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Core-shell nanostructures introduce multiple potential

barriers to enhance energy filtering for the improve-
ment of thermoelectric properties of SnTe
Zheng Ma,a Chao Wang,∗a Jingdan Lei,a De Zhang,a Yanqun Chen,a Yuanxu Wang,a
Jianli Wang,∗a and Zhenxiang Cheng∗ab

Nanoscale Accepted Manuscript

Published on 20 December 2019. Downloaded on 1/2/2020 11:04:46 PM.

Using dispersed nanostructures to induce energy filtering effect is an easy and effective mecha-
nism to optimize the performance of bulk thermoelectric materials. Comparing with other nanos-
tructures, core-shell nanostructures possess more interfaces and multiple potential barriers, which
would lead to significant impact on the thermal and electrical properties of materials. In this pa-
per, after BiCuSeO alloy doping into SnTe, SnO2 layers were formed at the interfaces and the Bi-
CuSeO nanoparticles would be wrapped in SnO2 shell during the following high temperature solid
state reaction. The formation of SnO2 layers could be observed and confirmed by x-ray diffrac-
tion (XRD) and scanning electron microscope (SEM). BiCuSeO@SnO2 core-shell nanostructures
can introduce multiple potential barriers to enhance energy filtering effect. Once the BiCuSeO
doping concentration were over 3%, the carrier concentration could decrease to about 10% while
the mobility increase to 350% comparing to the value of undoped sample at room temperature.
Meanwhile, the Seebeck coefficients were improved to 176.05 µ VK−1 at 835 K. Additionally, due
to the scattering of core-shell nanostructures for the phonons, the lower thermal conductivity is
achieved with the value of 1.04 Wm−1 K−1 at 835 K in Sn1.03 Te-5% BiCuSeO. Combining with the
improvement of thermal and electrical properties by the BiCuSeO@SnO2 core-shell, a high ZT
value ∼ 1.21 was achieved for the Sn1.03 Te-5% BiCuSeO at 835 K, which was enhanced 190%
than pristine SnTe.

1 Introduction lattice thermal conductivity, respectively. It is obvious that high

Despite a growing shortage of non-renewable energy, more than
half of all energy is still wasted as heat 1,2 . Thermoelectric tech-
nology is the simplest technology that can realize the direct con-
version of thermal energy and electric energy. It can convert solar
energy, geothermal energy, motor vehicles and industrial waste
heat into electricity. However, the biggest challenge in the devel-
opment of thermoelectric technology is the improvement of ther-
moelectric performance of materials. The performance of a ther-
moelectric material is related to the figure of merit ZT =S2 σ T/κ ,
where σ is the electrical conductivity, S the Seebeck coefficient,
κ the total thermal conductivity and T the absolute temperature,
respectively. The total thermal conductivity, κ =κL +κe , consists of
two components, namely κe and κL , which are the electronic and
a
Institute for Computational Materials Science, School of Physics and Electronics,
Henan University, Kaifeng, 475004, China. E-mail: wangchao@vip.henu.edu.cn,
jianli@uow.edu.au
b structure and electronic structure to PbTe. Therefore, SnTe is con-
Institute for Superconducting and Electronic Materials, University of Wollongong,
Squires Way, North Wollongong, Australia. E-mail: cheng@uow.edu.au
ZT materials must have a high Seebeck coefficient, high electri-
cal conductivity and low thermal conductivity. However, these
parameters have strong coupling characteristics because they are
determined by more fundamental characteristics of the electron
and phonon systems 3,4 . Increasing Seebeck coefficient usually
results in a decrease of the electrical conductivity. Similarly, a de-
crease in thermal conductivity inevitably worsens electrical con-
ductivity. So far, nanostructures 5–7 , increase the slope of the elec-
tronic density of states 8,9 , energy filtering 10 and other strategies
can effectively weaken the coupling relationship between various
parameters 11,12 .
In the past decade, PbTe-based thermoelectric materials have
made remarkable progress with the optimum content of ZT ex-
ceeding 2, especially for p-type compositions 2,13,14 . However,
due to the toxicity of Pb, the popularization and application of
PbTe-based thermoelectric materials is limited. Another attractive
thermoelectric material compound, SnTe, has the similar crystal
sidered as one of the most promising alternatives to lead-free
thermoelectricity 15–19 , whereas the thermoelectric performance

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of SnTe is not as good as that of PbTe 20,21 . The poor intrinsic
thermoelectric performance results from the very high hole con-
centration (1020 ∼1021 cm−3 ) due to the intrinsic Sn vacancies,
which led to low Seebeck coefficient and high electronic thermal
conductivity 22,23 . In addition, although SnTe has a similar band
structure to PbTe, its light (L point) and heavy (Σ point) valence
band energy separation is larger (0.35 eV at 300 K) and the band
gap is smaller (0.18 eV at 300 K) 24,25 . This further leads to very
small Seebeck coefficient for the pristine SnTe 26 . It can be seen
that the most important way to optimize the thermoelectric per-
formance of SnTe is to improve Seebeck coefficient, as well as
reducing thermal conductivity.
The relation between Seebeck coefficient and electrical conduc-
tivity can be expressed as 27 :
Published on 20 December 2019. Downloaded on 1/2/2020 11:04:46 PM.
{ }
π 2 kB d[ln(σ (E))]
S= kB T
3 q dE E=EF
{ }
π 2 kB 1 dn(E) 1 d µ (E)
= kB T + ,
3 q n dE µ dE E=EF
where n(E) and µ (E) are energy dependent carrier density and
mobility, respectively. It can be seen from Equation 1 that there
are two mechanisms to enhance the Seebeck coefficient: (I) in-
creasing the density of states near the Fermi level, e.g., reso-
nant level or valence band convergence 27–29 , and (II) increas-
ing energy dependence of µ (E) by energy filtering (or carrier
filtering) 30 . L. W. Fu et al. showed that enhancement of ther-
moelectric properties of Yb-filled skutterudites by an Ni-induced
"core-shell" structure 31 ; C. L. Ou et al. demonstrated that the
introduction of double-barrier through TiC1−x Ox @TiOy -TiO2 het-
erostructure improved the Seebeck coefficient of the material 32 ,
and so on 33,34 . In this work, we introduced BiCuSeO@SnO2
core-shell nanostructures into SnTe matrix by doping BiCuSeO
nano-alloy. During high-temperature solid state reaction, Sn ion
in SnTe matrix can react with O ion in BiCuSeO surface to form
SnO2 envelope, thus forming BiCuSeO@SnO2 core-shell nanos-
tructures. BiCuSeO is composed by alternately stacking the in-
sulating oxide (Bi2 O2 )2+ layer acting as charge reservoir and the
conductive selenide (Cu2 Se2 )2− layer constituting a conduction
pathway for carrier transport 35,36 . The presence of layered struc-
ture leads to the formation of more complex nonplanar poten-
tial barrier. At the same time, as a shell, SnO2 can form energy
barriers on the interface of contact with SnTe matrix and core
due to its wide bandgap (Eg = 3.59eV 37 ). Therefore, the pres-
ence of BiCuSeO@SnO2 core-shell nanostructures can introduce
multiple potential barriers in the matrix to induce an enhanced
energy filtering effect. The strengthened energy filtering effect
can more effectively prevent low-energy carriers from participat-
ing in conductivity through the material. Higher energy electrons
can cross these energy barriers. Because the high-energy carriers
are nothing but the matter of energy transfer, the Seebeck coeffi-
cient gradually increase. It is worth mentioning that this ability
is not possessed by sole energy barriers. The ineffectiveness of
the sole energy barriers to enhance thermoelectric efficiency has
been rather extensively proved in the literature 38,39 . The exis-
tence of enhanced energy filtering effect also inhibits the elec-
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Nanoscale Page 2 of 8
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DOI: 10.1039/C9NR09331A
tronic thermal conductivity, thus further optimizing the thermo-
electric properties of materials. Finally, a high Seebeck coefficient
of 176.05 µ VK−1 and an extremely low thermal conductivity of
1.04 Wm−1 K−1 at 835 K can be obtained, which also results in a
very high ZT value of 1.21 at 835 K for Sn1.03 Te-5% BiCuSeO.
2 Experimental section
In the preparation of materials, we set the ratio of Sn to Te as
1.03:1 to solve the deterioration of material properties caused
by Sn volatilization in the preparation process. To synthesize
Sn1.03 Te, starting materials with suitable proportion, Sn (powder,
Aladdin, 99.9%) and Te (powder, Aladdin, 99.9%), were mixed
and ground in a planetary ball mill (MSK-SFM-1, Hefei Kejing
Materials Technology Co. Ltd.) at 150 rpm for 4 h and placed
Nanoscale Accepted Manuscript
into a quartz tube. Then the quartz tube was evacuated to high
vacuum (∼2.5×10−2 Pa) and sintered at 1173 K for 15 h inside
a muffle furnace (KSL-1200X, Hefei Kejing Materials Technology
Co. Ltd.). After the quartz tube cooled to room temperature, the
sintered material was put into a ball mill to crush into powder.
(1)
Finally, the crushed material was sintered in a 12.7 mm diameter
mold into a wafer by a spark plasma sintering system (SPS-211LX,
Fuji Electronic Industrial Co. Ltd.). The similar preparation pro-
cess was used to BiCuSeO (wt %) alloy powder doped SnTe. The
production process for BiCuSeO was same as previous reports 36 .
The BiCuSeO alloy particles range in size from a few nanome-
ters to a few microns and BiCuSeO nanoparticles only refer to the
particles with size below 100 nm.
Crystal structure of the obtained samples were characterized
by X-ray diffraction using Bruker D8 Advance with Cu Kα ra-
diation accelerated in a 2θ range of 20-80◦ . The Synchrotron
powder diffraction (SPD) patterns were collected on the Powder
Diffraction beamline at the Australian Synchrotron with a wave-
length of 0.727464 Å. During the SPD measurement, the sam-
ple was heated from 300 to 700 K. The microstructure examined
on a freshly broken surface of the samples was observed by a
field emission scanning electron microscope (FESEM, JSM-7001F,
JEOL Co., Ltd.). The obtained pellets after spark plasma sintering
processed were cut into bars with dimensions of 12 mm × 2 mm
× 3 mm that were used to measure electrical conductivity and
Seebeck coefficient simultaneously using a static DC thermoelec-
tric property measurement system (ZEM-3, ULVAC-RIKO, Inc.)
under a low-pressure He atmosphere from room temperature to
835 K. Carrier concentration and mobility were analyzed at room
temperature using DC Hall measurement system (ET9005, East
Changing Technologies, Inc.). The thermal conductivity was de-
termined from the thermal diffusivity obtained by the laser flash
method (DLF-1/EM1200, TA Inc.) in a Ar atmosphere. In our
work, the density was determined using the dimensions and mass
of the sample. A typical disk shaped sample is obtained which is
12.7 mm in diameter with density no less than 96% of theoretical
density (6.46 gcm−3 ).
3 Results and Discussion
Fig. 1a) shows the XRD patterns of the Sn1.03 Te-x% BiCuSeO (x =
0, 1, 2, 3, 4, 5 and 6) samples. The position of the Bragg diffrac-
tion peak exhibit a phase that can be indexed to the rock-salt SnTe
 Page 3 of 8
a) SnO2 SnO2 SnO2
x=6
x=5
x=4
x=3
x=2
x=1
x=0
BiCuSeO
c)
Intensity (arb.units)
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4 7 10 13 16
2θ
Fig. 1 a) XRD patterns for Sn1.03 Te-x% BiCuSeO samples and doped
BiCuSeO alloy powder; b) Synchrotron powder diffraction (SPD)
patterns of Sn1.03 Te-5% BiCuSeO collected with the temperature
increasing from 300 to 700 K. c) (Color online) Results of the Rietveld
profile refinement for the low-temperature face-centered cubic phase of
Sn1.03 Te-5% BiCuSeO. The green small vertical lines indicate the
positions of the Bragg peaks corresponding to the Sn1.03 Te phases and
SnO2 phases. The blue curves at the bottom denote differences
between the measured and calculated intensities.
(Fm3̄m) structure. In addition, the diffraction peak of the phase
of BiCuSeO was not detected by X-ray characterization, but the
diffraction peak of the second phase SnO2 was found. The exis-
tence of a large amount of SnO2 second phase is caused by the
reaction of O ions in BiCuSeO with Sn ions at high-temperature
solid state. For Sn to react with O ions in BiCuSeO, it is essentially
to react with O ions in (Bi2 O2 )2+ layer. Sn is less electronegative
than Bi, that is, the electronegative of Sn and Bi are 1.477 and
2.342 respectively 40 . In other words, Bi element has a stronger
oxidation ability than Sn element. Moreover, SnO2 ’s Gibbs free
energy is smaller than that of Bi2 O3 , so SnO2 is easier to gen-
erated than Bi2 O3 41 . Therefore, the BiCuSeO nanoparticles dis-
tributed in SnTe matrix are coated with a layer of SnO2 to from
BiCuSeO@SnO2 core-shell nanostructures. In order to more ac-
curately explore the crystal structure of the sample, Sn1.03 Te-5%
BiCuSeO sample was studied using the SPD with the temperature
increasing from 300 to 700 K, as shown in Fig. 1b). In addition
to the results similar to those of X-ray diffraction, the SPD exper-
iment also proved that the sample structure did not change with
the increase of temperature. This means that BiCuSeO@SnO2
core-shell nanostructures is always present in the test temper-
ature range. Results of the Rietveld refinements performed at
low-temperature structure is shown in Fig. 1c). The fits are ex-
ceptionally good, which vouches for the high quality of our data
and lends confidence to the claim that the cubic model accurately
describes the average and local structure at this temperature.
A scanning electron microscopy (SEM) instrument equipped
with an energy dispersive spectrometer (EDS) apparatus was used
to further characterize the phase composition, as shown in Fig. 2.
Nanoscale
View Article Online
DOI: 10.1039/C9NR09331A
b) SnO 2
SnO2
SnO2
700K
600K
500K
400K
300K
Yobs
Ycalc
Yobs-Ycalc
Bragg-position
Nanoscale Accepted Manuscript
Fig. 2 FESEM images: a) Sn1.03 Te sample, b)-d) doped 1%, 2%, 3%
BiCuSeO alloy, respectively; g)-h) doped 4%,5% BiCuSeO alloy,
19 22 25 28 31 34 37 respectively ; i) and j) doped 6% BiCuSeO alloy. e) and f) The energy
dispersive spectrum of 3% and 4% BiCuSeO alloy , respectively. d1)-d6)
The elemental energy dispersive spectroscopy (EDS) mapping of the
Sn1.03 Te-3% BiCuSeO sample.
In Fig. 2a)-d) and g)-j), we can clearly see that the BiCuSeO alloy
particles were embedded into SnTe matrix and the size of alloy
particles ranges from tens of nanometers to several micrometers.
EDS images are shown in Fig. 2e) and f), which indicated obvious
Bi, Cu, Se and O peaks. The elements EDS mapping for the sam-
ple Sn1.03 Te-3% BiCuSeO in Fig. 2 d1)-d6) exhibit Sn, Te, Bi, Cu,
Se, and O distribution, respectively. Some dark areas appear in
EDS mapping of Te, which are corresponding to the bright areas
in EDS mapping of Cu and O. Therefore, the presence of BiCuSeO
alloy particles was further confirmed. Especially, these areas are
also bright in EDS mapping of Sn. Combining with the XRD pat-
terns, we can conclude that the surface of BiCuSeO alloy particles
was covered by SnO2 . Thus, the existence of BiCuSeO@SnO2
core-shell structures are proved.
TEM images of the BiCuSeO@SnO2 core-shell nanostructures
after SPS treatment using the obtained Sn1.03 Te-5% BiCuSeO
powder composites are presented in Fig. 3. The region I (the
area enclosed by the yellow dotted line) in Fig. 3 a)-c) is the
core structure formed by BiCuSeO nanoparticles, and the region
II (the area between the dotted yellow line and the solid red line)
is the shell structure formed by SnO2 . EDS pattern analysis in
Fig. 3 d) also proves that region II is SnO2 . In Fig. 3 c), we can
see that the outer layer of BiCuSeO nanoparticles as the nucleus
is covered by an insulating layer SnO2 that is different from the
core material. This result is similar to other experimental reports
on core-shell structures 42,43 . Thus the existence of core-shell
structure is further confirmed. The high magnification in Fig. 3
a) and b) reveals that the dispersed BiCuSeO@SnO2 core-shell
nanostructures are in incoherent phase with the pure SnTe ma-
trix, and the interface boundary between the matrix phase SnTe
and the BiCuSeO@SnO2 core-shell nanostructures can be clearly
observed. Such formations of interfaces act as multiple potential
barriers which provide the energy filtering behavior.
Further understanding of energy filtering mechanism, the hall
test on Sn1.03 Te-x% BiCuSeO samples were carried out, and
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DOI: 10.1039/C9NR09331A

shown in Fig. 4a). It is noted that carrier concentration grad-

ually decreased with the increase of BiCuSeO doped concentra-
tion. Once the BiCuSeO doping concentration were over 3%,
the carrier concentration could decrease to about 10% while the
mobility increase to 350% comparing to the value of undoped
sample at room temperature. This phenomenon is caused by a
band-structure mismatch between the dispersed BiCuSeO@SnO2
core-shell nanostructures and the host material 47,48 , that is be-
cause of large band gap and less number electrons for trans-
portation about SnO2 layer. In other words, the formation of the
BiCuSeO@SnO2 core-shell nanostructures results in a heteroge-
neous interface between the interface of the matrix and the shell,
the interface between the shell and the core, and the layers within
the core. The heterogeneous interfaces can act as an energy bar-

Nanoscale Accepted Manuscript

rier to substantially scatter low-energy carriers; thus, high-energy
Published on 20 December 2019. Downloaded on 1/2/2020 11:04:46 PM.

carriers can tunnel through the thin SnO2 layers, while the low-
energy carries can not tunnel through. In addition, the hall mobil-
ity was enhanced by the dispersion of BiCuSeO@SnO2 core-shell
Fig. 3 a)-b) High-magnification TEM image of the Sn1.03 Te-5% nanostructures, and it is expected that the formation of asym-
BiCuSeO sample; c) STEM image of the Sn1.03 Te-5% BiCuSeO sample;
d) EDS pattern of region II (area II refers to the area between the dotted
metric potentials from the BiCuSeO@SnO2 core-shell nanostruc-
yellow line and the solid red line). tures within the host matrix could weaken scattering of the ma-
jority carriers 48 . It is worth noting that the introduction of Bi-
CuSeO nano-alloy can significantly improve hall mobility and ob-
viously reduce carrier concentration compared with other doped
a) b) nano-alloys 18,49–51 . This is due to the fact that the doping of
BiCuSeO@SnO2 core-shell nanostructures can introduce multiple
potential barriers in the matrix to induce an enhanced energy fil-
tering effect. In a nutshell, energy filtering occurs when a poten-
tial barrier in an otherwise uniform medium prevents the diffu-
sion/drift of carriers with energy E lower than the barrier height
Vb 38 . The relationship between potential barriers and thermo-
electric properties has been studied in theory. Use of potential
Fig. 4 a) The carrier concentration and mobility of Sn1.03 Te-x%
BiCuSeO at room temperature; b) Electrical conductivities as a function barriers to increase ZT through energy filtering was advanced by
of temperature for Sn1.03 Te-x% BiCuSeO. Nishio and Hirano, who estimated the optimal barrier height and
spacing using the Boltzmann transport equation (BTE) 52 . Ka-
jikawa applied the energy filtering model in BTE to the polycrys-
talline semiconductor, and obtained the analytic expressions of S
Pristine SnTe grain boundary Dopde SnTe and σ , assuming energy barriers of uniform heights. 53,54 . Z. X.
BiCuSeO@SnO
et al. then obtained a simple generic parametric equations are
core-shell nanostructures found that are in agreement with the exact Boltzmann transport
I Core : BiCuSeO
formalism in a wide range of parameters 55 . For a bulk semi-
conductor and for Vb − EF ≥ 2kB T, simple generic parametric
II Shell : SnO equations analytical expressions for the conductivity σ and the
Seebeck coefficient S can be written as
CB SnTe SnO2 BiCuSeO SnO2 SnTe
+
h (low E)
CB CB CB CB CB σ = σC Fp (xb ) (2)
EF Eg=1eV EF
+
h (high E) Eg=0.18eV
VB Eg=3.59eV
VB
and [ ( ) ]
VB VB VB VB kB 5
No Energy Filtering
S=− ηF − p + − ∆p (xb ) (3)
e 2
Fig. 5 A schematic diagram of doped BiCuSeO@SnO2 core-shell where ( )
4e2 p+ 23 3 ηF 5
nanostructures introducing multiple potential barriers. The color σC = N0 τ 0 (kB T ) e Γ p + (4)
illustration is present band diagrams model for BiCuSeO@SnO2 3m∗ 2 2
core-shell nanostructures heterostructured interface. The work functions
with
for SnTe, SnO2 and BiCuSeO are 5.1 eV, 4.34 eV and 3.94 eV, ∞ xk
p+ 25
respectively 44–46 . Fp (xb ) = 1 − e−xb xb ∑ Γ (k + bp + 7 ) (5)
k=0 2

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a) b)
Fig. 6 a) Seebeck coefficients as a function of temperature for
Sn1.03 Te-x% BiCuSeO; b) Room temperature Seebeck coefficient
versus carrier concentration (the solid line is Pisarenko curve based on
two-valence-band model). In the calculation, Eg =0.18 eV; ∆E=0.35 eV;
mlight =0.168; mheavy =1.92.
and
p+ 5
e−xb xb 2
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∆p (xb ) = ( ) (6)
Γ p + 52 Fp (xb )
In the above equations, Γ(z) is the gamma function, EF is the
Fermi level, and ηF =EF /kB T, xb = Vb /kB T are the reduced Fermi
energy and barrier height, respectively. The parameter p charac-
terizes the type of scattering, being p = -1/2 for phonon scatter-
ing and for highly screened ionized impurity scattering, and p =
3/2 for ionized impurity scattering 56 . The parameter k can sim-
ply be thought of as the number of barriers 55 . At the same time,
it should be clear that the barrier height introduced by the core-
shell nanostructures is not all the same, but this simple generic
parametric equations still applies. Therefore, it can be seen that
the conductivity of the material decreases and the Seebeck co-
efficient increases as the height and number of potential barri-
ers increase. In the SnTe-BiCuSeO@SnO2 heterogeneous inter-
faces, a mass of low energy carriers can be filtered by multiple
potential barriers, thus the electrical conductivity significantly de-
creases. From Fig. 4b), we can clearly see that the electrical con-
ductivity significantly decreases in the whole temperature range
due to the introduction of BiCuSeO. For example, the electrical
conductivity of Sn1.03 Te-6% BiCuSeO at room temperature was
2.73×103 Scm−1 , which was 55% lower than that of the pure
phase SnTe. Present band diagrams model for BiCuSeO@SnO2
core-shell nanostructures heterostructured interface is shown in
Fig. 5. The BiCuSeO@SnO2 core-shell nanostructures can build
the multiple potential barriers filter the charge carrier transfer,
where the first interfacial SnO2 barrier at the SnTe-SnO2 interface
selectively scatters low-energy carriers rather than high-energy
carriers, and the barrier at the BiCuSeO-SnO2 interface can fur-
ther scatter partial high-energy carriers rather than higher ones.
In addition, the barrier inside BiCuSeO also can re-filter the car-
riers that have passed through the barrier at the SnO2 shell. Be-
cause the high-energy carriers are nothing but the matter of en-
ergy transfer, the Seebeck coefficient gradually increase.
As shown in Fig. 6a), the Seebeck coefficient of Sn1.03 Te-x%
BiCuSeO samples gradually increases with the increase of tem-
perature. It can also be seen from the Fig. 6a) that the Seebeck
coefficient of the sample doped with BiCuSeO is greater than that
of the pure phase SnTe. From Equation 1 and 3, we can also know
that the energy filtering effect will effectively improve the See-
beck coefficient of the material. The room-temperature Seebeck
View Article Online
DOI: 10.1039/C9NR09331A
a) b)
c)
Nanoscale Accepted Manuscript
Fig. 7 a) Total thermal conductivity, b) lattice thermal conductivity and c)
electronic thermal conductivity as functions of temperature for
Sn1.03 Te-x% BiCuSeO.
coefficient as a function of the hole concentration, the so-called
Pisarenko curve, is presented in Fig. 6b), which is calculated ac-
cording to two-valence-band model. It can be seen that the See-
beck coefficient of the doped sample is above the dark solid curve.
The Seebeck coefficient values of nanocomposites must lie on the
Pisarenko line (dark solid curve) if there is no energy filtering
effect or band engineering effect 57 . As is known to all, doping
Bi,Cu and Se elements cannot introduce band engineering effect
(valence band convergence) in SnTe matrix 16,26,58 . Therefore,
the Seebeck coefficient of the Sn1.03 Te-x% BiCuSeO samples at
room temperature occur above the dark solid curve, strengthen-
ing the notion of an enhanced energy filtering effect.
The heterostructured interfaces act as scattering centers against
phonons. They can effectively scatter middle and low frequency
phonons 59 . Therefore, the thermal conductivity of the sample de-
creases with the increase of doped concentration in the medium-
low temperature region, as shown in Fig. 7a). It can be clearly
seen from Fig. 7a) that the total thermal conductivity of Sn1.03 Te-
x% BiCuSeO significantly decreases in the medium-low tempera-
ture region. The effect of reducing thermal conductivity due to
energy filtering effect is weak at high temperature. In order to
further explore the reasons for the special dependence between
Sn1.03 Te-x% BiCuSeO thermal conductivity and temperature, we
calculated the lattice thermal conductivity κL and the electronic
thermal conductivity κe and the results are shown in Fig. 7b) and
c). The electronic thermal conductivity κe can be calculated base
on the formula κe = Lσ T, where L is the Lorenz number. κL is
obtained using the equation κL =κ −κe . Here, the Lorenz num-
ber is obtained based on the two band model and the calculated
details is given in Supporting Information 60–66 . The variation of
Lorenz number with the doping concentration is shown in Fig.
S1. We can find that κe of the sample significantly change with
the increase of the BiCuSeO doped concentration. As the tem-
perature increases, more carriers would cross the energy barrier
due to the increase of the average energy of carriers, so the effect
of energy filtering on the thermal conductivity decrease. It can
be seen from Fig. 7b) that the κL gradually decreases with the
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 Nanoscale
a) b)
0%
19
Fig. 8 a) Power factors and b) ZT as functions of temperature for
Sn1.03 Te-x% BiCuSeO.
increase of doping concentration, which is because the scatter-
ing probability of medium-low frequency phonons increases with
the increase of the number of BiCuSeO nanoparticles. However,
Published on 20 December 2019. Downloaded on 1/2/2020 11:04:46 PM.
with the increase of temperature, high-frequency phonons heat
transfer dominates, and the phonon scattering effect caused by
nanoparticles weakens 67,68 . Thus, the effect of doped BiCuSeO
on reducing the thermal conductivity is deteriorative at high tem-
perature. Finally, the lower thermal conductivity is achieved with
the value of 1.04 Wm−1 K−1 at 835 K in Sn1.03 Te-5% BiCuSeO.
Fig. 8a) shows dependence of the power factor on temperature
of Sn1.03 Te-x% BiCuSeO samples. It can be seen that the power
factor of Sn1.03 Te-x% BiCuSeO is deteriorated in the low tempera-
ture region and strengthened in the high temperature region. The
essential reason of this phenomenon lies in the intrinsic relation
between Seebeck coefficient and conductivity. An overall increase
of the PF is then possible if the Seebeck coefficient enhancement
compensates for the decrease of the conductivity. This is an in-
evitable disadvantage when the core-shell structure is introduced
to optimize the thermoelectric properties of materials 69 . In addi-
tion, due to the influence of strong energy filtering effect, the elec-
trical conductivity decreases significantly, which make it reason-
able that the power factor increases at high temperature. A high
power factor of 15.17 µ W cm−1 K−2 is achieved for the Sn1.03 Te-
5% BiCuSeO at 835 K. Finally, high ZT value ∼ 1.21 is achieved
for the Sn1.03 Te-5% BiCuSeO at 835 K, which is enhanced 190%
than pristine SnTe.
4 Conclusion
In summary, the BiCuSeO@SnO2 core-shell nanostructures lead
to a large number of heterogeneous interfaces, thus can intro-
duce multiple potential barriers to enhance energy filtering ef-
fect. The enhanced energy filtering effect can significantly im-
prove hall mobility and obviously reduce carrier concentration
comparing to the value of undoped sample at room temperature.
In other word, the strengthened energy filtering effect can more
effectively prevent low-energy carriers from participating in con-
ductivity through the material. Because the high-energy carriers
are nothing but the matter of energy transfer, the Seebeck coef-
ficient gradually increase. For example, a Seebeck coefficient of
176.05 µ VK−1 and a high power factor of 15.17 µ W cm−1 K−2 are
achieved for the Sn1.03 Te-5% BiCuSeO at 835 K. In terms of op-
timizing thermal performance, BiCuSeO@SnO2 core-shell nanos-
tructures can not only reduce the electronic thermal conductivity
by introducing enhanced energy filtering effect, but also reduce
the lattice thermal conductivity due to the core-shell nanostruc-
6| J
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Page 6 of 8
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DOI: 10.1039/C9NR09331A
tures act as scattering centers against phonons. Therefore, the
lower thermal conductivity is achieved with the value of 1.04
Wm−1 K−1 at 835 K in Sn1.03 Te-5% BiCuSeO. Finally, a high ZT
value ∼ 1.21 is achieved for the Sn1.03 Te-5% BiCuSeO at 835 K.
Acknowledgments
This research was sponsored by the National Natural Science
of China (No. U1504511, 51371076, 51571083, 11674083),
the Science and Technology fund of Henan Province (No.
182102210227). We would like to thank the help from the Aus-
tralian Nuclear Science and Technology Organization and Aus-
tralian Synchrotron during our experiments.
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