Accepted Manuscript

Thermoelectric properties of KCaF3

Asad Ali, Altaf Ur Rahman, Gul Rahman

PII: S0921-4526(19)30251-0
DOI: https://doi.org/10.1016/j.physb.2019.04.019
Reference: PHYSB 311427

To appear in: Physica B: Physics of Condensed Matter

Received Date: 28 January 2019

Revised Date: 15 April 2019
Accepted Date: 17 April 2019

Please cite this article as: A. Ali, A.U. Rahman, G. Rahman, Thermoelectric properties of KCaF3,
Physica B: Physics of Condensed Matter (2019), doi: https://doi.org/10.1016/j.physb.2019.04.019.

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 ACCEPTED MANUSCRIPT

Thermoelectric properties of KCaF 3

Asad Ali, Altaf Ur Rahman, and Gul Rahman ∗

Department of Physics, Quaid-i-Azam University, Islamabad 45320, Pakistan
(Dated: April 17, 2019)

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Using first-principles calculations based on density functional theory (DFT) with
generalized gradient approximation (GGA), the electronic and thermoelectric prop-

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erties of KCaF3 are calculated. The electronic structure calculated with GGA shows
that KCaF3 is an insulator. The thermoelectric properties of KCaF 3 are computed

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as a function of chemical potential μ and charge carrier concentrations (10 18 -1022
cm−3 ). Both hole and electron doping decrease the absolute value of Seebeck coef-

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ficient. The calculated power factor shows that p-type KCaF 3 has a larger power
factor at the optimized charge carriers. The maximum figure of merit (ZT) occurs
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around 1021 cm−3 hole carrier concentrations and the largest value of ZT ∼ 0.7 is
achieved at 800 K. When KCaF3 is doped with electron, the maximum ZT occurs
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around 1020 cm−3 and the largest value of ZT at 800 K is about 0.4. Hence, high ZT
in KCaF3 is possible at high hole carrier concentrations as compared with electron
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carrier concentrations. Compared with n-type KCaF 3 , p-type KCaF3 has good ther-
TE

moelectric properties, which are attributed to larger effective mass and low thermal
conductivity of holes.
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I. INTRODUCTION

Materials having ABX3 type crystal structure are known as perovskite materials 1 . In
ABX3 , A and B are metallic cations such as Ba, Sr, Bi, Pb, Ti, Fe, etc. and X can be a
nonmetallic anion2 like O, F, Cl, Br or I. 3,4 The ABX3 type crystal structure is adopted

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by many famous materials such as PbTiO 3 , BaTiO3 5 , CaTiO3 , SrTiO3 , etc. and are highly
attracted from both theoretical and experimental point of views. 2,6 Due to their super-

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conductivity, magneto-resistance, ferro-electricity, dielectric, and thermoelectric transport
properties these materials can be thought to be candidates for spintronic devices, sensors,

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catalyst electrodes, and microelectronics. 7,8 Generally, perovskite compounds are oxides and
much attention has been given to such materials both experimentally and theoretically, but

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fluoride perovskites (also known fluoroperovskite) with formula ABF 3 forms another inter-
esting sub class of perovskites family, 9 are less studied. Due to its simple structure and wide
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band gap, the fluoroperovskite materials are highly useful. Theoretical and experimental
investigations show that KCaF 3 is a typical fluoroperovskite and the chemical production
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of the KCaF3 shows that it has a simple cubic structure. 10 Fast ionic conductivity was
observed in KCaF3 at a higher temperature, 11 and F− vacancies are responsible for the
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fast ionic conductivity. 12 The structural, electronic, optical, elastic, and temperature related
properties of cubic KCaF 3 are studied,9,13–16 but not in the context of thermoelectrics. In
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this paper, KCaF3 has been chosen for thermoelectric (TE) transport properties because
KCaF3 has lower lattice thermal conductivity (κl = 1.06) than oxides and it is dynamically
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stable.17

Materials with good TE properties are of great interest because good TE materials can be
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used as an alternate source for renewing wasting amount of heat from vehicles and factories. 18
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Devices based on these materials can be used to convert waste heat into electrical power. 19
The direct conversion of heat energy to electricity, based on thermoelectric effect, is a topic
of long-standing interest in material physics. In order to understand the mechanism involved
and to enhance the TE properties of materials, experimental and theoretical investigations
have been going on for more than fifty years. In general the potential of a material for TE
applications, both power generation and refrigeration can be determined from its dimension-
less figure of merit ZT. 20 The dimensionless figure of merit ZT determines the thermoelectric
performance of a material. Generally, a material having larger ZT value provides better TE
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performance.21 ZT is defined as
σS 2
ZT = T
κ e + κl
where σ, S, κe , κl , and T are electrical conductivity, Seebeck coefficient, electronic ther-
mal conductivity, lattice thermal conductivity, and temperature respectively. For practical
applications materials required ZT ≥ 1. Much efforts in the enhancement of ZT of ther-

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moelectric materials have been focused in two main directions, i.e., the reduction in lattice
thermal conductivity and the improvement of power factor. 20 TE properties of materials are

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studied in bulk, interfaces, and nano-structures. 22–26 Currently, only a few materials fulfill
the requirement of high ZT, and efforts are being made to increase ZT in PbTiO 3 , BaTiO3 ,

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SrTiO3 , Bi2 Te3 and CoSb3 .27–29 The increasing demand of high ZT is also highlighted in
the composite structures where reduced graphene oxide (RGO) is mixed with oxides, e.g.,

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Al-ZnO/RGO,30 BaTiO3 /RGO,31 TiO2 /RGO,32 and La-SrTiO3 /RGO.33 Such nanocompos-

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ites also gave birth to larger ZT as compared with individual material. Therefore, material
scientists are searching for new materials having a higher value of ZT which results in good
thermoelectric performance. Density functional theory (DFT) and Boltzmann transport
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theory are explicitly used in searching for new thermoelectric materials. In DFT calcula-
tions, the electronic group velocity is obtained from the band dispersion. Then using the
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electronic group velocity and Boltzmann transport equation, the transport coefficient can
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be determined, this approach has been applied successfully to certain materials such as half
Heusler,34 CoSb3 and Bi2 Te3 .21 KCaF3 is a semiconductor and it can become n-type or p-
type semi-conductors by substituting trivalent impurities such as Y 3+ or La3+ for K1+ ,35 or
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by substituting pentavalent impurities such as Nb 5+ for Ca1+ .36

The figure of merit mainly depends on the Seebeck coefficient S, total thermal con-
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ductivity κ = κe + κl , and electrical conductivity σ, where κe and σ are linked through

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Wiedemann−−Franz law. Larger ZT requires larger σ and smaller κ. Hence, a low κl

is the required ingredient in the recipe for a good thermoelectric system. Fluorides also
have smaller heat capacities due to their larger lattice parameters as compared with oxides.
Therefore, smaller lattice thermal conductivity can be expected in fluorides which can lead to
good TE properties in fluorides as compared with oxides. Recently, Roekeghem et.al.,17 ex-
tensively studied about 400 semiconducting oxides and fluorides with cubic perovskite struc-
tures, using finite-temperature phonon calculations and machine-learning methods. They
found that KCaF3 is one of the dynamically stable fluoroperovskite materials with low lat-
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tice thermal conductivity. In the same article, they also show that oxides display a higher
thermal conductivity than the fluorides, and hence KCaF 3 is expected to be a promising
material for TE applications.

II. METHOD OF COMPUTATION

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Using first-principles calculations based on DFT with plane wave pseudo-potential 37 as

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implemented in the Quantum Espresso (QE) code, 38 the electronic structure was optimized.
The norm-conserving pseudopotential within the generalized gradient approximation (GGA-

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PBE)39 and local density approximation (LDA-PZ) 40 were used for these calculations. The
plane wave energy cutoff was chosen to be 60 Ry and electronic convergence criterion was set
at 1× 10−6 Ry. The Monckhorst-Pack 41 scheme k-point grid sampling was set as 20 ×20×20

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for band structure and geometry optimization, while a 40 × 40 × 40 is used for the ther-
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moelectric properties. For the prediction of thermoelectric transport properties of KCaF 3 ,
the BoltzTrap code based on the Boltzmann transport theory was used. 42 Using the Boltz-
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mann transport theory, we have calculated the thermoelectric transport coefficients form
the analysis of electronic band structure 43,44 with constant relaxation time approximation
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as implemented in BoltzTrap package 42 which is based on the transport distribution 45 .

e2 X δ(ε − εi,k )
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σαβ (ε) = τ να (i, k) (1)

N i,k dε

In the above equation, e is the electronic charge, N is the number of k-points grid, α and β
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are tensor indices, ε is the band energy, τ is the relaxation time and να (i, k) is the component
of the group velocity, which is given by the mathematical equation.
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1 ∂εik
να (i, k) = (2)
ˉ ∂kα
h
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Now integrating the transport distribution 45 one can obtain the transport properties as a
function of chemical potential,
Z  
1 ∂f0 (T, ε, μ)
σαβ (T, μ) = σαβ (ε) − ∂ε (3)
Ω ∂ε
Z  
1 ∂f0 (T, ε, μ)
Sαβ (T, μ) = σαβ (ε − μ) − ∂ε (4)
eT σαβ Ω(T, μ) ∂ε
Z  
el 1 2 ∂f0 (T, ε, μ)
καβ (T, μ) = 2 σαβ (ε − μ) − ∂ε (5)
e T σαβ Ω(T, μ) ∂ε
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Here Ω is the volume of a unit cell, μ is the chemical potential, f0 (T, ε, μ) is the Fermi
distribution function and σαβ (ε) is the electrical conductivity tensor. 42 The semiclassical
Boltzmann equation within the constant relaxation time approximation was used to cal-
culate the thermoelectric properties. 46 This approximation is based on the postulate that

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the scattering time does not strongly change with energy, and this approximation is being
successfully used in the past to predict thermoelectric properties of materials. 47–49 In order

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to calculate the Seebeck coefficient, electrical and thermal conductivities of n-type and p-
type KCaF3 , the rigid band associated with constant time scattering approximation is used.

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Generally 1018 − 1022 /cm3 is considered as higher electronic n and hole p carrier concentra-
tion for thermoelectric materials, therefore in the present work 10 18 − 1022 /cm 3
range is

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considered as a doping level both for electrons and holes and the thermoelectric properties
of KCaF3 were calculated.
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In this paper, we carried out the thermoelectric properties of KCaF 3 as a function of
chemical potential and charge carriers. In the BoltzTrap code the electrical conductivity



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and thermal conductivity are expressed as στ and κτ , respectively and we have used τ =
10−14 s as relaxation time.The total thermal conductivity κ is expressed as κ = κe + κl ,
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where κe is calculated by the BoltzTrap code, and the lattice thermal conductivity κl = 1.06
Wm−1 K−1 is used as calculated by Roekeghem et.al.17 The same κ is used in the figure of
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merit of KCaF3 .
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III. RESULTS AND DISCUSSION

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Using GGA and LDA, we have computed the lattice constant of KCaF 3 by minimizing the
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total energy determined for different values of lattice parameter. We then used the equation
of state50 to determine the equilibrium lattice constant shown in Fig. (1). According to our
calculations the optimized lattice constant of KCaF 3 is 4.47 Å with GGA and 4.31 Å with
LDA, which match very well with the previously calculated and experimental values. 9,13,16,51
Fig. 1 shows that GGA gives larger lattice constant as compared with LDA. Our calculated
values of GGA and LDA for the bulk modulus of KCaF 3 are 51 GPa and 62 GPa, respectively
which match excellently with the previously calculated values 51.30 GPa and 62.04 GPa. 13,14
Using these optimize values of lattice constants of KCaF 3 , the band structures with LDA
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and GGA are calculated (see Fig. (2). In both the cases, an indirect band gap of 6.01 eV
and 5.95 eV was observed at (Γ-M), which also match excellently well with the previously
calculated values.9,16,52 Our calculations indicate that including gradient correction to the
exchange and correlation functional does not change the band gap of KCaF 3 . At the valence
band maxima (VBM) the electronic states are remarkably flat, which is an indication of small

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mobility and higher effective mass of hole, which is essential for efficient p-type thermoelectric
materials. In addition, there is a large number of literature reviews of such wide band gap

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materials which exhibit promising TE properties. 53–57 At higher temperature the valance and
conduction band overlap at T = 800 K. So perovskites are promising materials at higher

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temperature. Some wide bandgap oxides also exhibit promising TE properties, with ZT =
0.65 at 1247 K in Zn0.96 Al0.02 Ga0.02 O (3.3 eV)53 or ZT = 0.45 at 1273 K in In 1.8 Ge0.2 O3

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(3.6 eV).54 These results open a way for exploring high-performance TE materials within
the family of wide-band-gap semiconductors. The partial density of states (PDOS)[see
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Fig. (2)(b)] shows that the valence band is mostly contributed by the F-2 p electronic states,
with minor influence of the K-2s and the Ca-2s orbitals. On the other hand the conduction
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band (in the shallow region) is dominated by the K-2s and Ca-2s orbitals, and deep in energy
(∼ 9 eV above the Fermi energy) the Ca-3d orbitals also contribute to the conduction band.
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In condensed matter physics, the position of chemical potential μ plays an important role
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in determining the TE properties. The position of μ in the band structure determines which
electrons in the valence or conduction band take part in the thermal and electrical transport.
Hence, the chemical potential influences both the conductivity and the Seebeck coefficient.
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Generally, doping is used to manipulate the chemical potential by varying the number of
valence electrons in materials. By definition, μ = 0 corresponds to the top of the valence
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band in semiconductors. In the following paragraph, we investigate the TE properties of

KCaF3 as a function of chemical potential. In the following we will consider the general case
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and will focus on the shallow acceptors or donors by presenting the thermoelectric properties
in the energy interval of about 0.06 eV above or below the band edges, respectively.
Figure 3(a) shows the calculated Seebeck coefficient S as a function of chemical potential
μ for different temperatures. One can see that S is positive when the chemical potential lies
in the valence band, and S increases with T when μ is inside the valance band. However,
above the valence band maxima (VBM), which is set to zero eV, S decreases with T. Similar
behavior is also observed in Fig. 3(f). In both cases, hole or electron doping increases S and
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S lies in 200-400 μV/K. Note that for practical applications TE materials require S ≥200
μV/K. The thermal conductivity (Fig. 3(b, g)) and electrical conductivity (Fig. 3(c, h))
increase with T. At higher temperature electrons get more thermal energy and can move
from high temperature region to low temperature region in a thermoelectric device. Both
hole doping and electron doping in KCaF 3 reduce both the conductivities. The power factor

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(PF = σS 2 ), which mainly determines the figure of merit, is shown in Fig. 3(e, j), and
it is clear to see that hole doped KCaF 3 has larger PF as compared with electron doped

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KCaF3 . At the VBM, the calculated PF is about 6.0 ×10−3 W/ΩK2 m at 900K, whereas at
the CBM it is about 1.0×10−3 W/ΩK2 m. Hence, larger figure of merit ZT is expected in hole

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doped KCaF3 as compared with electron doped KCaF 3 . The figure of merit ZT is the most
important parameter in thermoelectric materials, and for practical applications, ZT ∼ 1.0

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However, it is difficult to achieve ZT close to 1.0 because ZT depends on both electrical
conductivity and thermal conductivity. Larger electrical and smaller thermal conductivity
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would be needed for larger ZT. We also evaluated ZT near the VBM and CBM, and Fig. 3(d,
i) shows that ZT increases with T in both the cases, and hole carrier concentrations in KCaF 3
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can have larger ZT as compared with electron carrier concentrations, e.g., ZT∼0.6 when the
chemical potential lies at the edge of the valence band, whereas ZT∼0.4 when the chemical
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potential is at the conduction band edge. Note that these values are comparable with the
other studied TE materials i.e., SrTiO3 , BaTiO3 , PbTiO3 , CH3 NH3 PbI3 , Mg2 Ge1−x Snx , etc
TE

and their ZT values are 0.4 − 2.1.27,28,58,59

To experimentally realize our theoretically calculated TE properties of KCaF 3 , it is also

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essential to investigate how the TE properties change with electron and hole doping car-
rier concentrations, and also to find the optimum carrier concentrations. Figure 4(a) shows
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the GGA calculated Seebeck coefficient as a function of hole carrier concentrations (10 18 -
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1022 /cm3 ) and temperature (300-800 K). The Seebeck coefficient S increases (decreases) with
temperature (carrier concentrations) which is typical behavior semiconductors. No bipolar
effect is observed in the whole temperature and carrier concentration ranges. The calculated
S value at 300 K at low hole carrier concentration is about 800 μV/K and for practical appli-
cations TE materials require 200 μV/K. Similarly the absolute value of Seebeck coefficient
increases (decreases) with temperature (electron carrier concentration) as shown in Fig. 4(e),
and the calculated S at 300 K is about -400μV/K, which is smaller than the hole doped
case. Hence, it is expected that KCaF 3 will have good TE properties when doped with holes.
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The thermal conductivity, which includes both the electronic and lattice parts as mentioned
above, of hole doped KCaF 3 is shown in Fig. 4(b). The thermal conductivity increases with
both temperature and hole carrier concentrations. Comparing the thermal conductivity of
KCaF3 under hole (Fig. 4(b)) and electron (Fig. 4(f)) carrier concentrations, one can see
that hole doped case has about four times smaller κ than electron doped case, e.g., κ= (8.0)

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35 W/mK at 800 K for (p = 1022 )n = 1022 /cm3 . The conductivity increases strongly with
the number of charge carrier, and for applications the power factor PF is more interesting

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than the Seebeck coefficient alone. The calculated PF also increases with temperature and
hole and electron carrier concentrations (see Fig. 4(c),(g)). One can see PF increases with

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p and the maximum PF occurs around 10 21 /cm3 at 300 K. And this maximum shifts to
higher carrier concentrations as the temperature increases. Similar observations for PF are

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observed in the electron doped KCaF 3 . However, the maximum PF occurs at higher hole
carrier concentrations as compared with electron carrier concentrations. For example, at
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800 K the maximum PF occurs around 10 22 /cm3 hole concentrations, whereas at the same
temperature the maximum PF occurs around 10 20 /cm3 electron concentrations. Though
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electron doped KCaF3 has maximum PF at low carrier concentrations, but the peak values
of PF are very small as compared with hole doped KCaF 3 . Our calculated PF suggests that
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the p-type KCaF3 has a larger power factor at the optimized number of charge carriers.
Hence, larger ZT is expected in hole doped KCaF 3 , but in real materials this may not be
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the case due to different behavior of the relaxation time τ for electron and hole states.
To further quantify our calculated results, we show ZT as a function of temperature in
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Fig. 4(d) and Fig. 4(h) for p-type and n-type doped KCaF 3 , respectively. We see the ZT
increases with temperature and hole/electron carrier concentrations. The maximum ZT
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occurs around 1021 /cm3 hole carrier concentrations, and the largest value of ZT ∼ 0.7 is
achieved at 800 K, and it is expected that ZT will further increase with T. On the other
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hand when KCaF3 is doped with electrons, the maximum ZT occurs around 10 20 /cm3 and
the largest value of ZT at 800 K is about 0.4. Hence, we conclude that high ZT in KCaF 3 is
possible at high hole carrier concentrations as compared with electron carrier concentrations
consistent with our predicted κ.
To gain insight into the TE properties of KCaF 3 at the atomic level, the band structure
and partial density of states are further analyzed. In Fig. 2(a) a clear parabolic band at the
Γ-point in the conduction band can be seen, and Fig. 2(b) further shows two sharp peaks
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occurring at -0.5 eV and -1.0 eV below the Fermi level. The first peak at -0.5 eV is mainly
derived from the p electrons of F atom, while the other peak has a contribution from both
the p electrons of F and s electrons of K atoms. The conduction band (in the shallow region)
is mainly formed by the s electrons of K and Ca, and thus the parabolic band in Fig. 2(a) at
6 eV above the Fermi level has s electron character. So from these band structures, we can

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judge that the TE properties of p( n)-type KCaF 3 are mainly governed by the F-p (Ca-s)
electrons. To further elaborate this conjecture, we show the electron density of the valance

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band and conduction band in Fig. 5. The electron density is mostly localized around the
F atoms in the valence band region (Fig. 5(a,b)), which is mainly dominated by the F- p

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electrons. Interestingly in the conduction band the electronic density is mostly localized
around the Ca atoms which has s electrons character. In the (002) plane one can see a

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significant electron density is accumulated at the K site in the conduction band, whereas a
negligible electron density at the K site can be seen in the valence band.
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As shown that the flat valence band (see Fig.2 (a)) at M point near the Fermi energy,
which is contributed mainly by F-p, has smaller curvature and hence large effective hole
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mass is expected that will lead to larger Seebeck coefficient based on the work of Pei et.al.60
Similarly, the conduction band minima, which is dominated by Ca/K- s electrons, has larger
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curvature that can lead to a smaller effective mass of an electron. Therefore, smaller Seebeck
coefficient would be expected when the chemical potential lies in the conduction band, i.e., for
TE

n-doped KCaF3 . Indeed we observed larger (smaller) thermopower in KCaF 3 when doped
with holes (electrons). As the TE properties are mainly governed by the thermopower,
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hence, we attribute the larger (smaller) ZT of p(n)-type KCaF3 to larger (smaller) effective
mass of holes (electrons).
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IV. CONCLUSION

A series of first-principles calculations were carried out to evaluate the electronic, struc-
tural, and thermoelectric transport properties of cubic fluoroperovskite KCaF 3 . The elec-
tronic structures calculated with LDA and GGA revealed that KCaF 3 is an insulator. The
TE properties of KCaF3 were computed as a function of chemical potential in the shallow
acceptors or donors levels, about 0.06 eV above or below the bands edges. We showed that
the Seebeck coefficient lies 200-400 μV/K for both negative and positive values of chemical
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potential– moreover the figure of merit has a larger value at the VBM. We also investigated
the variation of TE properties of KCaF 3 with electron and hole doping carrier concentra-
tions (1018 − 1022 cm−3 ). The calculated values of Seebeck coefficient at 300 K are 800 μV/K
and -400 μV/K, respectively for hole and electron carriers concentrations, and for practical
applications TE materials require S≥200 μV/K. The largest value of ZT ∼ 0.7 is achieved

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at low hole carriers concentrations at 800 K. We have shown that the hole doped KCaF 3 has
good TE properties than the electron doped KCaF 3 , and such properties were attributed to

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a larger effective mass of hole at the VBM and smaller effective mass of electron at CBM.
Our extensive calculations suggest that hole doped KCaF 3 could be a promising material

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for thermoelectric applications.

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V. ACKNOWLEDGEMENT

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GR acknowledges the higher education commission (HEC) of Pakistan under the project
“electronic structure calculations using density functional theory”.
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∗ Corresponding author: gulrahman@qau.edu.pk

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0.25
GGA
LDA
0.2

PT
Energy (Ry)
0.15

RI
0.1

SC
0.05

U
0 AN
400 500 600 700 800 900
Volume (a.u)3
M
D

FIG. 1. The GGA (red color) and LDA (green color) calculated total energy (in Ry) versus
volume (in atomic unit) plot of KCaF 3 . The total energy is plotted with respect to the equilibrium
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structure.
C EP
AC
 ACCEPTED MANUSCRIPT
15

(a)
10

8
(b)

PT
6
F
4 Ca
6
K
2

RI
Energy (eV)

0
4
4 GGA F
LDA Ca

SC
2

PDOS (states/eV)
K
0
2 F
0.5 Ca

U
K
0
0 AN 20
10
TDOS

0
M
-2 −2 0 2 4 6 8 10
X R M G R Energy (eV)
D

FIG. 2. (a) Band structure of KCaF 3 calculated with GGA (blue lines) and LDA (red lines). (b)
The total density of states and partial density of states of KCaF 3 calculated with GGA.
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C EP
AC
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16

400 −100
900 K
600 K (a) 900 K
600 K (f)
−200

S (μV/K)
300 K 300 K
300
−300
200
−400

PT
100 −500
0 0.02 0.04 0.06 −0.06 −0.04 −0.02 0
10 1.5
8 (b) (g)
κ (W/Km)

RI
1
6
4
0.5

SC
2
0 0
0 0.02 0.04 0.06 −0.06 −0.04 −0.02 0
2
σ (10 Ω m )

(c) (h)

U
−1

1.5
−1

0.15
1 AN
5

0.5
0 0
M
0 0.02 0.04 0.06 −0.06 −0.04 −0.02 0
PF (10−3 W/Ω K2m)

8
(d) (i)
6
D

1
4
TE

2
0 0
0 0.02 0.04 0.06 −0.06 −0.04 −0.02 0
1 0.6
EP

0.8 (e) (j)

0.4
0.6
ZT

0.4
C

0.2
0.2
AC

0 0
0 0.02 0.04 0.06 −0.06 −0.04 −0.02 0
μ−VBM(eV) μ−CBM(eV)

FIG. 3. GGA calculated thermoelectric properties of the KCaF3 as function of Fermi energy with
respect to VBM (left) and CBM (right). The Seebeck coefficient S (a-f), thermal conductivity κ
(b-g), electrical conductivityσ(c-h), power factor P F (d-i), and the figure of merit ZT (e-j) are
shown for 300K, 600K, and 900K.
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PT
1000 0
(a) (e)
800 −100
S (μV/K)

RI
−200
600
−300
400
−400

SC
200 −500
0 −600
1018 1019 1020 1021 1022 1018 1019 1020 1021 1022
9 40

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8 300 K (b) (f)
400 K 35
7
κ (W/mK)

500 K
600 K 30
6
5
4
3
700 K
800 K AN 25
20
15
2 10
1 5
M
0 0
1018 1019 1020 1021 1022 1018 1019 1020 1021 1022
6 1.2
σS (10 W/ΩK m)

(c) (g)
D
2

5 1
4 0.8
TE
−3

3 0.6
2 0.4
2

1 0.2
EP

0 0
1018 1019 1020 1021 1022 1018 1019 1020 1021 1022
0.7 (d) 0.7 (h)
0.6 0.6
C

0.5 0.5
ZT

0.4 0.4
AC

0.3 0.3
0.2 0.2
0.1 0.1
0 0
1018 1019 1020 1021 1022 1018 1019 1020 1021 1022
p(cm−3) n(cm−3)

FIG. 4. GGA calculated thermoelectric properties of electrons and holes doped KCaF3.(a) Seebeck
coefficient (b) thermal conductivity (c) power factor and (d) figure of merit, which is expected to
be the real figure of merit because we have added the contribution of lattice thermal conductivity.
Different colors lines represent different values of temperature
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PT
RI
U SC
AN
M
D
TE

FIG. 5. Calculated electron density near the valance band in the (001)(a) and (002)(b) planes of
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KCaF3 , and the electron density near the conduction band in the (001)(c) and (002)(d) planes of
KCaF3 .
C
AC