Journal of ELECTRONIC MATERIALS, Vol. 46, No.

5, 2017
DOI: 10.1007/s11664-016-4824-7
Ó 2016 The Minerals, Metals & Materials Society

Effects of Lanthanum Substitution on Thermoelectric

Properties of YbZn2Sb2

XIONG ZHANG,1,2,3 KUNLING PENG,2 LIJIE GUO,2 YANCHI YAN,2

HEN ZHAN,2 XU LU,2 HAOSHUANG GU,1,4 and XIAOYUAN ZHOU2,5

1.—Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials-Hubei Key
Laboratory of Ferro & Piezoelectric Materials and Devices, Faculty of Physical and Electronic
Sciences, Hubei University, Wuhan 430062, People’s Republic of China. 2.—College of Physics,
Chongqing University, Chongqing 401331, People’s Republic of China. 3.—College of Science,
Hubei University of Automotive Technology, Shiyan 442002, China. 4.—e-mail: guhsh@hubu.
edu.cn. 5.—e-mail: xiaoyuan2013@cqu.edu.cn

LaxYb1xZn2Sb2 polycrystalline are prepared by solid-state reaction followed

by spark plasma sintering. The effect of La substitution on the thermoelectric
properties of LaxYb1xZn2Sb2 has been investigated. It is found that the
substitution of La for Yb donates extra electrons to compensate for the
vacancies and produces point defects to scatter phonons, leading to a signifi-
cant reduction of the lattice thermal conductivity. As a result, a maximum ZT
of 0.4 is obtained at x = 0.01, 18% enhancement in contrast to that of a pure
sample as a result of the identical electrical properties and the largely reduced
thermal conductivity.

Key words: Thermoelectric, substitution, point defects, optimization

INTRODUCTION compounds have exhibited excellent thermoelectric

performance, such as EuZn2Sb2 (ZT = 0.9 at 700 K)3
Thermoelectric (TE) devices have attracted
and YbCd2Sb2 (ZT = 0.98 at 700 K).4
renewed interest for power generation due to their
Further optimization of thermoelectric perfor-
ability to directly convert waste heat into electricity.1
mance for existing Zintl compounds is often realized
The heat-to-electricity conversion efficiency of ther-
through doping or solid solution, such as Yb14Alx
moelectric materials is determined by the thermoelec-
Mn1xSb11,5 Yb13.6La0.4MnSb11,6 EuZnxCd2xSb2,7
tric figure of merit ZT = a2rT/j, where T is absolute
YbCd2–xMnxSb2,8 YbxEu1xCd2Sb2,9 NdxFe3Co
temperature, r is electrical conductivity, a is the
Sb12,10–12 and Yb1xCaxCd2Sb2.13 Isoelectronic sub-
Seebeck coefficient, and j is total thermal conductivity
stitution was always adopted to optimize the ther-
(j = je + jL, where je is the electronic contribution
moelectric performance for AM2Sb2, such as Yb
and jL is the lattice contribution). Thus, a large
Zn2xCdxSb2,4 YbZn2xMnxSb2,14 and CaxYb1xZn2
Seebeck coefficient (a) with high electrical conductiv-
Sb2.15 However, there is no study on the effect of
ity (r) and low thermal conductivity (j) are required to
thermoelectric properties of rare earth elements
obtain an ideal thermoelectric performance. However,
substitution with A3+ in AM2Sb2 based compounds.
it is not easy to improve ZT because of interrelated
In this study, anisoelectronic substitution of La on
relations in these three parameters. Zintl phases, such
Yb sites in YbZn2Sb2 based compounds is investigated
as AM2Sb2, where A is alkaline earth (Sr and Ca) or
to improve the thermoelectric properties. As we know,
rare earth (Yb and Eu) and M is transition metal (Mn,
La is considered to be 3+ and have equal electroneg-
Zn and Cd), possess many characteristics required for
ativity (1.1) to Yb based on the Pauling scale. Substi-
a promising thermoelectric material.2 Several Zintl
tuting Yb2+ with La3+ would be expected to strongly
influence the electronic properties. But the electrical
properties were maintained probably due to a Yb
vacancy compensating for extra electrons. Meanwhile,
(Received June 8, 2016; accepted July 21, 2016; the thermal conductivity was decreased due to defects
published online August 1, 2016)

2611
2612
scattering in YbZn2Sb2- based compounds, leading to
the consequent improvement of ZT value.
EXPERIMENTAL PROCEDURES
Ingots of LaxYb1xZn2Sb2 alloys were prepared by
direct reaction of the elements in carbon-coated
fused-silica ampoules sealed under dynamic vac-
uum (106 torr).14 The reactants were melted by
heating to 1323 K, followed by an isothermal hold
for 30 h. The ampoules were cooled to 723 K at a
rate of 1 K/min, followed by a 30 h anneal at 723 K.
The obtained ingots were pulverized into powders
and sintered by a spark-plasma sintering (SPS)
technique at 923 K for 4 min in order to obtain
highly densified disc-shaped samples. The density
was then determined by an Archimedes technique.
The relative packing densities after SPS were over
95% of the theoretical density.
High temperature electrical conductivity (r) and
the Seebeck coefficient (a) were measured on rectan-
gular-shape samples using a commercial apparatus
(LSR-3) under the protective atmosphere of helium.
The room temperature Hall coefficient was measured
with a ±1 T field under ambient atmosphere.Thermal
diffusivity (D) was obtained by the laser flash method
(LFA 457, Netzsch) from 300 K to 720 K, and con-
verted into thermal conductivity (j) using j = CpDq.
Cp was estimated using the method of Dulong-Petit
law. Sample density q was determined by Archimedes
method. We used pressure contacts, and at all times
the sample was under an atmosphere of Ar to prevent
oxidation at elevated temperatures. The errors in the
measurement were about 5%, 3%, and 5% for electri-
cal conductivity and Seebeck coefficient, thermal
diffusivity and Cp, respectively. Powder x-ray diffrac-
tion (XRD) patterns were collected on powders in a
Panalytic X’ pert using Cu Ka radiation.
RESULTS AND DISCUSSION
YbZn2Sb2 is described as (Zn2Sb2)2 covalent
slabs with separated monolayers of Yb2+ (and La3+)
Fig. 1. (a) The crystal structure of YbZn2Sb2 compound, Yb is shown in green, Zn in grey, and Sb in blue. (b) XRD patterns of LaxYb1xZn2Sb2
(x = 0.00, 0.01, 0.03, 0.05) (Color figure online).
Zhang, Peng, Guo, Yan, Zhan, Lu, Gu, and Zhou
cations in the x–y plane (as shown in Fig. 1a). XRD
analysis is used to clarify the phase structure of
LaxYb1xZn2Sb2 for x = 0.00, 0.01, 0.03, and 0.05
(as presented in Fig. 1b). The main peaks can be
indexed to the trigonal CaZn2Sb2 structure type
(PDF: 01-071-1815) with space group P-3 ml, indi-
cating LaxYb1xZn2Sb2 phase has been obtained.
Consistent with previous reports,16,17 a small
amount of impurity phase ZnSb is also detected.
The temperature-dependent electrical conductivity
and the Seebeck coefficient for all samples are shown
in Fig. 2a and b, respectively. A typical behavior of
heavily doped semiconductors with a small-band gap
can be observed. Specifically, the electrical conductiv-
ity of all samples decreases gradually with the
increased temperature, while the Seebeck coefficient
exhibits an opposite trend. The positive Seebeck
values indicate the p-type conduction. During the
whole temperature measured, the electrical conduc-
tivity decreases with the increase substitution of La
on Yb until x is 0.03, further increase of the amount of
La yields a rise of electricity conductivity. As shown in
the inset of Fig. 2b, La-doping moderately affects the
power factor. A maximum power factor of
2.0 mW m1 K2 is obtained for the x = 0.01 sample,
comparable to that of the pure sample.
In order to understand the underlying mechanism
of the observed changes in the electronic transport
properties, we conducted room temperature Hall
coefficient measurements. The results are shown in
Fig. 3. The carrier concentration of the pure
YbZn2Sb2 (12.8 9 1019 cm3) is comparable to that
reported by Gascoin15 and Wang 4. Mobility (lH) is
calculated from carrier concentration (nH) and
electrical conductivity (r) based on the equation
lH = r/(enH). As demonstrated in Fig. 3a, with
increasing x, both the carrier concentration and
mobility first decreases up to x = 0.03 and then
increases. Therefore, the decrease in electrical
conductivity as x less than 0.05 can be attributed
to the lowered carrier concentration and mobility
due to the substitution of La on Yb. According to the
Pauling scale, lanthanum and ytterbium have the
Effects of Lanthanum Substitution on Thermoelectric Properties of YbZn2Sb2 2613

Fig. 2. The temperature dependence of (a) electrical conductivity and (b) the Seebeck coefficient for LaxYb1xZn2Sb2 (x = 0.00, 0.01, 0.03,
0.05); the inset of (b) shows power factor (PF) as functions of temperature.

Fig. 3. (a) The room-temperature carrier concentration and mobility; (b) the effective mass (m*) as functions of x.

same electronegativity (1.1), thereby the impact of
the electronegativity difference on the electronic
properties can be neglected. The observed difference
should be accounted for by the difference in valence
state between La and Yb. In this work, we believe
La and Yb display +3 and +2 based on the Zintl or
the Zintl-Klemm formula. As such, the substitution
of La on Yb reduces the hole concentration at the
scale of one hole per unit.6 According to this
hypothesis, carrier concentration of La0.01Yb0.99
Zn2Sb2 should be decreased to only 4.9 9
1019 cm3, much smaller than the actual experi-
ment data (12 9 1019 cm3). Thus, we propose that
the extra electrons owing to La substitution are
compensated by the holes generated via Yb vacan-
cies,16,17 which gives rise to a slight decrease in
carrier concentration as La substitution.
A simple parabolic band model for a degenerate
semiconductor is applied to calculate the effective
mass (m*) assuming a charge-carrier scattering
distance independent of energy by using Eq. 1. Here
kB is the Boltzmann constant, h the Planck con-
stant, and e the electric charge. As shown in Fig. 3b,
there exists no change in m*, implying that the
valence band edge is minimally altered by the
substitution of Yb with La.18,19
8p2 k2B T   p 2=3
a¼ m ð1Þ
3eh2 3n
The total thermal conductivity (j) and lattice ther-
mal conductivity (jL) as functions of temperature
are shown in Fig. 4a and b, respectively. At the
same temperature, the total thermal conductivity
decreases with the increase of La content, but it
turns over as x reaches 0.03 due to the increased
electrical conductivity. Moreover, the j for all
samples tends to overlap at high temperatures as
2614
Fig. 4. The temperature dependence of (a) the total thermal conductivity (j) and (b) lattice thermal conductivity (jL) for LaxYb1xZn2Sb2
(x = 0.00, 0.01, 0.03, 0.05).
Fig. 5. Temperature dependence of the dimensionless figure of
merit ZT for LaxYb1xZn2Sb2 (x = 0.00, 0.01, 0.03, and 0.05).
observed in CaxYb1xZn2Sb2 and YbZn2xMnxSb2
compounds. The jL is calculated by subtracting je
from j, where the je was estimated using the
Wiedemann–Franz relationship (je = LrT). The
Lorentz constant (L) was calculated using a single
parabolic band model. Because the enhanced pho-
nons scattering due to point defects introduced by
La substitution, the lattice thermal conductivity for
La substituted samples is significantly lower than
that of YbZn2Sb2. The lattice thermal conductivity
decreases from 3.4 Wm1 K1 to 2.3 Wm1 K1,
making dominant contributions to the decrease in
total thermal conductivity as mentioned above. For
all samples, the jL decreases with temperature
roughly agreeing with jL  1/T due to the Umklapp
process of phonon–phonon scattering.
Zhang, Peng, Guo, Yan, Zhan, Lu, Gu, and Zhou
Figure 5 presents the temperature dependence of
the dimensionless figure of merit ZT. A maximum
ZT of 0.4 is obtained as x = 0.01, a 18% increase as
compared with that of a pure sample, as a result of
the reduced thermal conductivity, while maintain-
ing the power factor. Further improvement of the
figure merit of ZT could be obtained by considering
the following factors: (1) optimization of the chem-
ical composition. Double and/or multi substitutions
are widely considered to effectively further reduce
the lattice thermal conductivity as well as improve
the electronic properties. (2) Preparing nanocom-
posites to largely decrease the thermal conductivity,
in other words, dispersing metallic and/or non-
metallic nanoparticles to p-type Zintl matrix, where
various forms of nanoinclusions are uniformly dis-
persed. Meanwhile, one could broaden the range of
embedded nanoparticle sizes to scatter phonons
with a much wider wavelength. All these scenarios
seem very interesting and are being studied.
CONCLUSIONS
In summary, we successfully synthesized poly-
crystalline compounds of LaxYb1xZn2Sb2 (x = 0.00,
0.01, 0.03, 0.05) using the solid state reaction
followed by spark plasma sintering and investigated
the effect of La substitution on Yb sites on the
electrical and thermal transport properties of p-type
LaxYb1xZn2Sb2 compounds. It is found that La
substitution slightly decreases the carrier density
along with the electrical conductivity, while it keeps
the identical power factor in contrast to the pure
sample. Furthermore, the thermal conductivity is
significantly reduced due to the enhanced phonons
scattering from point defects. Finally, an improve-
ment of 18% in ZT value is achieved in sample
x = 0.01.
Effects of Lanthanum Substitution on Thermoelectric Properties of YbZn2Sb2
ACKNOWLEDGEMENTS
This work was financially supported in part by
the National Natural Science Foundation of China
(Grant Nos. 11404044, 51472036, 11474088), the
Fundamental Research Funds for the Central
Universities (106112016CDJZR308808). The work
was conducted at the Chongqing Institute of Green
and Intelligent Technology, Chinese Academy of
Sciences is supported by the 100 Talent Program of
the Chinese Academy of Sciences (Grant No. 2013-
46), the National Natural Science Foundation of
China (Grant No. 51401202), and the Project for
Fundamental and Frontier Research in Chongqing
(CSTC2015JCYJBX0026).
REFERENCES
1. L.E. Bell, Science 321, 1457 (2008).
2. A.M. Mills, R. Lam, M.J. Ferguson, L. Deakin, and A. Mar,
Coord. Chem. Rev. 233, 207 (2002).
3. H. Zhang, J.T. Zhao, Y. Grin, X.J. Wang, M.B. Tang, Z.Y.
Man, H.H. Chen, and X.X. Yang, J. Chem. Phys. 129,
164713 (2008).
4. X.J. Wang, M.B. Tang, H.H. Chen, X.X. Yang, J.T. Zhao, U.
Burkhardt, and Y. Grin, Appl. Phys. Lett. 94, 092106 (2009).
5. E.S. Toberer, C.A. Cox, S.R. Brown, T. Ikeda, A.F. May,
S.M. Kauzlarich, and G.J. Snyder, Adv. Funct. Mater. 18,
2795 (2008).
2615
6. E.S. Toberer, S.R. Brown, T. Ikeda, S.M. Kauzlarich, and
G.J. Snyder, Appl. Phys. Lett. 93, 062110 (2008).
7. H. Zhang, M. Baitinger, M.B. Tang, Z.Y. Man, H.H. Chen,
X.X. Yang, Y. Liu, L. Chen, Y. Grin, and J.T. Zhao, Dalton
Trans. 39, 1101 (2010).
8. K. Guo, Q.G. Cao, X.J. Feng, M.B. Tang, H.H. Chen, X.
Guo, L. Chen, Y. Grin, and J.T. Zhao, Eur. J. Inorg. Chem.
2011, 4043 (2011).
9. H. Zhang, L. Fang, M. Tang, Z. Man, H. Chen, X. Yang, M.
Baitinger, Y. Grin, and J.T. Zhao, J. Chem. Phys. 133,
194701 (2010).
10. L. Guo, Z. Cai, X. Xu, K. Peng, G. Wang, G. Wang, and X.
Zhou, J. Nanosci. Nanotechnol. 16, 3841 (2016).
11. L. Guo, G. Wang, K. Peng, Y. Yan, X. Tang, M. Zeng, J. Dai,
G. Wang, and X. Zhou, Scr. Mater. 116, 26 (2016).
12. L. Guo, Y. Zhang, Y. Zheng, W. Yao, G. Wang, G. Wang,
and X. Zhou, J. Electron. Mater. 45, 1271 (2016).
13. Q.G. Cao, H. Zhang, M.B. Tang, H.H. Chen, X.X. Yang, Y.
Grin, and J.T. Zhao, J. Appl. Phys. 107, 053714 (2010).
14. T.J. Zhu, C. Yu, J. He, S. Zhang, X. Zhao, and T.M. Tritt, J.
Electron. Mater. 38, 1068 (2009).
15. F. Gascoin, S. Ottensmann, D. Stark, S.M. Haı̈le, and G.J.
Snyder, Adv. Funct. Mater. 15, 1860 (2005).
16. A. Zevalkink, W.G. Zeier, E. Cheng, G.J. Snyder, J.P.
Fleurial, and S. Bux, Chem. Mater. 26, 5710 (2014).
17. E.S. Toberer, A.F. May, B.C. Melot, E.F. Larsen, and G.J.
Snyder, Dalton Trans. 39, 1046 (2010).
18. P. Alemany, M. Llunell, and E. Canadell, J. Comput.
Chem. 29, 2144 (2008).
19. C. Kranenberg, D. Johrendt, and A. Mewis, Z. Anorg. Allg.
Chem. 625, 1787 (1999).