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Enhanced Thermoelectric Properties in Bulk Nanowire Heterostructure-
based Nanocomposites through Minority Carrier Blocking
Haoran Yang, Je-Hyeong Bahk, Tristan W Day, Amr Mohammed, G. Jeffrey Snyder, Ali Shakouri, and Yue Wu
Nano Lett., Just Accepted Manuscript • DOI: 10.1021/nl504624r • Publication Date (Web): 09 Jan 2015
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Page 1 of 21 Nano Letters

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Enhanced Thermoelectric Properties in Bulk
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12 Nanowire Heterostructure-based Nanocomposites
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16 through Minority Carrier Blocking
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33 Haoran Yang1, Je-Hyeong Bahk2, Tristan Day3, Amr M. S. Mohammed2, 4, G. Jeffrey Snyder3, Ali
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35 Shakouri2, 4 and Yue Wu1, 2, 5 *
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38 1. School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, USA
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42 2. Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47907, USA
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45 3. Materials Science, California Institute of Technology, Pasadena, California 91125, USA
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49 4. School of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana
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51 47907, USA
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54 5. Department of Chemical and Biological Engineering, Iowa State University, Ames, Iowa
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57 50011, USA
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ABSTRACT: To design superior thermoelectric materials, the minority carrier blocking effect,
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6 in which the unwanted bipolar transport is prevented by the interfacial energy barriers in the
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8 heterogeneous nanostructures, has been theoretically proposed recently. The theory predicts an
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enhanced power factor and a reduced bipolar thermal conductivity for materials with a relatively
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13 low doping level, which could lead to an improvement in the thermoelectric figure of merit (ZT).
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15 Here we show the first experimental demonstration of the minority carrier blocking in lead
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18 telluride-silver telluride (PbTe-Ag2Te) nanowire heterostructure-based nanocomposites. The
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20 nanocomposites are made by sintering PbTe-Ag2Te nanowire heterostructures produced in a
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22 highly-scalable solution-phase synthesis. Compared with Ag2Te nanowire-based nanocomposite
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25 produced in similar method, the PbTe-Ag2Te nanocomposite containing ~5 atomic % PbTe
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27 exhibits enhanced Seebeck coefficient, reduced thermal conductivity, and ~40% improved ZT,
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which can be well explained by the theoretical modeling based on the Boltzmann transport
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32 equations when energy barriers for both electrons and holes at the heterostructure interfaces are
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34 considered in the calculations. For this p-type PbTe-Ag2Te nanocomposite, the barriers for
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37 electrons, i.e. minority carriers, are primarily responsible for the ZT enhancement. By extending
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39 this approach to other nanostructured systems, it represents a key step towards low-cost solution-
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41 processable nanomaterials without heavy doping level for high-performance thermoelectric
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44 energy harvesting.
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48 KEYWORDS: Thermoelectric, heterostructures, PbTe, Ag2Te, nanocomposites, minority carrier
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50 blocking.
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A high thermoelectric figure of merit (ZT) requires simultaneous optimization of electrical
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6 conductivity (σ), thermal conductivity (κ), and Seebeck coefficient (S) in one material, which is
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8 a great challenge because these three properties are highly interrelated.1,2 To partially decouple σ
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11 and κ, a heterogeneous nanostructuring approach has been developed with secondary-phase
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13 nano-inclusions introduced into the bulk matrix. The nano-inclusions can be designed to scatter
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16 phonons more effectively than electrons, leading to a net enhancement of ZT.3-6 In addition,
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18 nano-inclusions can be intentionally tuned to affect electron transport in a constructive way: by
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20 selectively blocking low-energy carriers, the Seebeck coefficient and the power factor can be
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23 enhanced, which is previously known as the energy filtering effect.3,4,7-10 The fulfillment of
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25 energy filtering, however, requires a high carrier density and a precise control of the energy
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27 barrier height relative to the Fermi level, which is very difficult to achieve experimentally.9
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30 Recently, Bahk et al. proposed an alternative approach of using heterostructures to block the
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32 detrimental minority carriers and ZT is expected to increase due to a reduction of the bipolar
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thermal conductivity and an increase in power factor even at relatively low doping levels.10 This
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37 effect is of great interest especially for thermoelectric nanomaterials produced from scalable
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39 solution phase synthesis, since high carrier densities (1019/cm3 to 1021/cm3) usually required for
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42 optimal thermoelectric properties3 are very hard to achieve in solution phase synthesized
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44 nanomaterials due to the “self-purification” effect.11,12
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46 Ag2Te is a promising thermoelectric material due to its high electron mobility13 and very low
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49 intrinsic lattice thermal conductivity.14,15 Recently, our group reported carrier density modulation
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51 in solution phase synthesized Ag2Te nanowires.16 Although we showed that the electron density
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could be greatly increased through silver doping to achieve higher ZT than that of the undoped
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56 Ag2Te, the doping process is inefficient as evidenced by the demand for a large amount of extra
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Ag precursor. Here, we report the first experimental demonstration of the minority carrier
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6 blocking effect, which is observed in a PbTe-Ag2Te nanowire heterostructure-based
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8 nanocomposite system. The dumbbell-shaped PbTe-Ag2Te nanowire heterostructures feature
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well-defined morphology and size with two PbTe nanocubes grown at the two ends of each
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13 Ag2Te nanowire. Using these heterostructures as building blocks, we fabricated PbTe-Ag2Te
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15 nanocomposites with PbTe nano-inclusions uniformly distributed in the Ag2Te matrix through
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18 hot pressing. We show that the Seebeck coefficient and the power factor are enhanced, while the
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20 thermal conductivity is reduced in these nanocomposites, compared with the values of the pure
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22 Ag2Te nanowire nanocomposites produced by a similar process.16 As a result, ZT is greatly
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25 enhanced by more than 40% to reach ~ 0.66 at 390 K in the PbTe-Ag2Te nanocomposites, even
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27 though the system is not intentionally doped and the carrier density still remains low. We
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propose that the band offset between Ag2Te and PbTe provides energy barriers for electron
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32 transport, which introduces the minority carrier blocking effect responsible for the power factor
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34 enhancement. Under the minority carrier blocking scheme, the measured thermoelectric transport
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37 properties are in excellent agreement with the theoretical calculations based on the Boltzmann
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39 transport equations (BTE), taking into account the interfacial energy barriers for both carrier
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41 types.
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Figure 1. Figure 1. Synthesis and characterization of the Te nanowires, PbTe-Te nanowire
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39 heterostructures and PbTe-Ag2Te nanowire heterostructures. (a) Schematic for the three-step
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41 synthesis of PbTe-Ag2Te nanowire heterostructures; (b) XRD patterns compared with the
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44 standards, (c-e) SEM images, (f-h) low-magnification TEM images with high-magnification
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46 TEM image insets of the Te nanowires (c and f), PbTe-Te nanowire heterostructures (d and g),
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48 and PbTe-Ag2Te nanowire heterostructures (e and h). Scale bars in the main images represent
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51 500 nm and scale bars in the insets represent 50 nm.
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54 The synthesis of PbTe-Ag2Te nanowire heterostructures, highlighted in Fig. 1a, is
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56 accomplished through a three-step reaction with the details described in the Supporting
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 Nano Letters Page 6 of 21

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Information. To obtain the nanowire heterostructures, Tellurium (Te) nanowires are synthesized
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6 first; a small amount of Lead precursor is then injected, which triggers the growth of PbTe
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8 nanocubes at the two ends of each Te nanowire to form dumbbell-like PbTe-Te nanowire
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heterostructures; and finally the rest of the Te part is further converted into Ag2Te to obtain the
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13 desired structures. Notably, this is a very general method developed by our group to produce
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15 many kinds of Telluride-based nanowire heterostructures, such as Bi2Te3-Te, Bi2Te3-PbTe and
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18 Bi2Te3-Ag2Te nanowire heterostructures.17-19 The conversion from Te to Ag2Te follows the same
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20 procedure as described in our previous report on the synthesis of undoped Ag2Te nanowires.16
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22 Fig. 1b presents the powder X-ray diffraction (XRD) patterns of the products from each step.
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25 After the first step, the XRD pattern of the product (Fig. 1b top) can be readily indexed to the
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27 pure hexagonal Te phase (JCPDS 36-1452). After the second step, another set of peaks
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corresponding to the altaite PbTe (JCPDS 38-1435) appear in addition to the Te peaks, indicating
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32 the formation of PbTe. After the final step, the Te peaks are replaced by the monoclinic Ag2Te
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34 peaks (JCPDS 34-0142) in the XRD pattern (Fig. 1b bottom), indicating complete transformation
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37 of Te into Ag2Te.
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39 The microstructures of the products are further investigated by electron microscopy. The low-
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41 magnification scanning electron microscopy (SEM) images (Fig. 1c to 1e) show that the Te
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44 nanowires, dumbbell-like PbTe-Te, and PbTe-Ag2Te nanowire heterostructures from each step
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46 are all uniform, which proves the excellent control of the morphology of these nanostructures.
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48 The transmission electron microscopy (TEM) images (Fig. 1f to 1h) reveal more details of the
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51 nanostructures. As shown in Fig. 1f, the Te nanowires synthesized in the first step have an
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53 average length of 1563±34 nm and an average diameter of 19.9±0.5 nm. The products obtained
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after the second step (Fig. 1e) contain two PbTe nanocubes grown at the two ends of each Te
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nanowire. The Te part of the nanowire heterostructure grows slightly longer and thicker
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6 compared to the pure Te nanowires, the average diameter reaches 23.6±0.9 nm and the average
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8 length reaches 1723±33 nm. Meanwhile, the PbTe nanocubes have an average side length of
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34.4±1.8 nm. The increase of the length and diameter of the Te part in the nanowire
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13 heterostructure is likely due to the elevated reaction temperature in the second step where the
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15 unreacted Te precursors decompose and incorporate into the existing Te nanowires (see
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18 Methods). After the completion of the final step, as shown in Fig. 1h, the PbTe nanocubes
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20 remain almost unchanged in size and shape with an average side length of 34.6±1.5 nm. On the
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22 contrary, the originally straight Te parts transform into curved Ag2Te nanowires, and the average
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25 diameter become 27.7±1.0 nm. Since the nanowires become curved, the length distribution
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27 cannot be easily measured accurately and the average length is increased to about 2 µm. The
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30 diameter and length growth during this self-templated transformation from Te to Ag2Te is likely
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32 due to the volume expansion from the hexagonal Te lattice to the monoclinic Ag2Te lattice.20
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34 According to ref. 20, the mechanical stress accumulation due to large volume change during the
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37 transformation could break the nanowires into shorter nanorods. In our study, however, the
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39 nanowires remained intact after transformation. We believe the stress is possibly relaxed by
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forming bends and kinks. Similar morphology has been observed in many other solution phase
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44 synthesized Ag2Te nanowires.21-23
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34 Figure 2. HRTEM characterizations. (a), (b), and (c) are the HRTEM images of the Te wire part,
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37 the PbTe head part, and the junction part of a typical PbTe-Te nanowire heterostructure. The
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39 insets are the corresponding FFT images. (d) and (e) are the HRTEM images of the PbTe head
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part and the Ag2Te wire part of a typical PbTe-Ag2Te nanowire heterostructure. (f) and (g) are
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44 the FFT images of the wire region (red solid rectangle) and the head region (blue dashed
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46 rectangle) of the PbTe-Te nanowire heterostructure in (c). (h) and (i) are the FFT images of (d)
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49 and (e).
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52 In order to further understand the formation of the dumbbell structures, high-resolution
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54 transmission electron microscopy (HRTEM) has been used to study the wire part, the head part,
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and the junction part of the PbTe-Te and PbTe-Ag2Te nanowire heterostructures, respectively.
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As shown in the HRTEM image (Fig. 2a) and its fast Fourier transform (FFT, Fig. 2a inset), the
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6 wire part of the PbTe-Te heterostructure is single crystalline hexagonal Te with growth direction
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8 along [001]. The head part (Fig. 2b) is indexed to single crystalline altaite PbTe phase. HRTEM
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image (Fig. 2c) and the corresponding FFT images (Fig. 2f, and 2g) at the junction part between
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13 Te wire and PbTe head reveal several important features. First, PbTe heads grow epitaxially on
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15 Te nanowires, and the (111) planes of PbTe heads align in parallel with the (001) planes of Te
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18 nanowires. Crystallographically, the (111) planes of the fcc PbTe and the (001) planes of the
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20 hexagonal Te share the same close packed atomic arrangement,24 and the in-plane lattice
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22 mismatch is only 2.4% while the cross plane lattice mismatch is 5.6%, which is schematically
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25 shown in Supporting Information Fig. S1. The small lattice mismatch allows for epitaxial growth
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27 of PbTe on Te. Second, the PbTe heads wrap and cover the tips of the Te wires. After converting
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the Te parts into Ag2Te, the HRTEM of the heads (Fig. 2d) and its corresponding FFT pattern
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32 (Fig. 2h) show that the heads remain unchanged as PbTe, however, the nanowire parts indeed
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34 transform into monoclinic Ag2Te (Fig. 2e and 2i). As shown in Supporting Information Fig. S2,
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37 the junctions between the PbTe heads and the Ag2Te wires become not clearly defined, and
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39 various features at the boundaries have been observed. This is probably due to the fast diffusion
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41 of Ag into the Te lattice.20,25
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44 The well-controlled synthesis of PbTe-Ag2Te nanowire heterostructures allows us to use them
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46 as building blocks to fabricate bulk nanocomposites with Ag2Te as the primary phase (matrix)
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48 and PbTe as secondary-phase (nano-inclusions) through hot pressing. Before hot pressing, the
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51 electrically insulating surface ligands on the heterostructures are removed with hydrazine hydrate
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53 treatment.17 We keep the hot press temperature low (423 K) intentionally to avoid grain growth
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as well as alloying and elemental diffusion between PbTe and Ag2Te, which could become
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significant when the temperature is above 420 K according to the PbTe-Ag2Te phase
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43 Figure 3. Characterization of the hot pressed PbTe-Ag2Te nanocomposite sample. (a) XRD, (b)
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46 cross-section SEM image, and (c) HRTEM image, in which the dashed blue line defined region
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48 is PbTe while the solid purple lines defined regions are Ag2Te. Inset of (a) shows the photograph
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50 of a hot-pressed bulk PbTe-Ag2Te nanocomposite sample disk.
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The hot-pressed sample (Fig. 3a, inset) is re-examined by XRD and the diffraction pattern is
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56 presented in Fig. 3a. The diffraction pattern of the hot-pressed disk is identical to the diffraction
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pattern of the as-synthesized PbTe-Ag2Te nanowire heterostructures, which confirms that hot
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6 pressing does not result in any noticeable phase change. Additionally, the XRD pattern from the
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8 hot-pressed disk shows a similar degree of peak broadening, which indicates that the grain
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growth during hot pressing is negligible. Indeed, the SEM image (Fig 3b) of the cross section of
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13 the hot pressed sample shows that the original nanowires are broken during hot pressing, which
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15 possibly occurs at the bend or kink sites, with a lot of short rod-like grains as long as 150 nm and
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18 with diameters around 30 to 40 nm. The SEM observation confirms that grain growth is
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20 insignificant and the morphological features of the raw materials are partially preserved in the
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22 hot pressed sample. To further confirm the phase separation, HRTEM studies are performed on
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25 the hot pressed sample. Fig. 3c shows that distinguishable PbTe grains and Ag2Te grains around
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27 30~50 nm coexist, which verifies that the heterogeneity of the raw material is preserved after hot
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pressing and a uniform distribution of PbTe nano-inclusions in the Ag2Te matrix structure is
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32 obtained. In both the SEM and HRTEM images, nanoscale pores can be seen, which is consistent
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34 with the fact that the relative density of the hot-pressed pellet is about 88.5% of the theoretical
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37 density. In comparison, the pure Ag2Te nanowires-based nanocomposite sample we previously
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39 reported has a similar relative density of 88.7%. The composition of the binary composite is
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41 determined to be (PbTe)0.049(Ag2Te)0.951 by energy dispersive X-ray spectroscopy (EDX), and the
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44 cation/anion ratio is close to stoichiometric ((Ag/2+Pb)/Te=100/98.6).
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42 Figure 4. Experimental data and theoretical fitting of the thermoelectric properties. (a) Electrical
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44 conductivity, (b) Seebeck coefficient, (c) power factor, (d) thermal conductivity, and (e) ZT of
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47 the PbTe-Ag2Te nanocomposite compared with those of the Ag2Te nanocomposite. (f) The
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49 schematic band alignment between PbTe and Ag2Te.
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52 Fig. 4a to Fig 4e present the electrical and thermal transport properties of the PbTe-Ag2Te
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55 nanocomposite sample at temperatures ranging from 300 K to 390 K, which is compared with
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under the identical conditions.16 Also shown are the fitting curves calculated based on the
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6 Boltzmann transport equations with barrier heights for both carrier types.9,10 Fig. 4f
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8 schematically shows the presumed band alignment between Ag2Te and PbTe in the
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nanocomposite. Because Ag2Te has a small band gap of ~0.05 eV14 whereas PbTe has a wider
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13 band gap of 0.31 eV27 at room temperature, after the Fermi level alignment, the discontinuity in
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15 the conduction band and the valence band will form energy barriers for both electrons and holes.
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18 Since the atomic percentage of PbTe is small, we can model the system such that most of the
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20 diffusive transport is assumed to be occurring in the Ag2Te matrix, and PbTe nano-inclusions
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22 simply act as heterostructure barriers to fit the experimental data. From the calculation, we find
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25 that the energy barrier heights that best fit the experimental data are ~110 meV and ~45 meV for
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27 electrons and holes, respectively. Note that these effective energy barrier heights are not simply
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the band offsets, because the charge transfer between the two materials can induce band bending
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32 at the interface, so that the barrier heights are adjusted. Also, tunneling through the narrowed
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34 potential width near the interface, as well as the non-negligible barrier influence on high-energy
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37 carriers can potentially vary the effective barrier height.11
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39 As shown in Fig. 4a, the electrical conductivity of the PbTe-Ag2Te nanocomposite is lower
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41 than that of the Ag2Te sample over the entire temperature range. Such a reduction in the
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44 electrical conductivity is a result of the electron and hole blocking by the heterostructure barriers.
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46 The electron and hole mobilities of the Ag2Te sample at room temperature are estimated to be
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48 837 and 169 cm2V-1s-1, respectively. Due to the scattering from the PbTe nano-inclusions, the
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51 electron and hole mobilities at room temperature are reduced to 289 and 103 cm2V-1s-1,
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barrier blocking, which, combined with the mobility reduction, lowered the electrical
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6 conductivity as anticipated in the theory.9
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8 On the other hand, the Seebeck coefficient of the PbTe-Ag2Te sample is increased significantly
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compared to that of the Ag2Te sample over the entire temperature range. At 380 K, the peak
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13 Seebeck coefficient reaches 271 µV/K for the PbTe-Ag2Te nanocomposite, while for the Ag2Te
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sample it is only 192 µV/K, corresponding to a more than 40 % enhancement in the PbTe-Ag2Te
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18 nanocomposite. The Seebeck coefficient in the bipolar transport regime is given by28
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25 where n and p are electron and hole densities respectively, the subscripts e and h refer to the
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27 partial properties of electrons and holes respectively, and b is the mobility ratio, i.e. b = µe/µh.
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Since electrons and holes have partial Seebeck coefficients with opposite signs, the absolute
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32 value of the total Seebeck becomes smaller than those of the partial Seebeck coefficients
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34 according to Eq. (1). Previously, we reported that the “undoped” Ag2Te nanowire based sample
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37 has a significant contribution from minority carriers (electrons) in the Seebeck coefficient even
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39 though the electron density (1×1017 cm-3) is much lower than the hole density (8×1017 cm-3), due
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to their higher mobility.15 When these minority electrons are effectively blocked from
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44 participating in transport by the heterostructure barriers, their contribution to the Seebeck
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46 coefficient is reduced, and thus the magnitude of the total Seebeck coefficient is increased.
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As shown in Fig. 4b, the theoretical calculations show that the enhancement of the Seebeck
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53 negative contribution to the positive total Seebeck coefficient. Meanwhile, the barrier for holes is
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relative contribution of electrons becomes more significant, which results in the reduction of the
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6 total Seebeck coefficient. Consequently, if there were hole barriers only, the magnitude of the
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8 total Seebeck coefficient would have been even smaller than that of the Ag2Te sample due to the
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increased electron contribution. This is clearly shown in Fig. 4b, in which the simulated cases of
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18 temperatures. At high temperatures above 360 K, however, a small effect of hot-carrier energy
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20 filtering comes into play for the holes when the hole barriers are also included because the Fermi
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22 level approaches to the optimal position as temperature increases. This results in a slight increase
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25 in the Seebeck coefficient compared to that in the case of only electron barriers. Only when both
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27 the electron and the hole barriers are taken into account in the BTE calculations, the measured
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Seebeck coefficients can be fit very well over the entire temperature range.
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32 Fig. 4c presents the measured and calculated power factors. In the whole measured
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34 temperature range, the PbTe-Ag2Te sample exhibits larger power factors than those of the Ag2Te
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37 sample, and the relative power factor increase is around 17% to 38%. As shown as a separate
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39 curve in Fig. 4c, if only hole barriers were to exist, the power factor would have decreased
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41 significantly due to the reduced electrical conductivity and Seebeck coefficient, which indicates
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44 that the blocking of majority carriers (holes in this case) has a detrimental influence on the
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46 thermoelectric performance in the bipolar transport region. On the contrary, if only electron
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48 barriers were to exist, the power factor could have been enhanced even more, by greater than 50 %
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51 at around 380 K, and greater than 200 % at around room temperature, mainly due to the lessened
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53 electrical conductivity reduction. The calculation suggests that an even higher power factor could
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be expected if the valence band alignment between the two phases were improved to reduce the
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6 effective hole barrier height. The experimental realization is subject to future research.
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8 Fig. 4d shows that the measured thermal conductivity of the PbTe-Ag2Te sample is 0.29 W m-1
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K-1 at 300 K and decreases to 0.19 W m-1 K-1 as temperature increases to 390 K, which is lower
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13 than that of the Ag2Te sample by ~ 35 %. The electronic thermal conductivity (κe) is calculated
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from the Wiedemann-Franz relation29 using the Lorenz number obtained from our electron
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18 transport modeling, and it is seen that the electronic contribution to the total thermal conductivity
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20 is very small, less than 0.02 W m-1 K-1 in the PbTe-Ag2Te nanocomposite. This is much lower
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than that of the Ag2Te sample (0.04 W m-1 K-1) due to the carrier blocking by the barriers. The
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25 reduction in total thermal conductivity largely comes from the reduction of the lattice plus
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27 bipolar part (κl + κbi), which is obtained by subtracting κe from the total thermal conductivity.
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30 Accurate quantification of the bipolar thermal conductivity is difficult since κbi is very sensitive
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32 to the band structure but the valence band of Ag2Te has not been well studied so far. Although it
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35 is difficult to quantitatively separate κbi from κl, we expect that a larger portion of κ reduction is
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37 associated with a reduction in kbi since the electrical measurements clearly indicate a reduced
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bipolar effect in this sample compared to the Ag2Te sample. On the other hand, although it’s well
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42 known that nano-inclusions may introduce phonon scattering to suppress κl,30-32 a significant
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reduction of κl in the PbTe-Ag2Te nanocomposites would be unlikely because bulk Ag2Te
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47 already exhibits a remarkably low κl of 0.1~0.2 W m-1 K-1.14,15
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Due to the enhanced power factor and the extremely low thermal conductivity, the figure of
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52 merit ZT reaches 0.66 at 390 K for the PbTe-Ag2Te nanocomposite sample, as shown in Fig. 4e,
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54 which is, to our best knowledge, the highest ZT among ever reported Ag2Te based thermoelectric
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57 materials at the same temperature range. The enhanced ZT demonstrates that the minority carrier
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blocking with heterostructure barriers is an effective approach for improving the thermoelectric
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6 performance of solution-processed nanomaterials. Compared to the conventional high-
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8 temperature solid-state synthesis of thermoelectric bulk materials, our novel approach represents
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an alternative design towards high-performance thermoelectric bulk materials because: (1) it
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13 does not require an energy-intensive process to achieve high performance through heavy doping
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15 and it bypasses the doping limitation in most typical solution-phase nanostructure growth
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18 methods; (2) the colloidal nanowire suspension could enable solution processing of
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20 nanomaterials for direct printing of thermoelectric devices; (3) the low-cost solution-phase
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22 synthesis approach and the hot press process have been demonstrated to be general and highly-
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25 scalable for other Telluride-based material systems based on our previous research.
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27 Finally, we would like to discuss the difference between our nano-composite sample and the
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bulk PbTe-Ag2Te sample with similar composition reported in ref. 14. The bulk composites are
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32 n-type materials that contain micron-size PbTe region and the thermoelectric properties are
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34 dominated by the Ag2Te matrix, which might suggest an important nanostructuring size effect on
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37 the thermoelectric properties of the binary composites, which needs further investigation.
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39 In summary, we have developed a novel low-cost scalable solution-phase synthesis of
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41 dumbbell-like PbTe-Ag2Te nanowire heterostructures. These nanowire heterostructures have
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44 been utilized as building blocks to fabricate bulk PbTe-Ag2Te nanocomposites through hot
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46 pressing, after which the PbTe nano-inclusions are uniformly distributed in the Ag2Te matrix.
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48 The thermoelectric transport properties of the binary nanocomposite have been studied and
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51 compared with our previously reported undoped Ag2Te nanowire-based nanocomposite
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53 fabricated under identical conditions. The experimental data have been explained by taking into
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account the band offset between PbTe and Ag2Te and adding energy barriers for both electrons
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and holes in the BTE calculations. We have shown evidence of power factor enhancement due to
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6 minority carrier blocking, which leads to a 40% to 55% enhancement of ZT in the
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8 heterostructure nanocomposite. The energy barrier for the majority carriers has been found to be
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detrimental to the thermoelectric properties, and a further ZT enhancement could be possible if
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13 the hole barrier height could be reduced in the future. Furthermore, the minority carrier blocking
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15 approach through heterostructuring may be applied to other systems to improve ZT in which
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18 heavy doping is difficult to achieve.
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20 ASSOCIATED CONTENT
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23 Supporting Information. Detailed experimental processes, theoretical modeling procedures,
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26 schematic presentation of the lattice mismatch between Te (001) planes and PbTe (111) planes,
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28 and HRTEM images showing the junctions of several PbTe-Ag2Te heterostructures. This
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material is available free of charge via the Internet at http://pubs.acs.org.
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34 AUTHOR INFORMATION
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36 Corresponding Author
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39 *[email protected]
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42
Author Contributions
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44 Yue Wu led the project. Haoran Yang was the main contributor for the PbTe-Ag2Te
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47 heterostructure synthesis, nanocomposite fabrications and structural characterizations. Je-
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49 Hyeong Bahk and Ali Shakouri performed the theoretical modeling. Tristan Day and G. Jeffrey
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Snyder performed the electrical conductivity measurements. Haoran Yang and Amr M. S.
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54 Mohammed performed Seebeck coefficient measurements.
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57 Funding Sources
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This work is supported by US Air Force Office of Scientific Research (Award Number FA9550-
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6 12-1-0061).
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