mV/K) and low
thus takes place in the Mn-O1 direction [155]. The formation of O1 thermal conductivity (3 W/m-K), which is good for its thermo-
vacancies can disturb the conduction path and weaken the carrier electric properties [162]. However, the drawback of CaMnO3 is its
mobility [155]. Additionally, O vacancies can also change the high electrical resistivity [163]. One easy solution is to introduce
valence states of some Mn from 4þ to 3þ; thereby making Mn eg electrons into CaMnO3 via doping [163e166]. The substitution of Ca
states partially occupied, which induces Jahn-Teller distortions by rare-earth elements and Mn by transition metals have been
[158]. Small polarons are produced due to the interactions between widely investigated [163e166]. It is shown that these dopants have
electrons and lattice. Hence, CaMnO3-d shows small polaron hop- capabilities to increase the carrier concentration by partially
ping conduction. When small polaron hopping takes place, the changing Mn4þ to Mn3þ, thereby improving the electrical con-
electrical conductivity s can be expressed as [160]: ductivity by a few orders of magnitude. The CaMnO3 shows metallic
behavior upon appropriate doping [159,163]. Besides, the formation
of Mn3þ induces Jahn-Teller distortions and thus reduces thermal
gd e2 n0 kEsT
s ¼ e B ; (11) conductivity [167]. Among all rare-earth element-doped CaMnO3
a kB T materials, Yb-doped CaMnO3 has been reported to show the
highest ZT which is around 0.16 at 1000 K [164]. It is reported that
where gd is a factor which depends on lattice geometry, a is the the radius of rare-earth element (R) dopant can have an influence
polaron jump distance, n0 is characteristic frequency, and Es is the on the thermoelectric properties of CaMnO3 [164]. The sub-
activation energy. There is a linear relationship between ln ðsTÞ and stitutions of the Mn by R of different radii can cause different de-
1=T. The electrical conductivity of CaMnO3-d as a function of tem- gree of distortions in the oxygen octahedron. It is known that Mn-
perature is shown in Fig. 12, which indicates a typical small polaron O1 is the dominant conduction path in CaMnO3 [155]. Therefore,
behavior. As d increases, the electrical conductivity decreases and the size of R plays a significant role in the electrical conductivity of
activation energy increases [161]. CaMnO3. The smaller the radius of R is, the lower the electrical
conductivity will be [165]. Apart from rare-earth elements, Bi-
substitution for Ca-site has also been investigated, showing
significantly improved ZT [165]. Kabir et al. reported studies on Bi-
substituted CaMnO3 prepared by solid-state reactions, over the
temperature range of 300 Ke973 K [165]. They found that the
incorporation of Bi reduced the Seebeck coefficient, but at the same
time improved the electrical conductivity. The thermal conductiv-
ity reduced significantly up to a certain doping level, but increased
with further doping which was attributed to the structural disorder
due to Bi-doping and increase of carriers. A high ZT of 0.25 at 973 K
was found for the relatively low concentration (3%) Bi-substituted
CaMnO3. Among CaMnO3 materials with Mn substitutions, W-or
Nb-doped CaMnO3 are reported to show excellent thermoelectric
properties. Kabir et al. reported stoichiometric CaMn1-xWxO3 with
an increased electrical conductivity and decreased Seebeck coeffi-
cient which showed ZT of 0.15 for the 1% W-substituted CaMnO3
[162]. Thiel et al. investigated the effects of the concurrence of W
substitutions and oxygen deficiency on the thermoelectric prop-
erties [163]. The thermal conductivity was significantly reduced
and power factor increased for all the W-doped samples up to the
Fig. 12. Plots of ln(sT) vs 1/T for samples CaMnO3-d(d ¼ 0.03, 0.06, 0.11, 0.14) with
temperature range of 1000 K. Above 1000 K, oxygen vacancy played
linear fitting lines, showing typical small polaron behavior. Reprinted from M. Schrade,
R. Kabir, S. Li, T. Norby and T. Finstad, High temperature transport properties of ther- important role compared to W-substitution. A maximum ZT value
moelectric CaMnO3-d-Indication of strongly interacting small polarons, J. Appl. Phys. of 0.25 at 1225 K was achieved for the W-doped sample,
115 (2014) 103705, with the permission of AIP Publishing.
CaMn0$96W0$04O3-d [163]. The highest ZT reported so far for these

systems is 0.3 in Nb-doped CaMnO3 [166]. The authors did a
comparative study by preparing samples using solid-state reactions
(SSR) and soft chemistry method (SC). There was no obvious dif-
ference in Seebeck coefficient for the samples prepared by these
different methods. However, the electrical conductivity of samples
obtained by SC method was noticeably improved compared to
samples obtained by SSR method, as shown in Table 4. This was
attributed to the well inter-connected nano-sized grains formed in
the samples prepared by SC method. Nanocrystallite grains induce
phonon scattering centers, which explains lower thermal conduc-
tivity in SC samples [166]. Therefore, SC method may be considered
for the optimization of thermoelectric properties in CaMnO3 based
materials.
4. Oxides based thermoelectric modules
A thermoelectric module is made up of a series of arrays of p-

and n-type legs connected by metallic wires [168]. The schematic
illustration of a typical thermoelectric module is shown in Fig. 13.
To create a temperature difference across the module, a heater and
a cooler are used. The energy conversion efficiency of a thermo-
electric module is related to the dimensionless figure of merit, ZT
and the temperature difference between hot and cold side of the
module (Equation (1)). For practical applications, thermoelectric
efficiency of >10% is required which can be achieved by a high ZT Fig. 13. The schematic illustration of a typical thermoelectric (TE) module, which
comprises of n- and p-type TE legs, metallization layers, solder layers, conducting
(>1) and a large temperature difference [169]. The ZT of thermo-
strips and ceramic plates. The metallization layer is used to prevent degradation of
electric modules are calculated using the following equation: solder layers. Reprinted from W. Liu, Q. Jie, H. Kim and Z. Ren, Current progress and
future challenges in thermoelectric power generation: From materials to devices, Acta
S2module T Mater. 87 (2015) 357e376, copyright (2015), with permission from Elsevier.
ZTmodule ¼ ; (12)
Rmodule Kmodule
where Smodule, Rmodule and Kmodule, respectively denotes the Seebeck p-type semiconductor [168]. Furthermore, thermoelectric mate-
coefficient (which is equal to open-circuit voltage, Vopen divided by rials with good mechanical properties should be used.
the temperature difference DT), resistance and thermal conduc- At present, the most studied thermoelectric modules are made
tance of the module [169]. In addition to the use of thermoelectric of intermetallic compounds, like Bi2Te3 and PbTe, which are used
materials with high ZT, there are other approaches to improve the for low- or mid-temperature applications [168]. Due to their
ZTmodules [170]. The first approach is to increase the number of n/p- instability at high temperatures, the scope of increasing the tem-
type leg couples. The open-circuit voltage increases with the perature difference is limited. Recently, several studies have been
number of n/p-type legs, therefore the Seebeck coefficient of the performed on oxide modules [169e172]. Ca3Co4O9 has been used as
modules can be improved. The second approach is to reduce the p-type leg while CaMnO3, SrTiO3 or ZnO have been used as n-type
contact resistance. Generally, the metallic conducting wires are leg [169e172]. Choi et al. fabricated an oxide module comprised of
connected with the thermoelectric legs by soldering. However, the Ca3Co4O9 and (ZnO)7(In2O3) couples and studied its thermoelectric
high interfacial energy makes a poor adhesion of metals to the performance in the high-temperature regime [172]. A hot plate and
surfaces of thermoelectric materials. Besides, metals have a ten- a fan were employed to generate the temperature difference. A
dency to diffuse into thermoelectric materials at high temperatures thermally insulated material filled the spaces between the ther-
resulting in deterioration of thermoelectric performance [170]. moelectric legs to increase the temperature difference. The open-
Therefore, other methods, like chemical vapor deposition, sput- circuit voltage (Vopen), short-circuit current (Ishort) and resistance
tering etc. have been proposed to make a firm connection between (Rmodule) of this module were measured. The maximum output
metal and thermoelectric legs [170]. In addition, Ohmic contacts power was calculated using the following equation:
should be formed at the metal-semiconductor interfaces. In case of 2
Vopen
an n-type semiconductor, the work function of the metal should be P¼ ; (13)
smaller than that of semiconductor, whereas greater in the case of 4Rmodule
Table 4
Density and electrical resistivity of Nb-doped CaMnO3 samples prepared by SSR and SC methods (Reprinted with permission from L. Bocher, M. Aguirre, D. Logvinovich, A.
Shkabko, R. Robert, M. Trottmann and A. Weidenkaff, CaMn1-x NbxO3 (x ¼ 0.08) perovskite-type phases as promising new high-temperature n-type thermoelectric materials,
Inorg. Chem. 47 (2008) 8077e8085. Copyright (2008) American Chemical Society).
Niobium substitution Mn valency Synthesis method Relative density r (mU cm) at 800 K
0.02 3.98 SSR 86.01% 37.7
SC 80.77% 32.4
0.05 3.94 SSR 82.74% 19.5
SC 67.79% 15.6
0.08 3.91 SSR 78.12% 14.8
SC 72.25% 13.7
Table 5
Number of p-n pairs, temperature differences DT, open-circuit voltage V0, maximum output power Pmax of several oxide thermoelectric power generators (Reprinted from S.
Choi, K. Lee, C. Lim and W. Seo, Oxide-based thermoelectric power generation module using p-type Ca3Co4O9 and n-type (ZnO)7In2O3 legs, Energy Convers. Manage. 52 (2011)
335e339, copyright (2011), with permission from Elsevier).
Materials # of p-n couples Element dimension (mm) Joining technique DT (K) V0 (V) Pmax Pmax/DT (mW/ Ref. #
(mW) K)
p: NaCo2O4 n: ZnO 12 Diffusion 455 0.79 52.5 0.115 [173]

welding
p: Ca2$7Bi0$3Co4O9 n: La0$9Bi0$1NiO3 140 1.3 1.3 5 Ag-paste 551 4.5 150 0.272 [174]
p: Ca2$7Bi0$3Co4O9 n: La0$9Bi0$1NiO3 8 3.7 4e4.5 4.7 Ag-paste 565 1 170 0.301 [174]
p: Ca2.75Gd0.25Co4O9 n: Ca0$92La0$08MnO3 8 3 5e6 30 Pt-paste 390 0.988 63.5 0.163 [175]
p: Ca3Co4O9 n: (ZnO)7In2O3 44 p: 15 15 27 n: 15 15 18 Ag-paste 673 1.8 423 0.629 Choi et al.
[172]
The output power increased with the increase in hot-side 5. Summary

temperature and the total number of p-n couples. The increase in
hot-side temperature raised the temperature difference resulting in In conclusion, oxide thermoelectric materials are promising
a higher open-circuit voltage. Table 5 shows the comparison of the candidates for high-temperature applications due to their robust
thermoelectric characteristics of their modules with previously properties and environmentally friendliness. Transition metal-
reported oxide modules. It can be seen that their modules show based oxides have recently attracted intense attention due to
excellent thermoelectric performance [172e175]. Inagoya et al. their excellent thermoelectric performance compared to other
assembled perovskite oxide modules using Nd-doped CaCoO3 (p- metal oxides. However, the dimensionless figure of merit, ZT of
type) and Mn-doped LaCoO3 (n-type) thermoelectric legs [176]. The these oxides are still low (<1) compared to traditional thermo-
maximum output power of their module was 44 mW (~power electric materials, like Bi2Te3, SiGe etc. Notable advances have been
density of 100 W/m2) corresponding to a temperature difference of made to optimize their thermoelectric performance. For the p-type
399 K, which is satisfactory considering the small temperature Ca3Co4O9, doping and nanostructuring can improve the Seebeck
difference they used. Tome^s et al. provided a systematic charac- coefficient by modifying the band structures and reducing the
terization of a four leg thermoelectric module [177]. The module carrier density. The introduction of grain boundaries and point
was composed of two pairs of p-type Ni-doped GdCoO3 and n-type defects can significantly reduce the thermal conductivity by
Nb-doped CaMnO3 materials. They reduced the contact resistance impeding the phonon traveling path. Novel sintering fabrication
by addition of CuO in Ag paste, which increased the wettability of methods (SPS, SPT and magnetic field sintering) have been applied
Ag on the interfaces. To obtain accurate information on tempera- to improve the morphological textures and densities; thereby
ture change across the module, they utilized a micro-infrared (IR) improving the electrical conductivity. Among n-type oxides, ZnO,
camera to measure temperature. Fig. 14 shows the plot of the SrTiO3 and CaMnO3 have been widely investigated. Undoped ZnO
temperature distribution as a function of distance starting from the shows insulating electrical character because of its wide band gap.
hot side. The homogeneous color distribution indicates a uniform It has a non-parabolic conduction band with light effective mass;
distribution of temperature in their modules. The output power of therefore ZnO has high carrier mobility as well as high thermal
their module was 40 mW for the temperature difference of 500 K. conductivity. Improvement of its electrical conductivity by electron
Fig. 14. (a) Temperature distribution (detected by an IR camera) of the perovskite thermoelectric module prepared by Tomes et al.; (b) The plot of temperature vs distance measured
from the hot side. P. Tomes, R. Robert, M. Ttrottmann, L. Bocher, M. Aguirre, A. Bitschi, J. Hejtmanek and A. Weidenkaff, Synthesis and characterization of new ceramic thermo-
electrics implemented in a thermoelectric oxide module, J. Electron. Mater. 9 (2010) 1696e1703, with permission of Springer.
doping and suppressing the thermal conductivity by defects engi- high thermoelectric performance in CoSb3 skutterudites, Nat. Mater 14
(2015) 1223e1229.
neering have been widely studied. Nanostructuring along with Al-
[10] H. Anno, M. Hokazono, R. Shirataki, Y. Nagami, Crystallographic, thermo-
doping is an effective method to improve its electrical conductivity. electric, and mechanical properties of polycrystalline type-I Ba8Al16Si30-
Similar to ZnO, stoichiometric SrTiO3 shows insulating behavior, based clathrates, J. Mater. Sci. 48 (2013) 2846e2854.
which becomes highly conductive on doping. SrTiO3 exhibits [11] E.S. Toberer, A. Zevalkink, G.J. Snyder, Phonon engineering through crystal
chemistry, J. Mater. Chem. 21 (2011) 15843e15852.
excellent Seebeck coefficient due to its highly symmetric crystal [12] J.L. Cohn, G.S. Nolas, V. Fessatidis, T.H. Metcalf, G.A. Slack, Glasslike heat
structure and degenerate conduction bands. The incorporation of conduction in high-mobility crystalline semiconductors, Phys. Rev. Lett. 82
small amount of dopants (La, Nb, W et al.) raises the fermi energy (1999) 779e782.
[13] M. Christensen, A.B. Abrahamsen, N.B. Christensen, F. Juranyi, N.H. Andersen,
level from the forbidden band region to the bottom of conduction K. Lefmann, J. Andreasson, C.R.H. Bahl, B.B. Iversen, Avoided crossing of
band, making it a highly conductive material. Moreover, introduc- rattler modes in thermoelectric materials, Nat. Mater 7 (2008) 811e815.
tion of appropriate oxygen vacancies can contribute to the [14] T. Tadano, Y. Gohda, S. Tsuneyuki, Impact of Rattlers on Thermal conductivity
of a thermoelectric clathrate: a First-Principles study, Phys. Rev. Lett. 114
improvement of electrical conductivity. Both ZnO and SrTiO3 can (2015) 095501.
form 2DEG regions accompanied by a considerable enhancement of [15] Y. Pei, X. Shi, A. LaLonde, H. Wang, L. Chen, G.J. Snyder, Convergence of
ZT. The simpler subbands in ZnO, compared to SrTiO3 can lead to an electronic bands for high performance bulk thermoelectrics, Nature 473
(2011) 66e69.
enhancement of power factor for a wide range of carrier concen- [16] J. He, Y. Liu, Oxide thermoelectrics: the challenges, progress, and outlook,
tration. In the case of SrTiO3, 2DEG can be created at the interfaces J. Mater. Res. 26 (2011) 1762e1772.
between SrTiO3 and other specific oxides (e.g LaAlO3, TiO2), which [17] X. Chen, D. Parker, D.J. Singh, Importance of non-parabolic band effects in the
thermoelectric properties of semiconductors, Sci. Rep. 3 (2013) 1e6.
opens up new avenues to improve the thermoelectric properties of
[18] C. Wood, Materials for thermoelectric energy conversion, Rep. Prog. Phys. 51
SrTiO3. Quantum confinements and energy filtering effects can (1988) 459e539.
improve the ZT of 2DEG systems beyond 2. In case of CaMnO3, the [19] Y. Tang, Y. Qiu, L. Xi, X. Shi, W. Zhang, L. Chen, S.-M. Tseng, S.-w. Chend,
thermoelectric properties can be improved by addition of rare- G.J. Snyder, Phase diagram of IneCoeSb system and thermoelectric prop-
erties of In-containing skutterudites, Energy Environ. Sci. 7 (2014) 812e819.
earth metals or transition metals which can induce Jahn-Teller [20] W. Xie, A. Weidenkaff, X. Tang, Q. Zhang, J. Poon, T.M. Tritt, Recent advances
distortions and increase the carrier concentration. The maximum in nanostructured thermoelectric Half-Heusler compounds, Nanomaterials 2
reported ZT in this case is 0.3, which has been achieved in Nb- (2012) 379e412.
[21] Y. Takagiwa, Y. Pei, G. Pomrehn, G.J. Snyder, Dopants effect on the band
doped CaMnO3. Additionally, improvements in fabrication and structure of PbTe thermoelectric material, Appl. Phys. Lett. 101 (2012)
preparation processes can also contribute to high ZT values in 092102.
electron-doped CaMnO3, e.g. introducing oxygen deficiency by [22] Y. Pei, A. LaLonde, S. Iwanaga, G.J. Snyder, High thermoelectric figure of merit
in heavy hole dominated PbTe, Energ. Environ. Sci. 4 (2011) 2085e2089.
treating sample in reduced atmosphere, and making nano-crystals [23] K. Ahn, K. Biswas, J. He, I. Chung, V. Dravid, M.G. Kanatzidis, Enhanced
via soft chemistry method. These can produce a number of defects thermoelectric properties of p-type nanostructured PbTeeMTe (M¼ Cd, Hg)
and grain boundaries which can effectively decrease the thermal materials, Energ. Environ. Sci. 6 (2013) 1529e1537.
[24] R. Venkatasubramanian, E. Siivola, T. Colpitts, B. O'Quinn, Thin-film ther-
conductivity without affecting the electrical conductivity. Using the moelectric devices with high room-temperature figures of merit, Nature 413
n-type Ca3Co4O9 and p-type thermoelectric oxides, stable and low- (2001) 597e602.
cost modules for high-temperature applications can be fabricated [25] M. Ohtaki, Recent aspects of oxide thermoelectric materials for power gen-
eration from mid-to-high temperature heat source, J. Ceram. Soc. Jpn. 119
with an output power comparable to that of solar cells. Thus, oxide
(2011) 770e775.
thermoelectric materials have the potential to solve the current [26] M. Imada, A. Fujimori, Y. Tokura, Metal-insulator transitions, Rev. Mod. Phys.
energy issues. Further studies are needed for increasing their 70 (1998) 1039e1263.
thermoelectric efficiency. [27] M.B. Salamon, M. Jaime, The physics of manganites: structure and transport,
Rev. Mod. Phys. 73 (2001) 583e628.
[28] S. Pal, A. Banerjee, E. Rozenberg, B.K. Chaudhuri, Polaron hopping conduction
and thermoelectric power in LaMnO3þd, J. Appl. Phys. 89 (2001) 4955e4961.
Acknowledgements [29] W. Khan, A.H. Naqvi, M. Gupta, S. Husain, R. Kumar, Small polaron hop ping
conduction mechanism in Fe doped LaMnO3, J. Chem. Phys. 135 (2011)
Support from the National Science Foundation through grant # 054501.
[30] T.T.M. Palstra, A.P. Ramirez, S.-W. Cheong, B.R. Zegarski, P. Schiffer, J. Zaanen,
1407650 is thankfully acknowledged. B.T. thanks UGC, Government
Transport mechanisms in doped LaMnO3: evidence for polaron formation,
of India for Raman Post-doctoral fellowship. Phys. Rev. B 56 (1997) 5104e5107.
[31] Y. Lin, C. Nan, Y. Liu, J. Li, T. Mizokawa, Z. Shen, High-temperature electrical
transport and thermoelectric power of partially substituted Ca3Co4O9-based
References ceramics, J. Am. Ceram. Soc. 90 (2007) 132e136.
[32] Y. Liu, Y. Lin, Z. Shi, C. Nan, Preparation of Ca3Co4O9 and improvement of its
[1] Terry M. Tritt, Thermoelectric phenomena, materials, and applications, Annu. thermoelectric properties by spark plasma sintering, J. Am. Ceram. Soc. 88
Rev. Mater. Res. 41 (2011) 433e448. (2005) 1337e1340.
[2] M. Elsheikh, D. Shnawah, M. Sabri, S. Said, M. Hassan, M. Bashir, [33] S. Altin, M.A. Aksan, A. Bayri, High temperature spin state transitions in
M. Mohamad, A review on thermoelectric renewable energy: principle pa- misfit-layered Ca3Co4O9, J. Alloy. Compd. 587 (2013) 40e44.
rameters that affect their performance, Renew. Sust. Energ. Rev. 30 (2014) [34] B.C. Zhao, Y.P. Sun, W.J. Lu, X.B. Zhu, W.H. Song, Enhanced spin fluctuations
337e355. in Ca3Co4xTixO9 single crystals, Phys. Rev. B 74 (2006) 144417.
[3] Z.G. Chen, G. Han, L. Yang, L. Cheng, J. Zou, Nanostructured thermoelectric [35] P. Limelette, V. Hardy, P. Auban-Senzier, D. Je rome, D. Flahaut, S. He bert,
materials: current research and future challenge, Chin. Mater. Res. Soc. 22 R. Fresard, C. Simon, Strongly correlated properties of the thermoelectric
(2012) 535e549. cobalt oxide Ca3Co4O9, Phys. Rev. B 71 (2005) 233108.
[4] G.J. Snyder, E.S. Toberer, Complex thermoelectric materials, Nat. Mater 7 [36] T.A. T.Wu, J. Tyson, K. Bai, C. Jayed Pandya, D. Fischer, On the origin of
(2008) 105e114. enhanced thermoelectricity in Fe doped Ca3Co4O9, J. Mater. Chem. C 1 (2013)
[5] G.S. Nolas, D.T. Morelli, T.M. Tritt, Skutterudites: a Phonon-Glass-Electron 4114e4121.
crystal approach to advanced thermoelectric energy conversion applica- [37] Y. Wang, N.S. Rogado, R.J. Cava, N.P. Ong, Spin entropy as the likely source of
tions, Annu. Rev. Mater. Sci. 29 (1999) 89e116. enhanced thermopower in NaxCo2O4, Nature 423 (2003) 425e428.
[6] H. Xie, H. Wang, Y. Pei, C. Fu, X. Liu, G.J. Snyder, X. Zhao, T. Zhu, Beneficial [38] W. Koshibae, S. Maekawa, Effects of spin and orbital degeneracy on the
contribution of alloy disorder to electron and phonon transport in Half- thermopower of strongly correlated systems, Phys. Rev. Lett. 87 (2001)
Heusler thermoelectric materials, Adv. Funct. Mater 23 (2013) 5123e5130. 236603.
[7] Y. Pei, H. Wang, G.J. Snyder, Band engineering of thermoelectric materials, [39] T. Takeuchi, T. Kondo, K. Soda, U. Mizutani, R. Funahashi, M. Shikano,
Adv. Mater 24 (2012) 6125e6135. S. Tsuda, T. Yokoya, S. Shin, T. Muro, Electronic structure and large ther-
[8] S. Walia, S. Balendhran, H. Nili, S. Zhuiykov, G. Rosengarten, Q. Wang, moelectric power in Ca3Co4O9, J. Electron. Spectrosc. 137e140 (2004)
M. Bhaskaran, S. Sriram, M.S. Strano, K. Kalantar-zadeh, Transition metal 595e599.
oxides e thermoelectric properties, Prog. Mater. Sci. 58 (2013) 1443e1489. [40] T. Takeuchi, K. Soda, R. Funahashi, M. Shikano, M. Mikami, S. Tsuda,
[9] Y. Tang, Z.M. Gibbs, L.A. Agapito, G. Li, H.-S. Kim, M. Nardelli, S. Curtarolo, T. Yokoya, S. Shin, T. Muro, Contribution of electronic structure to the large
G.J. Snyder, Convergence of multi-valley bands as the electronic origin of thermoelectric power in layered cobalt oxides, Phys. Rev. B 69 (2004)
125410. [69] G.D. Tang, Z.H. Wang, X.N. Xu, L. Qiu, Y.W. Du, Evidence of spin-density-wave
[41] M. Shikano, R. Funahashi, Electrical and thermal properties of single- transition and enhanced thermoelectric properties in Ca3-xCexCo4O9þd,
crystalline (Ca2CoO3)0.7CoO2 with a Ca3Co4O9 structure, Appl. Phys. Lett. 82 J. Appl. Phys. 107 (2010) 053715.
(2003) 1851e1853. [70] J. Nan, J. Wu, Y. Deng, C.-W. Nan, Thermoelectric properties of La doped Ca-
[42] M. Mikami, K. Chong, Y. Miyazaki, T. Kajitani, T. Inoue, S. Sodeoka, Co-O misfit cobaltites, Solid State Commun. 124 (2002) 243e246.
R. Funahashi, Bi-substitution effects on crystal structure and thermoelectric [71] I. Matsubara, R. Funahashi, T. Takeuchi, S. Sodeoka, Thermoelectric proper-
properties of Ca3Co4O9 single crystals, Jpn. J. Appl. Phys. 45 (2006) ties of spark plasma sintered Ca2.75Gd0.25Co4O9 ceramics, J. Appl. Phys. 90
4131e4136. (2001) 462e465.
[43] S. Bhattacharyaa, D. Aswala, A. Singha, C. Thinaharana, N. Kulkarnib, Aniso- [72] S. Butt, Y. Liu, J. Lan, K. Shehzad, B. Zhan, Y. Lin, C. Nan, High-temperature
tropic electrical transport studies of Ca3Co4O9 single crystals grown by the thermoelectric properties of La and Fe co-doped CaeCoeO misfit-layered
flux method, J. Cryst. Growth 277 (2005) 246e251. cobaltites consolidated by spark plasma sintering, J. Alloys Compd. 588
[44] F. Delorme, C. Martin, P. Marudhachalam, D. Ovono, G. Guzman, Effect of Ca (2014) 277e283.
substitution by Sr on the thermoelectric properties of Ca3Co4O9 ceramics, [73] N. Nong, N. Pryds, S. Linderoth, M. Ohtaki, Enhancement of the thermo-
J. Alloys Compd. 509 (2011) 2311e2315. electric performance of p - type layered oxide Ca3Co4O9þd through heavy
[45] Y. Wang, L. Xu, Y. Sui, X. Wang, J. Cheng, W. Su, Enhanced electron corre- doping and metallic nanoinclusions, Adv. Mater 23 (2011) 2484e2490.
lation in rare-earth doped Ca3Co4O9, Appl. Phys. Lett. 97 (2010) 062114. [74] H. Hao, Q. He, C. Chen, H. Sun, X. Hu, Textured structure and anisotropic
[46] E. Guilmeau, R. Funahashi, M. Mikami, K. Chong, D. Chateigner, Thermo- thermoelectric properties of Ca2.7Bi0.3Co4O9 oxide prepared by conventional
electric properties- texture relationship in highly oriented Ca3Co4O9 com- solid-state reactions, Int. J. Mod. Phys. B 23 (2009) 87e95.
posites, Appl. Phys. Lett. 85 (2004) 1490e1492. [75] J. Cho, O. Kwon, Y. Chung, J. Kim, W. Kim, K. Song, C. Park, Effect of trivalent
[47] Y. Chen, C. Chen, X. Li, Effect on the properties of different preparation Bi doping on the Seebeck coefficient and electrical resistivity of Ca3Co4O9,
processes in Ca3Co4O9 thermoelectric material, Int. Conf. Electr. Control Eng. J. Electron. Mater 44 (2015) 3621e3626.
(2010) 4672e4676. [76] G. Xua, R. Funahashic, M. Shikanoc, Q. Pub, B. Liu, High temperature trans-
[48] J.G. Noudem, M. Prevel, A. Veres, D. Chateigner, J. Galy, Thermoelectric port properties of Ca3-xNaxCo4O9 system, Solid State Commun. 124 (2002)
Ca3Co4O9 ceramics consolidated by Spark Plasma sintering, J. Electroceram 73e76.
22 (2009) 91e97. [77] Y. Huang, B. Zhao, S. Lin, Y. Sun, Enhanced thermoelectric performance
[49] J.G. Noudem, D. Kenfaui, D. Chateigner, M. Gomina, Toward the enhance- induced by misplaced substitution in layered Ca3Co4O9, J. Phys. Chem. C 119
ment of thermoelectric properties of lamellar Ca3Co4O9 by edge-free spark (2015) 7979e7986.
plasma texturing, Scr. Mater 66 (2012) 258e260. [78] J.P. Heremans, V. Jovovic, E.S. Toberer, A. Saramat, K. Kurosaki,
[50] Y. Huang, B. Zhao, J. Fang, R. Ang, Y. Sun, Tuning of microstructure and A. Charoenphakdee, S. Yamanaka, G.J. Snyder, Enhancement of thermoelec-
thermoelectric properties of Ca3Co4O9 ceramics by high-magnetic-field sin- tric efficiency in PbTe by distortion of the electronic density of states, Science
tering, J. Appl. Phys. 110 (2011) 123713. 321 (2008) 554e557.
[51] T. Suna, H. Hnga, Q. Yana, J. Ma, Effect of Ag-doping on crystal structure and [79] A. Santander-Syro, O. Copie, T. Kondo, F. Fortuna, S. Pailhe, R. Weht, X. Qiu,
high temperature thermoelectric properties of c-axis oriented Ca3Co4O9 thin F. Bertran, A. Nicolaou, A. Taleb-Ibrahimi, P.L. Fe{\curr `}vre, G. Herranz,
films by pulsed laser deposition, J. Alloys Compd. 511 (2012) 133e138. M. Bibes, N. Reyren, Y. Apertet, P. Lecoeur, A. Barthelemy, M.J. Rozenberg,
[52] T. Sun, H. Hng, Q. Yan, J. Ma, Enhanced high temperature thermoelectric Two-dimensional electron gas with universal subbands at the surface of
properties of Bi-doped c -axis oriented Ca3Co4O9 thin films by pulsed laser SrTiO3, Nature 469 (2011) 189e194.
deposition, J. Appl. Phys. 108 (2010) 083709. [80] H. Ohta, S. Kim, Y. Mune, T. Mizoguchi, K. Nomura, S. Ohta, T. Nomura,
[53] M. Kang, K. Cho, S. Oh, J. Kim, High-temperature thermoelectric properties of Y. Nakanishi, I.Y.M. Hirano, H. Hosono, K. Koumoto, Giant thermoelectric
nanostructured Ca3Co4O9, Appl. Phys. Lett. 98 (2011) 142102. Seebeck coefficient of a two-dimensional electron gas in SrTiO3, Nature 6
[54] Q. Qiao, A. Gulec, T. Paulauskas, S. Kolesnik, B. Dabrowski, M. Ozdemir, (2007) 129e134.
C. Boyraz, D. Mazumdar, A. Gupta, R. Klie, Effect of substrate on the atomic [81] N. Shanthi, D. Sarma, Electronic structure of electron doped SrTiO3: SrTiO3-
structure and physical properties of thermoelectric Ca3Co4O9 thin films, d and Sr1-xLaxTiO3, Phys. Rev. B 57 (1998) 2153e2158.
J. Phys. Condens. Matter 23 (2011) 305005. [82] W. Choi, H. Yoo, H. Ohta, Polaron transport and thermoelectric behavior in
[55] A. Sakai, T. Kanno, S. Yotsuhashu, A. Odagawa, H. Adachi, Control of epitaxial La-doped SrTiO3 thin films with elemental vacancies, Adv. Funct. Mater 25
growth orientation and anisotropic thermoelectric properties of misfit-type (2015) 799e804.
Ca3Co4O9 thin films, Jpn. J. Appl. Phys. 44 (2005) L 966eL 969. [83] D. Cuong, B. Lee, K. Choi, H. Ahn, S. Han, J. Lee, Oxygen vacancy clustering and
[56] J. Lybeck, M. Valkeap, S. Shibasaki, I. Terasaki, H. Yamauchi, M. Karppinen, electron localization in oxygen-deficient SrTiO3: LDAþU study, Phys. Rev.
Thermoelectric properties of oxygen-tuned ALD-grown [Ca2CoO3]0.62[CoO2] Lett. 98 (2007) 115503.
thin films, Chem. Mater (2010) 5900e5904. [84] S. Ohta, T. Nomura, H. Ohta, K. Koumoto, High-temperature carrier transport
[57] R. Wei, H. Jian, X. Tang, J. Yang, L. Hu, L. Chen, J. Dai, X. Zhu, Y. Sun, Enhanced and thermoelectric properties of heavily La- or Nb doped SrTiO3 single
thermoelectric properties in Cu-doped c-axis-oriented Ca3Co4O9þd thin crystals, J. Appl. Phys. 97 (2005) 034106.
films, J. Am. Ceram. Soc. 96 (2013) 2396e2401. [85] T. Okuda, K. Nakanishi, S. Miyasaka, Y. Tokura, Large thermoelectric response
[58] T. Yin, D. Liu, Y. Ou, F. Ma, S. Xie, J. Li, J. Li, Nanocrystalline thermoelectric of metallic perovskites: Sr1xLaxTiO3 (0<~x<~0.1), Phys. Rev. B 63 (2001)
Ca3Co4O9 ceramics by sol-gel based electrospinning and Spark Plasma Sin- 113104.
tering, J. Phys. Chem. C 114 (2010) 10061e10065. [86] C. Gayner, Kamal K. Kar, Recent advances in thermoelectric materials, Prog.
[59] G. Constantinescu, S. Rasekh, M. Torres, M. Madre, A. Sotelo, J. Diez, Mater Sci. 83 (2016) 330e382.
Improvement of thermoelectric properties in Ca3Co4O9 ceramics by Ba [87] N. Wang, L. Han, H. Hea, Y. Ba, K. Koumoto, Effects of mesoporous silica
doping, J. Mater Sci. Mater Electron 26 (2015) 3466e3473. addition on thermoelectric properties of Nb-doped SrTiO3, J. Alloys Compd.
[60] G. Constantinescu, S. Rasekh, M. Torres, C. Chocarro, J. Diez, M. Madre, 497 (2010) 308e311.
A. Sotelo, Influence of Ca substitution by Mg on the Ca3Co4O9 performances, [88] N. Wang, H. Chen, H. He, W. Norimatsu, M. Kusunoki, K. Koumoto, Enhanced
Bol. Soc. Espan ~ ola Cera
mica Vidr. 53 (2014) 41e47. thermoelectric performance of Nb-doped SrTiO3 by nano-inclusion with low
[61] L. Xu, F. Li, Y. Wang, High-temperature transport and thermoelectric prop- thermal conductivity, Sci. Rep. 3 (2013) 3449.
erties of Ca3Co4-xTixO9, J. Alloys. Compd. 501 (2010) 115e119. [89] E. Li, N. Wang, H. He, H. Chen, Improved thermoelectric performances of
[62] N. Prasoetsopha, S. Pinitsoontorn, T. Kamwanna, V. Amornkitbamrug, SrTiO3 ceramic doped with Nb by surface modification of nanosized titania,
K. Kurasaki, Y. Ohishi, H. Muta, S. Yamanaka, The effect of Cr substitution on Nanoscale Res. Lett. 11 (2016) 188.
the structure and properties of misfit-layered Ca3Co4-xCrxO9þd thermoelec- [90] K. Park, J. Son, S. Woo, K. Shin, M. Oh, S. Park, T. Hyeon, Colloidal synthesis
tric oxides, J. Alloys. Compd. 588 (2014) 199e205. and thermoelectric properties of La-doped SrTiO3 nanoparticles, J. Mater.
[63] M. Prevel, E. Sudhakar Reddy, O. Perez, W. Kobayashi, I. Terasaki, C. Goupil, Chem. A 2 (2014) 4217e4224.
J. Guillaume Noudem, Thermoelectric properties of sintered and textured [91] A. Dehkordi, S. Bhattacharya, J. He, H.N. Alshareef, T.M. Tritt, Significant
Nb-substituted Ca3Co4O9 ceramics, Jpn. J. Appl. Phys. 46 (2007) 6533e6538. enhancement in thermoelectric properties of polycrystalline Pr-doped
[64] Q. Yao, D.L. Wang, L.D. Chen, X. Shi, M. Zhou, Effects of partial substitution of SrTiO3 d ceramics originating from nonuniform distribution of Pr dop-
transition metals for cobalt on the high-temperature thermoelectric prop- ants, Appl. Phys. Lett. 104 (2014) 193902.
erties of Ca3Co4O9þd, J. Appl. Phys. 97 (2005) 103905. [92] B. Zhang, J. Wang, T. Zou, S. Zhang, X. Yaer, N. Ding, C. Liu, L. Miao, Y. Li,
[65] Y. Wang, Y. Sui, J. Cheng, X. Wang, J. Miao, Z. Liu, Z. Qin, W. Su, High tem- Y. Wu, High thermoelectric performance of Nb-doped SrTiO3 bulk materials
perature transport and thermoelectric properties of Ag-substituted with different doping levels, J. Mater. Chem. C 3 (2015) 11406.
Ca3Co4O9þd system, J. Alloys Compd. 448 (2008) 1e5. [93] S. Kumar, A.Z. Barasheed, H. Alshareef, High temperature thermoelectric
[66] Y. Wang, Y. Sui, J. Cheng, X. Wang, W. Su, Comparison of the high temper- properties of strontium titanate thin films with oxygen vacancy and niobium
ature thermoelectric properties for Ag-doped and Ag-added Ca3Co4O9, doping, ACS Appl. Mater. Interfaces 5 (2013) 7268e7273.
J. Alloy. Compd. 477 (2009) 817e821. [94] A.I. Abutaha, S. Kumar, K. Li, A. Dehkordi, T.M. Tritt, H. Alshareef, Enhanced
[67] S. Butt, W. Xu, W.Q. He, Q. Tan, G.K. Ren, Y. Lin, C. Nan, Enhancement of thermoelectric figure-of-merit in thermally robust, nanostructured super-
thermoelectric performance in Cd-doped Ca3Co4O9 via spin entropy, defect lattices based on SrTiO3, Chem. Mater 27 (2015) 2165e2171.
chemistry and phonon scattering, J. Mater. Chem. A 2 (2014) 19479. [95] S. Ohta, T. Nomura, H. Ohta, M. Hirano, H. Hosono, K. Koumoto, Large ther-
[68] Y. Wang, Y. Sui, X. Wang, W. Su, X. Liu, Enhanced high temperature thermoelectric performance of heavily Nb-doped SrTiO3 epitaxial film at high
moelectric characteristics of transition metals doped Ca3Co4O9þd by cold temperature, Appl. Phys. Lett. 87 (2005) 092108.
high-pressure fabrication, J. Appl. Phys. 107 (2010) 033708. [96] G.H. Zhang, Z.X. Dai, H.B. Li, H.Q. Wang, Y.Q. Li, X.F. Xu, B.T. Huang, Y.Q. Ma,
G. Li, Improving the thermoelectric properties of Sr0.9La0.1TiO3 by Ag addi- [125] H. Colder, E. Guilmeau, C. Harnois, S. Marinel, R. Retoux, E. Savary, Prepa-
tion, J. Low. Temp. Phys. 174 (2014) 128e135. ration of Ni-doped ZnO ceramics for thermoelectric applications, J. Eur.
[97] L. Li, Y. Liu, X. Qin, D. Li, J. Zhang, C. Song, L. Wang, Enhanced thermoelectric Ceram. Soc. 31 (2011) 2957e2963.
performance of highly dense and fine-grained (Sr1-xGdx)TiO3-d ceramics [126] A. Janotti, C.G.V.d. walle, Hydrogen multicentre bonds, Nat. Mater 6 (2006)
synthesized by sol-gel process and spark plasma sintering, J. Alloy. Compd. 44e47.
588 (2014) 562e567. [127] Khuong O. Ong, David J. Singh, P. Wu, Analysis of the thermoelectric prop-
[98] G.H. Zheng, Z.H. Yuan, Z.X. Dai, H.Q. Wang, H.B. Li, Y.Q. Ma, G. Li, Improve- erties of n-type ZnO, Phys. Rev. B 83 (2011) 115110.
ment of the thermoelectric properties of (Sr0.9La0.1)3Ti2O7 by Ag addition, [128] J.P. Wiff, Y. Kinemuchi, H. Kaga, C. Ito, K. Watari, Correlations between
J. Low. Temp. Phys. 173 (2013) 80e87. thermoelectric properties and effective mass caused by lattice distortion in
[99] Y. Wang, C. Wan, X. Zhang, L. Shen, K. Koumoto, A. Gupta, N. Bao, Influence of Al-doped ZnO ceramics, J. Eur. Ceram. Soc. 29 (2009) 1413e1418.
excess SrO on the thermoelectric properties of heavily doped SrTiO3 ce- [129] T. Tsubota, M. Ohtaki, K. Eguchi, H. Arai, Thermoelectric properties of Al-
ramics, Appl. Phys. Lett. 102 (2013) 183905. doped ZnO as a promising oxide material for high temperature thermo-
[100] T. Teranish, Y. Ishikawa, H. Hayashi, A. Kishimoto, M. Katayama, Y. Inada, electric conversion, J. Mater. Chem. 7 (1997) 85e90.
Thermoelectric efficiency of reduced SrTiO3 ceramics modified with La and [130] K. Jung, K. Lee, W. Seo, S. Choi, An enhancement of a thermoelectric power
Nb, J. Am. Ceram. Soc. 96 (2013) 2852e2856. factor in a Ga-doped ZnO system: a chemical compression by enlarged Ga
[101] J. Liu, C.L. Wang, Y. Li, W.B. Su, Y.H. Zhu, J.C. Li, L.M. Mei, Influence of rare solubility, Appl. Phys. Lett. 100 (2012) 253902.
earth doping on thermoelectric properites of SrTiO3 ceramics, J. Appl. Phys. [131] D. Zhang, B. Zhang, D. Ye, Y. Liu, S. Li, Enhanced Al/Ni co-doping and power
114 (2013) 223714. factor in textured ZnO thermoelectric ceramics prepared by hydrothermal
[102] M. Lee, J. Rhyee, M. Vaseem, Y. Hahn, S. Park, H. Kim, S. Kim, H. Lee, C. Kim, synthesis and spark plasma sintering, J. Alloys. Compd. 656 (2016) 784e792.
Thermoelectric properties of SrTiO3 nano-particles dispersed indium sele- [132] T. Tian, L. Cheng, L. Zheng, J. Xing, H. Gu, S. Bernik, H. Zeng, W.R.K. Zhao, G. Li,
nide bulk composites, Appl. Phys. Lett. 102 (2013) 223901. Defect engineering for a markedly increased electrical conductivity and
[103] A.V. Kovalevsky, A.A. Yaremchenko, S. Populoh, J.R. Frade, Enhancement of power factor in doped ZnO ceramic, Acta Mater 119 (2016) 136e144.
thermoelectric performance in strontium titanate by praseodymium sub- [133] A. Roy, Y. Cheng, M.L. Falk, Amorphous ZnO-based compounds as thermo-
stitution, J. Appl. Phys. 113 (2013) 053704. electrics, J. Phys. Chem. C 120 (2016) 2529e2535.
[104] F. Dang, C. Wan, N. Park, K. Tsuruta, W. Seo, K. Koumoto, Thermoelectric [134] D. Tang, W. Zhu, P. Wei, H. Zhou, Z. Liu, J. Yu, W. Zhao, Preparation and
performance of SrTiO3 enhanced by nanostructuring- seif-assembled par- properties of Zn4Sb2.94In0.06/ZnO composite thermoelectric materials,
ticulate film of nanocubes, ACS Appl. Mater. Interfaces 5 (2013) J. Electron. Mater 44 (2015) 1902e1908.
10933e10937. [135] N. Vogel-Schauble, Yaroslav E. Romanyuk, S. Yoon, Kachirayil J. Saji,
[105] J. Liu, C.L. Wang, H. Peng, W.B. Su, H.C. Wang, J.C. Li, J.L. Zhang, L.M. Mei, S. Populoh, S. Pokrant, Myriam H. Aguirre, A. Weidenkaff, Thermoelectric
Thermoelectric properties of Dy-doped SrTiO3 ceramics, J. Electron. Mater 41 properties of nanostructured Al-substituted ZnO thin films, Thin Solid Films
(2012) 3073. 520 (2012) 6869e6875.
[106] H. Wang, C. Wang, W. Su, J. Liu, Y. Sun, H. Peng, L. Mei, Doping effect of La [136] N. Nguyen, T. Nguyen, Y. Liu, M. Aminzare, A. Pham, S. Cho, Deniz P. Wong,
and Dy on the thermoelectric properties of SrTiO3, J. Am. Ceram. Soc. 94 K. Chen, T. Seetawan, N. Pham, H. Ta, V. Tran, T. Phan, Thermoelectric
(2011) 838e842. properties of indium and gallium dually doped ZnO thin films, ACS Appl.
[107] H.C. Wang, C.L. Wang, W.B. Su, J. Liu, H. Peng, Y. Sun, J.L. Zhang, M.L. Zhao, Mater. Interfaces 8 (2016) 33916e33923.
J.C. Li, N. Yin, Li M. Mei, Synthesis and thermoelectric performance if Ta [137] S. Saini, P. Mele, H. Honda, D. Henry, P. Hopkins, L. Luna, K. Matsumoto,
doped Sr0.9La0.1TiO3 ceramics, Ceram. Int. 37 (2011) 2609e2613. K. Miyazaki, A. Ichinose, Enhanced thermoelectric performance of Al-doped
[108] Y. Wang, K. Lee, H. Hyuga, H. Kita, H. Ohta, K. Koumoto, Enhancement of ZnO thin films on amorphous substrate, Jpn. J. Appl. Phys. 53 (2014) 060306.
thermoelectric performance in rare earth-doped Sr3Ti2O7 by symmetry [138] S. Saini, P. Mele, H. Honda, T. Suzuki, K. Miyazaki, A. Ichinose, L. Luna,
restoration of TiO6 octahedra, J. Electroceram 24 (2014) 76e82. R. Carlini, A. Tiwari, Effect of sef-grown seed layer on thermoelectric prop-
[109] N. Wang, H. Li, Y. Ba, Y. Wang, C. Wan, K. Fujinami, K. Koumoto, Effects of YSZ erties of ZnO thin films, Thin Solid Films 605 (2016) 289e294.
additions on thermoelectric properties of Nb-doped Strontium Titanate, [139] J. Loureiro, N. Neves, R. Barros, T. Mateus, R. Santos, S. Filonovich, S. Reparaz,
J. Electron. Mater 39 (2010) 1777e1781. C.M. Sotomay, F. Wyczisk, L. Divay, R. Martinsa, I. Ferreira, Transparent
[110] J. Ravichandran, W. Siemons, D.W. Oh, J.T. Kardel, A. Chari, H. Heijimerikx, aluminium zinc oxide thin films with enhanced thermoelectric properties,
M.L. Scullin, A. Majumdar, R. Ramesh, D.G. Cahill, High-temperature ther- J. Mater. Chem. A 2 (2014) 6649.
moelectric response of double-doped SrTiO3 epitaxial films, Phys. Rev. B 82 [140] L. Li, L. Fang, X.M. Chen, J. Liu, F.F. Yang, Q.J. Li, G.B. Liu, S.J. Feng, Influence of
(2010) 165126. oxygen argon ratio on the structural, electrical, optical and thermoelectrical
[111] Y. Wang, K.H. Lee, H. ohta, K. Koumoto, Thermoelectric properites of electron properties of Al-doped ZnO thin films, Phys. E 41 (2008) 169e174.
doped SrO (SrTiO3)n (n¼1, 2) ceramics, J. Appl. Phys. 105 (2009) 103701. [141] L. Li, L. Fang, X. Zhou, Z. liu, L. Zhao, S. Jiang, X-ray photoelectron spectros-
[112] H. Muta, K. Kurosaki, S. Yamanaka, Thermoelectric properties of rare earth copy study and thermoelectric properties of Al-doped ZnO thin films,
doped SrTiO3, J. Alloys. Compd. 350 (2003) 292e295. J. Electron Spectrosc. Relat. Phenom. 173 (2009) 7e11.
[113] A.V. Kovalevsky, A.A. Yaremchenko, S. Populoh, P. Thiel, D.P. Fagg, [142] P. Fan, Y. Li, Z. Zheng, Q. Lin, J. Luo, G. Liang, M. Zhang, M. Chen, Thermo-
A. Weidemkaff, J.R. Frade, Towards a high thermoelectric performance in electric properties optimization of Al-doped ZnO thin films prepared by
rare-earth substituted SrTiO3: effects provided by strongly-reducing sinter- reactive sputtering Zn-Al alloy target, Appl. Surf. Sci. 284 (2013) 145e149.
ing conditions, Phys. Chem. Chem. Phys. 16 (2014) 26946e26954. [143] P. Mele, S. Saini, H. Honda, K. Matsumoto, K. Miyazaki, H. Hagino, A. ichinose,
[114] S. Stemmer, S.J. Allen, Two-dimensional electron gases at complex oxide Effect of substrate on thermoelectric properties of Al-doped ZnO thin films,
interfaces, Annu. Rev. Mater. Res. 44 (2014) 151e171. Appl. Phys. Lett. 102 (2013) 253903.
[115] R. Zhang, C. Wang, J. Li, K. Koumotow, Simulation of thermoelectric perfor- [144] M. Ohraki, T. Tsubota, K. Eguchi, H. Arai, High-temperature thermoelectric
mance of bulk SrTiO3 with two-dimensional electron gas grain boundaries, properties of (Zn1-xAlx)O, J. Appl. Phys. 79 (1996) 1816e1818.
J. Am. Ceram. Soc. 93 (2010) 1677e1681. [145] D. Berardan, C. Byl, N. Dragoe, Influence of the preparation conditions on the
[116] S. Shimizu, S. Ono, T. Hatano, Y. Iwasa, Y. Tokura, Enhanced cryogenic thermoelectric properites of Al-doped ZnO, J. Am. Ceram. Soc. 93 (2010)
thermopower in SrTiO3 by ionic gating, Phys. Rev. B 92 (2015) 165304. 2353e2358.
[117] P. Samanta, P. Chaudhuri, Substrate effect on morphology and photo- [146] X. Qu, W. Wang, S. Lv, D. Jia, Thermoelectric properties and electronic
luminescence from ZnO monopods and bipods, Front. Optoelectron. China 4 structure of Al-doped ZnO, Solid State Commun. 151 (2011) 332e336.
(2011) 130e136. [147] N. Ma, J. Li, B.P. Zhang, Y.H. Lin, L.R. Ren, G.F. Chen, Microstructure and
[118] P. Schroer, P. Kriiger, J. Pollmann, First-principles calculation of the electronic thermoelectric properties of Zn1-xAlxO ceramics fabricated by spark plasma
structure of the wurtzite semiconductors Zno and ZnS, Phys. Rev. B 47 (1993) sintering, J. Phys. Chem. Solids 71 (2010) 1344e1349.
6971e6980. [148] L. Han, N. Nong, L. Hung, T. Holgate, N. Pryds, M. Ohtaki, S. Linderoth, The
[119] E. Ohshimaa, H. Oginoa, I. Niikurab, K. Maeda, M. Satob, M. Ito, T. Fukuda, influence of a- and g-Al2O3 phases on the thermoelectric propertiets of Al-
Growth of the 2-in-size bulk ZnO single crystals by the hydrothermal doped ZnO, J. Alloys. Compd. 555 (2013) 291e296.
method, J. Cryst. Growth 260 (2003) 166e170. [149] L. Hoong, Y. Keat, A. Chik, T. Leng, Band structure and thermoelectric prop-
[120] F. Li, Y. Ding, P. Gao, X. Xin, Z.L. Wang, Single-crystal hexagonal disks and erties of inkjet printed ZnO and ZnFe2O4 thin films, Ceram. Int. 42 (2016)
rings of ZnO: low-temperature, large-scale synthesisand growth mechanism, 12064e12073.
Angew. Chem. Int. Ed. 43 (2004) 5238e5242. [150] S. Shimizua, M. Bahramy, T. Iizukab, S. Ono, K. Miwac, Y. Tokura, Y. Iwasa,
[121] J. Wiff, Y. Kinemuchi, H. Kaga, C. Ito, K. Watari, Correlations between ther- Enhanced thermopower in ZnO two-dimensional electron gas, Proc. Natl.
moelectric properties and effective mass caused by lattice distortion in Al- Acad. Sci. 113 (2016) 6438e6443.
doped ZnO ceramics, J. Eur. Ceram. Soc. 29 (2009) 1413e1418. [151] J. Lee, T. Park, S. Lee, N. Park, W. Lee, J. Lim, S. Lee, J. Park, Enhancing the
[122] A. Janotti, C. Van de Walle, Fundamentals of zinc oxide as a semiconductor, thermoelectric properties of super-lattice Al2O3/ZnO atomic film via inter-
Rep. Prog. Phys. 72 (2009) 126501. face confinement, Ceram. Int. 42 (2016) 14411e14415.
[123] H. Cheng, X. Xu, H. Hn, J. Ma, Characterization of Al-doped ZnO thermo- [152] T. Tynell, I. Terasaki, H. Yamauchi, M. Karppinen, Thermoelectric character-
electric materials prepared by RF plasma powder processing and hot press istics of (Zn, Al)O/hydroquinone superlattices, J. Mater. Chem. A 1 (2013)
sintering, Ceram. Int. 35 (2009) 3067e3072. 13619.
[124] A. Catellani, A. Ruini, M. Nardellide, A. Calzolari, Unconventional co- [153] Antti J. karttunen, T. Tynell, M. Karppinen, Layer-by-layer design of nano-
existence of plasmon and thermoelectric activity in In:ZnO nanowires, RSC structured thermoelectrics: first-principles study of ZnO:organic super-
Adv. 5 (2015) 44865. lattices fabricated by ALD/MLD, Nano Energy 22 (2016) 338e348.
[154] P. Jood, R.J. Mehta, Y. Zhang, G. Peleckis, X. Wang, R.W. Siegel, T. Borca- promising new high-temperature n-type thermoelectric materials, Inorg.
Tasciuc, S. Dou, G. Ramanath, Al-doped zinc oxide nanocomposites with Chem. 47 (2008) 8077e8085.
enhanced thermoelectric properties, Nano Lett. 11 (2011) 4337e4342. [167] M. Matsukawa, A. Tamura, Y. Yamato, T. Kumagai, S. Nimori,
[155] F. Zhang, Q. Lu, X. Zhang, J. Zhang, First principle investigation of electronic R. Suryanarayanan, Thermal transport in electron-doped manganites Ca1-
structure of CaMnO3 thermoelectric compound oxide, J. Alloys. Compd. 509 xCexMnO3, J. Magn. Magn. Mater 310 (2007) e283ee285.
(2011) 542e545. [168] W. Liu, Q. Jie, H. Kim, Z. Ren, Current progress and future challenges in
[156] C. Martin, A. Maignan, F. Damay, M. Hervieu, B. Raveau, CMR Effect in thermoelectric power generation:From materials to devices, Acta Mater 87
electron-doped manganites Ca1-xSmxMnO3, J. Solid State Chem. 134 (1997) (2015) 357e376.
198e202. [169] P. Mele, H. Kamei, H. Yasumune, K. Matsumoto, K. Miyazaki, Development of
[157] S. Satpathy, Zoran S. Popovic, Filip R. Vukajlovic, Electronic structures of the thermoelectric module based on dense Ca3Co4O9 and Zn0.98Al0.02O Legs, Met.
perovskite oxides: La1-xCaxMnO3, Phys. Rev. Lett. 76 (1996) 960e963. Mater. Int. 20 (2014) 389e397.
[158] N. Loshkareva, L. Nomerovannaya, E. Mostovshchikova, A. Makhnev, [170] L. Hung, N. Nong, S. Linderoth, N. Pryds, Segmentation of low-cost high ef-
Y. Sukhorukov, N. Solin, T. Arbuzova, S. Naumov, N. Kostromitina, Electronic ficiency oxide-based thermoelectric materials, Phys. Status Solidi 212 (2015)
structure and polarons in CaMnO3d single crystals: optical data, Phys. Rev. B 767e774.
70 (2004) 224406. [171] S. Saini, P. Mele, K. Miyazaki, A. Tiwari, On-chip thermoelectric module
[159] B. Zhan, J. Lan, Y. Liu, Y. Lin, Y. Shen, C. Nan, High temperature thermoelectric comprised of oxide thin film legs, Energy Convers. Manage 114 (2016)
properties of Dy-doped CaMnO3 ceramics, J. Mater. Sci. Technol. 30 (2014) 251e257.
821e825. [172] S. Choi, K. Lee, C. Lim, W. Seo, Oxide-based thermoelectric power generation
[160] M. Jaime, H. Hardner, M. Salamon, M. Rubinstein, P. Dorsey, D. Emin, Hall- module using p-type Ca3Co4O9 and n-type (ZnO)7In2O3 legs, Energy Convers.
effect sign anomaly and small-polaron conduction in (La1- Manage 52 (2011) 335e339.
xGdx)0.67Ca0.33MnO3, Phys. Rev. Lett. 78 (1997) 951e954. [173] T. Souma, M. Ohtaki, K. Ohnishi, M. Shigeno, Y. Ohba, T. Shimozaki, Power
[161] M. Schrade, R. Kabir, S. Li, T. Norby, T. Finstad, High temperature transport generation characteristics of oxide modules incorporating nanostructured
properties of thermoelectric CaMnO3-dd indication of strongly interacting ZnO sintered materials, In: Procceding of the 26th international conference
small polarons, J. Appl. Phys. 115 (2014) 103705. in thermoelectrics. (2007) 38e41.
[162] R. Kabir, T. Zhang, D. Wang, R. Donelson, R. Tian, T. Tan, S. Li, Improvement in [174] R. Funahashi, S. Urata, Fabrication and application of an oxide thermoelectric
the thermoelectric properties of CaMnO3 perovskites by W doping, J. Mater. system, Int. J. Appl. Ceram. Technol. 4 (2007) 297e307.
Sci. 49 (2014) 7522e7528. [175] I. Matsubara, R. Funahashi, T. Takeuchi, S. Sodeoka, T. Shimizu, T. Ueno,
[163] P. Thiel, J. Eilertsen, S. Populoh, G. Saucke, M. DVobeli, A. Shkabko, L. Sagarna, Fabrication of an all-oxide thermoelectric power generator, Appl. Phys. Lett.
L. Karvonen, A. Weidenkaff, Influence of tungsten substitution and oxygen 78 (2001) 3627.
deficiency on the thermoelectric properties of CaMnO3-d, J. Appl. Phys. 114 [176] A. Inagoya, D. Sawaki, Y. Horiuchi, S. Urata, R. Funahashi, I. Terasaki, Ther-
(2013) 243707. moelectric module made of perovskite cobalt oxides with large thermo-
[164] Y. Wang, Y. Sui, W. Su, High temperature thermoelectric characteristics of power, J. Appl. Phys. 110 (2011) 123712.
Ca0.9R0.1MnO3 (R¼La,Pr,… ,Yb…), J. Appl. Phys. 104 (2008) 093703. [177] P. Tomes, R. Robert, M. Ttrottmann, L. Bocher, M. Aguirre, A. Bitschi,
[165] R. Kabir, R. Tian, T. Zhang, R. Donelson, T. Tan, S. Li, Role of Bi doping in J. Hejtmanek, A. Weidenkaff, Synthesis and characterization of new ceramic
thermoelectric properties of CaMnO3, J. Alloys Compd. 628 (2015) 347e351. thermoelectrics implemented in a thermoelectric oxide module, J. Electron.
[166] L. Bocher, M. Aguirre, D. Logvinovich, A. Shkabko, R. Robert, M. Trottmann, Mater 9 (2010) 1696e1703.
A. Weidenkaff, CaMn1-x NbxO3 (x ¼ 0.08) perovskite-type phases as

1 s2.0 S0042207X17300544 Main

Uploaded by

Copyright:

Available Formats

1 s2.0 S0042207X17300544 Main

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

1 s2.0 S0042207X17300544 Main

Uploaded by

Copyright:

Available Formats

Vacuum 146 (2017) 356e374

Contents lists available at ScienceDirect

Recent advances in oxide thermoelectric materials and modules

1. Introduction " pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi #

Wiedemann-Franz law concentration of typical broad-band materials is presented in

time due to a slow cooling rate of ~1 K/h. Besides this, it is also

2.2.1. Fabrication process

substituted Ca3Co4O9 samples were observed to have the highest

the electrical conductivity. Moreover, the addition of Cd suppressed p2 dNA kB m*

98: 2 RF (St-AZO target) 240 RT 4 10 4

nanostructured Al-doped ZnO (Fig. 10). However, since these de-

3.3.1. Electronic structures of CaMnO3

CaMn0$96W0$04O3-d [163]. The highest ZT reported so far for these

4. Oxides based thermoelectric modules

A thermoelectric module is made up of a series of arrays of p-

p: NaCo2O4 n: ZnO 12 Diffusion 455 0.79 52.5 0.115 [173]

The output power increased with the increase in hot-side 5. Summary

You might also like