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Magnetism-induced huge enhancement of the

room-temperature thermoelectric and cooling
Cite this: DOI: 10.1039/c9ee03446c
performance of p-type BiSbTe alloys†
Cuncheng Li,a Shifang Ma,a Ping Wei, ab Wanting Zhu,a Xiaolei Nie,a
Xiahan Sang,ab Zhigang Sun,a Qingjie Zhanga and Wenyu Zhao *a

Received 24th October 2019,
Accepted 10th December 2019
DOI: 10.1039/c9ee03446c
rsc.li/ees
Bi2Te3-Based alloys are the only thermoelectric material for commercial applications while their low
performance is extremely difficult to improve. Herein, superparamagnetic Fe3O4 nanoparticles (Fe3O4-NPs)
are incorporated into a commercial p-type Bi0.5Sb1.5Te3 matrix to improve the thermoelectric and cooling
performance near room temperature. It is discovered that the Seebeck coefficient of the Fe3O4/Bi0.5Sb1.5Te3
nanocomposites remarkably increased while the thermal conductivity significantly decreased because of the
carrier multiple scattering and the enhanced phonon scattering induced by the Fe3O4-NPs, respectively.
The maximum ZT reaches 1.5 at 340 K for the nanocomposite with 0.15 wt% of Fe3O4-NPs, being 32%
higher than that of the matrix. At near room temperature, the huge cooling temperature difference reaches
5.4 K for a single-leg device made with the nanocomposite, increased by about 3 times as compared
with the 1.8 K of the device made with the Bi0.5Sb1.5Te3 matrix. This work reveals that introducing
superparamagnetic nanoparticles is a universal approach to simultaneously enhance the thermoelectric
and cooling performance of p-type BiSbTe-based alloys.

Broader context
Thermoelectric (TE) materials, which can achieve direct conversion between heat and electricity, are expected to be widely used in solid-state refrigeration.
Bi2Te3-Based alloys are the state-of-the-art and only commercialized low-temperature TE materials near room temperature. However, the low performance restricts
their wide application. In recent years, magnetic interaction has been proposed to improve the electrical and thermal properties of medium- and high-temperature TE
materials. It is of greater significance for commercial application of low-temperature TE materials if the new strategy could be used to simultaneously improve the
electrical and thermal properties of Bi2Te3-based alloys near room temperature by magnetic nanoinclusions. Herein, we attempt to enhance the TE and cooling
performances of p-type BiSbTe alloys by embedding superparamagnetic Fe3O4 nanoparticles. The excellent power factor is maintained and the thermal conductivity is
suppressed because of the carrier multiple scattering and the enhanced phonon scattering, respectively. A repeatable peak ZT of about 1.5 is obtained and the cooling
temperature difference reaches 5.4 K near room temperature. This work reveals that embedding superparamagnetic nanoparticles into commercialized low-
temperature TE materials is a universal approach to simultaneously enhance the TE and cooling performance.

Introduction figure of merit ZT = a2sT/k, where a, s, T, and k are the Seebeck

As a green and environment-friendly energy technology, thermo-
electric (TE) technology has attracted more and more attention
from industry and academia due to its ability to achieve direct
and reversible heat-to-electricity conversion.1–3 The conversion
efficiency of a TE material can be assessed by the dimensionless
a
State Key Laboratory of Advanced Technology for Materials Synthesis and
Processing, Wuhan University of Technology, Wuhan 430070, China.
E-mail: wyzhao@whut.edu.cn
b
Nanostructure Research Center, Wuhan University of Technology, Wuhan 430070,
China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c9ee03446c
coefficient, electrical conductivity, absolute temperature, and
thermal conductivity (including the carrier thermal conductivity
kE and lattice thermal conductivity kL), respectively. Ideally, an
excellent TE material should combine a good electrical property
(high a2s) and good thermal one (low k).
Bi2Te3-Based alloys are the only TE material for commercial
applications near room temperature. In the past few decades,
numerous efforts have been made to improve the TE performance of
Bi2Te3-based alloys, such as superlattices,4 nanograins,5–7 dislocation
arrays,8,9 nanoprecipitates,10–12 alloying,13 energy filtering,14–16 and
point defects.17–19 However, the ZT of commercial p-type BiSbTe
alloys is still about 1.0, which greatly limits their wide applications.
More unfortunately, it was discovered that most nonmagnetic

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Paper
nanoinclusions embedded into p-type BiSbTe alloys generally cause
a decrease in a2s though they can effectively reduce k.20–30 How to
simultaneously enhance the electrical and thermal properties of
commercial p-type BiSbTe alloys near room temperature is of critical
significance for their commercial applications.
In the last several years, more and more studies are focusing
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on the roles of external magnetic fields and magnetic nano-
inclusions in enhancing the TE performance. It was reported that
the a of Dirac semimetal Cd3As2 could be greatly boosted by
applying a transverse magnetic field and the ZT could be enhanced
by 6.5 times at 350 K,31 having been confirmed by the theoretical
result.32 Unfortunately, this strategy has little effect on traditional
semiconductor TE materials.33,34 Recently, we discovered that the
degradation of the electrical and thermal properties induced
by intrinsic excitation could be effectively suppressed by the
ferromagnetism–paramagnetism transition of BaFe12O19 nano-
inclusions in a medium-temperature filled CoSb3 matrix,35 and
that the electrical and thermal properties of the filled CoSb3 matrix
could be simultaneously enhanced due to the dual control of
phonon and electron transport by superparamagnetic Co
nanoinclusions.36 Very recently, Poudeu et al. also reported that
the magnetic interaction between Ti(Ni,Fe)Sn nanoinclusions and
the spin of itinerant carriers could cause significant enhancement
of the electrical and thermal properties of a high-temperature
(Ti,Zr,Hf)Ni(Sn,Sb) alloy.37 These results indicate that the intro-
duction of magnetic nanoinclusions may be an effective and novel
strategy to simultaneously enhance the electrical and thermal
properties of medium- and high-temperature TE materials. It is of
greater significance for commercial application of TE materials if
the new strategy could simultaneously enhance the electrical and
thermal properties of commercial p-type BiSbTe-based alloys near
room temperature by magnetic nanoinclusions.
In this work, superparamagnetic Fe3O4 nanoparticles (Fe3O4-NPs)
were incorporated into a commercial p-type Bi0.5Sb1.5Te3 matrix in
order to reveal the roles of Fe3O4-NPs in enhancing the TE and
cooling performance near room temperature. We discover that the
Seebeck coefficient of Fe3O4/Bi0.5Sb1.5Te3 nanocomposites remark-
ably increased while the thermal conductivity significantly decreased
because of the carrier multiple scattering and the enhanced phonon
scattering induced by Fe3O4-NPs, respectively. The maximum
ZT reaches 1.5 at 340 K for the nanocomposite with 0.15 wt% of
Fe3O4-NPs, being 32% higher than that of the matrix. At near room
temperature, the huge cooling temperature difference reaches 5.4 K
for a single-leg device made with the nanocomposite, increased by
about 3 times as compared with the 1.8 K of the device made with
the Bi0.5Sb1.5Te3 matrix. This work reveals that introducing super-
paramagnetic nanoparticles is a universal approach to simulta-
neously enhance the thermoelectric and cooling performance of
p-type BiSbTe-based alloys.
Experimental section
Sample preparation
A series of xFe3O4/Bi0.5Sb1.5Te3 magnetic nanocomposites
(x = 0, 0.05%, 0.10%, 0.15%, and 0.25%) have been fabricated
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with a similar method to that reported by us earlier,35 which are
referred to as MNC00, MNC05, MNC10, MNC15 and MNC25,
respectively. Commercial p-type Bi0.5Sb1.5Te3 ingots (Guangdong
Fuxin Technology Co., Ltd) were manually crushed and screened
(120 mesh) to obtain Bi0.5Sb1.5Te3 powder. The Fe3O4 magnetic
nanoparticles were synthesized by means of a chemical
co-precipitation method. An aqueous solution of FeCl36H2O
and FeSO47H2O was added dropwise to ammonia under
continuous stirring at 363 K in an inert atmosphere. The reaction
mixture was subsequently aged for 1 hour based on the Ostwald
ripening mechanism. After that, the as-prepared Fe3O4-NPs were
mixed with the Bi0.5Sb1.5Te3 powder by mechanical agitation and
ultrasonic dispersion to form xFe3O4/Bi0.5Sb1.5Te3 nanocomposite
powder. In order to reduce the agglomeration of the Fe3O4-NPs,
the as-prepared nanocomposite powder was hydrothermally
treated for 10 hours at 383 K by using deionized water and
ethanol as a solvent. After vacuum drying, the nanocomposite
powder was compacted by spark plasma sintering (SPS) (SPS-1050:
Dr Sinter) under a uniaxial stress of 50 MPa at 673 K in a vacuum
for 5 minutes.
Structural characterization
The phase constituents of the as-prepared Fe3O4-NPs and
xFe3O4/Bi0.5Sb1.5Te3 nanocomposites have been examined by
powder X-ray diffraction (XRD) (New D8 Advance) using a Cu Ka
radiation (l = 0.15418 nm) source. The chemical compositions
were qualitatively analyzed by using electron probe microanalysis
(EPMA) (JXA-8230) in conjunction with an Oxford energy-
dispersive spectroscopy (EDS) instrument. The microstructures
were observed by field emission scanning electron microscopy
(FESEM) (JEM-7500F). The high-resolution transmission electron
microscopy (HRTEM) images and high-angle annular dark-field
(HAADF) images were obtained using an FEI Talos F200S TEM,
which were used to further analyze the nanostructures in the
xFe3O4/Bi0.5Sb1.5Te3 nanocomposites. The ultraviolet photo-
electron spectroscopy (UPS) spectra were measured on a Thermo
Fisher ESCALAB 250Xi with a He Ia radiation source (hn = 21.22 eV)
to determine the work function of the Bi0.5Sb1.5Te3 matrix.
Transport property measurement
Due to the intrinsic anisotropic nature of Bi2Te3, the transport
properties of all samples were measured along the in-plane
direction, as shown in Fig. S1 (ESI†). The Seebeck coefficient (a)
and electrical conductivity (s) were measured simultaneously
using a standard four-probe method (ZEM-3, ULVAC-RIKO) in a
helium atmosphere from 300 K to 500 K. The thermal con-
ductivity (k) was calculated by the equation k = lrCp, where
the density (r) was determined by the Archimedes method, the
specific heat capacity (Cp) was measured with a TA Q20 differential
scanning calorimeter, and the thermal diffusivity (l) was measured
with a laser flash method (LFA-457, Netzsch) in an argon atmo-
sphere. Cp is about 0.18 J g1 K1 at 300 K (Fig. S2, ESI†). The
uncertainties are 5–7% for s and k, and about 5% for a. The
Hall coefficient was obtained via linearly fitting the Hall voltage
versus magnetic field curves under different magnetic fields
(above the saturation magnetic field).36 The traditional Van der
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Pauw Hall method is not applicable for the magnetic samples

due to the anomalous Hall effect.

Magnetic property measurement

The magnetization versus magnetic field (M–H) curves at
different temperatures and the zero-field cooling (ZFC) and field
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cooling (FC) curves were measured with a physical property

measurement system (PPMS-9, Quantum Design INC., USA).
The ZFC and FC curves of the Fe3O4-NPs were measured in the
range of 50–400 K. The samples were first heated from room
temperature to 400 K to demagnetize and subsequently cooled
down to 50 K without a magnetic field. After that, the samples
were heated from 50 K to 400 K in order to measure the ZFC curve
under an external magnetic field of 100 Oe. Lastly, under an
external magnetic field of 100 Oe the same samples were first
cooled from 400 K to 50 K and then heated from 50 K to 400 K in
order to measure the FC curve.

Results and discussion

Phase constituents and microstructures
The XRD patterns of the as-prepared Fe3O4-NPs and xFe3O4/
Bi0.5Sb1.5Te3 nanocomposites are shown in Fig. 1. All the
diffraction peaks of the Fe3O4-NPs are in good accordance with
the standard pattern of JCPDS 26-1136, revealing that these
nanoparticles are single-phase Fe3O4. The characteristic diffraction
peaks of all the nanocomposites can be well indexed to the
rhombohedral phase of Bi0.5Sb1.5Te3 (JCPDS 49-1713). As compared
to the XRD pattern of the matrix, no other impurity is observed
in the xFe3O4/Bi0.5Sb1.5Te3 nanocomposites, suggesting that the Fig. 1 Phase constituents from XRD. (a) XRD patterns of the as-prepared
Fe3O4-NPs and xFe3O4/Bi0.5Sb1.5Te3 nanocomposites. (b) Lattice para-
Bi0.5Sb1.5Te3 matrix can maintain good chemical stability in the
meters of samples with different addition content.
presence of the Fe3O4-NPs during the SPS process. The lattice
parameters a and c (Fig. 1b) nearly keep constant with different
addition content, indicating that the dispersion of Fe3O4-NPs
has no effect on the crystal structure of the matrix. No char-
acteristic diffraction peaks of Fe3O4 were detected in all nano-
composites due to the too low content because the highest
content is only 0.25%, which is far less than the detection limit
of XRD technology (about 1%).
Fig. 2a depicts the back-scattered electron image of the
polished surface of MNC15. It can be seen that a lot of black
contrast distributes along the grain boundaries. The EDS of the
area (Fig. 2b) delineated by the pink rectangle in Fig. 2a and
mapping of Fe element (Fig. S3, ESI†) reveal that this black
contrast is the distribution area of Fe3O4-NPs. Fig. 2c and d are
the fracture surfaces of MNC00 and MNC15, respectively. It can
be seen that the Bi0.5Sb1.5Te3 matrix exhibits clean and fine
fracture surfaces. However, large amounts of nanoparticles of
30–110 nm in diameter are randomly distributed on the inter-
faces and grain boundaries. The distribution law of Fe3O4-NPs
along the grain boundaries is related to the preparation
process. Unlike mechanical alloying, in which the secondary
Fig. 2 Microstructures from EPMA and FESEM. (a) Back-scattered elec-
phase nanoparticles act as the nucleation sites for the mechano- tron image of the polished surface for MNC15. (b) EDS result of the square
chemical formation of the matrix and are pinned into Bi0.5Sb1.5Te3 area in (b). FESEM images of the fracture surfaces of (c) MNC00 and
grains,16 the ultrasonic mixing only makes Fe3O4-NPs adhere to the (d) MNC15.

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surfaces of the Bi0.5Sb1.5Te3 powder but the process cannot make
Fe3O4-NPs into monodisperse particles (Fig. S4, ESI†). During the
sintering process, Fe3O4-NPs would exist at the grain boundaries,
which could provide additional interfacial scattering of heat-
carrying phonons.
Fig. 3a displays a typical low-magnification TEM image of
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overlapping of characteristic spectra lines. These results show
that the nanoparticles are composed of Fe and O, while the
matrix is composed of Bi, Sb and Te, forcefully confirming the
successful preparation of xFe3O4/Bi0.5Sb1.5Te3 nanocomposites.
Magnetic properties of xFe3O4/Bi0.5Sb1.5Te3

MNC15. It can be seen that large particles with size over 50 nm
are adhered on the grain boundaries of the Bi0.5Sb1.5Te3 matrix,
which is consistent with the results from FESEM. Fig. 3b is the
enlarged high-magnification HRTEM image of Area 1 in Fig. 3a,
which shows good crystallization. The corresponding selected
area electron diffraction (SAED) pattern (Fig. 3c) can be indexed
to the [21% 1% 0] zone axis of Bi0.5Sb1.5Te3 with rhombohedral
structure. This is completely consistent with the simulated
pattern (Fig. 3d). The HRTEM image of Area 2 is shown in
Fig. 3e. It can be seen that the large particles in fact are softly
agglomerated by a lot of small nanoparticles with diameters in
the range of 9–18 nm. To determine structural information on
these nanoparticles, a fast Fourier transformed (FFT) pattern is
obtained, as shown in the inset of Fig. 3e. The points presented
in the FFT pattern are aligned into several circles, which are in
good agreement with the diffraction pattern of Fe3O4 with cubic
symmetry. Therefore, these nanoparticles are magnetic Fe3O4.
The corresponding HAADF image of the whole area (Fig. 3a) is
shown in Fig. 3f. Elemental mapping images of Fe (Ka line), O
(Ka line), Bi (Ma line), Sb (La line), and Te (La line) from energy
dispersion X-ray spectroscopy (EDX) are presented in Fig. 3f–k.
The mapping image of Fig. 3h actually consists of the signals
from O (Ka line) and Sb (M lines), which is due to the
The M–H and FC–ZFC curves of xFe3O4/Bi0.5Sb1.5Te3 are
presented in Fig. 4. The M–H curve (Fig. 4a) reveals that the
Bi0.5Sb1.5Te3 matrix is diamagnetic at 300 K, which is consistent
with the results reported by other groups.38–40 However, MNC15
exhibits apparently superparamagnetic behavior at 300 K
(Fig. 4b). The ZFC and FC curves under an applied magnetic
field of 100 Oe (Fig. 4c) show that the blocking temperature (TB)
of the magnetic transition of the Fe3O4-NPs from ferromagnetism
to superparamagnetism is about 210 K. The M–H curves (Fig. 4d)
show that the Fe3O4-NPs exhibit strong ferromagnetism and a
coercivity of 105 Oe at 50 K, however, they are in a superpara-
magnetic state at 300 K and exhibit a saturation magnetization
value of 62.16 emu g1 with negligible coercivity and remnant
magnetization. To further confirm that the Fe3O4-NPs are indeed
in a superparamagnetic state at 300 K, the M–H curve measured at
300 K was fitted by the Langevin function41,42
M = M0[coth(mmH/kBT)  1/(mmH/kBT)] (1)
where mm, H, kB, and T are the moment of the magnetic
nanoparticles, the external applied magnetic field, the Boltzmann
constant, and absolute temperature, respectively. M0 = Nmm
(where N is the total number of particles). mm is given by MshVi,
where Ms is the saturation magnetization, and hVi is the average

Fig. 3 Microstructures from HRTEM. (a) Typical low-magnification TEM image of MNC15; (b) enlarged HRTEM image of Area 1 in (a); (c) corresponding
SAED pattern of (b); (d) simulated SAED pattern along the [21% 1% 0] zone axis of Bi0.5Sb1.5Te3; (e) enlarged HRTEM image of Area 2 in (a), the inset is the
corresponding FFT pattern; (f–k) STEM-HAADF image and corresponding STEM-EDX elemental mapping images of Fe (Ka line), O (Ka line), Bi (Ma line), Sb
(La line), and Te (La line) of (a). The mapping image of (h) in fact consists of signals from O (Ka line) and Sb (M lines).

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Fig. 4 Proof of the superparamagnetic state of the Fe3O4-NPs. M–H curves of (a) the Bi0.5Sb1.5Te3 matrix and (b) MNC15 at room temperature. (c) ZFC
and FC curves of Fe3O4-NPs with diameters of 9–18 nm. (d) M–H curves of Fe3O4-NPs at 50 K (black) and 300 K (red). (e) Experimental and Langevin
function fitted M–H curves of Fe3O4-NPs at 300 K. The fitting results are given at the lower right corner. (f) TEM image of the as-prepared Fe3O4-NPs.
The insets in (a, b and d) show the M–H curves near zero field (H = 0).
volume of the particles. Based on the fitted results from
the Langevin function shown in Fig. 4e, M0 = 62.26 emu g1,
mm = 2.34  1019 A m2, hVi = 4.94  1019 cm3, and average
particle size D = 9.80 nm were obtained. The fitted M0 is very
close to the experimental value of 62.16 emu g1. As is shown in
Fig. 4f, the diameter of the as-prepared Fe3O4-NPs is in the
range of 9–18 nm, revealing that the fitted D of 9.80 nm is also
in this range. To verify the experimental data and determine the
magnetic state of the Fe3O4-NPs in the whole range of 300–500 K,
we theoretically calculated the critical diameter (Dc) dependence
of TB and the Curie temperature (TC) (Fig. S5, ESI†). For Fe3O4-
NPs of 9–18 nm in diameter, the theoretical TB and TC should be
about 250 K and 750 K, respectively. Evidently, the theoretical TB
is very close to the experiment data and TC is much higher than
the operation temperature of 500 K. These results clearly indicate
that the Fe3O4-NPs incorporated into the Bi0.5Sb1.5Te3 matrix are
in a superparamagnetic state in the range of 300–500 K.
Thermoelectric properties of xFe3O4/Bi0.5Sb1.5Te3
The temperature dependence of the electrical conductivity and
Seebeck coefficient of the xFe3O4/Bi0.5Sb1.5Te3 nanocomposites
is shown in Fig. 5a and b, respectively. It is very apparent that s
of all samples decreases with increasing temperature, exhibiting a
typical metal-like nature or degenerate semiconductor behavior.
We plotted the fitted curve of s with a function of T1.5 to reveal
the scattering mechanism of carriers (Fig. 5a). The fitted s curve
indicates that acoustic phonon scattering is predominant below
380 K. However, the fitted s values deviate from the experimental
data above 380 K because of the influence of minority carriers
induced by intrinsic excitation. Regardless of the temperature, s
decreases monotonically with increasing Fe3O4 content. s is about
10.11  104 S m1 for the Bi0.5Sb1.5Te3 matrix and decreases to
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7.52  104 S m1 for the sample with x = 0.25% at 300 K. The a
values of all samples are positive (Fig. 5b), indicating that the
major carriers are holes and the conduction type is unaffected by
the presence of Fe3O4-NPs. The magnitude of a is gradually
increased with temperature and then decreased as the tem-
perature further increases. The decrease in a is mainly due to
the intrinsic excitation as described above. However, the left
shift of the maximum a indicates that the intrinsic excitation
appears at a relatively low temperature with gradually increasing
addition content. Additionally, the a values of all nanocomposites
are much higher than that of the matrix over the entire temperature
range. With the measured a and s values above, the a2s values of all
the samples are calculated and the results are shown in Fig. 5c.
Interestingly, the a2s values of all samples are very close in the whole
temperature range, which should be attributed to the remarkable
increase in a compensating for the deterioration of s. Therefore,
maintaining high a2s without deterioration plays an important role
in improving the TE performance of the nanocomposites.
In order to figure out the reasons for the changes in
electrical transport properties described above, Hall effect
measurements were performed. The test current i is kept at
150 mA and the applied magnetic field H is varied from 0.06 to
1.25 Tesla. The Hall voltages DVxy of all samples were measured
in the range from room temperature to 500 K. The Hall voltages
DVxy in the range of 0.25–1.25 Tesla are used to linearly fit the
slope kH. For example, Fig. 5d shows Hall voltage versus magnetic
field curves at room temperature. The Hall coefficient (RH) can be
obtained by the formula RH = kHd/(im0), where d is the sample
thickness and m0 is the permeability of a vacuum. The fitting
curves for all the samples containing Fe3O4-NPs do not pass
through the origin due to the influence of the anomalous Hall
effect, as shown in Fig. 5d. The carrier concentration (n) and
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Fig. 5 Electrical properties of xFe3O4/Bi0.5Sb1.5Te3. Temperature dependence of the (a) electrical conductivity, (b) Seebeck coefficient, (c) power factor,
and (e) carrier concentration. (d) Hall voltage versus magnetic field curves at room temperature. The inset is the enlarged curves near the low magnetic
field region. (f) Seebeck coefficient versus carrier concentration curve of the Bi0.5Sb1.5Te3 matrix at 300 K obtained by the Pisarenko relation using
m* = 1.12 m0. The inset in (e) is the carrier mobility.

mobility (m) at different temperatures were calculated on the basis energy–momentum dispersion relation, formula (2) can be
of RH = 1/ne and m = sRH, where e is the electron charge. The expressed as:29
increase in n with temperature (Fig. 5e) is mainly due to the 2 3
1
thermal excitation of majority carriers. Compared with the matrix, 2 2
p kB T 61 @nðE Þ r 
a¼ 4 þ 27
5 (3)
n of the nanocomposites gradually decreases with increasing x. 3e n @E E
This phenomenon is caused by the carrier change between the E¼Ef
Fe3O4-NPs and the matrix.43,44 Fe3O4 is an n-type semiconductor
where r is a scattering parameter. According to formula (3), the
with a relatively small bandgap of 0.10 eV.45 When Fe3O4-NPs are
enhancement of a may originate from the decrease of n and/or
embedded into the p-type Bi0.5Sb1.5Te3 matrix, p–n heterojunc-
the increase of r. Obviously, the decrease in n of the xFe3O4/
tions must be formed at the interfaces. Although the volume of
Bi0.5Sb1.5Te3 nanocomposites must have a contribution to the
the Fe3O4-NPs is relatively small, the interface areas are large
improvement of a. Further efforts have been made to verify
because of their nanometer size. These p–n heterojunctions will
whether the Fe3O4-NPs affect r. Based on the assumption of the
consume part of the majority carriers and result in the decrease
single parabolic band (SPB) model, a and n can be written as
in n. The decrease in m with increasing temperature (see the inset
the following equations:46
of Fig. 5e) is caused by the enhanced phonon scattering at  
elevated temperatures. However, the introduction of Fe3O4-NPs kB ð5=2 þ rÞFrþ3=2 ðZÞ
a¼ Z (4)
did not lead to a remarkable deterioration of m because of two e ð3=2 þ rÞFrþ1=2 ðZÞ
aspects of enhanced carrier scattering and decreased carrier
concentration (Fig. S6, ESI†). Therefore, the gradual reduction 4pð2m kB T Þ3=2
n¼ F1=2 ðZÞ (5)
in s with increasing x is mainly caused by the decrease in h3
n according to the formula s = nem. with a Fermi integral order of i
We further analyzed the important contribution of the ð1
Fe3O4-NPs to the enhancement of a for the xFe3O4/Bi0.5Sb1.5Te3 wi
Fi ðZÞ ¼ dw (6)
nanocomposites. In general, a of a degenerate semiconductor 0 1 þ expðw  ZÞ

can be expressed by the Mott equation:25 where m*, h, Fi (Z) and Z correspond to the effective mass,
  Planck constant, Fermi–Dirac integral and reduced Fermi level
p2 kB2 T 1 @nðE Þ 1 @mðE Þ
a¼ þ (2) Ef/(kBT). The effective mass m* = 1.12 m0 (where m0 is the free
3e n @E m @E E¼Ef
electron mass) of the Bi0.5Sb1.5Te3 matrix at 300 K was calculated
where kB, e, and Ef are the Boltzmann constant, carrier charge with the carrier concentration at 250 K and the Seebeck coefficient
and Fermi energy, respectively. If the bands have a parabolic according to the assumption that acoustic phonon scattering is

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Table 1 Charge transport properties and scattering parameters of xFe3O4/Bi0.5Sb1.5Te3 at 300 K

Samples x (%) RH (102 cm3 C1) m (cm2 V1 s1) n (1019 cm3) s (104 S m1) a (mV K1) r
MNC00 0 0.26 266.18 2.37 10.11 200.63 0.50
MNC05 0.05 0.31 260.02 2.02 8.41 223.06 0.38
MNC10 0.10 0.32 266.49 1.93 8.25 227.32 0.37
MNC15 0.15 0.33 258.32 1.88 7.78 232.76 0.33
MNC25 0.25 0.35 266.37 1.76 7.53 238.78 0.32
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the dominant carrier scattering mechanism (r = 1/2).47 Here, to

eliminate the effects of minority carriers on the calculation
results, the carrier concentration at 250 K (Fig. S7, ESI†) is
adopted. In xFe3O4/Bi0.5Sb1.5Te3, since the Fe3O4-NPs as a
secondary phase hardly change the band structure of the
Bi0.5Sb1.5Te3 matrix, the additional scattering mechanism
induced by the Fe3O4-NPs only changes r but does not
affect m*. Hence, we assumed that m* of different samples did
not change and the r values of all samples were calculated with
formula (4)–(6). As shown in Table 1, r increased from 0.50 to
0.32, indicating that the scattering of carriers was enhanced
due to the incorporation of the Fe3O4-NPs. Moreover, as shown
in Fig. 5f, the Pisarenko plot was drawn using the SPB model
with m* = 1.12 m0 for the Bi0.5Sb1.5Te3 matrix at 300 K. It is very
evident that the a of the xFe3O4/Bi0.5Sb1.5Te3 nanocomposites at
300 K all fall just above the solid orange line, revealing that the
increase in r also contributes to the enhancement of a.
For the xFe3O4/Bi0.5Sb1.5Te3 nanocomposites, the enhancement
in r may come from two aspects: one is the energy filtering effect48
and the other is the carrier multiple scattering effect.36 When
n-type Fe3O4-NPs contact with the p-type Bi0.5Sb1.5Te3 matrix, their
band alignment will create band bending at the interfaces because
the electronic structures of the two phases are different from
each other. The carriers will suffer energy-dependent scattering
as a result of the interface potential. The work function of Fig. 6 Change of the electronic structure near the interface between
the Bi0.5Sb1.5Te3 matrix (jm) is about 5.65 eV, which was Fe3O4 and Bi0.5Sb1.5Te3. (a) UPS spectrum of the Bi0.5Sb1.5Te3 matrix. The
insets show the close-up of the ringed regions of the spectrum, high-
determined by UPS measurements (Fig. 6a) according to the
lighting the cut-off Ecut-off (I) and Fermi edge EFermi (II) of the UPS
formula jm = hn + Ecut-off  EFermi. Combining the measured jm spectrum. (b) The diagram of the electronic structure near the interface
of Bi0.5Sb1.5Te3 and the reference data of Fe3O4 (js = 5.78 eV),49 between the Fe3O4-NPs and the Bi0.5Sb1.5Te3 matrix.
the cross-sectional schematics of the energy bands near the
interfaces are given in Fig. 6b. As can be seen, the charge
carriers only need to overcome a Schottky potential barrier with Fig. 7 presents the temperature dependence of the thermal
a mean height of B0.13 eV. This energy barrier is far less than transport properties and ZT values of the xFe3O4/Bi0.5Sb1.5Te3
the data (0.7 eV,50 0.2 eV,51 and 0.3 eV52) from other literature, nanocomposites in the range of 300–500 K. k of all samples has
meaning that the energy filtering effect in the xFe3O4/Bi0.5Sb1.5Te3 a similar tendency with temperature, which decreases in the
nanocomposites must be very weak. Different from a conventional range of 300–350 K and then increases above 350 K owing to the
nonmagnetic secondary phase, the Fe3O4-NPs would lead to onset of the bipolar thermal diffusion effect. It is noteworthy
additional unique thermo-electro-magnetic effects. As mentioned that all the nanocomposites have much lower k values than the
above, the Fe3O4-NPs are in a superparamagnetic state in the matrix over the entire temperature range investigated. kE can be
whole working temperature range of 300–500 K, thus their calculated by the Wiedemann–Franz law kE = LsT, where L is
magnetic moments will be no longer fixed and be turned ran- the Lorenz number. To obtain an accurate kE, the L values of all
domly due to thermal fluctuation. As a result, the carriers would the samples were estimated with the SPB model in the range of
undergo temperature-dependent multiple scattering. The carrier 300–500 K.53
multiple scattering induced by the superparamagnetic Fe3O4-NPs
can effectively enhance r. Therefore, the increase in a of the  2 (   )
kB ð7=2 þ rÞFrþ5=2 ðZÞ ð5=2 þ rÞFrþ3=2 ðZÞ 2
xFe3O4/Bi0.5Sb1.5Te3 nanocomposites can be attributed to both L¼  (7)
e ð3=2 þ rÞFrþ1=2 ðZÞ ð3=2 þ rÞFrþ1=2 ðZÞ
the decrease in n and the increase in r.

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Paper
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Fig. 7 Thermal properties and ZT of xFe3O4/Bi0.5Sb1.5Te3. Temperature
dependence of (a) the total thermal conductivity, (b) the Lorentz number,
(c) the lattice thermal conductivity, and (d) ZT. The inset in (c) shows the
carrier thermal conductivity.
The calculated L, kL and kE are shown in Fig. 7b and c, and the
inset of Fig. 7c, respectively. One can see that the L values of the
xFe3O4/Bi0.5Sb1.5Te3 nanocomposites gradually decrease with
increasing x. The reduction in kE mainly originated from the
simultaneous decreases in L and s. Besides MNC25, kL of the
other nanocomposites decreases with the increase of x.
The slight increase in kL of MNC25 may be due to the relatively
high k of Fe3O4 (B5.1 W m1 K1@300 K).54 These evolutions
of kL benefit from enhanced low and middle frequency phonon
scattering as a result of both magnetic moment fluctuation and
Fig. 8 Cooling performance of xFe3O4/Bi0.5Sb1.5Te3. Time dependence of Tc and Th for MNC00D and MNC15D under different working currents I. DT is
the working temperature difference between Th and Tc while DTc represents the cooling temperature difference between Tc and Tr. Subscripts 00 and 15
represent the corresponding MNC00D and MNC15D, respectively.
Energy Environ. Sci.
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Energy & Environmental Science
heterogeneous interfaces. Because of the integrated effects of
well-maintained a2s and decreased k, the ZT values of the
xFe3O4/Bi0.5Sb1.5Te3 nanocomposites are significantly higher
than that of the Bi0.5Sb1.5Te3 matrix in the whole range of
300–500 K, as shown in Fig. 7d. The maximum ZT is about
1.5 at 340 K, increased by 32% as compared with that of the
matrix, and this value is repeated in the repeatability test
(Fig. S8, ESI†). Therefore, optimizing the content of Fe3O4-NPs
can significantly enhance the ZT values of the xFe3O4/Bi0.5Sb1.5Te3
nanocomposites. Additionally, to investigate the anisotropic
thermoelectric properties of the Fe3O4/Bi0.5Sb1.5Te3 nano-
composites, the transport properties of MNC15 along the
out-of-plane direction were measured and the results are shown
in Fig. S9 (ESI†). The maximum ZT value at 350 K is only about
1.2 along the out-of-plane direction.
Cooling performance of xFe3O4/Bi0.5Sb1.5Te3
In order to evaluate the beneficial role of the enhanced TE
performance induced by the superparamagnetic Fe3O4-NPs in
enhancing the cooling performance, two single-leg devices of
2.5  2.5  9.5 mm3 in size were fabricated with MNC00 and
MNC15, which are referred to as MNC00D and MNC15D,
respectively. Fig. 8 shows the time dependence of the cooling-
side temperature (Tc) and the heating-side one (Th) for MNC00D
and MNC15D under different working currents (I). It can be seen
that Th and Tc change rapidly in the first 50 s and then gradually
approach equilibrium in the next 50 s under I = 0.2 A. The stable
Th and Tc are about 290.3 K and 287.3 K for MNC00D, and 291.4 K
and 286.6 K for MNC15D, respectively. Tc of MNC00D was
decreased by about 1.2 K as compared with room temperature
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Energy & Environmental Science
(Tr) of 288.5 K, thus the cooling temperature difference DTc00
(where DTc = Tr  Tc) is only about 1.2 K. However, DTc15 of
MNC15D is up to about 1.9 K, increased by 58% as compared to
that of MNC00D. The working temperature difference DT15 (where
DT = Th  Tc) of MNC15D is about 4.8 K, which is increased by
60% as compared to the DT00 of 3.0 K for MNC00D. When I is
Published on 10 December 2019. Downloaded by Auckland University of Technology on 1/3/2020 4:49:28 AM.
about 0.6 A, the changes of Th and Tc are similar to those in
Fig. 8a. The stable Th and Tc are about 296.6 K and 286.7 K for
MNC00D, and 298.6 K and 283.9 K for MNC15D, respectively.
DTc00 and DTc15 are 1.8 K and 4.6 K, respectively. DT00 and DT15
are 9.9 K and 14.7 K. When I is more than 0.6 A, Tc first rapidly
decreases and then gradually increases until equilibrium. The
Peltier effect can achieve refrigeration in a short time, while
Fourier heat and Joule heat need time to transfer; the time
difference between them causes the lag effect. The larger the
current, the longer the time to reach a stable temperature at both
sides. When I exceeds a certain threshold (0.6 A for MNC00D and
1.0 A for MNC15D, respectively), Tc gradually increases, which is
further verified by infrared imaging detection (Fig. S10, ESI†). This
trend mainly depends on the relationship between the Peltier
effect, Fourier heat, and Joule heat. When the energy change
produced by the Peltier effect is no longer greater than the sum of
Fourier heat and Joule heat, Tc would approach or/and exceed Tr.
Therefore, an appropriate working current is very important for
the device to establish the maximum cooling temperature differ-
ence. Under the threshold I, the maximum DTc is about 1.8 K for
MNC00D and 5.4 K for MNC15D. The DT values of MNC00D and
MNC15D increase monotonically with increasing I. The greater
the DT values, the better the cooling performance on the condi-
tion that Tc is not higher than Tr. Based on this consideration, the
maximum DT is 27.2 K under 1.4 A for MNC00D and 47.3 K under
1.8 A for MNC15D. It can be seen that MNC15D is superior to
MNC00D in terms of both cooling DTc and working DT. The high
stability and good cyclability of MNC15D (Fig. S11 and Table S1,
ESI†) are exhibited by the repeatability test.
Conclusions
In summary, a series of p-type xFe3O4/Bi0.5Sb1.5Te3 nanocom-
posites (x = 0, 0.05%, 0.10%, 0.15% and 0.25%) have been
prepared by a combination method of ultrasonic dispersion
and the SPS process, and their TE properties were system-
atically investigated. The Fe3O4-NPs incorporated into these
nanocomposites have been proved to be in a superparamagnetic
state and can produce the carrier multiple scattering effect due
to the interaction between the magnetic moment and spin of
electrons. The increase in the scattering parameter induced by
the carrier multiple scattering further resulted in the remarkable
increase in the Seebeck coefficient, thus keeping a high power
factor under the condition of the decrease of electrical conductivity.
The significant decrease in thermal conductivity is ascribed to
the enhanced phonon scattering caused by magnetic moment
fluctuation and newly formed heterointerfaces. As a result, the
ZT values of the xFe3O4/Bi0.5Sb1.5Te3 nanocomposites are
significantly higher than that of the Bi0.5Sb1.5Te3 matrix in
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the whole range of 300–500 K. The nanocomposite with
0.15 wt% Fe3O4-NPs possessed the highest ZT of 1.5 at 340 K,
which is 32% higher than that of the Bi0.5Sb1.5Te3 matrix. The
huge cooling temperature difference near room temperature
reaches 5.4 K for a single-leg device made with the nano-
composite, increased by about 3 times as compared with the
1.8 K of the device made with the Bi0.5Sb1.5Te3 matrix. This
work proves that introducing superparamagnetic nanoparticles
is an effective approach to simultaneously enhance the thermo-
electric and cooling performance of p-type BiSbTe-based alloys.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 11834012, 51620105014, 51572210,
51521001) and National Key R&D Program of China (No.
2018YFB0703603). XRD, FESEM, EPMA and HRTEM experi-
ments were performed at the Center for Materials Research
and Testing of Wuhan University of Technology (WUT). The
Hall measurements were conducted at the State Key Laboratory
of Advanced Technology for Materials Synthesis and Processing
at WUT. The authors thank Y. Liu from Wuhan University for
help with the magnetic properties and UPS measurements. The
authors also want to thank M. J. Yang and C. H. Shen for their
help in the structure characterization.
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