Ceramics International xxx (xxxx) xxxxxx

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Eect of Spark Plasma Sintering (SPS) on the thermoelectric properties of

SrTiO3 :15 at% Nb

Pinku Roy, Vijyeta Pal, Tanmoy Maiti
Plasmonics and Perovskites Laboratory, Department of Materials Science and Engineering, Indian Institute of Technology Kanpur, UP, 208016, India

A R T I C L E I N F O A BS T RAC T

Keywords: Recently Nb doped SrTiO3 has been reported as one of the most promising n-type thermoelectric materials. In
Thermoelectrics this report SrTiO3: 15 at% Nb ceramics were synthesized by Spark Plasma Sintering (SPS) route, which is a fast
Perovskite, SrTiO3, SPS sintering process. Eect of sintering temperature, pressure and atmosphere on the thermoelectric power factor
of STN ceramics were investigated in the present work in order to optimize the sintering condition using SPS. It
was observed that STN samples sintered at 1673 K using 30 MPa pressure in Ar-atmosphere showed best
thermoelectric power factor. Room temperature XRD results veried STN as a single phase solid solution with
cubic crystal structure. Microstructure of these ceramics were studied using FESEM where the results conrmed
the formation of sub micron range grains as expected in SPS. All the STN samples behaved as n-type
semiconductor throughout the measurement. The conduction mechanism of these ceramic samples were
studied using the Variable Range Hopping (VRH) and Small Polaron Hopping (SPH) model.

1. Introduction
As the fossil fuel resources have been depleting gradually over the
past decades, search for alternative energy sources has become an area
of research for many scientists across the globe. Technology of mutual
conversion between electric and thermal energy by using a thermo-
electric (TE) material is considered as one of the key technologies to
solve the future energy demands. The performance of a thermoelectric
material for energy conversion is given by the dimensionless gure of
merit [1] called ZT =S2T/k. Where S is the Seebeck coecient, is the
electrical conductivity, k is the thermal conductivity and T is the
absolute temperature of the material. TE material with high ZT value
should have high Seebeck coecient, high electrical conductivity and
low thermal conductivity [24]. The thermal conductivity of a material
has an electronic contribution (ke) and lattice vibration contribution
(kl). The electronic thermal conductivity ke is related with the electrical
conductivity by Wiedemann Franz law as ke= LT, where L is the
Lorentz number [1], is the electrical conductivity and T is the
temperature. Since we need high electrical conductivity in a TE
material and electronic thermal conductivity is proportional to elec-
trical conductivity, we can only aord to reduce the thermal conduc-
tivity by reducing the lattice thermal conductivity part of a material.
Lattice thermal conductivity (kl) can be reduced by modern solid state
chemistry approaches such as complex inorganic structures [5,6],
crystal structures with rattlers [69], engineered crystal lattice
[10,11] etc. Various kinds of materials with good ZT values e.g.
skutterudites [9,12], chalcogenides [13,14], clatharates [14,15], half-
heusler alloy [1518], etc. have been developed over the past two
decades. But due to poor durability at high temperature, toxicity, cost,
low abundance of the constituting elements of these materials, the
search for a new environmental friendly TE material has become a
topic of research.
The discovery of NaxCoO4, Ca3Co4O9 based [19,20] thermoelectric
material with good ZT values has motivated the scientic community to
work on oxides for TE applications. Recently authors [2124] have
performed extensive research on double perovskite based thermo-
electric materials such as Sr2TiMO6 (M=Fe, Co, Mo), BaxSr2xTiMO6
(M=Fe, Co), BaxSr2xTi0.8Fe0.8Nb0.4O6. All these materials have shown
a great potential for thermoelectric application. However, these
materials are p type semiconductor or some of them exhibit p-n type
switching at high temperature. In the present work eorts have been
made to develop n-type thermoelectric material. Many researchers
have reported n-type TE behavior in Nb doped SrTiO3 [2527]
showing good potential to use it as n-type TE device module.
However no such reports have been found in the literature on TE
behavior of Nb doped SrTiO3 synthesized by Spark Plasma Sintering
(SPS) route. SPS is a fast sintering technique for consolidation of
powders utilizing uniaxial force and pulsed direct electric current under
low atmospheric pressure. Wide range of materials (metals, compo-
sites, ceramics) can be compacted using spark plasma sintering at few

Corresponding author.
E-mail address: tmaiti@iitk.ac.in (T. Maiti).

http://dx.doi.org/10.1016/j.ceramint.2017.06.170
Received 10 April 2017; Received in revised form 22 June 2017; Accepted 26 June 2017
0272-8842/ 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Roy, P., Ceramics International (2017), http://dx.doi.org/10.1016/j.ceramint.2017.06.170
P. Roy et al.
hundred Kelvin lower processing temperature than in conventional
sintering process [28,29]. MM Moreover, overall duration of proces-
sing is generally 520 min. As a result, SPS can produce uniformly
sintered nano size grains which is necessary to reduce lattice thermal
conductivity of our TE samples. In this article we have studied the
thermoelectric properties of Nb doped SrTiO3 prepared by SPS route.
We have optimized the processing paramters by sintering STN samples
at dierent temperatures, pressures and atmospheres (vacuum, Ar). To
the best of our knowledge this is the rst report of thermoelectric
properties of 15 at% Nb doped SrTiO3 synthesized by SPS.
Furthermore, we investigated the charge transport phenomena of these
sintered samples using variable range hopping and small polaron
hoping model.
2. Experimental procedure
Dense pellets of 15 at% Nb doped SrTiO3 (STN) was prepared by
spark plasma sintering (SPS) route. Initially the precursors such as
SrCO3, TiO2 and Nb2O5 were mixed using zirconia balls and ethanol as
a medium in a roller ball mill for 24 h. The mixed and dried up powder
was then kept for calcination at 1773 K for 48 h in H2 atmosphere to
ensure the single-phase formation. The calcined powder was then
further milled using a planetary micro mill (Fritsch, PULVERISETTE
7 premium Line, Rhineland-Palatinate, Germany) for 120 min at
600 rpm using zirconia grinding balls. The calcined powder was then
sintered with SPS (El Tek Co., Korea) at various temperature and
pressure using cylindrical graphite of 15 mm dia. Initial pressure and
sintering temperature was set to 30 MPa and 1523 K, respectively and
the holding time at 1523 K was set 5 min. We further changed the
pressure from 30 MPa to 50 MPa but since no great change in the
thermoelectric properties were observed in STN ceramics, we contin-
ued with the 30 MPa. Further we raised the sintering temperature to
1623 K, 1673 K and 1723 K and tried to optimize the temperature for
Spark plasma sintering of STN. The thermoelectric measurements
(electrical conductivity and Seebeck coecient) of these pellets were
carried out from room temperature to 1223 K at the interval of 50 K
using a ZEM-3M10 apparatus (ULVAC-RIKO Inc.), consecutively the
power factor (S2) was calculated for all the samples. Microstructural
investigation of the polished ceramic samples was performed using
scanning electron microscope (SEM, Carl Zeiss NTS GmbH, EV050,
Germany). The powder X-ray diraction (XRD) patterns of annealed
oxide powders were measured using a PANalytical X'Pert diract-
ometer.
3. Results and discussion
3.1. Structural and microstructural characterization
The phase purity, chemical compatibility and structure of SrTiO3:
15 at% Nb (STN) composition was examined at room temperature by
powder x-ray diraction studies. Powder x-ray diraction pattern of
STN veries the single-phase solid solution. For all the STN samples
XRD peaks were properly indexed with respect to the perovskite
structure as shown in Fig. 1. It is apparent from Fig. 1 that the room
temperature XRD of STN samples exhibit a cubic structure as no peak
splitting was observed in XRD proles.
The microstructure of STN samples were investigated by capturing
FESEM images of fracture surface as shown in Fig. 2. These images
demonstrate densely packed microstructure with nano-meter size
grains obtained by SPS in the STN samples. However, as we increased
the sintering temperature grains looked melted locally, resulting fused
grains in the microstructure. which is good for a thermoelectric
material for reducing lattice thermal conductivity.
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Ceramics International xxx (xxxx) xxxxxx
Fig. 1. XRD pattern of STN samples sintered at 1523 K,1623 K,1673 K and 1723 K.
4. Thermoelectric measurement
To check the potential for thermoelectric application of STN
samples prepared by SPS route at various temperature, electrical
conductivity and Seebeck coecient were simultaneously measured
from room temperature to 1223 K at 50 K interval. Variation of
electrical conductivity with temperature is shown in Fig. 3(a).
Initially the 1523 K sintered STN sample exhibit a semiconductor
(d/dT > 0) to metal like (d/dT < 0) transition at around 800 K and
with further increase in temperature the semiconductor phase reap-
pears. When we increase sintering temperature to 1623 K, the
semiconductor to metal (M-S) like transition occurred at lower
temperature than that of 1523 K sintered STN sample. However, the
metal-like behavior (d/dT < 0) appears for a short temperature range
in STN sample sintered at 1623 K, after which it exhibits semiconduc-
tor-like (d/dT > 0) conductivity throughout the measurement. Finally,
for STN samples sintered at higher temperatures (1673 K) it exhibits
semiconductor-like (d/dT > 0) conductivity behavior throughout the
temperature range of measurement, which can be seen in Fig. 3(a).
However, for high temperature (1673 K) sintered STN samples,
conductivity curve seems to be saturated at higher temperature making
it look like approaching towards M-S transition. Similar kind of M-S
transition behavior in STN sample has been observed by other
researchers [26,27]. We have further compared our conductivity data
with STN sample sintered conventionally at 1773 K in H2 atmosphere
for 12 h. As shown in Fig. 3(a), conductivity values of STN ceramics
sintered by SPS are higher than that of conventionally sintered sample.
The Seebeck coecient of all the STN samples continuously increases
with temperature in the whole range of measurement. It is evident
from Fig. 3(b) that S value decreases with increase in sintering
temperature by from 1523 K to 1673 K for SPS samples. When we
have compared the thermos power (S) data of SPS ceramic samples
with conventionally sintered sample it has been found that 1523 K SPS
sample showed higher Seebeck coecient (S); but other SPS samples
produced lower S values than conventionally sintered sample.
However, Seebeck coecient doesnt change much when we raised
the SPS temperature further from 1673 K to 1723 K. It is to be noted
that SPS@1673 K sintered STN sample shows maximum electrical
conductivity values in the temperature range of measurement resulting
highest thermoelectric power-factor (S2).
The maximum thermo-power (S2) of 33.21 W/mK2 at 1229 K is
observed in STN sample sintered at 1673 K by SPS route. Hence the
optimum sintering temperature for STN by spark plasma route is
P. Roy et al. Ceramics International xxx (xxxx) xxxxxx

Fig. 2. FESEM of STN samples sintered at (a) 1523 K (b) 1623 K (c) 1673 K and (d)1723 K.

considered as 1673 K to achieve maximum S2 value as shown in structure is the source of ve charge carriers in STN. Further we tried
Fig. 3(c). to study the conduction mechanism in this compounds. Since multi
valent cations (Ti4+ and Nb5+) are present in these solids we have
5. Discussion investigated the samples polaron hopping conduction model. So we
have to t the variable range hopping (VRH) model [30,31] which is
Furthermore, electrical conductivity mechanism and charge trans- given by,
port phenomena of all the STN samples were investigated. The STN
samples demonstrate negative Seebeck coecient throughout the
T 1/4
= o exp o
measurement temperature range, implying electron as a majority T (2)
carrier in these ceramic samples which can be dened by the following Where o and To are constants and To is given by
possible defect reaction,
1 To = 24/[kBN (Ef ) 3] (3)
4SrO + 2TiO2 + Nb2O5 4Sr Sr + 2TiTi + 12OO + 2NbTi + O2 + 2e
2 Where N(Ef) is the density of localized states at the fermi level and is
(1) the decay length of the localized wave function. In Fig. 4(a) the
Above defect reaction suggests that es generated due to incorpora- electrical conductivity is plotted as a function of ln() vs T1/4 for all
tion of Nb5+ in the B-site (+4 formal value) of ABO3 perovskite the STN samples where the red line indicates the tted curve of the

Fig. 3. The variation of electrical conductivity(), Seebeck coecient(S) and power factor (S2) with temperature for STN samples sintered at dierent temperatures.

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o Ehop
= exp
T kBT (4)
Where o is the constant and Ehop is the activation energy for electron
to transport through the multivalent cation sites. In Fig. 4(b) experi-
mental data were tted with respect to the small poloron hopping
model for all the STN samples. For 1523 K and 1623 K STN samples it
is apparent from Fig. 4(a) and (b) that the conduction mechanism is
governed by the variable range hopping in the low temperature range
till they undergo semiconductor to metal transition. VRH normally
occurs in such a temperature range wherein the energy is insucient to
excite the charge carrier across the Coulomb gap [36]. Fig. 4(b) depicts
good t in the conductivity data with SP model at higher temperatures.
For 1523 K and 1623 K sintered STN.
samples conduction mechanism was found to be governed by SP
model beyond semiconductor-metal transition. It is evident from
Fig. 4(a) and (b) that high temperature conductivity of 1673 K and
1723 K sintered samples followed the SP model from the temperature
range where gradual departure from VRH model was observed.
Departure from VRH to SP hopping conduction mechanism in
these materials suggests the electrons require to overcome an activa-
tion energy barrier to become delocalised from the defect sites. The
activation energy required to move electron by SP hopping model is
shown in Table 1. From Table 1 we can see that the activation energy
required for the electron hopping by small polaron hopping model
decreases with the increase in sintering temperature. Due to the drastic
decrease in activation energy from SPS@1523 K sample to SPS@1673
K sample the electron density increased which raised the electrical
conductivity.
Further we tried to investigate the transport mechanism by analys-
ing the Seebeck coecient of all the STN samples. The Seebeck
coecient of such materials where conduction mechanism is governed
by the polaron hopping mechanism can be expressed by Heike's
formula. However, Heikes formula neglected the spin degeneracy of
carriers assuming that only one spin orientation per site is allowed.
Chaikin and Beni later modied Heikes formula [33] to better address
the spin interactions of the electrons and corrected the equation as
kB 2 c
S= ln
e c (5)
Where c is the fractional small polaron concentration. Using modied
Heikes formula we estimated the small-polaron concentration (c) for
all the STN samples which is shown in Table 2. The fractional small
polaron concentration (c) was found to be increased with increase in
sintering temperature and maximum c was found in 1673 K sintered
sample which justies maximum electrical conductivity observed in
this sample.

6. Conclusion

In summary we have optimized sintering temperature, time and

other parameters for the synthesis of STN15 using SPS route. Nb doped
SrTiO3 has produced n-type semiconductor throughout the measure-
ment temperature range of measurement with high Seebeck coecient
Fig. 4. Conduction mechanism governed by (a) Variable range hopping at lower ranging from 70 to 200 V/K. All the STN samples processed in
temperature and (b) Small polaron hopping at higher temperature for STN samples the present work were single phase solid solution with dense micro-
sintered at (i) 1523 K, (ii) 1623 K, (iii) 1673 K, and (iv) 1723 K.
Table 1
experimental data. From Fig. 4(a) it is evident that conduction Calculated activation energy using small polaron hopping model.
mechanism of all STN samples are driven by VRH model at low
STN samples SPS at various Calculated Ehop value using SP model
temperature, apparently 1523 K and 1623 K sintered sample followed
temperature (K) in eV
VRH conduction mechanism till semiconductor to metal transition
temperature. Further, attempts have been made to check if the small 1523 0.683
polaron (SP) hopping conduction mechanism [3235] is followed by 1623 0.155
1673 0.141
these STN oxides. SP model is described by,
1723 0.137

4
P. Roy et al. Ceramics International xxx (xxxx) xxxxxx

Table 2 597602.
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33.21 W/mK2 at 1229 K was observed in SPS@1673 K sample Y. S, K.U.I. Terasaki, I. M. H. I. T. T. U. M, S.S.R. Funahashi, R. F. I. M. K. U. S. S,
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[21] P. Roy, I. Bose, T. Maiti, Integr. Ferroelectr. (2016) 174.
[22] P. Roy, V. Waghmare, T. Maiti, RSC Adv. 6 (2016) 5463654643.
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58185829.
[24] M. Saxena, P. Roy, M. Acharya, I. Bose, K. Tanwar, T. Maiti, Appl. Phys. Lett. 109
This work is supported by the grant from Science and Engineering (2016) 263903.
Research Board, DST (SERB-DST), India (Grant No: SB/S3/ME/008/ [25] A. Kovalevsky, M.H. Aguirre, S. Populoh, S.G. Patrcio, N.M. Ferreira,
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