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Crystals 2017, 7(9), 256; doi:10.3390/cryst7090256

Article
High Temperature Transport Properties of Yb and In Double-Filled p-Type Skutterudites
Dean Hobbis 1, Yamei Liu 2, Kaya Wei 1, Terry M. Tritt 2 and George S. Nolas 1,*
1
Department of Physics, University of South Florida, Tampa, FL 33620, USA
2
Department of Physics and Astronomy, Kinard Laboratory, Clemson University, Clemson, SC 29634, USA
*
Correspondence: Tel.: +1-813-974-2233
Academic Editor: Helmut Cölfen
Received: 18 July 2017 / Accepted: 18 August 2017 / Published: 23 August 2017

Abstract

:
Yb and In double-filled and Fe substituted polycrystalline p-type skutterudite antimonides were synthesized by direct reaction of high-purity elements, followed by solid-state annealing and densification by hot pressing. The stoichiometry and filling fraction were determined by both Rietveld refinement of the X-ray diffraction data and energy dispersive spectroscopic analyses. The transport properties were measured between 300 K and 830 K, and basically indicate that the resistivity and Seebeck coefficient both increase with increasing temperature. In both specimens, the thermal conductivity decreased with increasing temperature up to approximately 700 K, where the onset of bipolar conduction was observed. A maximum ZT value of 0.6 at 760 K was obtained for the Yb0.39In0.018Co2.4Fe1.6Sb12 specimen.
Keywords:
thermoelectric; skutterudite; p-type; figure of merit; double-filled; bipolar diffusion

1. Introduction

Thermoelectric materials research is of current significant interest for improving device performance in order to efficiently convert waste heat into electrical power [1]. Thermoelectric device improvement would result in an expanded array of potential applications, including automobile applications [2]. The efficiency of a thermoelectric material is given by the dimensionless figure of merit ZT = S2T/ρ κ, where S is the Seebeck coefficient, T is the absolute temperature, ρ is the resistivity, and κ is the thermal conductivity. The larger both the average and the peak ZT value are, the better the thermoelectric properties of a material. Both n-type and p-type materials are required in a thermoelectric device; the efficiency of the device is characterized by the combination of both materials’ thermoelectric properties.
Skutterudites have been studied extensively—not only due to their encouraging thermoelectric performance at intermediate temperatures, but also due to their good mechanical properties [3,4,5,6]. Optimization of p-type skutterudites is difficult due to the relatively small effective mass of holes compared to the effective mass of electrons in these materials [4]; therefore, the optimum carrier concentration of n-type skutterudites is larger than that of p-type, leading to a larger power factor (S2σ, where σ is electrical conductivity) [7]. It is well documented that the twelve Sb atoms in the skutterudite crystal structure form relatively large icosahedral cages [1,3,8]; thus, reduction of the lattice thermal conductivity, κL, can be achieved by fractional filling of these cages with rare-earth, alkali-earth, or alkali-metal atoms, since these cage-fillers result in the scattering of lattice phonons [3,8]. Yb filling has been shown to be a good filler candidate for skutterudites because of its large mass and small ionic radius, which results in strong phonon scattering. Furthermore, in skutterudites Yb has been shown to have an intermediate valence state (+2~+3), demanding less charge compensation for p-type materials [9]. The thermoelectric properties of n-type (Yb, In) double-filled skutterudite antimonides have been previously reported with a maximum ZT of 0.97 [10]. The pursuit of p-type materials is also needed; herein we investigate similar double filling in p-type skutterudites in order to determine their potential for thermoelectric applications.

2. Experimental

The high-purity elements were weighed and loaded into silica crucibles in a N2 environment inside a glove box to minimize exposure to air. Yb chunks (99.9%, Ames Labs), In foil (99.9975%, Alfa Aesar), Co powder (99.998%, Alfa Aesar), Fe powder (99.998%, Alfa Aesar), and crushed Sb chunks (99.5%, Alfa Aesar) were reacted in the nominal compositions Yb0.4In0.02Co3FeSb12 and Yb0.8In0.02Co2.5Fe1.5Sb12 for this study, which were chosen based off of previous studies of Yb single-filled Fe substituted skutterudites [11,12]. The specimens were sealed in a quartz tube under vacuum and reacted in a furnace at 1173 K for 48 h. The tube was removed and allowed to cool to room temperature in air before the specimens were ground into fine powders in a N2 glove box and cold pressed into pellets. These pellets were again sealed under vacuum in a quartz tube and annealed at 973 K for 7 days. This grinding and annealing process was repeated once more to further encourage homogeneity. The specimens were then finely ground and sieved (325 mesh) before being loaded into a graphite die inside the glove box for hot pressing. The hot pressing conditions for densification were performed under constant N2 flow at 923 K and 120 MPa for 3 h, resulting in high-density polycrystalline skutterudites as measured by the Archimedes method.
Analyses of the homogeneity and stoichiometry of the specimens were performed by Rietveld refinement of the powder X-ray diffraction (XRD) data using a Bruker D8 Focus Diffractometer in Bragg–Brentano geometry with Cu Kα radiation and a graphite monochromator, and energy dispersive spectroscopy (EDS) using an Oxford INCA X-Sight 7852 equipped scanning electron microscope (SEM, JEOL, JSM-6390LV). The densified pellets were cut with a wire saw for high-temperature transport measurements. A rectangular parallelepiped (2 × 2 × 5 mm3) was used for four-probe ρ and S measurements on a ULVAC ZEM-2 system. Thermal diffusivity measurements on a thin disk were performed by the laser flash method on a NETZSCH LFA 457 system, under constant Ar flow. The experimental uncertainties in both these measurements were 5–10%. Heat capacity measurements were performed using a NETZSCH DSC 404C system. Separate pieces of the specimens were also used for room-temperature Hall measurements and air stability tests. Air stability tests indicated that the specimens began to oxidize and degrade at 673 K, similar to that of previously reported skutterudites [13,14].
CCDC contains the supplementary crystallographic data for this paper, with deposition numbers 1562579 and 1562580 for Yb0.13In0.02Co3FeSb12 and Yb0.39In0.02Co2.4Fe1.6Sb12, respectively. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336033; E-mail: deposit@ccdc.cam.ac.uk).

3. Results

3.1. Structural Characterization

Rietveld refinement profiles from the powder XRD data are shown in Figure 1, displaying calculated and observed data and the difference between them. Table 1 indicates the refinement results. The crystal structures were refined with space group Im 3 ¯ (#204), and the initial atomic positions were based on data from previously reported Yb filled skutterudites [11,12]. The filler Yb atoms at the 2a site occupy less than the nominal composition, due in part to a trace amount of Yb2O3 (observed in profiles at 29.7°) and to steric effects [11,12,15,16]. The Co-to-Fe ratios are extremely close to the nominal compositions. The lattice parameters are 9.0661 Å and 9.0877 Å for Yb0.13In0.02Co3FeSb12 and Yb0.39In0.02Co2.4Fe1.6Sb12, respectively, with an increase in lattice parameter with Yb and In filling fractions and Co-to-Fe ratio, in agreement with previously reported data. Furthermore, the Yb filling fraction increases from 33% to 49% with increased Fe substitution, similarly reported for Gd and (Ba, Yb) filled skutterudites [10,11,12,13,14,15,16,17]. Elemental mapping from EDS data shows an even dispersion of elements for both specimens, indicating good homogeneity of the specimens, and corroborate our refinement results.

3.2. Transport Properties

Figure 2a,b show temperature-dependent (300–800 K) S and ρ data, respectively. The Yb0.13In0.02Co3FeSb12 specimen exhibits a metallic-like temperature dependence with ρ increasing with temperature, although these values saturate to 1.6 mΩ cm−1 at 650 K. The ρ values for Yb0.39In0.02Co2.4Fe1.6Sb12 do not exhibit as strong a temperature dependence in the measured temperature range. The S values for both specimens increase with increasing temperature and peak at 700 K, with values of 140 µV/K and 160 µV/K for Yb0.13In0.02Co3FeSb12 and Yb0.39In0.02Co2.4Fe1.6Sb12, respectively. Both specimens have positive S values, indicating that holes are the majority carriers, in agreement with room-temperature Hall measurements that provide carrier concentrations (p) of 2.6 × 1020 cm−3 and 4 × 1020 cm−3 for Yb0.13In0.02Co3FeSb12 and Yb0.39In0.02Co2.4Fe1.6Sb12, respectively.
In the single parabolic band model, S and p are given by [18]
S = ± k B e ( ( 2 + r ) F 1 + r ( η ) ( 1 + r ) F r ( η ) η )
and
p =   4 π ( 2 m e k B T ) 3 / 2 h 3 ( m m e ) 3 / 2 F 1 / 2 ( η )
where the plus and minus signs in Equation (1) are for holes (+) and electrons (), η is the reduced Fermi energy (=EF/kBT, where EF is the Fermi energy, kB is the Boltzmann constant, and T is absolute temperature), Fr is the Fermi integral of order r, and r is the exponent of the energy dependence of the electron mean free path. r = 0 for scattering from acoustic phonons (lattice vibrations) and r = 2 for ionized impurity scattering. In our estimate for effective mass, m*, the intermediate value of r = 1 is used. Using our room-temperature S and p values, we estimate m* to be 0.7me for Yb0.13In0.02Co3FeSb12 and 1.4me for Yb0.39In0.02Co2.4Fe1.6Sb12. These values are much smaller than that for YbxFe3.5Ni0.5Sb12 compositions, but are similar to Yb0.5Fe1.5Co2.5Sb12 and Ca0.17Ce0.05Fe1.47Co2.53Sb12 which have a comparable Co-to-Fe content [19,20,21].
Figure 2c shows κ data calculated from thermal diffusivity and heat capacity measurements using the equation κ = D∙d∙Cp, where D is measured density, d is measured thermal diffusivity, and Cp is measured heat capacity. Figure 3 shows κL as calculated using the Wiedmann–Franz relation, where κE = L0T/ρ (L0 being the Lorenz number taken to be 2.45 × 10−8 V2 K−2). These κ values are smaller compared to those of previously reported (Yb, In) and (Ba, In) double-filled n-type skutterudites, as well as that of (Ce, Nd) double-filled p-type skutterudites [10,22,23]. An increase in κ and κL is observed above 700 K, which can be attributed to bipolar diffusion. The contribution of bipolar diffusion, κB, is given by κB = σeσh(Sh-Se)2T/σe + σh, where σe is the electron conduction, σh is the hole conduction, Sh is the hole Seebeck coefficient, and Se is the electron Seebeck coefficient [1]. An estimation of κB can be made from the high-temperature data using κL = 3.5(kB/h)3 (MV1/3θD 32T), where h is Planck’s constant, M is the average mass per atom, V is the average atomic volume, θD is the Debye temperature, and γ is the Grüneisen parameter. It is clear that Umklapp scattering dominates κL above θD [1]. Therefore, the inset to Figure 3 illustrates the procedure of using a fit κL ~ T−1 to estimate κB for the Yb0.13In0.02Co3FeSb12 specimen, resulting in proportions of 53%, 33%, and 14% for κE, κL, and κB, respectively. The estimations for the Yb0.39In0.02Co2.4Fe1.6Sb12 specimen were done with the same method, and gave values of 48%, 44%, and 8% for κE, κL, and κB, respectively. These κB values are higher than that of single-filled Yb compositions, possibly due to the additional low-lying donor states with In filling [3,10]. An increase in Fe content resulted in a near 50% reduction in κB [11].
Figure 4 shows the ZT values for both specimens. These values have been calculated from the measured data, and both specimens show increasing ZT with increasing temperature, with a maximum value of 0.6 at 760 K for the Yb0.39In0.02Co2.4Fe1.6Sb12 specimen. This maximum ZT value is lower than that of the n-type (Yb, In) double-filled skutterudite but greater than (Ce, Yb) double-filled p-type skutterudites with comparable filling fraction and Co-to-Fe ratio [10,21]. However, other reported p-type (Ce, Yb) double-filled skutterudites with greater filling fraction and Fe substitution exhibit a larger ZT (=0.87) [24].

4. Conclusions

The structural and high-temperature transport properties of p-type (Yb, In) double-filled skutterudites were investigated. We observed an increase in both ρ and S for Yb0.39In0.02Co2.4Fe1.6Sb12, whereas κ was less for the specimen with lower Yb content. Above 700 K, both specimens exhibited a fairly large κB contribution that significantly increased κ above this temperature, although κB decreased with increasing Fe content. Both specimens exhibited the largest ZT values at 750 K. The performance of these p-type skutterudites may be enhanced by a further increase in overall filling fractions of (Yb, In), corresponding to an increase in Fe content.

Acknowledgments

This work was supported by the II-VI Foundation Block-Gift Program. The authors thank Jeff Sharp of Marlow Industries for air stability testing.

Author Contributions

George S. Nolas conceived and designed the experiments; Dean Hobbis and Kaya Wei performed synthesis, densification and preparation of specimens; Yamei Liu and Terry M. Tritt performed high temperature transport measurements on specimens; Dean Hobbis, Kaya Wei and George S. Nolas analyzed the data; Dean Hobbis wrote the manuscript. All authors contributed to the experiment, the analysis of the data, and edition of the manuscript.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Nolas, G.S.; Sharp, J.W.; Goldsmid, H.J. Thermoelectrics: Basic Principles and New Material Developments; Springer: Berlin, Germany, 2001. [Google Scholar]
  2. Stabler, F.R. Commercialization of Thermoelectric Technology. Mater. Res. Symp. Proc. 2006, 886, 13–21. [Google Scholar] [CrossRef]
  3. Uher, C. Skutterudites: Prospective novel thermoelectrics. In Semiconductors and Semimetals; Tritt, T.M., Ed.; Academic Press: San Diego, CA, USA, 2001; Volume 69, pp. 139–253. ISSN 978-0-12-752178-7. [Google Scholar]
  4. Dahal, T.; Kim, H.S.; Gahlawat, S.; Dahal, K.; Jie, Q.; Liu, W.; Lan, Y.; White, K.; Ren, Z. Transport and mechanical properties of the double-filled p-type skutterudites La0.68Ce0.22Fe4-xCoxSb12. Acta Mater. 2016, 117, 13–22. [Google Scholar] [CrossRef]
  5. Salvador, J.R.; Yang, J.; Shi, X.; Wang, H.; Wereszczak, A.A.; Kong, H.; Uher, C. Transport and mechanical properties of Yb-filled skutterudites. Philos. Mag. 2009, 89, 1517–1534. [Google Scholar] [CrossRef]
  6. Zhang, L.; Rogl, G.; Grytsiv, A.; Puchegger, S.; Koppensteiner, J.; Spieckermann, F.; Kabelka, H.; Reinecker, M.; Rogl, P.; Schranz, W.; et al. Mechanical properties of filled antimonide skutterudites. Mater. Sci. Eng. B 2010, 170, 26–31. [Google Scholar] [CrossRef]
  7. Nolas, G.S.; Fowler, G. Partial filling of skutterudites: Optimization for thermoelectric applications. J. Mater. Res. 2005, 20, 3234–3237. [Google Scholar] [CrossRef]
  8. Nolas, G.S.; Morelli, D.T.; Tritt, T.M. Skutterudites: A phonon-glass-electron-crystal approach to advanced thermoelectric energy conversion applications. Annu. Rev. Mater. Res. Bull. 1999, 29, 199–205. [Google Scholar] [CrossRef]
  9. Nolas, G.S.; Kaeser, M.; Littleton, R.T.; Tritt, T.M. High figure of merit in partially filled ytterbium skutterudite materials. Appl. Phys. Lett. 2000, 77, 1855. [Google Scholar] [CrossRef]
  10. Peng, J.Y.; Alboni, P.N.; He, J.; Zhang, B.; Su, Z.; Holgate, T.; Gothard, N.; Tritt, T.M. Thermoelectric properties of (In,Yb) double-filled CoSb3 skutterudite. J. Appl. Phys. 2008, 104, 053710. [Google Scholar] [CrossRef]
  11. Dong, Y.; Puneet, P.; Tritt, T.M.; Nolas, G.S. Crystal structure and high temperature transport properties of Yb-filled p-type skutterudites YbxCo2.5Fe1.5Sb12. J. Solid State Chem. 2014, 209, 1–5. [Google Scholar] [CrossRef]
  12. Dong, Y.; Puneet, P.; Tritt, T.M.; Nolas, G.S. High temperature thermoelectric properties of p-type skutterudites YbxCo3FeSb12. Phys. Status Solidi RRL 2013, 7, 418–420. [Google Scholar] [CrossRef]
  13. Zhao, D.; Tian, C.; Tang, S.; Liu, Y.; Chen, L.D. High temperature oxidation behavior of cobalt triantimonide thermoelectric material. J. Alloys Compd. 2010, 504, 552–558. [Google Scholar] [CrossRef]
  14. Shin, D.K.; Kim, I.H.; Park, K.H.; Lee, S.; Seo, W.S. Thermal Stability of La0.9Fe3CoSb12. J. Electron. Mater. 2015, 44, 1858–1863. [Google Scholar] [CrossRef]
  15. Dong, Y.; Puneet, P.; Tritt, T.M.; Martin, J.; Nolas, G.S. High temperature thermoelectric properties of p-type skutterudites BaxYbyCo4-zFezSb12. J. Appl. Phys. 2012, 112, 083718. [Google Scholar] [CrossRef]
  16. Liu, R.; Chen, X.; Qiu, P.; Liu, J.; Yang, J.; Huang, X.; Chen, L. Low thermal conductivity and enhanced thermoelectric performance of Gd-filled skutterudites. J. Appl. Phys. 2011, 109, 023719. [Google Scholar] [CrossRef]
  17. Zhou, C.; Morelli, D.; Zhou, X.; Wang, G.; Uher, C. Thermoelectric properties of P-type Yb-filled skutterudite YbxFeyCo4-ySb12. Intermetallics 2011, 19, 1390–1393. [Google Scholar] [CrossRef]
  18. Slack, G.A.; Hussain, M.A. The maximum possible conversion efficiency of silicon-germanium thermoelectric generators. J. Appl. Phys. 1991, 70, 2694. [Google Scholar] [CrossRef]
  19. Cho, J.Y.; Ye, Z.; Tessema, M.M.; Waldo, R.A.; Salvador, J.R.; Yang, J.; Cai, W.; Wang, H. Thermoelectric properties of p-type skutterudites YbxFe3.5Ni0.5Sb12 (0.8 < x < 1). Acta Mater. 2012, 60, 2104–2110. [Google Scholar]
  20. Tang, X.; Li, H.; Zhang, Q.; Niino, M.; Goto, T. Synthesis and thermoelectric properties of double-atom-filled skutterudite compounds CamCenFexCo4-xSb12. J. Appl. Phys. 2006, 100, 123702. [Google Scholar] [CrossRef]
  21. Yang, K.; Cheng, H.; Hng, H.H.; Ma, J.; Mi, J.L.; Zhao, X.B.; Zhu, T.J.; Zhang, Y.B. Synthesis and thermoelectric properties of double-filled skutterudites CeyYb0.5-yFe1.5Co2.5Sb12. J. Alloys Compd. 2009, 467, 528–532. [Google Scholar] [CrossRef]
  22. Zhao, W.; Wei, P.; Zhang, Q.; Dong, C.; Liu, L.; Tang, X. Enhanced Thermoelectric Performance in Barium and Indium Double-Filled Skutterudite Bulk Materials via Orbital Hybridization Induced by Indium Filler. J. Amer. Chem. Soc. 2009, 131, 3713–3720. [Google Scholar] [CrossRef] [PubMed]
  23. Jie, Q.; Wang, H.; Liu, W.; Wang, H.; Chen, G.; Ren, Z. Fast Phase formation of double-filled p-type skutterudites by ball-milling and hot-pressing. Phys. Chem. Chem. Phys. 2013, 15, 6809–6816. [Google Scholar] [CrossRef] [PubMed]
  24. Joo, G.S.; Shin, D.K.; Kim, I.H. Synthesis and Thermoelectric Properties of p-Type Double-Filled Ce1-zYbzFe4-xCoxSb12 Skutterudites. J. Electron. Mater. 2016, 45, 1251–1256. [Google Scholar] [CrossRef]
Figure 1. Powder X-ray diffraction (XRD) data for (a) Yb0.13In0.02Co3FeSb12 and (b) Yb0.39In0.02Co2.4Fe1.6Sb12, including profile fit, profile difference, and profile residuals from Rietveld refinement.
Figure 1. Powder X-ray diffraction (XRD) data for (a) Yb0.13In0.02Co3FeSb12 and (b) Yb0.39In0.02Co2.4Fe1.6Sb12, including profile fit, profile difference, and profile residuals from Rietveld refinement.
Crystals 07 00256 g001
Figure 2. Temperature-dependent (a) ρ, (b) S, and (c) κ for Yb0.13In0.02Co3FeSb12 (circle) and Yb0.39In0.02Co2.4Fe1.6Sb12 (triangle).
Figure 2. Temperature-dependent (a) ρ, (b) S, and (c) κ for Yb0.13In0.02Co3FeSb12 (circle) and Yb0.39In0.02Co2.4Fe1.6Sb12 (triangle).
Crystals 07 00256 g002
Figure 3. Temperature-dependent κL for Yb0.13In0.02Co3FeSb12 (circle) and Yb0.39In0.02Co2.4Fe1.6Sb12 (triangle). The inset illustrates the method used to estimate κB for both specimens, with Yb0.13In0.02Co3FeSb12 shown here, where the solid line is the T−1 dependence between 400 K and 700 K.
Figure 3. Temperature-dependent κL for Yb0.13In0.02Co3FeSb12 (circle) and Yb0.39In0.02Co2.4Fe1.6Sb12 (triangle). The inset illustrates the method used to estimate κB for both specimens, with Yb0.13In0.02Co3FeSb12 shown here, where the solid line is the T−1 dependence between 400 K and 700 K.
Crystals 07 00256 g003
Figure 4. Temperature-dependent ZT for Yb0.13In0.02Co3FeSb12 (circle) and Yb0.39In0.02Co2.4Fe1.6Sb12 (triangle).
Figure 4. Temperature-dependent ZT for Yb0.13In0.02Co3FeSb12 (circle) and Yb0.39In0.02Co2.4Fe1.6Sb12 (triangle).
Crystals 07 00256 g004
Table 1. Rietveld refinement results for Yb0.13In0.02Co3FeSb12 and Yb0.39In0.02Co2.4Fe1.6Sb12.
Table 1. Rietveld refinement results for Yb0.13In0.02Co3FeSb12 and Yb0.39In0.02Co2.4Fe1.6Sb12.
Nominal CompositionYb0.4In0.02Co3FeSb12Yb0.8In0.02Co2.5Fe1.5Sb12
CompositionYb0.13In0.02Co3FeSb12Yb0.39In0.02Co2.4Fe1.6Sb12
Space Group (Z)Im 3 ¯ (#204), 8
a (Å)9.0660(6)9.0872(8)
V (Å3)745.1(7)750.4(2)
RadiationGraphite Monochromated CuKα (1.54056 A)
Dcalc. (g/cm3)6.437.17
2θ range (deg.)20–1002–100
Step Width (deg.)0.0050.005
Reduced χ22.402.84
wRp, Rp0.0739, 0.05810.0779, 0.0610
Uiso2) for Yb0.0095(0)0.0125(6)
Uiso2) for In0.0090(3)0.0101(7)
Uiso2) for Co/Fe0.0070(1)0.0039(4)
Uiso2) for Sb0.0037(4)0.0041(2)
y (Sb)0.8436(7)0.8423(6)
z (Sb)0.6654(4)0.6649(9)
Atomic Positions: Yb/In, 2a (0, 0, 0); Co/Fe, 8c (¼, ¼, ¼); Sb, 24g (0, y, z).
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