pubs.acs.

org/journal/ascecg Research Article

High-Entropy Perovskites: An Emergent Class of Oxide

Thermoelectrics with Ultralow Thermal Conductivity
Ritwik Banerjee,# Sabitabrata Chatterjee,# Mani Ranjan, Tathagata Bhattacharya, Soham Mukherjee,
Subhra Sourav Jana, Akansha Dwivedi, and Tanmoy Maiti*
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ABSTRACT: Although SrTiO3-based perovskites showed a lot of promise as n-type thermoelectric (TE) materials, they
demonstrated a low figure of merit value primarily because of their high lattice thermal conductivity (kl). Researchers found it
difficult to reduce kl, as a popular route like nanostructuring did not work well with these perovskites possessing low phonon mean
free paths. Here, we put forward a novel strategy of designing high-entropy perovskite (HEP) oxides having five transition metals in
the B site to induce more anharmonicity causing enhanced multiphonon scattering in order to decrease kl. Using detailed
thermodynamic calculations, we designed and synthesized a highly dense Sr(Ti0.2Fe0.2Mo0.2Nb0.2Cr0.2)O3 HEP ceramic. An ultralow
thermal conductivity of 0.7 W/mK at 1100 K was achieved in this n-type rare-earth-free HEP oxide TE material. The concept of
designing HEPs to achieve ultralow thermal conductivity potentially opens up a new avenue for enhancing TE performance of
environmentally benign bulk oxides for high-temperature TE power generation.
KEYWORDS: high entropy, perovskites, oxides, thermoelectric, low thermal conductivity

■ INTRODUCTION
High-entropy alloys (HEAs),1−3 whose essence lies in the
effect. However, these reports on HEP bulk oxides hardly
explored their functional properties, except the one on magnetic
mixing of five or more elements in equal proportion giving rise to behavior.16 Herein, we posited the concept of HEPs for
a single-phase solid solution, resulting in favorable Gibbs free designing novel thermoelectric (TE) materials. TE materials
energy by overcoming the usual phase separation caused by the
are considered for clean energy generation using the waste heat
high enthalpy effect,4 has demonstrated exciting properties in
recent times.5 HEAs showed promise for various applications in produced by manufacturing industries, furnaces, combustion
transportation and automobile industries,6 coatings,7 and so on, engines, various electronic appliances, and so on. Energy
due to their better performance than that of constituent conversion efficiency of a TE power generator is typically
elements.8 In 2015, Rost et al.9 developed high-entropy oxides dictated by a single dimensionless quantity called figure of merit
by incorporating five cations equiatomically in an oxide structure
(ZT):
to convert the multiphase structure into a single phase, utilizing
the similar concept of HEAs. Later, few more reports on the
electrical and magnetic properties of high-entropy oxides were Received: May 23, 2020
made in the last 3 years.10−13 Over the past one year, high- Revised: October 16, 2020
entropy perovskites (HEPs) or HEP oxides14−16 have been Published: November 5, 2020
developed by researchers, where the A site or B site of the ABO3
perovskite structure were populated with five cations, most of
the time mixed equiatomically to maximize the high-entropy

© 2020 American Chemical Society https://dx.doi.org/10.1021/acssuschemeng.0c03849

17022 ACS Sustainable Chem. Eng. 2020, 8, 17022−17032
ACS Sustainable Chemistry & Engineering
Figure 1. (a) Schematic representation of the crystal structure of Sr(TiFeNiCrNb)O3. (b) Estimated configurational entropy as a function of mol % of
the n-th component in the solid solution of n-component systems. The black dots indicate the compositions showing the maximum configurational
entropy.
S2σ S2σ
ZT = T= T investigation, we synthesized a novel HEP oxide, Sr-
κ ke + kl (1)
where S is the Seebeck coefficient, σ is the electrical conductivity,
and k is thermal conductivity. k is written as a combination of
electronic (ke) and lattice thermal conductivity (kl). Oxides were
contemplated as promising TE materials17,18 for high-temper-
ature power generation due to their low processing cost, high
temperature durability, and environmental friendliness com-
pared with intermetallics and chalcogenides. Although there are
some cobaltite-based p-type oxides with good ZT values,19−21
scientists found it hard to design high-performance n-type TE
oxide materials. Nevertheless, for the efficient energy con-
version, a TE generator22 requires both n-type and p-type TE
materials, where they are connected thermally in parallel and
electrically in series. Among various n-type oxide materials,
SrTiO3-based perovskites doped with La and Nb have shown a
lot of promise in recent years.23−26 However, these perovskites
suffer from high thermal conductivity (>10 W/mK),27−29
resulting in poor ZT values compared with those of the state-
of-the-art bulk TE materials like tellurides, which exhibit k less
than 1 W/mK.30,31 Because lattice thermal conductivity (kl)
accounts for the lion’s share of total thermal conductivity of
these materials, it is of utmost concern to strategize for inducing
enhanced phonon scattering in order to achieve higher ZT
values in oxide perovskite systems. The nanostructuring
approach was proven to be the effective way for reducing kl in
intermetallic- and chalcogenide-based TE materials by increas-
ing grain boundary scattering.32 However, the same strategy
cannot be implemented in SrTiO3-based perovskite systems
unless a microstructure with nm-scale grain size is achieved
because the phonon mean free path of these perovskites typically
lies around <2 nm.33 Hence, the attention of the scientific
community has been diverted34,35 toward evolving a new
strategy to design novel oxide TE materials with intrinsically
ultralow lattice thermal conductivity, similar to what is generally
found in the state-of-the-art TE materials like tellurides, in order
to achieve high ZT values in oxide perovskites.
Herein, we propose that designing HEPs by colonizing the B
site of SrTiO3 with five transition metals equiatomically could
potentially induce multiphonon scattering resulting in lower kl.
Also, being a multicationic oxide, the HEP structure could be
tailored in such a way that it could exhibit good electrical
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conductivity as well as the Seebeck coefficient. In the current
(Fe0.2Ti0.2Mo0.2Nb0.2Cr0.2)O3, using the solid-state reaction
method and evaluated its potential for high-temperature TE
applications in the temperature range from 300 to 1100 K. The
HEP was designed by calculating Goldschmidt’s tolerance factor
and configurational entropy. An ultralow lattice thermal
conductivity of 0.7 W/mK at 1050 K was obtained in the
Sr(Fe0.2Ti0.2Mo0.2Nb0.2Cr0.2)O3 HEP by inducing enhanced
electron−phonon and Umklapp scattering, determined by the
Debye−Callaway model. To the best of our knowledge, this is
the first report on TE properties of HEPs.
■
DESIGN AND THERMODYNAMIC CALCULATIONS
OF HEPS
Over the years, scientists have relied on Goldschmidt’s tolerance
factor to design novel ABO3 perovskite structures. In order to
check the stability of the Sr(Fe0.2Ti0.2Mo0.2Nb0.2Cr0.2)O3 HEP
structure as shown schematically in Figure 1a in the present
work, we further considered the expression of tolerance factor
(t) as follows:
rA + rO rSr + rO
t= = rFe + rTi + rMo + rNb + rCr
2 (rB + rO) 2 ( 5 )
+ rO
= 0.906 (2)
where rA, rB, rSr, rFe, rTi, rMo, rNb, rCr, andrO are the radii of cations
A, B, Sr, Fe, Ti, Mo, Nb, Cr, and anion O, respectively. A cubic
phase is likely to be stable when 0.9 ≤ t ≤ 1, while an
orthorhombic or rhombohedral phase may form when t<0.9,
and a tetrahedral or hexagonal phase may form when t>1. From
the calculated tolerance factor, it is apparent that the stable cubic
HEP crystal structure could be formed in the present work.
Thermodynamics calculations were performed to understand
the formation mechanism of complex HEPs keeping in mind
Hess’ law at 1500 K. In the present work, precursors such as
SrCO3, Fe2O3, MoO3, TiO2, Nb2O5, and Cr2O3 were used to
obtain the single-phase solid solution Sr-
(Fe0.2Ti0.2Mo0.2Nb0.2Cr0.2)O3 at 1500 K.
Thermal enthalpy (H) and thermal entropy (S) of all the
oxides can be calculated as follows:
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ACS Sustainable Chemistry & Engineering
Figure 2. (a) Experimental (open circles), calculated (continuous line), difference profile (continuous line), and Bragg position (vertical bars)
obtained after Rietveld refinement of XRD data. (b) FE-SEM image of the HEP ceramics. (c) EDXS of Sr(Ti0.2Fe0.2Mo0.2Nb0.2Cr0.2)O3 ceramics
showing elemental mapping.
H = Ht0 − H298
0 Thermodynamic Gibbs free energy change (ΔGThermo) has
= At + (Bt 2)/2 + (Ct 3)/3 + (Dt 4)/4 − E /t + F
− Hf
(3)
S = St0 = Alnt + Bt + Ct 2/2 + Dt 3/3 − E /(2t 2) + G
(4)
where A, B, C, D, andE are the substance-dependent constants
and “t” is the temperature(K)/1000.
To calculate enthalpy of formation (Hf) for AaBbOy oxides, the
natural extension rule was employed on Pauling’s proposed
formula36 slightly modifying the one proposed by Aronson.37
Hf = −96.5 × y[xA(χA − χO )2 + x B(χB − χO )2 ] + 108.8y
(5)
where χ represents the electronegativity taken from Pauling
electronegativity series; x, the mole fraction; and y, the number
of oxygen atoms (O) in the oxide molecule under consideration.
Consequently, the natural extension for mixed oxide Sr-
(Ti0.2Mo0.2Fe0.2Nb0.2Cr0.2)O3 takes the following form:
Hf = −96.5 × y[xSr(χSr − χO )2 + x Fe(χFe − χO )2
2 2
+ xMo(χSr − χO ) + x Nb(χSr − χO ) + xCr
(χSr − χO )2 + x Ti(χSr − χO )2 ] + 108.8y
= −987.93KJ/mol (6)
Putting back the value of Hf and using the boundary
conditions H = 0 at a temperature of 298 K and S = 0 at 0 K,
two integration constants such as F and G were calculated using
eqs 3 and 4. We used the values of A, B, C, D, and E and the
formation enthalpy (Hf) for precursor oxides from earlier
reports.38,39 By fitting the CP data of the HEP sample shown in
Figure S1a and putting the boundary conditions, the values of A,
B, C, D, E, F, and G were calculated for HEPs as presented in
Table S1 in the Supporting Information. Furthermore, we
calculated the change in enthalpy (ΔH) and entropy (ΔS) by
plugging all the values of constants in eqs 3 and 4, which is
shown in the Supporting Information.
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been calculated as −2.35KJ/mol, as depicted in the Supporting
Information.
ΔGT is the total free energy change of the reaction,
summation of thermodynamic Gibbs free energy change
(ΔGThermo) and free energy change due to mixing (ΔGmix).
ΔGmix = ΔHmix − T ΔSmix (7)
In our system of HEP oxides, the A site (0,0,0) is always
occupied by Sr2+ ions and O2− ions always occupy the (1/2,1/
2,0) site. Hence, it is assumed that the mixing happens only in
the B site (1/2,1/2,1/2). The B site has been populated by Ti,
Fe, Mo, Nb, and Cr, and mixing enthalpy was calculated only for
B-site cations. The calculation of ΔHmix40,41 for HEAs is usually
done using the equation originally proposed by Miedema.42 The
detailed calculations for enthalpy of mixing and entropy of
mixing are provided in the Supporting Information. Free energy
change due to mixing (ΔGmix) has been calculated as ΔGmix =
29.128KJ/mol.
Finally, ΔGTotal can be calculated as follows:
ΔGTotal = ΔGThermo + ΔGmix = −2.35 − 29.128
= −31.488 KJ/mol (8)
The abovementioned calculations have been further demon-
strated in Figure 1b, where it is shown that for any component,
an equiproportional system gives the maximum entropy and
adding another element to that n-component system increases
the entropy starting from the maximum entropy of the n-th
component system.
■
EXPERIMENTAL PROCEDURE
Dense samples of Sr(Fe0.2Ti0.2Mo0.2Nb0.2Cr0.2)O3 HEP were synthe-
sized by the conventional solid-state reaction method. To obtain the
stoichiometric composition of the HEP, powders of SrCO3 (≥99.9%;
Sigma-Aldrich), Fe2O3 (≥99.995%; Sigma-Aldrich), MoO3(≥99%;
Sigma-Aldrich), TiO2 (≥99.5%; Sigma-Aldrich), Nb2O5(≥99%;
Sigma-Aldrich), and Cr2O3(≥99.5%; Sigma-Aldrich) were mixed in
appropriate ratios in a ball-mill at 350 rpm for 24 h using ethanol as the
milling medium. The milled and dried powder was then calcined at
1500 K for 10 h in a H2 atmosphere. The agglomerated powder
obtained after the calcination process was milled again to breakdown
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the agglomerates in a planetary micro mill (PULVERISETTE 7 To quantify the composition of the equimolar HEP, we further
premium line; Fritsch, Rhineland-Palatinate, Germany) for 120 min at carried out the XRF study on the as-synthesized ceramic
600 rpm using zirconia grinding balls and ethanol as milling media. samples. XRF peaks corresponding to all the elements present in
After adding binders, the milled powder was uniaxially pressed into our HEP sample are shown in Figure S2 in the Supporting
pellets and sintered at 1550 K for 10 h in a H2 atmosphere. The X-ray
diffraction (XRD) patterns of HEP powders were measured in the
Information. Table 2 shows weight percentages of the different
range of 2θ = 10−100° using a PANalytical X’Pert diffractometer to
determine the phase purity of calcined and sintered powders. The Table 2. Chemical Composition of the HEP Sample Obtained
microstructure of the fracture surface was observed by field-emission from XRF Analysis
scanning electron microscopy (FE-SEM, Nova NanoSEM 450 N2),
and energy-dispersive X-ray spectroscopy (EDXS) analysis was done average chemical composition in wt %
using a WSEM (EV050; Carl Zeiss NTS GmbH, Germany) machine. element expected observed by XRF
X-ray fluorescence (XRF) analysis of the HEP sample was carried out to Sr 55.97 55.8 ± 0.5
estimate its chemical composition using a Rigaku WD-XRF machine (4
Ti 6.11 5.8 ± 0.3
kW, 60 kV, 150 mA). X-ray photoelectron spectroscopy (XPS) was
carried out using PHI 5000 VersaProbe II, FEI Inc. TE properties, such Cr 6.64 6.5 ± 0.3
as electrical conductivity (σ) and Seebeck coefficient (S), were Fe 7.13 7.0 ± 0.3
simultaneously measured in the temperature range from 300 to 1100 Nb 11.87 11.8 ± 0.4
K at an interval of 50 K using a ZEM-3M10R apparatus (ULVAC- Mo 12.26 12.8 ± 0.5
RIKO Inc.). Subsequently, the TE power factor S2σ was calculated for
all the compositions in the temperature range from 300 to 1100 K.
Density (ρ) of the sample was measured by Archimedes’ principle using
a custom-made density measurement kit. Thermal diffusivity (D) and elements present in the HEP composition. It can be concluded
specific heat (Cp) were measured in the temperature range from 300 to from the XRF study that almost an equimolar ratio of the five
1100 K using LFA-1000 (LINSEIS) and HDSC PT 1600 (LINSEIS) transition metals were obtained from our Sr-
instruments, respectively, to calculate the thermal conductivity (κ =
ρDCp). Nanoindentation was done using a Nanoindenter with in situ
(Ti0.2Fe0.2Mo0.2Nb0.2Cr0.2)O3 HEP sample, as expected.
scanning probe microscopy (TI 750; Hysitron Ltd.). XPS confirmed the presence of all the cations in the B site,

■
such as Ti, Fe, Mo, Nb, and Cr, possessing multiple oxidation
RESULTS AND DISCUSSION states. All the peaks were fitted using Lorentzian−Gaussian line
shapes after background correction as shown in Figure 3. The
Structural Analysis. The XRD pattern of the sintered calculated binding energies for all the transition metals present
Sr(Ti0.2Fe0.2Mo0.2Nb0.2Cr0.2)O3 HEP sample suggests the in HEPs are presented in Table 3. Figure 3a shows the existence
formation of a single-phase solid solution with a cubic perovskite of Ti in the form of ∼19% Ti2+, ∼58% Ti3+, and ∼23% Ti4+.
structure as no secondary phases or peak splitting was detected, Similarly, Fe was found to be present in the form of Fe2+ (∼72%)
shown in Figure 2a. Furthermore, we carried out Rietveld and Fe3+ (∼28%) as shown in Figure 3b. Mo was also found to
analysis of the XRD data using Fullprof software to determine possess a mixed valence state as Mo5+ (∼43%) and Mo6+
the crystal structure of the HEP sample. Figure 2a shows the (∼57%). XPS also revealed that ∼40% of Nb was present as
observed, calculated, and difference profiles obtained after Nb4+ and 60% of Nb as Nb5+. Interestingly, 17% Cr was detected
Rietveld refinement. This refinement analysis attributes to in the form of Cr6+ along with 83% Cr3+ in our HEP sample. All
excellent fitting (χ2 = 1.75) with a cubic perovskite structure the binding energies calculated for the HEP sample were found
possessing a Pm3̅m space group as shown in Figure 2a. The to be close to the reported values in the literature.44−54 The
lattice constant and other fitting parameters obtained from presence of higher oxidation states of Nb, Cr, and Mo occupying
Rietveld refinement are presented in Table 1. the B site of the perovskite structure, which has the formal
valency of +4, probably caused the reduced oxidation states of Ti
Table 1. Refined Structural Parameters for the HEP and Fe.
Composition Obtained after Rietveld Refinement of the XRD Thermoelectric Properties. The temperature-dependent
Data Using aPm3̅m Space Groupa Seebeck coefficient (S) of the HEP sample is plotted as shown in
atoms X Y Z B (Å2) Figure 4a. The Seebeck coefficient of the HEP was found to be
negative and increasing in magnitude in the temperature range
Sr 0.0 0.0 0.0 0.43
Ti/Nb/Fe /Cr/Mo 0.5 0.5 0.5 0.40
from 300 to 1100 K. It suggests the n-type TE behavior, that is,
O1 0.5 0.0 0.5 0.38
electrons being the majority charge carriers in a HEP system,
O2 0.5 0.5 0.0 1.74
which can be further analyzed by considering the defect
chemistry involved in this high-entropy ceramics. Equimolar
a
a = b = c = 3.94 Å; χ2 = 1.75; RF = 2.08; RP = 14.8; RWP = 8.06: RB = site occupancy by multivalent transition metals such as Ti, Fe,
1.09.
Mo, Cr, and Nb in the B site of ABO3 perovskites, which
formally occupies a charge valence of +4, gives rise to the
Microstructural studies of the HEP sample carried out by FE- formation of point defects explained by the following possible
SEM ascertained the formation of the dense ceramic pellet with defect reactions 9−13 expressed in the form of Kroger−Vink
low porosity as shown in Figure 2b. Micron-sized fused grains notation:55
were detected in the microstructure of HEP. The average grain BO2
MO2 ⎯⎯⎯→ M×B + 2OO
×
; For M = Ti4 +, Nb4 + (9)
size was estimated to be 0.85 ± 0.3 μm with the help of ImageJ
software.43 EDXS was done to check the compositional 2BO2 1
homogeneity of HEPs, and all the elements (Sr, Ti, Fe, Mo, M 2O5 ⎯⎯⎯⎯→ 2 M·B + 4 OO
×
+ O2 ↑ +2e′;For M
2
Nb, Cr, and O) were found to be uniformly distributed
throughout the area of the microstructure as shown in Figure 2c. = Nb5 + , Mo5 + (10)

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Figure 3. XPS spectra of (a) Ti 2p, (b) Fe 2p, (c) Nb 3d, (d) Mo 3d, and (e) Cr 2p peaks for the Sr(Ti0.2Fe0.2Mo0.2Nb0.2Cr0.2)O3 HEP.

Table 3. Measured Binding Energies of all the Elements 2BO2 ×

M 2O3 ⎯⎯⎯⎯→ 2M′B + 3 OO + V ··O; For M = Fe3 +, Cr 3 +
Present in the HEP Sample
(12)
element state binding energy(eV) area (%)
BO2
Mo Mo6+ 3d5/2 232.13 42.1 ×
MO ⎯⎯⎯→ M″O + OO + V ··O; For M = Fe 2 + (13)
Mo6+ 3d3/2 235.38 14.8
Mo5+ 3d5/2 231.36 25.3 It can be seen from the defect reactions 12 and 13 that lower
Mo5+ 3d3/2 234.54 17.8 oxidation states (<4) of transition metals auger the formation of
Fe Fe2+ 2p3/2 710.46 32.8 oxygen vacancies. On the other hand, higher oxidation states
Fe2+ 2p1/2 724.16 31.5 (>4) of Nb, Mo, and Cr occupying the B site generate electrons
Fe3+ 2p3/2 712.90 23.2 in the HEP samples as shown by eqs 10 and 11. Because we
Fe3+ 2p1/2 728.54 2.7 calcined as well as sintered our HEP samples in a reducing
satellite 2p3/2 717.94 1.6 atmosphere (H2), these defect reactions are expected to be
satellite 2p1/2 731.34 8.2 favored. Occurrence of a negative Seebeck coefficient suggest s
Cr Cr3+ 2p3/2 574.12 50.1 that the defect reactions 12 and 13 dominated in HEP ceramics.
Cr3+ 2p1/2 584.05 33.1 Furthermore, a monotonic increase in “S” with temperature
Cr6+ 2p3/2 577.01 15 indicates increased scattering of electrons with temperature
Cr6+ 2p1/2 587.64 1.8 implying a metallic or degenerate semiconductor-like behavior
Nb Nb4+ 3d5/2 206.12 21.9 of HEP samples.
Nb4+ 3d3/2 208.83 17.3 However, HEPs do not exhibit similar kind of metallic
Nb5+ 3d5/2 206.68 39.4 behavior in the temperature-dependent electrical conductivity
Nb5+ 3d3/2 209.36 21.4 graph as shown in Figure 4b. Indeed, electrical conductivity (σ)
Ti Ti2+ 2p3/2 457.2 11.3 was found to be continuously increasing from ∼500 S/m at 300
Ti2+ 2p1/2 462.06 7.7 K to ∼7.683 × 103 S/m at 1100 K, demonstrating a
Ti3+ 2p3/2 457.94 35.6 semiconductor-like (dσ/dT > 0) behavior. This can be
Ti3+ 2p1/2 463.72 22.7 explained by Anderson’s localization.56−58 Existence of multi-
Ti4+ 2p3/2 458.55 17.2 valent transition metals in HEPs creates lot of defect centers as
Ti4+ 2p1/2 465.59 5.4 explained by eqs 9−13 above, due to which large variations of
the local electrical field and lattice strain are expected to be
BO2 1
MO3 ⎯⎯⎯→ M··B + 2OO
×
+ O2 ↑ +2e′;For M present in the system. As a result, itinerant electrons can become
2 localized, which is called Anderson’s localization. Such kind of
= Mo6 +, Cr 6 + (11) behavior has been reported in the literature for perovskites57−59
and double perovskites.60−62 It is believed that the presence of
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Figure 4. Temperature-dependent (a) Seebeck coefficient (S), (b) electrical conductivity (σ), (c) power factor (S2σ), and (d) plot of ln(σT) versus 1/
KBT demonstrating the small polaron hopping (SPH) conduction mechanism in HEPs.

kB ij 2 − c yz
lnjj zz
five different transition metals possessing multiple oxidation
e k c {
S=
states caused the Anderson localization of charge carriers in (15)
HEPs. Hence, HEPs were not found to follow the degenerate
Fermi gas model in the temperature-dependent electrical where S is the Seebeck Coefficient at room temperature, kB is
conductivity behavior. As a result, we could achieve a rare feat Boltzmann’s constant, e is the electronic charge, and c is the
of simultaneous increases in both the Seebeck coefficient and fractional polaron concentration. For our HEP sample, the
fractional polaron concentration was calculated to be 0.71.
electrical conductivity with temperature, which potentially
Taguchi et al.65 calculated the number of carrier concen-
opens up a new way of designing oxide TE materials with an n
trations (n) using c = N in the original Heikes’ formula, which
enhanced power factor (S2σ). Figure 4c shows the continuous

ÄÅ ÉÑ
was further used in the recent works,66,67 given below:

kB ÅÅÅ ST* ÑÑÑ

increasing trend of TE power factor (S2σ) of the HEP sample
i
j y
z
S = ÅÅÅln β jj zz + ÑÑ
with temperature, where the highest value of 67.88 μW/mK2

e ÅÅÇ k c { KB ÑÑÑÖ
1 − c
was achieved at ∼1123 K.

Ä ÉÑ
Because certain activation energy barriers need to be (16)

A s ÅÅÅÅ ÑÑ
ÑÑ
overcome in order to delocalize the charge carriers trapped
Å
ÅÅ Ñ
V ÅÅÇ 1 + e(S × e)/ kB ÑÑÑÖ
around the defect sites, the SPH conduction model would be 1
appropriate for explaining the conduction mechanism in this n=
(17)

ÄÅ ÉÑ
HEP oxide, which is given by the following equation:63

σ0 ÅÅÅ −E H ÑÑÑ
where ST* is the vibrational entropy and is usually neglected, β is
σ = expÅÅÅ ÑÑ
ÅÅÇ KBT ÑÑÑÖ
the degeneracy factor taken as 1, and N is the number of
T (14) available sites per unit volume, further expressed as N = AS V . In
the present work, we used the following expression derived
where σ0 is a constant, EH is the activation energy of SPH, and KB similarly from the modified Heikes’ formula (eq 18) to calculate

Ä ÉÑ
A s ÅÅÅÅ
electron concentration:
ÑÑ
is Boltzmann’s constant. Figure 4d depicts the linear relationship

ÑÑ
ÅÅÅ ÑÑ
between ln(σT) and 1/KBT, indicating that the conduction
V ÅÅÇ 1 + e ÑÑÖ
2
mechanism of HEPs followed the SPH model in the entire range n= (S × e)/ k
of measurement temperature with an activation energy of (0.16
B
(18)
± 0.002) eV. When the charge transport is driven by SPH, the For cubic perovskites, the number of available sites per unit
effective charge carrier concentration can be determined using volume is taken as As= 1. Electron concentration in HEPs was
Heikes’ formula, which was further modified by Chaikin and estimated as 1.15 × 1022 per cm3. Furthermore, using σ = neμ,
Beni64 considering the spin interaction of electrons, elucidated mobility (μ) was calculated to be 0.0027 cm2/Vs. The effective
as follows: mass (m*) of electron was calculated from the Seebeck
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Figure 5. Variation of (a) total thermal conductivity (κ), (b) lattice thermal conductivity (κl), and (c) Lphonon with temperature for HEP composition.
(d) Comparative bar chart of Lphonon for SrTiO3-based perovskites in the temperature range of 300−1000 K.
coefficient expression for nondegenerate semiconductors (eqs
19 and 20).68
KB
S=− [ln( Nc n ) + A ]
e (19)
Nc = 2( 2πm*KBT h2 )3/2
where Nc is the density of states at the conduction band, h is
Planck’s constant, and A is the scattering parameter, ranging
between 0 and 4. Effective carrier mass (m*) for Sr-
(Ti0.2Fe0.2Mo0.2Nb0.2Cr0.2)O3 was found to be 4.26m0, consid-
ering A = 3. The low value of electron mobility and high effective
mass further corroborate with Anderson’s localization of
electrons in the HEP system as discussed above. It provides
further opportunity to tune the composition of the perovskites
in order to delocalize these electrons which in turn can increase
the electrical conductivity and power factor.
In order to calculate the total thermal conductivity (κ =
ρDCp), specific heat (Cp) and thermal diffusivity (D) of the HEP
ceramic were measured as displayed in Figure S1a,b in the
Supporting Information. Thermal conductivity (κ) of our HEP
ceramic decreased continuously with increasing temperature as
shown in Figure 5a. The primary reason behind such decreasing
trend observed in κ is attributed to the monotonic decreasing
behavior of dominant lattice thermal conductivity (κl) exhibited
by this equimolar HEP oxide as shown in Figure 5b. κl was
calculated by subtracting the electronic thermal conductivity
(κe) from the total thermal conductivity (κ = κl + κe) of the
material. The Wiedemann−Franz law (ke = LσT) was used to
estimate the electronic thermal conductivity (κe) of the HEP
oxide sample, shown in Figure S1c. The temperature-dependent
Lorenz number was calculated using the following equation69 as
ÄÅ É kB ij kBT yz
Å −|S| ÑÑÑ
illustrated in Figure S1d:
L = 1.5 + expÅÅÅÅ ÑÑ
ÅÅÇ 116 ÑÑÑÖ (21)
pubs.acs.org/journal/ascecg Research Article
The most interesting feature of this HEP system is its ultralow
lattice thermal conductivity of 0.7 W/mK exhibited at 1100 K.
To further gain insights into the lower lattice thermal
conductivity obtained in the HEP, the mean free path (Lphonon)
between two successive phonon collisions as a function of
temperature was estimated using following equation:70
(20) 3 Kl
L Phonon =
Cv × vm (22)
where vm is the acoustic mean velocity in the medium and Cv is
the heat capacity at a constant volume. vm was calculated from
the elastic modulus measured by the nanoindentation method as
described in the Supporting Information. The calculated Lphonon
is plotted as a function of temperature as shown in Figure 5c.
Lphonon was found to be decreased from 0.8 nm at room
temperature to 0.5 nm at 1100 K. The values of Lphonon estimated
for the HEP is further compared with that of the earlier reports
for other SrTiO3-based oxide TEs33,34,71 as depicted by the
comparative bar chart shown in Figure 5d. In the literature, the
strategy of making nanocomposites, nanostructuring, and rare-
earth doping had been adopted to lower the mean free path in
perovskites in order to decrease their κl. However, we achieved
such low mean free path intrinsically in the single-phase solid
solution of rare-earth-free HEP ceramics. This opens up the
possibility of further reducing Lphonon, leading to lower Kl by
making composites with nanoscale grain size of HEPs.
Reduction in lattice thermal conductivity is generally
governed by various kinds of phonon interactions, such as
defect scattering, electron−phonon scattering, phonon−pho-
non scattering. In order to understand the heat transport
mechanism in the HEP system, Callaway’s model was
considered. The Debye−Callaway model72 is given as
jj zz
2π 2vm jk ℏ z{
3 θD/ T
τ (y , T )y 4 e y
kl = ∫
0
(e y − 1)2
dy
(23)
17028 https://dx.doi.org/10.1021/acssuschemeng.0c03849
ACS Sustainable Chem. Eng. 2020, 8, 17022−17032
ACS Sustainable Chemistry & Engineering
where ℏ is the reduced Planck’s constant, kB is the Boltzmann
constant, τ is the relaxation time, vm is the average speed of
sound in that particular medium, θD is the Debye temperature
calculated as 338 K, and y = ℏω/kBT. The calculation of Debye
temperature is described in the Supporting Information.
Because most of the measured values of thermal conductivity
are in the range of temperature comparable with or greater than
the Debye temperature (i.e., 338 K), we implied a more
simplified form of the Callaway model derived by Slack73,74 as
shown in eqs 24 and 25:
kB ij kBT yz
jj zz
2π 2vm jk ℏ z{
3 θD/ T
kl = ∫
0
τ (y , T )y 2 d y
(24)
vm
where τ −1 = + Aω4 + BωαT ne−θD/mT + Cω 2
L (25)
where A, B, and C are the constants, and relaxation time (τ)
depends on grain boundary scattering ( vm ), defect or isotopes
L
scattering (Aω 4 ), phonon−phonon Umklapp scattering
(BωαT ne−θD/mT ), and electron−phonon scattering (Cω2). At
higher temperatures, the grain boundary scattering effects were
omitted, as suggested by Casimir.75 As suggested by Slack,76 for
the Umklapp process, αis ≤ 2 and n is strongly temperature-
dependent. Furthermore, the exponential term in the Umklapp
process can be approximated to one for high temperature as
suggested by Slack. The relaxation time for the three-phonon
Umklapp process in the Callaway model was given by Bω2T3.76
However, in the modified Callaway model, the three-phonon
Umklapp process was shown as T-dependent rather than T3-
dependent. Slack further deduced the relaxation times for four-
phonon processes by considering T2 dependence.74 Recently,
Petersen et al.77 used four-phonon scattering processes by
considering T2 dependence for a half-Heusler system. In the
present work, α was fixed at 2, while n was varied from 1 to 5
until we get good fittings for temperature-dependent lattice
thermal conductivity data of HEPs using eqs 24 and 25 as shown
in Figure 6 and Table 4. For n = 1 and 2, there was absolutely no
fitting observed. However, when fittings were done for n = 3, 4,
and 5, the Callaway fit got better upon increasing the n value and
the best fit was obtained for n = 5. This implies the manifestation
Figure 6. Lattice thermal conductivity plotted as a function of
temperature along with the Debye−Callaway model fitting for different
n values.
17029
pubs.acs.org/journal/ascecg Research Article
Table 4. Fitting Parameters Obtained from the Analysis of
Lattice Thermal Conductivity of
Sr(Ti0.2Fe0.2Mo0.2Nb0.2Cr0.2)O3 HEP Using Callaway’s Model
Described by Eqs 24 and 25 for Varying n Values
n values A [s3] B [sK−1] C [s]
−48
n=1 2.1 × 10 6.9 × 10−18 2.6 × 10−15
n=2 2.3 × 10−46 5.4 × 10−21 4.6 × 10−15
n=3 1.5 × 10−46 5.2 × 10−24 5.2 × 10−15
n=4 3.5 × 10−46 5.0 × 10−27 5.6 × 10−15
n=5 3.8 × 10−46 4.9 × 10−30 5.9 × 10−15
of higher-order phonon interaction processes in the HEP, which
might be arising due to increased anharmonicity occurred in the
HEP structure comprising five transition metals in the B site,
compared with a simple perovskite system like SrTiO3.
Noticeably, κ values obtained in the HEP were found to be
much lower than the best results available in the literature for
perovskites including SrTiO3-based TE materials34,78−81 as
shown in Figure 7a. The obtained κ values are also found to be
lower than various perovskite ferroelectrics.82 This is phenom-
enal because the major drawback of perovskite-based TE
materials is their high thermal conductivity. Our study shows
that designing rare-earth-free HEP-based oxides can be a
potential way of fabricating oxide TE materials with ultralow
thermal conductivity. The presence of five multivalent cations at
the B site enhances the phonon scattering by introducing higher
structural complexity in the HEP system, which in turn reduces
the value of κl. Synergic enhancement of the Seebeck coefficient
and electrical conductivity along with a decrease in thermal
conductivity with temperature is the ideal method to design TE
materials, and we achieved such kind of synergistic enhancement
of TE performance in HEP ceramic systems. As a result, ZT of
HEPs was found to be increased continuously with increasing
temperature as illustrated in Figure 7b. The highest ZT value
achieved for HEPs is ∼0.065 at 1043 K, which requires much
improvement in order to make it viable for commercialization.
Nevertheless, our study shows a new path of designing high-
performance perovskites, which are known to be amenable for
compositional modification. Moreover, using HEPs can be the
potential way of decoupling “electron crystal” and “phonon
glass” in oxide TEs by careful selection of transition metals in
HEP systems.
■ CONCLUSIONS
In summary, we successfully presented the first comprehensive
study of the TE properties of HEP oxides. A novel perovskite
composition of five transition metals in the B site and a single
element in the A site, Sr.(Ti0.2Fe0.2Mo0.2Nb0.2Cr0.2)O3, was
synthesized by the solid-state reaction route. A cubic crystal
structure possessing a Pm3̅m space group commensurate with
Goldschmidt’s tolerance factor was obtained. XRF analysis
revealed that the ratio of constituting elements is almost similar
to what was expected from the equimolar formula of HEPs. The
Seebeck coefficient signified HEPs to be an n-type material in
the entire temperature range from 323 to 1123 K. The
conductivity mechanism of the material was found to be driven
by the SPH model. Most importantly ultralow κ was achieved in
this HEP ceramic, which demonstrated synergistic enhancement
of the Seebeck coefficient and electrical conductivity. It is
anticipated that our HEP approach of designing oxide TEs will
lead to the discovery of novel TE materials with enhanced ZT
values, which can be used for fabricating high-temperature
https://dx.doi.org/10.1021/acssuschemeng.0c03849
ACS Sustainable Chem. Eng. 2020, 8, 17022−17032
ACS Sustainable Chemistry & Engineering
Figure 7. (a) Thermal conductivity of the HEP compared with other SrTiO3-based composition reported in the literature and (b) variation of TE
figure of merit (ZT) for the Sr(Ti0.2Fe0.2Mo0.2Nb0.2Cr0.2)O3 HEP with temperature.
thermoelectric generator for electricity generation from waste
heat.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.0c03849.
Calculation of Lorenz number, lattice thermal con-
ductivity (κl), and electrical thermal conductivity (κe);
the temperature-dependent plots of specific heat, thermal
diffusivity, and electronic thermal conductivity; XRF
analysis; calculation of the Debye temperature taking into
consideration of bulk modulus, sheer modulus, and
Poisson’s ratio; and thermodynamic calculation: the
mixing enthalpy and entropy part of our HEP material
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
Tanmoy Maiti − Plasmonics and Perovskites Laboratory, Indian
Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016,
India; orcid.org/0000-0003-1581-7614; Email: tmaiti@
iitk.ac.in
Authors
Ritwik Banerjee − Plasmonics and Perovskites Laboratory, Indian
Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016,
India
Sabitabrata Chatterjee − Plasmonics and Perovskites Laboratory,
Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh
208016, India; Department of Ceramic Engineering, Indian
Institute of Technology (BHU) Varanasi, Varanasi, Uttar
Pradesh 221005, India
Mani Ranjan − Plasmonics and Perovskites Laboratory, Indian
Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016,
India
Tathagata Bhattacharya − Plasmonics and Perovskites
Laboratory, Indian Institute of Technology Kanpur, Kanpur,
Uttar Pradesh 208016, India
Soham Mukherjee − Plasmonics and Perovskites Laboratory,
Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh
208016, India; Department of Ceramic Engineering, Indian
Institute of Technology (BHU) Varanasi, Varanasi, Uttar
Pradesh 221005, India
17030
pubs.acs.org/journal/ascecg Research Article
Subhra Sourav Jana − Plasmonics and Perovskites Laboratory,
Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh
208016, India
Akansha Dwivedi − Department of Ceramic Engineering, Indian
Institute of Technology (BHU) Varanasi, Varanasi, Uttar
Pradesh 221005, India
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.0c03849
Author Contributions
#
R.B. and S.C. equally contributed to this work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work is supported by the grant from the Science and
Engineering Research Board, DST (SERB-DST), India (Grant
No: IMP/20 l8/000955).
■
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