Reduced lattice thermal conductivity in Bi-

doped Mg2Si0.4Sn0.6
Cite as: Appl. Phys. Lett. 105, 202104 (2014); https://doi.org/10.1063/1.4901178
Submitted: 15 September 2014 • Accepted: 27 October 2014 • Published Online: 18 November 2014

Peng Gao, Xu Lu, Isil Berkun, et al.

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Appl. Phys. Lett. 105, 202104 (2014); https://doi.org/10.1063/1.4901178 105, 202104

© 2014 AIP Publishing LLC.

 APPLIED PHYSICS LETTERS 105, 202104 (2014)

Reduced lattice thermal conductivity in Bi-doped Mg2Si0.4Sn0.6

Peng Gao,1 Xu Lu,2 Isil Berkun,3 Robert D. Schmidt,1 Eldon D. Case,1
and Timothy P. Hogan1,3
1
Department of Chemical Engineering and Materials Science, Michigan State University, East Lansing,
Michigan 48824, USA
2
Department of Physics and Astronomy, Michigan State University, East Lansing, Michigan 48824, USA
3
Department of Electrical and Computer Engineering, Michigan State University, East Lansing,
Michigan 48824, USA
(Received 15 September 2014; accepted 27 October 2014; published online 18 November 2014)
This letter reports the thermoelectric properties of Bi-doped Mg2Si0.4Sn0.6 thermoelectric materials.
It was found that the ZTs of this material could be greatly enhanced by Bi-doping. Analyses on the
transport properties showed that the power factors of the material were enhanced while the lattice
thermal conductivities were reduced by Bi-doping. The reduction of the lattice thermal conductiv-
ity was likely caused by the interstitial Bi impurities. A peak ZT  1.55 at 773 K was obtained.
C 2014 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4901178]
V

Thermoelectric power generation could convert waste
heat to electricity and improve energy efficiency in places
such as power plants, automobiles, and nuclear generators.1
The thermoelectric efficiency is determined by the figure of
merit of a material
temperature densities (q0) of the pellets were measured by
the Archimedes method. The thermal diffusivity D and the
specific heat CP of the samples were measured using a
Netzsch LFA 457 system. The thermal conductivity (j) was
then calculated as

S2 r q0
ZT ¼ T; (1) j ¼ DCP ; (2)
j ½1 þ aðT  TRT Þ3

where S is Seebeck coefficient, r is the electrical conductiv- where a linear thermal expansion coefficient of 2.0  105
ity, and j is the thermal conductivity. The efficiency of heat was used.9 The temperature-dependent electrical conductiv-
to electricity conversion is directly related to ZT such that a ity and Seebeck coefficient were measured using a ULVAC
high ZT is needed for good thermoelectric performance. As ZEM-3 system, and the temperature-dependent carrier con-
those materials properties are dependent on each other, the centration and Hall mobility were measured using a
denominator (thermal conductivity j) could not be mini- laboratory-built Hall measurement system using a Hall-bar
mized without suppressing the numerator (power factor S2r), configuration.10
or vice versa. Finding a balance between these material pa- The XRD spectra for all the samples follow the pattern
rameters is one common way to optimize ZT and it is usually for anti-fluorite structured crystals (Figure 1). All character-
done by adjusting the carrier concentration of the mate- istic peaks lie between the peaks for single phase Mg2Si and
rial.2–5 Introducing new scattering mechanisms that only
affect j or S has also been proven to successfully increase
ZT.6,7
In this work, we present a possible route to increase ZT
by decreasing the lattice thermal conductivity while main-
taining the high power factor in the Mg2Si0.4Sn0.6 solid solu-
tion, which is one of the most promising candidate materials
for mid-temperature thermoelectric power generation
application.
Samples of Mg2.08Si0.4xSn0.6Bix (x ¼ 0, 0.005, 0.010,
0.015, 0.020, and 0.030) were synthesized using the flux syn-
thesis method.8,9 A p-type sample of Mg2.005Si0.4Sn0.6
Ag0.075 was also made to investigate hole conduction in these
materials. Excess Mg was used to compensate for the loss of
Mg during synthesis. The naturally cooled cast ingot was
ground into powders with particle size less than 53 lm and
densified using a Pulsed Electrical Current Sintering (PECS)
system at 973 K and 30 MPa for 15 min in a 304 stainless-
steel die.
A Rigaku MiniFlex x-ray diffractometer (XRD) with a
Cu Ka radiation source was used to identify the crystallo-
graphic phase of the synthesized materials. The room FIG. 1. XRD spectra for Mg2.08Si0.4xSn0.6Bix samples.

0003-6951/2014/105(20)/202104/5/$30.00 105, 202104-1 C 2014 AIP Publishing LLC

V
202104-2 Gao et al. Appl. Phys. Lett. 105, 202104 (2014)

Mg2Sn, indicating the formation of the single phase Mg2Si- where jl, je, and jbp are the lattice, electronic, and bipolar
Mg2Sn solid solution. thermal conductivities, respectively.
The temperature dependent S and r are shown in A single-parabolic-band model was employed to extract
Figures 2(a) and 2(b). The undoped specimen (x ¼ 0.000) the three components explicitly based on experimental
showed typical intrinsic semiconductor behavior as r monot- results.5 First, je is related to the electrical conductivity by
onically increased with increasing temperature. The absolute the Wiedemann-Franz law
value of S started decreasing at about 450 K. The
Mg2Si0.4Sn0.6 solid solution has a small band gap of about je ¼ LrT; (4)
0.44 eV at room temperature.11 This was in good agreement 8  9
with the value obtained from 2SmaxTmax, which gives >
> 7 >
>
> k þ Fkþ5=2 ðgÞ
 2 < >
=
Eg ¼ 0.45 eV.12 The roll-over of S at high temperatures was kB 2 2
L¼   d ; (5)
due to the increased bipolar conduction at higher tempera- q > > 7 >
>
>
: k þ Fkþ1=2 ðgÞ >
;
tures. For the Bi-doped samples, the values of r were greater 2
than those of the undoped specimen. The Bi doping
 
increased the room temperature carrier concentration by an 5
order of magnitude (Figure 2(c)). The roll-over temperatures k þ Fkþ3=2 ðgÞ
2
for S systematically increased with increased Bi doping. In d¼ ; (6)
3
the heavily doped samples, higher holes concentrations were k þ Fkþ1=2 ðgÞ
2
needed for the bipolar conduction to become significant,
which could only be obtained at elevated temperatures. ð1
1
The thermal conductivities j are shown in Figure 2(d). Fr ¼ xr dx; (7)
For all the samples, j decreased with increasing temperature 0 1 þ exg
until the bipolar conduction became significant, similar to
where L is the Lorenz number, q is the electron charge, and g
the roll-over observed in S. As the Bi content increased, the
is the reduced Fermi level measured from the bottom of the
room temperature j increased. The total thermal conductiv-
conduction band. There is no direct measure of g. An itera-
ities consist of three components
tive method was used to find g based on the experimental
j ¼ jl þ je þ jbp ; (3) Seebeck coefficient data as

FIG. 2. (a) Electrical conductivities, (b) Seebeck coefficients, (c) carrier concentration, and (d) thermal conductivities for Mg2.08Si0.4xSn0.6Bix samples.
202104-3 Gao et al. Appl. Phys. Lett. 105, 202104 (2014)

FIG. 3. High temperature hall mobilities for the n-type and p-type samples. FIG. 5. Dependence of j0/jl on the Bi content.

Bi-doped samples are heavily degenerate n-type semicon-

ln nSn þ lp pSp
S¼ ; (8) ductors, accurate Fermi-Dirac integrals were used in the cal-
ln n þ lp p culation for electrons, and the Boltzmann approximation
" # could be applied to simplify the formulas for holes.
kB ðk þ 5=2ÞFkþ3=2 ðgÞ
Sn ¼  g ; (9) Using the results from Eqs. (8) to (13), the bipolar ther-
q ðk þ 3=2ÞFkþ1=2 ðgÞ mal conductivity was calculated as
 
kB 5 ln n  lp p
Sp ¼ þ k  gp ; (10) jbp ¼ ðSn  Sp Þ2 T: (14)
q 2 ln n þ up p
Eg The lattice thermal conductivity was obtained from Eq.
g þ gp ¼  ; (11)
kB T (3). As seen in Figure 4(a), the je increases as Bi content
 3=2 increases, which resulted from the increase r. The jbp are
1 2mn kB T small at low temperatures but start to increase nearly expona-
n¼ 2 F1=2 ðgÞ; (12)
2p h2 tionally at high temperatures. Figure 4(b) shows that jl
 3=2 decreases as the doping concentration increases.
1 2mp kB T To verify the reliability of the jl derived in this method,
p¼ 2 eg ; (13)
2p h2 the pure lattice thermal conductivity of the undoped sample
was also estimated using Slack’s formula14
where Sn (Sp), n (p), and ln (lp) are the Seebeck coefficients,
carrier concentrations, and mobility for electrons (holes). As  3 V 1=3
Mh
stated previously, the bipolar conduction could be significant jl ¼ A ; (15)
c2 nV 2=3 T
at elevated temperatures because of the small band gap. The
density of states effective mass mn*(mp*) and the band gap 3bBVm
values were taken from the literature where the values have c¼ ; (16)
CV
been experimentally or theoretically verified.11,13 The mobi-
lities for electrons and holes were obtained by the high where A is a collection of physical constants and a value of
temperature Hall measurement (Figure 3). Since all of the 3.1  107 s3 K3 was used in our calculation,14–16 M  is

FIG. 4. (a) Electronic (line þ symbol) and bipolar (symbol), and (b) lattice thermal conductivities for the Mg2.08Si0.4xSn0.6Bix samples.
202104-4 Gao et al.
FIG. 6. (a) Power factors and (b) ZTs for the samples.
the average mass of the atoms in the crystal, V is the average
volume occupied by an atom, nV is the number of atoms per
primitive cell, b is the volume thermal expansion coefficient,
B is the bulk modulus, Vm is the molar volume and, CV
(CP) is the isochoric specific heat per mole. The Debye
temperature h and the Gr€uneisen parameter c were calculated
based on the mechanical properties measured in our previous
work on the undoped sample.9 The jl was estimated by Eq.
(15) (solid line in Figure 4(b)) and showed good agreement
with the result derived from Eqs. (1) to (14) (scatters in
Figure 4(b)).
Figure 4(b) shows that a reduction in the lattice thermal
conductivity could be achieved by introducing Bi impurity
atoms to the Mg2Si0.4Sn0.6 matrix. The most heavily doped
sample (x ¼ 0.030) had a jl  13% lower than the jl for the
undoped sample at room temperature. The influence of
impurities on the intrinsic lattice thermal conductivity has
been studied by Ioffe in various semiconductors, and an em-
pirical formula has been proposed as17–19
j0 ND l0
¼1þv ; (17)
jl N0 a
where j0 is the lattice thermal conductivity for the pristine
crystal and jl is that for the doped crystal. ND is the impurity
concentration, N0 is the number of atoms per unit volume, l0
is the mean free path of phonons in the materials, a is the lat-
tice constant, and v is a parameter determined by the effec-
tive scattering area of the impurity atoms. Interstitial
impurities would result in v > 1 and substitutional impurities
would make v < 1.
The jl of the samples under different temperatures in
our work were fit to Eq. (17), as shown in Figure 5. We did
not find accurate reported values for l0 in Mg2Si0.4Sn0.6, but
a range of 10–100 Å for l0 in Mg2Si has been reported.20 If l0
of 10–100 Å was used, the calculated v was in the range of
2.0–51. Noting that the lattice thermal conductivities of
Mg2Si0.4Sn0.6 are much lower than that of Mg2Si due to the
formation of solid solution,21 a smaller l0 should be expected
in Mg2Si0.4Sn0.6. Thus, the real values of v should be close
to the high end of the range 2.0–51, which is expected to be
much greater than 1. This indicates that there is at least a
Appl. Phys. Lett. 105, 202104 (2014)
portion of the Bi atoms occupied the interstitial sites. The in-
terstitial Bi atoms acted as strong phonon scattering centers
and reduced the lattice thermal conductivities.
One thing to note here is that Eq. (17) is an empirical
equation, so the existence of the interstitial Bi atoms needs
to be confirmed by further studies. It was observed that in
the lattice of GaSb v ¼ 7 for Te atoms and v ¼ 3 for Se
atoms. While for isovalent impurities such as Si in Ge, Sn in
Si, and Se in PbTe, v ¼ 1 held well. Bi is not an isovalent im-
purity compared with Si or Sn, so the behavior of Bi in
Mg2(Si,Sn) might be closer to Te in GaSb. One possible ex-
planation for origin of the off-site Bi atoms might be the sol-
ubility limit of Bi in the Mg2(Si,Sn) materials.5
While the lattice thermal conductivity is reduced,
increasing the Bi content showed no detrimental effect on
the power factors (Figure 6(a)). This should be attributed to
the low alloy scattering and deformation scattering potentials
to electrons in the Mg2(Si,Sn) solid solutions.22 In Figure 3,
the mobilities were not significantly altered by the Bi-
doping. As a result, all Bi-doped samples showed peak
ZT > 1 and increasing with increasing Bi content. A maxi-
mum ZT  1.55 was obtained at 773 K for x ¼ 0.030. Based
on the current results, it is likely that the peak ZT could be
pushed to a higher value for x > 0.030.
The thermoelectric properties of Mg2.08Si0.4xSn0.6Bix
have been studied in this work. The lattice thermal conduc-
tivities of the samples were extracted from total thermal con-
ductivities using a single parabolic band model with bipolar
conduction considered. Increasing Bi content could reduce
the lattice thermal conductivity by up to 13% while the
power factors were kept at high levels. The samples with
x ¼ 0.030 had the highest peak ZT of 1.55 at 773 K.
Further studies of higher Bi-doping content are of interest.
The authors are grateful for the generous support by the
U.S. DOE-EFRC Project DOE SC0001054.
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