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A novel chemical process of Bi2Te2.7Se0.3

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DOI: 10.1016/j.scriptamat.2016.03.010

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Contents lists available at ScienceDirect

Scripta Materialia

journal homepage: www.elsevier.com/locate/scriptamat

Regular Article

A novel chemical process of Bi2Te2.7Se0.3 nanocompound for effective

adjustment in transport properties resulting in remarkable n-type
thermoelectric performance
Cham Kim a,, Chang Eun Kim a, Ju Young Baek a, Dong Hwan Kim a, Jong Tae Kim a, Ji Hyeon Ahn a,
David Humberto Lopez b, Hoyoung Kim a
a
Daegu Gyeongbuk Institute of Science and Technology (DGIST), 50-1 Sang-ri, Hyeonpung-myeon, Dalseong-gun, Daegu 711-873, Republic of Korea
b
Department of Chemical and Environmental Engineering, University of Arizona, 1133 E. James. E. Rogers Way, Tucson, AZ 85721, USA

a r t i c l e i n f o a b s t r a c t

Article history: Chemical reaction processes for thermoelectric nanomaterials have received a lot of attention because of subse-
Received 27 January 2016 quent small and uniform nanostructures, causing a remarkable reduction in thermal conductivity; however, they
Received in revised form 9 March 2016 typically showed low electrical properties possibly due to contaminations by chemicals resulting in low ZT. We
Accepted 9 March 2016
devised a new chemical process for synthesizing an n-type Bi2Te2.7Se0.3 nanocompound without the chemicals
Available online xxxx
causing potential contaminations. The product exhibited a predominant electrical conductivity while retaining
Keywords:
the advantage of chemical reaction routes; thus, synergistic effect of the thermoelectric transport properties
Thermoelectric materials was greatly induced, resulting in the highest ZT among n-type Bi2Te3 materials in bulk phase.
Nanostructure 2016 Elsevier Ltd All rights reserved.
Bismuth telluride
Thermal conductivity
Electrical conductivity

For commercial thermoelectric applications at low temperatures
(below 200 C), n-type and p-type Bi2Te3 in bulk phase have been primar-
ily used. Since the n-type Bi2Te3 has generally exhibited lower thermo-
electric performance than the p-type Bi2Te3, it is required for the former
to enhance the performance. The comprehensive performance of thermo-
electric materials is evaluated via the dimensionless gure of merit ZT
(=2T/), where is the Seebeck coefcient, is the electrical conduc-
tivity, T is the absolute temperature, and is the thermal conductivity
[16]; thus, the enhancement of the n-type Bi2Te3 has been accomplished
by increasing the electrical conductivity and by reducing the thermal con-
ductivity, indicative of phonon glass electron crystal (PGEC) characteris-
tics [715]. For the reduction in thermal conductivity, various
nanostructures inducing vigorous phonon scattering have been proposed
[9,10]. Recently, chemical syntheses have been often adopted to prepare
n-type Bi2Te3 nanostructures because they showed remarkably low ther-
mal conductivities [1618]; however, they also had low electrical proper-
ties eventually degrading ZT values. In these studies, researchers have
only concentrated on achieving low thermal conductivities by synthesiz-
ing unique nanostructures, but they have not considered why the chem-
ically synthesized nanostructures exhibited low electrical properties and
how the properties can be improved.
We have endeavored to nd the way that we can synthesize an n-type
Bi2Te3 nanomaterial with high electrical properties as we retain its
Corresponding author.
thermal conductivity as low as possible; thus, the nanomaterial would
have the PGEC nature. The nanostructures in the previous studies had
low electrical conductivities due to low physical densities, resulting in
low power factors. We assumed that the nanostructures might be con-
taminated by chemicals used in the syntheses resulting in the low physi-
cal densities, followed by low carrier mobility. Therefore, we have devised
a water-based chemical process where we can synthesize the nanostruc-
tures without the chemicals causing potential contaminations. We
employed elemental raw materials (e.g., bismuth, tellurium) instead of
chemical precursors (e.g., bismuth(III) chloride, bismuth(III)
neodecanoate, tri-n-octylphosphine telluride, etc.). In addition, we did
not use any organic solvents (e.g., alkanediol, alkylamine, tri-n-
octylphosphine, etc.) to disperse the precursors or chemical stabilizers
(e.g., dodecanethiol, ethylenediaminetetraacetic acid, thioglycolic acid,
etc.) to form desired morphology as was done in previous studies
[1618]. Our process can be summarized as follows: (1) oxidizing disso-
lution of reactant elements, (2) co-precipitation of the oxidized sources,
and (3) liquid-phase reduction of the precipitate. The detailed synthesis
procedures were presented in Supplementary material 1.
Bismuth shots (Bi, Kojundo Chemical, 99.99%, 25 mm) dissolve in di-
luted nitric acid (2.5 M HNO3(aq)) to subsequently form a transparent so-
lution, which showed signs of bismuth oxidation to generate bismuth
ions (Bi3+) and nitrate (NO 3 ). Tellurium powders (Te, Kojundo Chemical,
99.99%, 45 m) do not dissolve in HNO3 but they turn to white precipi-
tates, indicative of tellurium oxidation to form tellurous acid (H2TeO3),

http://dx.doi.org/10.1016/j.scriptamat.2016.03.010
1359-6462/ 2016 Elsevier Ltd All rights reserved.
14 C. Kim et al. / Scripta Materialia 119 (2016) 1316

which is one of the most stable Te oxoacids. When exposing the reactant
elements to HNO3 simultaneously, we observed an entirely different phe-
nomenon; the Te powders gradually dissolved with the Bi shots, resulting
in a transparent solution. We assumed that the Te was oxidized by NO 3
from the Bi oxidation instead of HNO3, and thus tellurite (TeO2
3 ) might
form rather than H2TeO3 (Eq. (1)) a small portion of Te was replaced
with selenium powders (Se, Kojundo Chemical, 99.9%, 75 m) to prepare
a ternary compound.
(1) Oxidizing dissolution of the Bi and Te/Se mixture
2Bi yTe 3ySe 8HNO3 6NO3 2Bi3 yTeO3 2
3ySeO3 2 12NO2 2NO H 7OH 1 to observe the lattice vibrations using a Nicolet Almeca XR spectrometer
We tried to precipitate the oxidized substances in Eq. (1) by using
ammonium hydroxide (NH4OH, J.T.Baker, 2830%); thus, they were
possibly precipitated as bismuth hydroxide (Bi(OH)3), ammonium
tellurite ((NH4)2TeO3), and ammonium selenite ((NH4)2SeO3) (Eq. (2)).
[(2) Co-precipitation of the oxidized sources]
2Bi3 yTeO3 2 3ySeO 2

3 6NH4 OH2BiOH3
yNH4 2 TeO3 3y NH4 2 SeO3
We adopted hydrazine monohydrate (N2H4 H2O, Samchun, 80.0%)
to reduce the precipitates. When adding the reductant, the precipitates
immediately changed from white to gray and gradually turned black as
they aged, indicative of reduction of the precipitates. This reduction pos-
sibly occurs due to the strong reducing power of the reductant, thus
affording a ternary chalcogenide compound (i.e., Bi2TeySe3-y) in Eq. (3).
[(3) Reduction of the co-precipitates]

 9
2BiOH3 yNH4 2 TeO3 3y NH4 2 SeO3 N2 H4  H2 OBi2 Tey Se3y
2 (FE-SEM; Hitachi, S-4800) micrograph, the Bi2Te2.7Se0.3 consisted
9 27
6NH4 6OH N2 H2 O 3 of nanoparticles of approximately 50 nm in size with a highly uni-
2 2
Powder X-ray diffraction (XRD) patterns were recorded using a D/
MAX-2500 diffractometer (Rigaku) using Cu K radiation ( =
1.5406 ) and a scintillation counter detector. The XRD pattern of the re-
sultant powder (i.e., y = 2.7) exactly coincided with JCPDS card No. 50
0954 having the diffraction indices as shown in Fig. 1a, which is the
typical rhombohedral crystalline structure of Bi2Te2.7Se0.3. Compared
to the diffraction result of a binary compound (i.e., y = 3), the crystal-
line pattern showed a clear peak shift to a higher angle side, indicative
of the lattice distortion caused by the replacement of Te atoms with
smaller Se (i.e., generation of smaller unit cell). We rened the diffraction
patterns through the Rietveld method, and thus we possibly conrmed
the unit cell contraction from lattice parameters (Supplementary material
2). The rhombohedral structure is well known to consist of three quintu-
ple layers (QL) stacked by van der Waals forces. Each QL is alternately ar-
ranged with ve atomic layers, Te(1)BiTe(2)BiTe(1) (Fig. 1b), where
lattice vibrations of the atoms occur. We conducted Raman spectroscopy
(Thermo Scientic) with an excitation photon energy of 532 nm, which
covers a spectral range of Raman shift is from 100 to 4000 cm1. The ter-
nary compound showed both the Raman active vibrational modes of E2g
(117.0 cm1), A21g (140.5 cm1) and the infrared active vibration mode
of A21u (127.1 cm1) (Fig. 1c), which are assigned to in-plane (E2g) or
out-of-plane (A21g, A21u) vibrations of BiTe(1) (Fig. 1b) [19,20]. Compared
to vibrational modes of the binary compound, we found clear shifts to
higher frequency. This phenomenon indicates that Te atoms were
2 substituted by Se having smaller size and stronger electronegativity, and
thus the chemical bonds between Bi and Te(1) should be shortened.
This observation agrees well with the XRD result above, which in-
formed the smaller unit cell of the ternary compound due to Se in-
corporation. Therefore, the ternary compound was successfully
prepared via the chemical synthesis process with desired stoichi-
ometry (i.e., Bi 2 Te 2.7 Se 0.3 ), which was veried by the result of
inductively coupled plasma mass spectrometry (ICP-MS; Perkin-
Elmer Norwalk, CT) and the energy dispersive spectroscopy (EDS;
Hitachi, S-4800) (Supplementary material 3, 4).
According to the eld-emission scanning electron microscopy
form size distribution (Supplementary material 4). We tried to
pack this nanocompound using a spark plasma sintering equipment
(SPS; DR. Sinter, SPS-3, 20MK-IV) to minimize inevitable particle growth
during a sintering step. Approximately 15 g of the nanocompound was
placed into a cylindrical graphite mold (55 60 mm2 (d h)) with an
inner hole of 15 mm in diameter for compaction at 360 C for 5 minutes

Fig. 1. (a) Diffraction patterns of the compounds synthesized through the water-based chemical process, (b) schematic diagrams for the Raman active vibrational modes (E2g, A21g) and the
infrared active vibrational mode (A21u) in the lattices of rhombohedral Bi2Te3, and (c) Raman spectra of the compounds composed of E2g (), A21g (), and A21u ().
 C. Kim et al. / Scripta Materialia 119 (2016) 1316
under a pressure of 50 MPa in an Ar atmosphere, resulting in the produc-
tion of a cylindrical bulk specimen (20 30 mm2 (d h)). Considering
the typical anisotropic nature of Bi2Te3, we took only perpendicular
faces to the pressuring direction in the specimen for characterizations.
As shown in both electron backscatter diffraction (EBSD; Hitachi, S-
4300SE) and transmission electron microscopy (TEM; FEI Company,
Titan G2), the specimen was primarily composed of grains of below
500 nm in size (Fig. 2a, b). Applying the linear-intercept method to the
EBSD result, we conrmed the average grain size to be approximately
200 nm. As presented in the HR-TEM images (Fig. 2c, d), we found ran-
domly oriented crystalline grains. We observed highly crystallized lattice
fringes with interplanar spacing values (dhkl) of 3.21, 2.35, and 2.23
(Fig. 2d), nearly corresponding to those of 3.22, 2.37, and 2.23 for the
diffraction index of (015), (1010), and (0111) in rhombohedral
Bi2Te2.7Se0.3 (JCPDS card No. 500954), respectively. We detected the
two diffraction indices (i.e., (015) and (1010)) in the selected area elec-
tron diffraction (SAED) pattern (Fig. 2d, inlet), while nding all of the in-
dices in the XRD result (Fig. 1a).
We presented the details for thermoelectric characterizations in
Supplementary material 5. The Bi2Te2.7Se0.3 specimen recorded lower
lattice thermal conductivity than 0.5 Wm1 K1 (Fig. 3a). Considering
its grain size presented in the electron microscopy studies above, vigor-
ous phonon scattering is expected to occur at the grain boundaries be-
cause the mean free path of phonons is generally known to range
from 0.1 to 10 m [21]; thus, the specimen should exhibit the lattice
thermal conductivity, which is as low as those of other n-type Bi2Te3
nanostructures in bulk phase [1618] (Fig. 3a). We also predicted a lat-
tice thermal conductivity of Bi2Te2.7Se0.3 by employing the Debye
Callaway model (Eq. (4)) to theoretically conrm the experimental
lattice contribution above. By considering the relaxation time () for
Fig. 2. Electron microscopy observations for the sintered Bi2Te2.7Se0.3 specimen: EBSD image (a), TEM image (b), and HR-TEM images (c, d) with SAED (d inlet).
15
phonon-scattering processes, we derived the theoretical lattice contri-
bution of Bi2Te2.7Se0.3 versus temperature (Fig. 3b) detailed process
for the calculation has been discussed in Supplementary material 6.
Considering the experimental errors usually caused by measuring
both specic heat capacity and thermal diffusivity, which are presented
as error bars in Fig. 3b, the experimental values corresponded to the
calculated values with theoretical prediction errors of within 15% at all
temperatures.
Z kB =
1 2 4 exp=kB T
l d 4
2 2 0 kB T 2 exp=kB T 1 2
The specimen recorded the physical density of 7.81 g cm3, which is
about 99% of the theoretical density of Bi2Te2.7Se0.3 (i.e., ca. 7.86 g cm3
[22]). Many researchers have synthesized n-type Bi2Te3 nanostructures
with various morphologies to lessen thermal conductivity [1618] but
their nanostructures mostly had lower relative densities than ca. 95% in
common (Supplementary material 7). In the nanostructure syntheses,
various organic solvents or chemical stabilizers have been used, which
were possibly left as chemical residues contaminating products. They
might interfere with grain growth during sintering processes, and thus re-
searchers seemed to fail to densify their nanostructures completely. We
synthesized the Bi2Te2.7Se0.3 nanocompound via water-based chemical
reactions where chemical stabilizers as well as organic solvents were
not used; thus, no concerns might be involved in the product contamina-
tion causing interference in grain growth during the sintering process.
Since the resulting bulk specimen exhibited closer proximity to the theo-
retical density than the other nanostructures, it recorded the signicantly
higher electrical conductivity (Fig. 3c). Considering that the specimen did
16 C. Kim et al. / Scripta Materialia 119 (2016) 1316
Fig. 3. Comparisons of thermoelectric transport properties of the Bi2Te2.7Se0.3 specimen () to the Bi2Te3 nanoplates ( , [16]), the Bi2Te2.25Se0.75 nanoplatelet ( , [17]), and the Bi2Te3
nanoplate ( , [18]): (a) total thermal conductivity (lled marks) with lattice contribution (blank marks), (b) the lattice thermal conductivity (l) of the nanocompound () veried by
the DebyeCallaway model (line), (c) electrical conductivity, and (d) gure of merit.
not record predominant Seebeck coefcient compared to the other nano-
structures, the electrical conductivity decisively contributed to the superi-
or power factor (Supplementary material 8). In addition, the high physical
density of the specimen might be attributed to the predominant carrier
mobility (Supplementary material 7). The mobility led to the high carrier
thermal conductivity (Supplementary material 7), and thus the specimen
showed similar or somewhat higher total thermal conductivity values,
compared to the other nanostructures (Fig. 3a). However, the specimen
still maintained competitively low values (i.e., less than 1.0 Wm1 K1)
due to the low lattice contribution. Our material was not biased to low
thermal conductivity but it desirably kept a balance between the electrical
and thermal conductivities. As the thermoelectric transport properties
synergistically contributed to thermoelectric performance, we accom-
plished the highest ZT value at the low temperature (i.e., 1.15 at 100 C)
ever reported for n-type Bi2Te3. More detailed experimental and theoret-
ical analyses are currently conducted to give intensive discussion on the
predominant electrical conductivity, which should be greatly attributed
to the excellent ZT.
In summary, we developed an n-type Bi2Te2.7Se0.3 nanocompound via
a novel water-based chemical reaction process without organic solvents
and chemical stabilizers and packed the nanocompound using a spark
plasma sintering equipment. A sintered Bi2Te2.7Se0.3 specimen exhibited
approximately 99% of relative density, resulting in an excellent electrical
conductivity. In addition, the specimen retained the low level of thermal
conductivity possibly caused by vigorous phonon scattering the lattice
thermal conductivity was theoretically proved via the Debye-Callaway
model. The thermoelectric transport properties synergistically acted to
amplify thermoelectric performance, and thus we achieved the highest
ZT value ever reported for n-type Bi2Te3.
Acknowledgments
This work was supported by the DGIST R&D Program of the Ministry
of Science, ICT and Technology of Korea (16-EN-02). This work was also
supported by the Energy Efciency & Resources Core Technology Pro-
gram of the Korea Institute of Energy Technology Evaluation and Plan-
ning (KETEP), granted nancial resource from the Ministry of Trade,
Industry & Energy, Republic of Korea (No. 20152020001210).
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Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.scriptamat.2016.03.010.
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