Zhou 2011
Zhou 2011
Zhou 2011
5, 2011
DOI: 10.1007/s11664-010-1472-1
Ó 2010 TMS
1.—State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan
University of Technology, Wuhan, China. 2.—e-mail: liulish@whut.edu.cn
974
Electronic Structures and Transport Properties of RFe4Sb12 (R = Na, Ca, Nd, Yb, Sn, In) 975
regarding atomic combinations for filled skutteru- constant of 9.038 Å. The transition-metal Fe posi-
dites with better thermoelectric performance. tion is (0.25, 0.25, 0.25), the pnicogen (Sb) position is
(0, 0.385, 0.153), and the atom R position is (0, 0, 0).
THEORY CALCULATION This lattice model has 34 atoms.
Density functional calculations have been playing
an increasingly important role in material research RESULTS AND DISCUSSION
recently.9,10 Significant results for skutterudites, Lattice Constants and Electronic Structure
half-Heusler, and other compounds based on den-
sity functional calculations have been reported.11–13 The lattice structures of all the RFe4Sb12 mate-
In previous work, density functional calculations rials were first optimized by using the structure
were performed by the projector augmented wave relaxation method to allow change of the unit cell in
method as implemented in the Vienna ab initio terms of shape, size, and ionic positions. The opti-
simulation package (VASP).14–16 The exchange cor- mized lattice constants (LCs) and some experimen-
relation energy was dealt with by the generalized tal values for the RFe4Sb12 materials are listed in
gradient approximation (GGA). The k meshes for Table I. The results show that the optimized LCs of
optimization of the lattice structure and the calcu- NaFe4Sb12 (9.194 Å) and YbFe4Sb12 (9.185 Å) are
lation of the electronic structure were 8 9 8 9 8 in only slightly larger than the experimental values
the Monkhorst–Pack scheme. The ‘‘Accuracy’’ set- (9.178 Å for NaFe4Sb12 and 9.156 for YbFe4Sb12).6
ting for computing precision and an energy conver- This agreement is good considering the slightly high
gence criterion of 104 eV for self-consistency were calculation error of the GGA approximation. The
adopted, and the spin–orbit coupling effect was maximum LC was 9.220 Å for InFe4Sb12, and the
neglected in all calculations for simplicity. next largest was 9.217 Å for SnFe4Sb12. The results
The electrical transport properties were calcu- also reveal that the skutterudites filled with lan-
lated based on the Boltzmann transport equation thanide elements have smaller LCs compared with
under the rigid band approximation and the con- those filled with alkaline or alkaline-earth metal
stant relaxation time approximation. Under this elements.
condition, the Seebeck coefficient S and the electri- The band structures of RFe4Sb12 were calculated
cal conductivity r can be expressed as9,10,12,13 based on the optimized lattice structures, since the
Z characteristics of the band structure around the
@f0 X Fermi level generally determine the TE properties
r ¼ e2 de vk vk dðe ek Þ;
s
@e of a material. Therefore, the band structures of
k
RFe4Sb12 in the energy range of 1.0 eV to 1.0 eV
Z are plotted in Fig. 1a. To understand the effect of
1 @f0 X el atom R on the electronic structure, the band struc-
S ¼ ekB r de vk vk dðe ek Þ
s ;
@e k
kB T ture of pure FeSb3 is also shown in Fig. 1b. The
results reveal that the band structures of FeSb3 and
where l is the chemical potential, e is the electronic the six kinds of RFe4Sb12 investigated in our study
charge, kB is Boltzmann’s constant, s is the relaxa- have an indirect band gap and also valence bands
tion time, f0 is the Fermi function, vk is the group that cross the Fermi level, which indicates that all
velocity, and dðe ek Þ is the delta function. All six RFe4Sb12 are p-type semiconductors. Here, our
transport property calculations were implemented results are in agreement with previously reported
in the BoltzTraP package;13 the necessary crystal conclusions.6–8
structure and eigenenergies (needed for the calcu- Furthermore, one should note the very similar
lation of the group velocity vk ) in BoltzTraP were band structure for InFe4Sb12 and SnFe4Sb12,
transformed from the VASP results. To obtain NdFe4Sb12 and YbFe4Sb12, and NaFe4Sb12 and
reasonable electrical transport properties, the eige- CaFe4Sb12. It is implied that insertion of homolo-
nenergies were calculated on a 23 9 23 9 23 gous filling elements into skutterudite voids may
k-mesh with about 12,000 k points, which is suffi- have a similar effect on the electronic structure.
cient for good results.13 Further observation indicates that the valence band
The initial lattice model was a conventional cell of top in all cases is at the C point, and the highest
FeSb3 with space group Im-3 (no. 204) and lattice occupied band has parabolic shape, which implies a
Table I. Calculated lattice constants (LCs), band gap Eg, and hole concentration of RFe4Sb12 (R = Na, Ca, Nd,
Yb, Sn, In)
Compound NaFe4Sb12 CaFe4Sb12 NdFe4Sb12 YbFe4Sb12 SnFe4Sb12 InFe4Sb12
Fig. 1. (a) Band structures of RFe4Sb12 (R = Na, Ca, Nd, Yb, In, Sn) in the energy range of 1.0 eV to 1.0 eV; the horizontal dotted lines denote
the Fermi level Ef. (b) Band structure of pure FeSb3 in the energy range of 1.0 eV to 1.0 eV; the horizontal line denotes the Fermi level Ef.
light effective mass. However, the conduction band of 100 meV, and Dordevic et al.18 reported a minigap
bottom differs. The conduction band bottom (CBB) of 13 meV for YbFe4Sb12. These reported values are
of NdFe4Sb12 is at the N point, but between the H smaller than our result of 407.2 meV for YbFe4Sb12.
and N point for YbFe4Sb12. The main reason for the To evaluate the effect of the six filler atoms on the
different CBBs in the RFe4Sb12 materials could be electronic structure more directly, the partial den-
strong orbital hybridization between the host atoms sity of states (DOS) of the filler atoms R and the host
and the filler atoms in the conduction band (Figs. 1 atoms (Fe and Sb) are given in Fig. 2a–c, where
and 2). This orbital hybridization is more evident in Fig. 2a shows the partial DOS of Na, Ca and rela-
InFe4Sb12 and SnFe4Sb12 according to the band tive Fe and Sb, Fig. 2b the partial DOS of Nd, Yb
structure. In addition, in the case of SnFe4Sb12, it is and relative Fe and Sb, and Fig. 2c the partial DOS
found that there is a mini band gap with a value of of In, Sn and relative Fe and Sb. It is found that the
28.3 meV, far smaller than in the other cases. The band structure of RFe4Sb12 is mainly formed by the
maximum band gap value is 504 meV in pure Sb p orbitals and Fe d orbitals, and the six kinds of
FeSb3. The other band gap Eg values of the filler atoms in our study have little influence on the
RFe4Sb12 were around 400 meV, and the detailed valence band compared with the conduction band.
data are summarized in Table I. For the band gap We calculated the contributions of each element to
Eg, Nordstrom and Singh17 performed density the total DOS by integrating its partial DOS in the
functional calculations within the local-density energy range of 1.0 eV to 0 eV (Fermi level) and
approximation, obtaining indirect gaps in CeFe4Sb12 0 eV to 1.0 eV. Moreover, the contributions in the
Electronic Structures and Transport Properties of RFe4Sb12 (R = Na, Ca, Nd, Yb, Sn, In) 977
Table II. Contributions of each element R (R = Na, Ca, Nd, Yb, Sn, In) to the total DOS in the energy range
from 21.0 eV to 0 eV (Fermi level), from 0 eV to 1.0 eV, and from 0 eV to the valence band top Ev
NaFe4Sb12 (%) CaFe4Sb12 (%) NdFe4Sb12 (%) YbFe4Sb12 (%) InFe4Sb12 (%) SnFe4Sb12 (%)
(1.0 eV to 0 eV)
Fe d 82.9 81.5 82.0 82.7 82.7 81.4
Sb p 17.0 16.8 16.5 16.4 16.0 17.3
Atom R 0.1 1.7 1.5 1.0 1.3 1.3
(0 eV to 1.0 eV)
Fe d 74.6 67.3 70.7 67.4 67.3 56.3
Sb p 24.0 20.5 18.0 22.6 25.7 22.8
Atom R 1.4 12.3 11.3 10.0 7.1 20.9
(0 eV to Ev)
Fe d 75.7 75.6 82.7 73.5 69.8 71.2
Sb p 24.2 22.7 16.5 25.6 29.3 27.7
Atom R 0.1 1.7 0.8 0.9 1.0 1.1
Fig. 3. Temperature dependence of the Seebeck coefficient of Fig. 5. Calculated power factor with respect to s of RFe4Sb12
RFe4Sb12 (R = Na, Ca, Nd, Yb, In, Sn). (R = Na, Ca, Nd, Yb, In, Sn).
CONCLUSIONS 3. G.J. Snyder and E.S. Toberer, Nat. Mater. 7, 105 (2008).
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