Zhou 2011

Download as pdf or txt
Download as pdf or txt
You are on page 1of 6

Journal of ELECTRONIC MATERIALS, Vol. 40, No.

5, 2011
DOI: 10.1007/s11664-010-1472-1
Ó 2010 TMS

Electronic Structures and Transport Properties


of RFe4Sb12 (R = Na, Ca, Nd, Yb, Sn, In)

AN ZHOU,1 LI-SHENG LIU,1,2 CUI-CUI SHU,1 PENG-CHENG ZHAI,1


WEN-YU ZHAO,1 and QING-JIE ZHANG1

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

We report an investigation of the electronic structures and electrical transport


properties of a series of RFe4Sb12 skutterudites using density functional cal-
culations and Boltzmann transport theory. The band structure and density of
states are calculated and discussed. Based on the results of the band struc-
ture, the temperature dependence of the Seebeck coefficient, electrical con-
ductivity, power factor, and carrier concentration are calculated, and the
results are in good agreement with experimental data. The results of electrical
transport properties indicate that double-filled Fe4Sb12 with the atomic com-
binations (Na, Yb), (In, Yb), and (Ca, Yb) may be better compared with the
corresponding single-filled Fe4Sb12.

Key words: Electronic structure, thermoelectric, filled skutterudite


compounds, transport properties

INTRODUCTION with multiple elements. However, the choice of the


substitution and filling atoms, especially the filling
Thermoelectricity (TE) is becoming attractive
atoms or the atomic filling combinations, from the
because of its potential application in the fields of
numerous atoms available is a key issue.4 To
cooling, heating, power generation, and waste heat
answer this question, a series of chemical and
recovery.1,2 The performance of thermoelectric
physical properties of various RFe4Sb12 materials
materials is defined by the dimensionless figure of
(where R is the filling atom) have been studied and
merit, ZT = S2rT/j, where r is the electrical con-
reported. For example, Nolas et al.5 reported that
ductivity, S is the Seebeck coefficient, T is the
the HfFe4Sb12 skutterudite possesses very low
absolute temperature, and j = jE + jL is the ther-
thermal conductivity. Ferromagnetic ordering in
mal conductivity with its electronic and lattice
NaFe4Sb12 and KFe4Sb12 was researched by Jasper
contributions. A good thermoelectric material
et al.6 Furthermore, the magnetic, optical, and
should have a combination of high power factor
thermoelectric properties of LaFe4Sb12, CeFe4Sb12,
(rS2) and low thermal conductivity. However, in
YbFe4Sb12, EuFe4P12, and BaFe4P12 have also been
fact, it is very hard to find a material that simul-
reported.7,8 However, it is still not clear which kind
taneously possesses high power factor and low
of filled skutterudites will have satisfactory ZT
thermal conductivity because of the conflicting
values. In this work, the electronic structures and
thermoelectric material properties.3
transport properties of six kinds of RFe4Sb12 com-
Skutterudite compounds have a high S value, low
pounds (R = Na, Ca, Nd, Yb, In, Sn) have been
electrical conductivity, and high thermal conduc-
studied by density functional calculations and the
tivity. Fortunately, enhancement of the power fac-
Boltzmann transport equation under the constant
tor and decrease of the thermal conductivity can be
relaxation time approximation. The selected atoms
obtained simultaneously by replacing host atoms
R include three types of representative filling ele-
and filling the interstitial voids of skutterudites
ments: rare-earth elements (Nd, Yb), alkali metal or
alkaline-earth metal elements (Na, Ca), and third-
(Received May 29, 2010; accepted November 29, 2010; or fourth-row elements (In, Sn). From this study, we
published online January 4, 2011) expect that significant implications can be obtained

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

Optimized LCs (Å) 9.194 9.193 9.186 9.184 9.217 9.22


Band gap, Eg (meV) 473 473.9 371.7 407.2 28.3 387.2
Hole concentration (1021 cm3) 9.38 6.29 3.84 6.36 4.94 7.48
976 Zhou, Liu, Shu, Zhai, Zhao, and Zhang

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

contributions of R atoms are about 10% to 20%,


which is about five times larger than the contribu-
tions in the valence band. We note the maximum
contribution of 20.9% by the atom Sn. This could be
attributed to a similar electron configuration
between the filler atom Sn and the host atom Sb. A
large contribution by Sn in the conduction band
implies a possible repulsion between Sn and Sb. In
addition, the existence of this repulsion may also be
the main reason for the largest lattice expansion
occurring in the case of SnFe4Sb12. For the energy
window from the Fermi level to the valence band
top, the R atom contributions are very small (1%),
similar to the results for the energy range of
1.0 eV to 0 eV. The orbital contribution reveals
that the filler atoms have a weak effect on the
valence band top, but cause strong orbital hybrid-
ization at the conduction band bottom.

Electrical Transport Properties


The DOS indicates that there is only a small
influence of the R atoms on the band structure near
the Fermi level, thus the rigid band approximation
is reasonable for the electrical transport properties
of RFe4Sb12. The temperature dependence of the
Seebeck coefficients of RFe4Sb12 are given in Fig. 3,
and the temperature dependence of the electrical
conductivity with respect to s is plotted in Fig. 4.
The Seebeck coefficient of YbFe4Sb12 is 78 lV K1,
in agreement with the experimental value of
67 lV K1 as reported by Kuznetsov and Rowe.19 At
300 K, the maximum Seebeck coefficient is
94 lV K1 for NaFe4Sb12 and SnFe4Sb12. The low-
est Seebeck coefficient is 66 lV K1, for NdFe4Sb12.
At 800 K, the Seebeck coefficients of the six types
of RFe4Sb12 are about 150 lV K1. Based on our
results, the Seebeck coefficients of the six types of
RFe4Sb12 are very similar due to the similar band
structure near the Fermi level. The results of the
electrical conductivity with respect to s reveal that
the electrical conductivity increases with increasing
temperature and InFe4Sb12 and NaFe4Sb12 have
larger values compared with the other RFe4Sb12.
The calculated power factors with respect to s are
Fig. 2. Partial density of states (DOS) for (a) Ca, Na, Fe, and Sb, (b) given in Fig. 5. The results indicate that NaFe4Sb12,
Nd, Yb, Fe, and Sb, and (c) In, Sn, Fe, and Sb; the black dashed CaFe4Sb12, and InFe4Sb12 have larger power factors
lines denote the Fermi level Ef. compared with the other cases due to their good
electrical conductivity. In the case of YbFe4Sb12 and
NdFe4Sb12, we also note that YbFe4Sb12 has a lar-
energy range from 0 eV to the valence band top Ev ger power factor than NdFe4Sb12 because of its
(Ev = 0.25 eV) were also calculated, because this better electrical conductivity. The corresponding
energy window is the most important for the elec- carrier concentration bears the same conclusions
trical transport properties of the intrinsically p-type from another perspective, and the hole concentra-
materials. The results are listed in Table II. For the tion p0 is defined as:
Z
band from 1.0 eV to 0 eV, the main contributions 1 Ev
are from Fe d and Sb p orbitals, being about 80% p0 ¼ fp ðEÞgp ðEÞdE;
X 1
and 17%, respectively, and an admixture of contri-
butions from R s, R p, and R d orbitals of about 2%. where X is the volume of the computing cell, fp(E) is
A special low value of only 0.1% was contributed by the Fermi–Dirac distribution function, gp(E) is the
Na. In the energy range of 0 eV to 1.0 eV, the density-of-states function, and the numerical
978 Zhou, Liu, Shu, Zhai, Zhao, and Zhang

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).

g(E) functions are calculated by VASP. The results


for the hole concentration at 300 K are listed
in Table I. The results show that NaFe4Sb12,
CaFe4Sb12, and InFe4Sb12 have larger carrier con-
centrations compared with NdFe4Sb12 and SnFe4Sb12.
The hole concentration is 9.38 9 1021 cm3 for
NaFe4Sb12, 6.29 9 1021 cm3 for CaFe4Sb12, and
7.48 9 1021 cm3 for InFe4Sb12. In the cases of
YbFe4Sb12 and NdFe4Sb12, YbFe4Sb12’s hole concen-
tration is 6.36 9 1021 cm3, which is larger than that
of NdFe4Sb12.
As is known, the rare-earth atoms have larger
atomic masses, which is helpful for increasing pho-
non scattering and reducing the thermal conduc-
tivity. So, for double-filled Fe4Sb12, the atomic
combinations (Na, Yb), (In, Yb), and (Ca, Yb) may be
more promising according to our calculations due to
Fig. 4. Temperature dependence of the electrical conductivity with an enhancement of the power factor and a simul-
respect to s of RFe4Sb12 (R = Na, Ca, Nd, Yb, In, Sn). taneous decrease of the thermal conductivity.
Electronic Structures and Transport Properties of RFe4Sb12 (R = Na, Ca, Nd, Yb, Sn, In) 979

CONCLUSIONS 3. G.J. Snyder and E.S. Toberer, Nat. Mater. 7, 105 (2008).
4. A. Zhou, L.S. Liu, P.C. Zhai, W.Y. Zhao, and Q.J. Zhang,
The electronic structures and electrical transport J. Electron. Mater. 39, 1832 (2010).
properties of three representative RFe4Sb12 com- 5. G.S. Nolas, G. Yoon, and H. Sellinschegg, Appl. Phys. Lett.
86, 042111 (2005).
pounds have been studied by using density func- 6. A.L. Jasper, W. Schnelle, H. Rosner, N. Senthilkumaran, A.
tional theory and the Boltzmann transport equation Rabis, M. Baenitz, A. Gippius, E. Morozova, J.A. Mydosh,
under the constant relaxation time approximation. and Y. Grin, Phys. Rev. Lett. 91, 037208 (2003).
The band structure and DOS show that the six filler 7. K. Nouneh, A.H. Reshak, S. Auluck, I.V. Kityk,
atoms have a small influence on the valence band R. Viennois, S. Benet, and S. Charar, J. Alloy Compd. 437,
39 (2007).
compared with that on the conduction band. The 8. M.E. Danebrock, C.B.H. Evers, and W. Jeitschko, J. Phys.
results for the Seebeck coefficient and electrical Chem. Solids 57, 381 (1996).
conductivity of RFe4Sb12 indicate that NaFe4Sb12, 9. J. Yang, L. Xi, W. Zhang, L.D. Chen, and J.H. Yang,
CaFe4Sb12, InFe4Sb12, and YbFe4Sb12 have better J. Electron. Mater. 38, 1397 (2009).
10. P.P. Chaput, J. Tobola, and H. Scherrer, Phys. Rev. B 72, 11
TE performance in our study. For double filling, the (2005).
atomic combinations (Na, Yb), (In, Yb), and (Ca, Yb) 11. X. Shi, W. Zhang, L.D. Chen, and J. Yang, Phys. Rev. Lett.
may be more promising than the single-filled 95, 185503 (2005).
skutterudites RFe4Sb12. 12. J. Yang, H. Li, T. Wu, W. Zhang, L. Chen, and J. Yang, Adv.
Funct. Mater. 18, 2880 (2008).
ACKNOWLEDGEMENTS 13. G.K.H. Madsen and D.J. Singh, Comput. Phys. Commun.
175, 67 (2006).
The work was supported by China ‘‘973’’ plan (No. 14. G. Kresse and J. Hafner, Phys. Rev. B 47, 558 (1993).
2007CB607500), National Nature Science Founda- 15. G. Kresse and J. Furthmüller, Comput. Mater. Sci. 6, 15
tion of China (No. 10672127, No. 10832008, and A3 (1996).
16. G. Kresse and J. Furthmüller, Phys. Rev. B 54, 11169
Foresight Program-50821140308), and the Ministry (1996).
of Education of China (PCSIRT0644). 17. L. Nordstrom and D.L. Singh, Phys. Rev. B 53, 1103
(1996).
REFERENCES 18. S.V. Dordevic, N.R. Dilley, M.B. Maple, and D.N. Basov,
1. L.E. Bell, Science 321, 1457 (2008). Phys. Rev. Lett. 86, 684 (2001).
2. W.Y. Zhao, P. Wei, Q.J. Zhang, C.L. Dong, L.S. Liu, and 19. V.L. Kuznetsov and D.M. Rowe, J. Phys. Condens. Matter
X.F. Tang, J. Am. Chem. Soc. 131, 3713 (2009). 12, 7915 (2000).

You might also like