skip to main content


Title: Thermoelectric Properties of p‐ and n‐ type Eu 5 Sn 2 As 6
Abstract

Eu5Sn2As6is a Zintl phase crystalizing in the orthorhombic space groupPbamwith one‐dimensional chains of corner‐shared SnAs4tetrahedra running in thec‐direction. Eu5Sn2As6has an impressive room temperature Seebeck of >100 μV/K and < – 100 μV/K at 600 K crossing fromp‐ ton‐type at 650 K. The maximum thermoelectric figure of merit,zT, for Eu5Sn2As6is small (0.075), comparable to that of the Zintl phase Ca5Al2Sb6whose thermoelectric performance was improved by doping Na onto the Ca sites. In this study, we show that the thermoelectric properties of Eu5Sn2As6can be improved by substituting with K or La. The series Eu5‐xKxSn2As6provides an increase in maximumzTof 0.22 forx=0.15 due to a decrease resistivity while the onset of bipolar conduction systematically increases in temperature. Upon La substitution, Eu5‐xLaxSn2As6results in a newn‐type Zintl phase across the temperature range of 300–800 K.

 
more » « less
Award ID(s):
2001156
NSF-PAR ID:
10368119
Author(s) / Creator(s):
 ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Zeitschrift für anorganische und allgemeine Chemie
Volume:
648
Issue:
10
ISSN:
0044-2313
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    The Zintl phases, Yb 14 M Sb 11 ( M = Mn, Mg, Al, Zn), are now some of the highest thermoelectric efficiency p-type materials with stability above 873 K. Yb 14 MnSb 11 gained prominence as the first p-type thermoelectric material to double the efficiency of SiGe alloy, the heritage material in radioisotope thermoelectric generators used to power NASA’s deep space exploration. This study investigates the solid solution of Yb 14 Mg 1− x Al x Sb 11 (0 ≤ x ≤ 1), which enables a full mapping of the metal-to-semiconductor transition. Using a combined theoretical and experimental approach, we show that a second, high valley degeneracy ( N v = 8) band is responsible for the groundbreaking performance of Yb 14 M Sb 11 . This multiband understanding of the properties provides insight into other thermoelectric systems (La 3− x Te 4 , SnTe, Ag 9 AlSe 6 , and Eu 9 CdSb 9 ), and the model predicts that an increase in carrier concentration can lead to zT > 1.5 in Yb 14 M Sb 11 systems. 
    more » « less
  2. Thermoelectric materials can convert heat into electricity. They are used to generate electricity when other power sources are not available or to increase energy efficiency by recycling waste heat. The Yb 21 Mn 4 Sb 18 phase was previously shown to have good thermoelectric performance due to its large Seebeck coefficient (∼290 μV K −1 ) and low thermal conductivity (0.4 W m −1 K −1 ). These characteristics stem respectively from the unique [Mn 4 Sb 10 ] 22− subunit and the large unit cell/site disorder inherent in this phase. The solid solutions, Yb 21 Mn 4− x Cd x Sb 18 ( x = 0, 0.5, 1.0, 1.5) and Yb 21− y Ca y Mn 4 Sb 18 ( y = 3, 6, 9, 10.5) have been prepared, their structures characterized and thermoelectric properties from room temperature to 800 K measured. A detailed look into the structural disorder for the Cd and Ca solid solutions was performed using synchrotron powder X-ray diffraction and pair distribution function methods and shows that these are highly disordered structures. The substitution of Cd gives rise to more metallic behavior whereas Ca substitution results in high resistivity. As both Cd and Ca are isoelectronic substitutions, the changes in properties are attributed to changes in the electronic structure. Both solid solutions show that the thermal conductivities remain extremely low (∼0.4 W m −1 K −1 ) and that the Seebeck coefficients remain high (>200 μV K −1 ). The temperature dependence of the carrier mobility with increased Ca substitution, changing from approximately T −1 to T −0.5 , suggests that another scattering mechanism is being introduced. As the bonding changes from polar covalent with Yb to ionic for Ca, polar optical phonon scattering becomes the dominant mechanism. Experimental studies of the Cd solid solutions result in a max zT of ∼1 at 800 K and, more importantly for application purposes, a ZT avg ∼ 0.6 from 300 K to 800 K. 
    more » « less
  3. The Zintl compound Eu 2 ZnSb 2 was recently shown to have a promising thermoelectric figure of merit, zT ∼ 1 at 823 K, due to its low lattice thermal conductivity and high electronic mobility. In the current study, we show that further increases to the electronic mobility and simultaneous reductions to the lattice thermal conductivity can be achieved by isovalent alloying with Bi on the Sb site in the Eu 2 ZnSb 2−x Bi x series ( x = 0, 0.25, 1, 2). Upon alloying with Bi, the effective mass decreases and the mobility linearly increases, showing no signs of reduction due to alloy scattering. Analysis of the pair distribution functions obtained from synchrotron X-ray diffraction revealed significant local structural distortions caused by the half-occupied Zn site in this structure type. It is all the more surprising, therefore, to find that Eu 2 ZnBi 2 possesses high electronic mobility (∼100 cm 2 V −1 s −1 ) comparable to that of AM 2 X 2 Zintl compounds. The enormous degree of disorder in this series gives rise to exceptionally low lattice thermal conductivity, which is further reduced by Bi substitution due to the decreased speed of sound. Increasing the Bi content was also found to decrease the band gap while increasing the carrier concentration by two orders of magnitude. Applying a single parabolic band model suggests that Bi-rich compositions of Eu 2 ZnSb 2−x Bi x have the potential for significantly improved zT ; however, further optimization is necessary through reduction of the carrier concentration to realize high zT . 
    more » « less
  4. High-throughput calculations (first-principles density functional theory and semi-empirical transport models) have the potential to guide the discovery of new thermoelectric materials. Herein we have computationally assessed the potential for thermoelectric performance of 145 complex Zintl pnictides. Of the 145 Zintl compounds assessed, 17% show promising n-type transport properties, compared with only 6% showing promising p-type transport. We predict that n-type Zintl compounds should exhibit high mobility μ n while maintaining the low thermal conductivity κ L typical of Zintl phases. Thus, not only do candidate n-type Zintls outnumber their p-type counterparts, but they may also exhibit improved thermoelectric performance. From the computational search, we have selected n-type KAlSb 4 as a promising thermoelectric material. Synthesis and characterization of polycrystalline KAlSb 4 reveals non-degenerate n-type transport. With Ba substitution, the carrier concentration is tuned between 10 18 and 10 19 e − cm −3 with a maximum Ba solubility of 0.7% on the K site. High temperature transport measurements confirm a high μ n (50 cm 2 V −1 s −1 ) coupled with a near minimum κ L (0.5 W m −1 K −1 ) at 370 °C. Together, these properties yield a zT of 0.7 at 370 °C for the composition K 0.99 Ba 0.01 AlSb 4 . Based on the theoretical predictions and subsequent experimental validation, we find significant motivation for the exploration of n-type thermoelectric performance in other Zintl pnictides. 
    more » « less
  5. Abstract

    Calcium germanides with two mid‐late rare‐earth metals, Ca5−xGdxGe3and Ca5−xTbxGe3(x≈0.1−0.2), have been synthesized and structurally characterized. Additionally, a lanthanum‐rich germanide with calcium substitutions, La5−xCaxGe3(x≈0.5) has also been identified. The three structures have been established from single‐crystal X‐ray diffraction methods and confirmed to crystallize with the Cr5B3‐type in the tetragonal space groupI4/mcm(no. 140;Z=4; Pearson symboltI32), where part of the germanium atoms are interconnected into Ge2‐dimers, formally [Ge2]6−. Rare‐earth metal and calcium atoms are arranged in distorted trigonal prisms, square‐antiprisms and cubes, centered by Ge or rare‐earth/calcium metal atoms. These studies show that the amount of trivalent rare‐earth metal atoms substituting divalent calcium atoms is in direct correlation with the lengths of the Ge−Ge bond within the Ge2‐dimers, with distance varying between 2.58 Å in Ca5−xGdxGe3and 2.75 Å in La5−xCaxGe3. Such an elongation of the Ge−Ge bond is consistent with the notion that the parent Ca5Ge3Zintl phase (e. g. (Ca2+)5[Ge2]6−[Ge4−]) is being driven out of the ideal valence electron count and further reduced. In this context, this work demonstrates the ability of the germanides with the Cr5B3structure type to accommodate substitutions and wider valence electron count while maintaining their global structural integrity.

     
    more » « less