Enhanced electronic and thermoelectric

properties of p-type doped filled

skutterudites RFe4Sb12 (R = Pr, Nd)
Cite as: J. Appl. Phys. 128, 145104 (2020); https://doi.org/10.1063/5.0019797
Submitted: 25 June 2020 . Accepted: 26 September 2020 . Published Online: 13 October 2020

N. Limbu, M. Ram , H. Joshi , A. Saxena, S. Bin Omran, R. Khenata, and A. Shankar

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Enhanced electronic and thermoelectric

properties of p-type doped filled skutterudites
RFe4Sb12 (R = Pr, Nd)
Cite as: J. Appl. Phys. 128, 145104 (2020); doi: 10.1063/5.0019797
Submitted: 25 June 2020 · Accepted: 26 September 2020 · View Online Export Citation CrossMark
Published Online: 13 October 2020

N. Limbu,1,2 M. Ram,1,2 H. Joshi,2 A. Saxena,1 S. Bin Omran,3 R. Khenata,4 and A. Shankar2,a)

AFFILIATIONS
1
Department of Physics, North-Eastern Hill University, Shillong 793022, India
2
Department of Physics, Condensed Matter Theory Research Lab, Kurseong College, West Bengal 734203, India
3
Department of Physics and Astronomy, College of Science, King Saud University, P.O.Box 2455, Riyadh 11451, Saudi Arabia
4
Laboratoire de Physique Quantique et de Modélisation Mathématique de la Matière, (LPQ3 M), Université de Mascara 29000,
Mascara, Algeria

a)
Author to whom correspondence should be addressed: amitshan2009@gmail.com

ABSTRACT
A semimetallic type of electronic profile has been predicted for RFe4Sb12 (R = Pr, Nd) from a first-principles investigation, where the
presence of a small energy bandgap above the Fermi energy level (EF) is a key feature. The EF lies at the top of the valence band and it is
crossed by a single band more than twice, which improves the band concentration and electronic specific heat as reflected by the high
Seebeck coefficient. The doping of a heavy lanthanide atom at the center of the cage formed by pnictogen atoms has a significant effect on
the electronic structure that enhances the Seebeck coefficient and the thermoelectric power factor. The heavy atom at the center also
dampens the lattice vibration and lowers the lattice thermal conductivity. The Nd-doped system shows an enhanced Seebeck coefficient
with the highest power factor among the sample alloys. Moreover, due to significant reduction in the lattice thermal conductivity from
2.46 W/m K to 0.54 W/m K, a maximum ZT value of ∼1.11 at 800 K has been observed for an Nd-doped system. The covalent nature of
PrFe4Sb12, Pr-doped NdFe4Sb12, and Nd-doped PrFe4Sb12 and the ionic nature of NdFe4Sb12 have been confirmed, where Pr-doped
NdFe4Sb12 is the stiffest and a highly rigid material with strong bonding forces among the constituent atoms. The results presented in this
manuscript open the possibilities for further exploration of center atom-doped filled skutterudites with improved Seebeck coefficient and
reduced lattice thermal conductivity, which are promising materials for thermoelectric applications

Published under license by AIP Publishing. https://doi.org/10.1063/5.0019797

I. INTRODUCTION strongly correlated electron phenomena, such as superconductivity,8

Skutterudites (MX3; M = transition metal and X = pnictogen)
possess two voids in their unit cell, and filling of those voids by
suitable filler atoms, such as an alkaline earth metal, a lanthanide, or
an actinide, leads to ternary filled skutterudites (RM4X12; R = filler
atoms) that crystallize in a unique bcc structure. Currently,
lanthanide-filled skutterudites have gained much attention due to
the flexibility of choosing a suitable filler atom, which provides a
multifunctional character,1–5 and their possibility for thermoelectric
applications.6,7 These compounds with highly localized d and
f-electronic states are highly sensitive to the interactions of the filler
with the M and X atoms, which are also responsible for various
magnetic ordering,9 Kondo behavior,10 semiconductivity,11 ferro-
magnetism,12 heavy fermions, and valence fluctuations.13–15
Numerous theoretical and experimental studies starting from
lighter lanthanide-filled skutterudites have been reported in the
literature,10,16–22 where a high electronic specific heat coefficient (γ)
superconducting nature has been confirmed for La-filled skutteru-
dites16,17,23 along with a metallic profile for LaFe4Sb12.18 Similarly, as
we move toward the right in the periodic table for the filler atom, the
obtained Ce-filled skutterudites are hybridized semiconductors
(Eg ∼ 0.1–0.4 eV)24,25 with semimetallic profiles for CeRu4Sb1219 and
CeOs4Sb12.26 Furthermore, this semiconducting nature vanishes for

J. Appl. Phys. 128, 145104 (2020); doi: 10.1063/5.0019797 128, 145104-1

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 Journal of
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Pr filled skutterudite.9,10,21,22,27–29 In order to explore the most
notable thermoelectric properties of filled skutterudites, various tech-
niques both experimentally and theoretically18,30–39 have been
employed in the mid-temperature zone of 300–800 K. In this context,
Singh and Mazin40 have investigated the thermoelectric properties of
LaFe4Sb12 in its pure and doped forms using first-principles based
techniques within the local density approximation (LDA). A similar
approach has been used by Nouneh et al.18 to explore the thermo-
electric behavior of CeFe4Sb12 from the electronic energy band struc-
ture. Likewise, different transition metal dopant atoms, like Ni and
Co, have been used on the Fe site to optimize the thermoelectric per-
formance of LaFe4Sb12, and a ZT value of 0.82 at 800 K has been
observed for the Ni doped system.33,34 Similar to LaFe4Sb12, dopant
atoms like Ru and Co have been incorporated into CeFe4Sb12 to
enhance the thermoelectric performance (ZT ≈ 0.95 at 850 K).35,36
The lowering of the lattice thermal conductivity also improves the
thermal transport properties of filled skutterudite, which is achieved
by proper filling of doping of the guest atom inside the cage like
structure formed by the host lattice of M4X12. The rattling of this
guest atom inside the cage depends upon how loosely it is bound to
the host lattice, which results in the strong phonon scattering, thereby
producing low lattice thermal conductivity.6,41,42
Extensive work has been carried out during the last two
decades on Fe-Sb-based lanthanide-filled skutterudites25,29,43,44 to
understand the nature of the interaction between the constituent
atoms and explore the resultant physical properties considering the
present demand for energy and electronic applications. Further
analysis of the literature4,5,25,29,43,44 also revealed that the
Fe-Sb-based skutterudites also possess a variety of properties, as
discussed above, depending on the nature of the filler atom, which
can be used to understand and explore these alloys in more funda-
mental ways. Furthermore, various experimental studies have been
conducted on the members of the Pr and Nd-filled skutterudite
family30,45–48 to reliably predict their physical properties, and
meanwhile, the theoretical studies to understand these experimental
results are also equally progressing in unison. However, limited
studies have been reported thus far on RFe4Sb12 (R = Pr, Nd) on
their transport properties.
Therefore, to fill the gap between the theoretical and experi-
mental reports and predict the ground state properties of these
materials along with their thermoelectric behavior, a first-principles
based calculation has been carried out on RFe4Sb12 (R = Pr, Nd).
The motivation behind choosing Pr and Nd based skutterudites in
our present work lies in the fact that filler atoms Pr and Nd are
heavy atoms and are expected to rattle strongly inside the cages
formed by Sb atoms, thereby effectively reducing the lattice thermal
conductivity of these compounds and as a consequence will
enhance the thermoelectric performance of the material. An effort
has been made to understand the effect of the highly correlated
electron phenomena associated with these materials and their pos-
sible applications in different fields of science. The energy band
and the crystal structure of these materials are also analyzed along
with their mechanical properties that arise from the exact crystal
structure and the stability under ambient conditions. The thermo-
electric properties are analyzed, and the partial doping techniques
described in the previous literature have been adapted to enhance
the thermoelectric performance. The calculation has been carried
J. Appl. Phys. 128, 145104 (2020); doi: 10.1063/5.0019797
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out using an effective full potential linearized augmented plane
wave (FP-LAPW) method within the generalized gradient approxi-
mation, and the results thus obtained are validated by a compara-
tive analysis with available data and with analogous materials in
the case of unavailability of existing data.
II. COMPUTATIONAL DETAILS
A full potential linearized augmented plane wave (FP-LAPW)
method49 based computational tool50 within density functional
theory (DFT) was employed to explore the properties presented in
this manuscript. A 2 × 2 × 2 supercell of the pure sample crystal
was considered to perform the successful doping on the Nd site of
NdFe4Sb12 by Pr and on the Pr site of PrFe4Sb12 by Nd, as shown
in Fig. 1(b), where the dopant (Pr or Nd) occupies the center of
the icosahedral cage of the host lattice RFe4Sb12 (R = Pr or Nd)
formed by the pnictogen atoms. While solving the Kohn–Sham
equations, the effect of the exchange-correlation interaction of the
electrons was treated with the generalized gradient approximation
of the Perdew–Burke–Ernzerhof scheme (PBE-GGA).51 The con-
vergence of the plane wave basis set was enforced by setting the
RMT × KMAX value equal to 8, where RMT is the radius of the small-
est atomic sphere within the unit cell, and KMAX defines the
maximum amplitude of the plane wave vector (K). Different RMT
values were chosen for the constituent atoms depending on their
atomic size, such as 3.0, 3.0, 2.4, and 2.37 a.u. for Pr, Nd, Fe, and
Sb, respectively. The wave function was expanded within the MT
sphere and interstitial region with maximum lmax and Gmax values
of 6 and 13, respectively. The core and valence regions were sepa-
rated by an energy cut-off equal to −6.0 Ry for smooth convergence
of the self-consistent field calculations. A dense mesh of
12 × 12 × 12 k-points was considered for the integration over the
Brillouin zone (BZ) with energy convergence criteria of 10−4 Ry.
III. RESULTS AND DISCUSSION
A. Structural analysis and elastic constants
The RFe4Sb12 (R = Nd and Pr) materials are stable in a unique
bcc structure (space group: Im-3) as shown in Fig. 1, with 34 atoms
FIG. 1. Unit cell structure of (a) RFe4Sb12 (R = Pr, Nd), where R, Fe, and Sb
are denoted by blue, red, and yellow spheres, respectively, and (b) doped filled
skutterudites, where center pink spheres represent the dopant atom.
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TABLE I. Optimized positional parameter (u and v), optimized lattice constant (a0) in Å, formation energy (ΔEf ) in Ry, and independent elastic constants (C11, C12, and C44) in
GPa.

Material U v a0 ΔEf C11 C12 C44

PrFe4Sb12 0.334 0.161 9.207 −0.2240 190.347 23.336 56.908
9.13830
NdFe4Sb12 0.333 0.163 9.074 −0.2277 234.66 43.99 55.784
9.13630
Nd-doped 0.335 0.163 9.472 −0.1457 247.723 54.795 424.988
Pr-doped 0.334 0.162 9.372 −0.1459 456.593 264.532 95.435

per conventional unit cell, where the Sb atom occupies the Wyckoff
position of 24 g (0, u, v), which is slightly tilted from the octahedral
symmetry ring (0.25, 0.25, 0.25). Similarly, Fe is positioned at the
center of the distorted octahedral ring formed by the Sb pnictogen
atoms at 8c (0.25, 0.25, 0.25), and R occupies the center of the ico-
sahedral cage created by the 12 pnictogen atoms at 2a (0, 0, 0).
Here, the system-dependent positional parameters u and v usually
vary around u ∼ 0.35 and v ∼ 0.1652 with the lowest values for anti-
monides,53 and they were optimized by structural relaxation to the
minimal forces between the atoms, as shown in Table I. The crystal
structure was further optimized and then fitted into Murnaghan’s
equation of state54 to obtain the optimized lattice parameter (a)
(Table I), which is in close agreement with the experimental value
and depends on the ionic radius of the lanthanide atom, where the
effect of lanthanide contraction is clearly visible. A 2 × 2 × 2 supercell
was considered to perform the subsequent doping at the center of
the icosahedral cage of the host lattice formed by the pnictogen
atoms, where Pr and Nd atoms occupy the center icosahedral cage
of NdFe4Sb12 (Pr-doped) and PrFe4Sb12 (Nd-doped), respectively. A
similar approach to that of RFe4Sb12 (R = Nd and Pr) was considered
to optimize the doped structure (Pm-3 space group) thus formed
(Table I). The resultant of the asymmetric nature of the interactions
between the center R atom and the pnictogen cages is distinct with a
slightly enlarged crystal size compared to the pure alloys. RFe4Sb12
(R = Nd and Pr) have been experimentally synthesized30 and their
formation energies (Table I) are also consistent. However, in the
absence of any experimental synthesis of the Pr-doped and
Nd-doped structures, their thermodynamic stabilities are verified
from their formation energy (ΔEf ) calculation [Eq. (1)],55
ΔEf ¼ (Etot  wEd –xER  yEFe –zESb )/(w þ x þ y þ z),
where w = 1 for the doped system and w becomes 0 for the pure
system. Etot is the total energy of the pure/doped system, Ed, ER, EFe,
and ESb are the energies of the dopant, R (Pr,Nd), Fe, and Sb atoms,
respectively, in their solid state, and x, y, and z represent the number
of composite atoms of R, Fe, and Sb, whereas w defines the number
of dopant atoms in the unit cell. Here, in the present calculation, EPr,
ENd, EFe, and ESb are −18 485.254 Ry, −19 259.826 Ry, −2545.133 Ry,
and −12 967.099 Ry, respectively. One can conclude from these
values that the studied materials are energetically stable and possible
to be synthesized.
The elastic constants (Cij ) describe the response of a material
against an applied external stress and they are also related to ther-
modynamic parameters, such as the Debye temperature and
melting point. Hence, a set of three independent elastic stiffness
constants, namely, C11, C12, and C44 associated with the cubic sym-
metry of the samples that follow the mechanical stability criteria56
in their bcc phase were calculated and summarized in Table I.
Moreover, since the C11 values are larger than the C12 and C44
values of PrFe4Sb12, NdFe4Sb12, and the Pr-doped material, only a
high tensile stress can produce strain in these materials, whereas
the Nd-doped material is more responsive to shear stress as com-
pared to the other samples, with a high C44 value. One can also
note that Cij’s are comparatively large for the doped structures,
indicating that they are much stiffer, harder, and more resistive to
the external compression. Cij’s were calculated for single-crystal
samples, however, while synthesizing a crystal, a polycrystalline
sample grows, and to understand their mechanical properties, the
isotropic shear modulus (G), Young’s modulus (Y), bulk modulus
(B), Poisson’s ratio (ν), and anisotropy factor (A) were determined
and are summarized in Table II. The details of the calculations are
discussed in Ref. 57.
The bulk modulus (B) defines the hardness of a material, and
(1) in our study, the pure NdFe4Sb12 is harder than PrFe4Sb12, whereas
Nd doping in PrFe4Sb12 makes it the hardest of all the samples
considered herein. The pure alloys have a hardness comparable to
that of the analogous Ce-filled skutterudites.25,26,58–60 Furthermore,

TABLE II. Calculated values of the bulk modulus (B), Young’s modulus (Y), shear modulus (G), Cauchy pressure (C12–C44) in GPa, Debye temperature (θD) and melting tem-
perature (Tm) in K, Poisson’s ratio (v), and anisotropy factor (A).

Material B Y G C12–C44 θD Tm v A
PrFe4Sb12 79.006 155.574 66.382 −33.572 337.127 1677.95 0.172 0.681
NdFe4Sb12 107.547 171.026 69.244 −11.794 343.846 1939.84 0.235 0.585
Nd-doped 328.552 261.624 95.673 169.097 359.093 2017.04 0.367 0.994
Pr-doped 119.104 427.188 236.743 −370.193 551.093 3251.46 −0.098 4.406

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the hardness of NdFe4Sb12 is almost equal to that of the analogous The sound velocity is governed by the elastic properties and
UFe4Sb12 (106.45 GPa),29 whereas PrFe4Sb12 is slightly softer than density of the material (ρ). In a cubic crystal, the longitudinal (Vl )
LaFe4Sb12 (89.95 GPa).39 The values of the bulk modulus obtained and transverse (Vt) sound velocities in the three crystallographic
from the mechanical loading are also consistent with the bulk directions ⟨100⟩, ⟨110⟩, and ⟨111⟩ can be calculated from the rela-
modulus obtained from volume optimization calculations with their tions (2)–(4)66 and are summarized in Table III.
values of 78.97 GPa, 106.12 GPa, 329.25 GPa, and 120.71 GPa for Along the ⟨100⟩ direction,
PrFe4Sb12, NdFe4Sb12, Nd-doped, and Pr-doped alloys, respectively. In
a similar manner, NdFe4Sb12 is stiffer than the pure PrFe4Sb12 based sffiffiffiffiffiffiffi sffiffiffiffiffiffiffi
on Young’s modulus (Y) and the addition of Pr to NdFe4Sb12 makes C11 C44
Vl ¼ and Vt ¼ : (2)
it the stiffest of all the samples. Moreover, the stiffness of PrFe4Sb12 is ρ ρ
low compared to its prototype PrFe4P12 (389.53 GPa),61 which implies
that the P-based filled skutterudites are stiffer than the Sb-based Along the ⟨110⟩ direction,
alloys, consistent with the isostructural Ce-filled skutterudites.25,60
Likewise, the pure compounds also have a low stiffness compared to sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
the analogous Ce-filled skutterudites,25,26,58–60 UFe4P12 (637 GPa),62 C11 þ C12 þ 2C44 C11  C12
UFe4Sb12 (433.320 GPa),29 and ThFe4P12 (203 GPa),63 but are stiffer Vl ¼ and Vt ¼ : (3)
2ρ ρ
than LaFe4Sb12 (141 GPa).64 In line with this, the isotropic shear
modulus (G), which measures the rigidity of a given material, suggests
the rigid nature of NdFe4Sb12, which becomes more resistive to exter- Along the ⟨111⟩ direction,
nal shear when Pr is added to it. Here, the pure samples are also
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
softer as compared to isostructural CeFe4P12 (201.93 GPa), CeFe4As12 C11 þ 2C12 þ 4C44 C11  C12 þ C44
(140.72 GPa), CeRu4P12 (201.93 GPa), CeOs4P12 (274.58 GPa), Vl ¼ and Vt ¼ : (4)
3ρ 3ρ
CeOs4Sb12 (74 GPa), PrFe4P12 (169 GPa), ThFe4P12 (443 GPa),
UFe4P12 (329.56 GPa), and UFe4Sb12 (264.854 GPa).25,58,59,60 The pos-
itive or negative values of the Cauchy pressure (C12–C44) along with We observed that the magnitude of the longitudinal velocity
the critical value of 1.75 for the B/G ratio can be used to predict the decreases along the ⟨100⟩, ⟨110⟩, and ⟨111⟩ directions, while the
ductility or brittleness of a material, where a brittle nature can be magnitude of the transverse velocity increases along the ⟨100⟩,
expected for all the sample alloys except for the Nd-doped compound ⟨111⟩, and ⟨110⟩ directions for PrFe4Sb12 and NdFe4Sb12, which
which is ductile. The elastic constants are also closely related to the reveal the anisotropic behavior of the sound velocities in these
thermodynamic properties, including the Debye temperature (θD), compounds. In the case of the Nd-doped system, Vl increases along
which indicates the stability of the crystal structure, strength of the the ⟨100⟩, ⟨111⟩, and ⟨110⟩ directions, while in the case of Vt, it is
binding forces, and melting point of a material. This temperature is vice versa. Similarly, in the Pr-doped system, Vt increases along the
also related to the hardness of an alloy and its value for most of the ⟨100⟩, ⟨111⟩, and ⟨110⟩ directions, while Vl retains almost a same
crystals falls within 200–400 K.65 The computed values of θD and value along those directions. A dislocation, which is defined as a
the melting temperature (Tm) indicate that the Pr-doped system is the crystal imperfection (an abrupt change in the arrangement of
hardest among the sample materials and has a high melting tempera- atoms), can be used to understand a crystal defect and becomes sig-
ture, revealing strong binding forces between the atoms, which may be nificant for plastic deformation in alloys and metals.67 The
due to the ionic support in the atomic bonding, thus requires more mechanical properties of a material can be controlled by disturbing
energy to break the bonds. Likewise, the critical value of Poisson’s the movement of a dislocation in a crystal, as the movement of this
ratio (v) (0.26) implies the covalent type of interatomic bonding in the dislocation experiences a periodic potential and hence must pass
sample materials except for NdFe4Sb12 which has an ionic nature. through an energy barrier, known as the Peierls barrier. In the
These materials are highly elastically anisotropic with anisotropic Peierls–Nabarro (PN) model,68 the minimum stress needed to over-
factor (A) strongly deviating from unity, except for the Nd-doped come this barrier is known as the Peierls stress (or the minimum
material which is elastically isotropic. stress required to move the dislocation), which can be calculated

TABLE III. Estimated longitudinal (Vl ) and transverse (Vt) sound velocities in m/s along crystallographic directions ⟨100⟩, ⟨110⟩, and ⟨111⟩, Peierls stress (σP) for edge and
screw dislocation in GPa and Burgers vector (b) in Å.

⟨100⟩ ⟨110⟩ ⟨111⟩ σP

Compound Vl Vt Vl Vt Vl Vt Edge Screw b
PrFe4Sb12 1698.1 928.5 1574.9 1590.6 1531.7 1063.3 0.33 0.95 7.97
NdFe4Sb12 1842.9 898.6 1680.5 1661.3 1622.7 1090.5 0.22 1.07 7.86
Nd-doped 1010.2 1323.2 1540.8 891.5 1680.8 618.4 0.09 1.78 8.20
Pr-doped 1349.8 617.1 1348.9 875.5 1348.7 921.2 4.04 2.54 8.12

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using the shear modulus and Poisson’s ratio from relation (5),68

 of a material, such as the Seebeck coefficient and electrical conduc-
2G 2Πζ
σp ¼ exp : (5)
1ν b to a good distribution of charge carriers where the curvature of the
Here, ζ ¼ 1ν
d
for an edge dislocation = d for a screw disloca-
tion, where d is the interlayer distance between the slip planes
and b is the magnitude of the Burgers vector. We note that σP is
sensitive to d and b for the fixed values of the Poisson’s ratio and
shear modulus. The calculated values of σP are collected in
Table III, and one can infer that an edge dislocation is more
mobile than a screw dislocation in the sample materials except for
the Pr-doped system, which is possibly due to the negative magni-
tude of ν. We also observed that PrFe4Sb12, NdFe4Sb12, and the
Nd-doped material require comparatively similar magnitudes of
σP to move dislocations.
B. Electronic and magnetic properties
Binary filled skutterudites have drawn considerable attention
of the researchers working on theoretical and experimental investi-
gations exploring their exact electronic properties.5,25,47,69 Similarly,
the theoretical FP-LAPW60,62,70 based studies are also effective in
predicting accurate ground state properties of filled skutterudites.
An analysis of the energy band structure near the Fermi energy
level (EF), which reflects the distribution of the electrons in the
energy and momentum space, is significant for understanding the
origin of the thermoelectric behavior of these skutterudites.71 Here,
the lanthanide f-states dominate the energy band structure due to
the interplay between the f, d, and p-electronic states of the lantha-
nide, transition metals, and pnictogen atoms, as shown in Fig. 2,
which is sensitive to the position of the pnictogen atom in the
crystal.72,73 The energy band profiles of PrFe4Sb12 and NdFe4Sb12
are similar to each other and they are also identical to those of
analogous compounds.29,74 EF is fixed well inside the top of the
valence region, and the bands in the vicinity of EF are found to be
populated with a mixture of both flat and parabolic bands, indicat-
ing the motion of holes with varying effective mass along the dif-
ferent symmetry directions.
A careful analysis of the region close to EF between −0.5 and
0.5 eV was performed to reveal the distribution of electrons, and we
observed that EF is fixed well inside the top of the valence region.
Both PrFe4Sb12 and NdFe4Sb12 exhibit triply degenerate bands at
the H symmetry point of both the spin channels that are lifted
along the H-N direction. In PrFe4Sb12, these bands due to hybrid-
ized Fe-d and Pr-f states which correspond to the high peak in the
PDOS plot [Fig. 3(a)] occur at −0.27 eV in the majority spin
channel, whereas in the minority spin channel, these degenerate
bands are mainly of an Fe-d character (at −0.17 eV) and no such
hybridization between Pr-f and Fe-d states is observed. In the case
of NdFe4Sb12, these bands are observed at −0.22 eV (in the major-
ity spin channel) and −0.17 eV (in the minority spin channel) and
are mainly attributed to Fe-d electrons, with observable contribu-
tions from the Pr-f state in the majority spin channel. The para-
bolic and flatbands are important aspects of bands to elucidate the
distribution and motion of the charge carrier (hole/electron) with
varying effective mass along different symmetry directions near EF,
J. Appl. Phys. 128, 145104 (2020); doi: 10.1063/5.0019797
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which play a crucial role in explaining the thermoelectric properties
tivity. Generally, a perfect parabolic-shaped band can be correlated
parabola determines the magnitude of the effective mass, i.e., high
and low effective mass (HEM/LEM) for low and high curvature,
respectively, which means that a flatband denotes a very high effec-
tive mass. Such parabolic and flatbands were observed in the
sample materials.
The minority spin channel of PrFe4Sb12 reveals two para-
bolic bands at 0.22 eV (HEM) and 0.06 eV (LEM) around the Γ
symmetry point. These observed bands are mainly of Fe-d char-
acter with noticeable contributions from the Pr-f and Sb-p
states. In the majority spin channel, there is only one parabolic
band at the N point at 0.188 eV (HEM), which is found to be of
a Pr-f character. This band shows a linear response and crosses
EF along the N-Γ direction; however, it exhibits a flatband like
feature along the Γ-P direction, contributes to the high DOS
near EF and can be visualized as a high peak in the PDOS [Fig. 4(a)].
Unlike PrFe4Sb12, there are no parabolic bands near EF in NdFe4Sb12
at the N symmetry point, rather, four parabolic bands are
observed at the Γ point, two each for the majority and minority
spin channels. The first highest parabolic band at 0.214 eV is
wider (HEM) than the second highest band at 0.197 eV in the
minority spin channel. These bands are mainly formed by the
Fe-d electrons, as seen in the PDOS plot [Fig. 4(b)]. In the major-
ity spin channel, the first highest band at 0.068 eV (HEM) is of a
Fe-d character, whereas the band just below EF at the Γ point is
an admixture of Fe-d, Pr-f, and Fe-d characters in which the Fe-d
character is dominant.
The impurity atoms play a significant role in modifying the
band structure of the host lattice by interacting with them, which
is visible in the band structure of the doped alloys [Figs. 2(c)
and 2(d)], where the conduction region is more dispersive than the
valence region and sharp flatbands just above EF originating from
the Pr and Nd atoms are also distinct. The addition of the Nd atom
to PrFe4Sb12 induces the valence bands to move toward the con-
duction bands, which causes shifting of two parabolic bands to
higher energy, one from 0.06 eV to 0.123 eV and the other from
0.22 eV to 0.32 eV at the Γ symmetry point in the minority spin
channel. The doubly (at −0.02 eV) and triply (at −0.102 eV) degen-
erate bands at the Γ point due to Fe-d electrons are observed which
are lifted along the Γ-M direction. We observed that both the lifted
bands from the doubly degenerate band cross EF, whereas only one
band from the triply degenerate band crosses EF along the X-M
direction, which contributes to the higher DOS at the EF. No
hybridization between the dopant atom and the Fe-d atom is
observed near EF. However, the region in the vicinity of EF displays
densely populated bands that are mainly contributed by Fe atoms,
thereby enhancing the density of states and contributing toward a
high Seebeck coefficient for the compounds under consideration.
In the majority spin channel, a single band (at 0.41 eV) and a triply
degenerate band (at 0.12 eV) originating from the Γ point due to
the Nd-f states are observed and the degeneracy of the band is
lifted along the Γ-X-M direction with a flatband-like feature,
which is responsible for the high peak observed in the DOS plot
[Fig. 3(c)]. A parabolic band at 0.1 eV around the M-symmetry
128, 145104-5
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point is also observed, which has a mixture of Nd-f and Pr-f char-
acters, where Nd-f is the dominant one. The dominant character of
this Nd-f band is maintained along the M-X direction, however,
this band reflects a Pr-f character as it approaches EF along the X-Γ
direction and crosses EF. Another doubly degenerate band due to
Pr-f state electrons is observed, which is lifted along the Γ-X-M
direction with one band crossing EF along the X-M symmetry
point. Similarly, the band profile near EF in the Pr-doped alloy is
greatly influenced by the highly correlated electrons of Pr. The
bands near EF seem to be similar to those of the Nd-doped alloy at
first glance, but the difference in their band profile lies in the for-
mation of their parabolic and degenerate bands in the different
energy ranges. In the majority spin channel, a triply degenerate
band originating from the Γ point at −0.05 eV is observed, which is
J. Appl. Phys. 128, 145104 (2020); doi: 10.1063/5.0019797
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FIG. 2. Energy band structures of (a)
PrFe4Sb12, (b) NdFe4Sb12, (c)
Nd-doped, and (d) Pr-doped alloys.
(Color scheme: red for majority spin
and blue for minority spin channels.)
lifted along the Γ-X direction. One of the bands crosses EF along
the Γ-X point, forming a parabolic band at the M symmetry point
at 0.125 eV. Out of the other two bands, one band crosses EF along
the X-M and M-Γ directions and the other one is aligned flat along
the X-M direction. These bands have a dominant Pr-f character
and contribute to a high DOS, which corresponds to the peak at EF
[Fig. 4(d)]. In addition to this, the region at approximately
0.183 eV is found to be mostly populated by Pr-f electrons with a
sharp flatband like feature. In the minority spin channel, the bands
near EF are mainly of a Fe-d character with a few bands crossing EF
in the X-M direction. The two observed parabolic bands at the Γ
symmetry point at 0.214 eV and 0.197 eV in the minority spin
channel in NdFe4Sb12 shift to 0.276 eV and 0.08 eV, respectively,
whereas such parabolic bands in the majority spin channel vanish
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FIG. 3. Total DOS of (a) PrFe4Sb12, (b) NdFe4Sb12, (c) Nd-doped PrFe4Sb12, and (d) Pr-doped NdFe4Sb12.
with the addition of Pr atom at the center of the cage. The electrons
of the host Nd-f states contribute to the dense and flatband forma-
tion in the energy region between 0.6 and 0.75 eV in the majority
spin channel. In Fig. 2, the presence of an empty band region near
EF indicates a gap like feature in both the spin channels. The for-
mation of these gaps can be attributed to the octahedral symmetry
associated with the Fe-Sb lattice. The energies of the valence band
maximum (VBM) and conduction band minimum (CBM) along
the different symmetry directions along with the energy bandgaps
are listed in Table IV. The minority spin energy bandgaps are
wider than the majority spin bandgaps and NdFe4Sb12 (0.74 eV)
has the highest bandgaps of all the samples. The addition of
dopant atoms into the supercell structure enhances the density
of electronic states around EF, which reduces the energy bandgap of
the doped structures. An overall semimetallic type of the electronic
J. Appl. Phys. 128, 145104 (2020); doi: 10.1063/5.0019797
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structure can be concluded for these samples62,75 with enhanced
DOS and a narrow bandgap at EF.
The total and partial DOS were also analyzed to understand
the contribution and distribution of the electrons of the constituent
atoms in the bands (Figs. 3 and 4). The total DOS also reveals
sharp peak features near the EF, which can be analyzed using the
PDOS. To elucidate the DOS, the plots are divided into four sec-
tions: the lower valence region which ranges from −4 eV to −2 eV;
the upper valence region (−2 eV to EF); the lower conduction
region (EF to 2 eV), and the upper conduction region (2 eV to
4 eV). The contribution to the lower valence region of both the
spin channels is predominantly from the 5p-state of the Sb
atom, which is consistent with the energy band structure [Figs. 2(a)
and 2(b)], whereas the DOS in the vicinity of EF is controlled by
the R and Fe atoms. The upper valence region of all the sample
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Applied Physics

FIG. 4. Partial DOS plots of (a) PrFe4Sb12, (b) NdFe4Sb12, (c) Nd-doped PrFe4Sb12, and (d) Pr-doped NdFe4Sb12.

TABLE IV. Energy gap (Eg in eV) at different symmetry points in the majority (↑) materials in the minority spin channel is dominated by the
and minority (↓) spin channels and DOS at EF [N(EF)] in states/eV. 3d-states of the Fe atom (Fig. 4). However, in the majority spin
channel, this region is governed by the Fe-d and R-f states.
Symmetry direction Furthermore, in PrFe4Sb12, it is apparent from the PDOS
Material Spin VBM CBM Eg N(EF) [Fig. 4(a)] that the Fe-d state hybridizes with the Pr-f state (near
PrFe4Sb12 ↑ NP 0.43 44.45 EF) and Sb-p state (at −1.96 eV). A sharp peak due to the Pr-f state
↓ ΓN 0.61 at EF is observed in the PrFe4Sb12, Nd-doped, and Pr-doped alloys.
NdFe4Sb12 ↑ ΓH 0.30 73.56 No such sharp peak occurs at EF in NdFe4Sb12, rather, a sharp peak
↓ ΓN 0.74 is seen at −0.45 eV. This suggests that the f electrons of the Nd
Nd-doped ↑ M R- Γ 0.03 106.43 atom mainly occupy the valence region of NdFe4Sb12.
↓ ΓM 0.50 The lower conduction region of the sample alloys is mostly
Pr-doped ↑ MΓ 0.02 65.78 occupied by R-f electronic states and reveals an interesting feature
↓ ΓΓ 0.40 such as gaps and multiple peaks in the PDOS plot (Fig. 4). The
minority spin channel displays a wider gap than the majority spin

J. Appl. Phys. 128, 145104 (2020); doi: 10.1063/5.0019797 128, 145104-8

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channel in all the sample materials, with high gap values for the
undoped alloys. The magnitudes of these gaps have been already
discussed based on the energy band structure (Table IV). In the
case of PrFe4Sb12, two prominent sharp peaks due to the Pr-f state
are observed for each of the majority (at 0.65 eV) and minority
(1.49 eV) spin channels, consistent with the flatbands in the energy
band structure [Fig. 2(a)]. However, the plot of NdFe4Sb12
[Fig. 4(b)] reveals two sharp peaks due to Nd-f state electrons at
0.41 eV and 0.65 eV consistent with the energy band structure
[Fig. 2(b)]. In the doped alloys [Figs. 4(c) and 4(d)], a mixture of
Nd-f and Pr-f states is observed as expected from the band struc-
ture. The observed peaks from the Nd-f state are comparatively
higher in magnitude than those from the Pr-f state in the majority
spin channel in both alloys, whereas in the minority spin channel,
the Pr-f peak dominates. In the Nd-doped material, such peaks
occur at 0.14 eV (from the Nd-f state) and 0.74 eV (Pr-f state),
whereas in the case of the Pr-doped material, the peaks are
observed at 0.20 eV (Nd-f ) and 0.70 (Pr-f ). We see that the upper
valence region of the majority spin channel is mainly occupied by
the Fe-d and Sb-p states, whereas that of the minority spin channel
is dominated by R-f states.
Furthermore, we have observed that many bands cross the
Fermi level, amplifying the amplitude of the density of states at
EF and the calculated DOS at EF [N(EF)] are 53.53 states/eV,
89.73 states/eV, 160.05 states/eV, and 196.06 states/eV for PrFe4Sb12,
NdFe4Sb12, Pr-doped NdFe4Sb12, and Nd-doped PrFe4Sb12, respec-
tively. These N(EF) values are further utilized to compute the
Sommerfeld coefficient (γ) of 126.14 mJ/mol K2, 211.78 mJ/mol K2,
461.95 mJ/mol K2, and 377.11 mJ/mol K2 for PrFe4Sb12, NdFe4Sb12,
Pr-doped NdFe4Sb12, and Nd-doped PrFe4Sb12, respectively. The
high concentration of the DOS at EF along with the sufficiently large
electronic specific heat (γ) and semimetallic nature of these alloys
indicates their potential for use in effective thermoelectric devices
which will be discussed in detail in Sec. III C.
C. Electrical and thermal transport properties
The electronic band structure related to the charge carrier and
the nature of the bands, such as the flat (corresponding to a high
effective mass) and parabolic bands (corresponding to a low effec-
tive mass) near EF, plays an effective role in determining the mag-
nitude of Seebeck coefficient (S).76 As discussed in Sec. III B, the
highly populated bands near EF corresponding to high mobility of
charge carriers may enhance the Seebeck coefficient (S), which
measures the magnitude of the emf induced by a temperature gra-
dient across the material. A high S also indicates a favorable ther-
moelectric power factor of the material and typically a S value close
to 160 μV/K corresponds to a thermoelectric figure of merit (ZT)
close to unity for a material with negligible lattice thermal conduc-
tivity.77 In the present study, the semimetallic nature of the materi-
als with a clear appearance of flatbands at EF with a high effective
mass motivated us to further analyze the thermoelectric transport
properties within the Boltzmann semi-classical scheme (constant
relaxation time and rigid band approximation)78 using the
BoltzTraP code.79 Here, the valence electrons of the Pr/Nd atoms
(3+ oxidation states) are inadequate to neutralize the high concen-
tration of holes contributed by the host atoms, leaving the free
J. Appl. Phys. 128, 145104 (2020); doi: 10.1063/5.0019797
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holes as charge carriers which leads to a positive nature of S
over the whole temperature range (here 100–800 K) as shown in
Fig. 5(a). The nature of the variation of S with T for the pure
samples is identical to that of previous experimental and theoretical
reports.30,43
The estimated values of S at the room temperature (80 μV/K
and 83.4 μV/K) are in close agreement with the experimentally
reported values of 81.5 μV/K and 83.7 μV/K for PrFe4Sb12 and
NdFe4Sb12, respectively.30 However, they are somewhat higher than
the theoretical value of 66 μV/K for NdFe4Sb12.43 Furthermore, the
slightly higher amplitude of S at room temperature in the present
study as compared to LaFe4Sb12 (78.3 μV/K), EuFe4Sb12 (70.8 μV/K),
and YbFe4Sb12 (77.9 μV/K)30,43 indicates the advantage of trivalent
fillers (Pr, Nd) over divalent fillers. Here, the amplitude of S increases
with T and attains a maxima of 151.5 μV/K and 143.2 μV/K for
PrFe4Sb12 and NdFe4Sb12, respectively, at 800 K, consistent with
experimental reports30 but slightly lower than the theoretical results
of Zhou et al.43 The slight deviation in the present results from the
experimental reports may be due to the effect of the strongly corre-
lated 4f electron of the lanthanide atoms, which is not properly
described by the GGA and this may persist for other p-type
lanthanide-filled skutterudites as well. The variations of S for the
Pr-doped and Nd-doped materials are identical to that for pure
RFe4Sb12 (R = Pr, Nd), which may be related to their similar energy
band profile in the vicinity of EF and their high magnitudes can be
correlated with the dense flatbands (high effective mass of the holes)
from the localized Fe-d states in the vicinity of EF. Here, the effect of
choice of dopant atoms is distinctly visible, where the Nd dopant has
one electron more than Pr and the Nd doping yields a more
enhanced DOS at EF and a higher hole effective mass that produces
an amplified S (89.4 μV/K) at room temperature compared to the
other compounds. Unlike the Nd-doped material, in the Pr-doped
material, a low S (59.6 μV/K) can be expected. The maximum value
of S is calculated to be 154.5 μV/K at 800 K in the Nd-doped system,
and unlike the other samples, the Pr-doped alloy exhibits an S that
varies slowly up to 200 K and then follows a similar trend to the
other sample materials with its maximum (128 μV/K) at 800 K.
The outputs of the Boltztrap code except Seebeck coefficient
depend on the relaxation time and hence, in order to obtain the
transport properties, one must consider the relaxation time (τ). The
relaxation time (τ) for p-type Fe-Sb based skutterudites has been
found to be weakly dependent on the guest or filler atoms and the
value of τ was observed to be constantly varying with temperature
with τ values equal to (7–8.5) × 10−15 s and (6–7.5) × 10−15 s at 300
and 800 K, respectively.80 Therefore, in our present calculations, a
constant τ value of 7.5 × 10−15 s over the whole temperature range
of 100–800 K has been considered for RFe4Sb12 and its doped
alloys. A similar approach was also adopted by Yang et al.80 The
computed electrical conductivity (σ), total thermal conductivity
(KTotal ), and lattice thermal conductivity (KL) have been depicted
with respect to temperature in Fig. 5. The value of σ [Fig. 5(b)] for
all the sample materials decreases with increasing temperature,
which is one of the characteristic properties of heavily doped skut-
terudites. For all the compounds, the magnitude of σ is found to be
in the order of 105 S/m which is quite satisfactory. Our computed
variations of σ for PrFe4Sb12 and NdFe4Sb12 are similar to that of
experimental investigation.30 Among the sample materials, the
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FIG. 5. Variation of (a) Seebeeck coefficient (S), (b) electrical conductivity (σ), (c) total thermal conductivity (KTotal ), and (d) lattice thermal conductivity (KL) as a function
of temperature (T) for pure and doped structures.
variation of σ with respect to temperature is highest in NdFe4Sb12
where for both the doped systems it falls between that of
NdFe4Sb12 and PrFe4Sb12. A material suitable for thermoelectric
application must have low thermal conductivity, which is defined
as the material’s ability to transfer heat. In a crystal, the heat is
carried out by electrons and lattice vibrations (phonons).
Therefore, in a normal crystal, the thermal conductivity is the sum
of the contributions from both electronic and lattice parts, i.e.,
Ktotal = Ke + KL, where Ke and KL are electronic and lattice thermal
conductivities, respectively.77 The variation of total thermal con-
ductivity (KTotal ) with respect to temperature for all the sample
alloys is shown in Fig. 5(c).
From the figure, one can notice that the variation of thermal
conductivity is lowest in Nd-doped alloys followed by NdFe4Sb12
where the highest variation is observed in Pr-doped alloys. The
constituent atoms in the filled skutterudites are arranged in such a
way that the presence of heavy lanthanide filler atoms within the
pnictogen cages is significant for reducing the lattice thermal con-
ductivity of these systems by increasing the lattice phonon scatter-
ing which also makes them to have potential for thermoelectricity.
Hence, a proper choice of filler atom also plays a significant role in
optimizing the phonon scattering due to the rattling phenomena
J. Appl. Phys. 128, 145104 (2020); doi: 10.1063/5.0019797
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inside the void of the host lattice, which leads to a further reduction
of the lattice thermal conductivity (KL) without affecting the elec-
tronic properties of the material.1,81 This rattling effect depends on
how loosely the filler atom interacts with the host lattice, and for
this reason, the filler atoms with heavier mass and smaller ionic
radius can significantly reduce KL, as they have comparatively suffi-
cient space inside the void to rattle. Here, the heavy filler atoms Pr
and Nd act as an independent oscillators that interact with acoustic
phonons, thereby reducing the KL of RFe4Sb12 (R = Pr and Nd).
We have computed the lattice thermal conductivity of the sample
materials within the slack formalism82 using Eq. (6),
KL ¼ AMδθ3D n2/3 /γ 2 T, (6)
8
where A ¼ 10:514/γþ0:228/γ
2:4310
2 :
γ is the Grüneisen parameter, M is defined as the average
mass of the alloy, δ3 is the volume occupied by an atom, and n is
the total number of atoms in the unit cell. The temperature depen-
dence of KL for our studied materials are plotted in Fig. 5(d). It is
observed that KL decreases with increase in temperature in all the
alloys. The curve shows that the temperature dependence of KL sig-
nificantly reduced when the pure alloy was doped with heavy
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FIG. 6. The temperature dependence of (a) power factor (PF) and (b) ZT for the pure and doped alloys.
atoms. The room temperature KL values of PrFe4Sb12 and NdFe4Sb12
are 6.96 W/m K and 5.55 W/m K, respectively, and for the Pr-doped
and Nd-doped structures, the values are 10.48 W/m K and
1.92 W/m K, respectively. Here, the response to doping inside the
cage of the host lattice Fe4Sb12 was identical to that of S. The replace-
ment of the center Pr atom at the atomic site (0.5, 0.5, 0.5) with Nd
contributes to the large phonon scattering arising from the heavy
atom with small atomic radius Nd due to the high rattling effect
inside the void. A notable reduction in KL (from 6.96 W/m K to
1.92 W/m K at 300 K) of pure PrFe4Sb12 due to Nd doping with a
lowest KL value of 0.54 W/m K at 800 K also gives a satisfactory result
of the heavy atom doping. Now, in the case of Pr doping at the
center (0.5, 0.5, 0.5) atomic site of NdFe4Sb12, the lighter atom with a
larger atomic radius compared to Nd results in low phonon scattering
due to the low rattling effect thus, KL is significantly enhanced in
Pr-doped from 5.55 W/m K to 10.48 W/m K at 300 K and 0.80 W/
m K to 3.83 W/m K at 800 K. Thus, an overall study of KL reflects
that doping the rare-earth atomic site with heavy atoms significantly
reduces the thermal conductivity of the sample alloys and validates
that the rattling effect is sensitive to the heavy atom, as observed in
various analogous skutterudites.81,83–85
Figure 6(a) describes the power factor (PF) with respect to
temperature for all the sample alloys. The obtained nature of the
curve for pure alloys is consistent to that obtained by Qiu et al.30
From the figure, we note that the PF curve for the sample alloys
varies in a similar manner except Pr-doped alloys, where PF varies
slowly up to 300 K, thereafter increases linearly till 600 K and then
again varies constantly up to 800 K. The similar values of PF of the
sample materials are possibly due to their comparative magnitude
of electrical conductivities. The most important point to note down
here is the PF values of Nd-doped and Pr-doped alloys where the
Nd-doped alloy shows the highest PF values among the studied
materials in the whole temperature range, whereas the Pr-doped
alloy reflects the least. The enhanced PF values for Nd-doped
system reflect the fact that the doping with the heavier atom in the
cage void of the filled skutterudites is the effective way to optimize
J. Appl. Phys. 128, 145104 (2020); doi: 10.1063/5.0019797
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the thermoelectric performance of the material. The same fact can
also be observed for the fully filled skutterudites, where PF values
for NdFe4Sb12 are higher than that of PrFe4Sb12 in the temperature
range of 100 to 600 K. The highest PF value of 30 mW/m K is
found for the Nd-doped alloy at 800 K, whereas at the room tem-
perature, PF are found to be 6 mW/m K, 7 mW/m K, 7.7 mW/m K,
3.4 mW/m K for PrFe4Sb12, NdFe4Sb12, Nd-doped, and Pr-doped
alloys, respectively.
The viability of the thermoelectric material as industrial appli-
cations is assessed by the dimensionless figure of merit, defined as
ZT = S2σT/(Ke + KL). The computed values of ZT as a function of
temperature for the sample materials are shown in Fig. 6(b). From
the plot, one can observe that the ZT increases with a rise in temper-
ature for all the alloys. Due to the high Seebeck coefficient and low
KL value, Nd-doped alloys revealed the highest ZT value of 1.11 at
800 K, whereas pure alloys PrFe4Sb12 and NdFe4Sb12 show highest
ZT values of 0.79 and 0.85 at 800 K. The important aspect to focus
here is ZT values of doped alloys. The ZT value of PrFe4Sb12 is
found to be enhanced from 0.79 to 1.11 when doped with Nd,
whereas it is reduced from 0.85 to 0.65 when NdFe4Sb12 is doped
with Pr. The enhanced ZT (1.11) value of Nd-doped alloy is found
to be greater than the recently calculated ZT value of potential
n-type doped ZnS2 based thermoelectric material.86 Our present
work on the doped system is just the theoretical approach to
enhance the thermoelectric performance of the material and requires
the future experimental verification and thereby opening the possi-
bility of these compounds as future thermoelectric materials.
IV. CONCLUSIONS
The results reported in this manuscript suggest a semimetallic
nature of the pure and doped RFe4Sb12 (R = Pr, Nd) from the
FP-LAPW method based investigation. The energy bands and DOS
reveal the presence of a unique small pseudogap type of feature in
these alloys. The energy bands are densely populated in the super-
cell of the doped structures and consequently, the Seebeck
128, 145104-11
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coefficient is high where the Nd atom is added in the center of the
cage formed by the pnictogen atoms in PrFe4Sb12 and similarly for
the Pr atom in NdFe4Sb12. Nd-doped PrFe4Sb12 has a high value of
S (154.5 μV/K) at room temperature and the addition of the heavy
atom at the center of the cage also affects the rattling of the host
atom, dampening the lattice vibration and hence reducing the
lattice thermal conductivity of the Nd-doped structures signifi-
cantly from 2.46 W/m K to 0.54 W/m K at 800 K. It is observed
that the pure alloys, PrFe4Sb12 and NdFe4Sb12, reveal maximum ZT
values of 0.79 and 0.85, respectively, at 800 K. Furthermore, due to
the enhanced Seebeck coefficient and lowest lattice thermal con-
ductivity, the Nd-doped alloy is found to possess a maximum
power factor (30 mW/m K) and ZT (1.11) among the sample alloys
implying enhancement of the thermoelectric properties of the
material on doping the cage atom of the filled skutterudite by
heavy dopants. The elastic constants and the formation energy
indicate the mechanical and thermodynamic stability of the doped
structures thus formed, which awaits further experimental verifica-
tion. Moreover, Young’s modulus, shear modulus, and bulk
modulus values are also improved by doping, which enhances the
respective properties of the materials and makes them suitable for
commercial applications. These sample alloys have a brittle nature
except for the Nd-doped structure with a highly elastically aniso-
tropic nature, where the sound waves travel more efficiently in the
pure crystals and the movement of a dislocation in PrFe4Sb12 and
NdFe4Sb12 indicates the same magnitude of the Peierls stress. The
present work may act as a platform for choosing the dopant atom
to improve the ZT, which may pave the way for further design of
candidate compounds for efficient thermoelectric applications.
AUTHORS’ CONTRIBUTIONS
All authors contributed equally to this manuscript.
ACKNOWLEDGMENTS
N. Limbu acknowledges a fellowship grant from CSIR-INDIA
[File No. 09/347(0231)/2019-EMR 1] and A. Shankar acknowledges
DST-SERB India for the computational facility (No. YSS/2015/
001101). S. Bin Omran acknowledges financial support of Research
Supporting Project No. RSP-2020-82 at the King Saud University,
Riyadh, Saudi Arabia. R. Khenata acknowledges financial support
of the General Direction of Scientific Research and Technological
Development (DGRSDT).
The authors declare no conflict of interest.
DATA AVAILABILITY
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
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