Effects of ZnSb and Zn inclusions on the thermoelectric properties of β-Zn4Sb3

Zhang, L.T; Tsutsui, Makusu; Ito, Kazuhiro; Yamaguchi, M.

doi:10.1016/s0925-8388(03)00074-4

Cited by 120 publications

(74 citation statements)

References 10 publications

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“…This leaching can be inhibited through the use of excess lithium, which is consistent with the decomposition product at higher Li concentrations being c-LiZnSb We also find that β-Zn8Sb7 forms at short reaction times and 215 °C. 30 This is exciting as all zinc antimonide binaries have shown high thermoelectric figures of merit. Studies of ZnSb have been limited by its high thermal conductivity.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

et al. 2018

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Soft chemistry methods offer the possibility of synthesizing metastable and kinetic products that are unobtainable through thermodynamically-controlled, high-temperature reactions. A recent solution-phase exploration of Li-Zn-Sb phase space revealed a previously unknown cubic half-Heusler MgAgAs-type LiZnSb polytype. Interestingly, this new cubic phase was calculated to be the most thermodynamically stable, despite prior literature reporting only two other ternary phases (the hexagonal half-Heusler LiGaGe-type LiZnSb, and the full-Heusler Li2ZnSb). This surprising discovery, coupled with the intriguing optoelectronic and transport properties of many antimony containing Zintl phases, required a thorough exploration of syn-thetic parameters. Here, we systematically study the effects that different precursor concentrations, injection order, nucleation and growth temperatures, and reaction time have on the solution-phase synthesis of these materials. By doing so, we identify conditions that selectively yield several unique ternary (c-LiZnSb vs. h*-LiZnSb), binary (ZnSb vs. Zn8Sb7), and metallic (Zn, Sb) products. Further, we find one of the ternary phases adopts a variant of the previously observed hexagonal LiZnSb struc-ture. Our results demonstrate the utility of low temperature solution phase-soft synthesis-methods in accessing and mining a rich phase space. We anticipate that this work will motivate further exploration of multinary I-II-V compounds, as well as encourage similarly thorough investigations of related Zintl systems by solution phase methods. Disciplines Materials ChemistryComments "This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Chemistry of Materials, copyright © American Chemical Society after peer review. To access the final edited and published work see http://dx.doi.org/10.1021/acs.chemmater.8b02910. ABSTRACT: Soft chemistry methods offer the possibility of synthesizing metastable and kinetic products that are unobtainable through thermodynamically-controlled, high-temperature reactions. A recent solution-phase exploration of Li-Zn-Sb phase space revealed a previously unknown cubic half-Heusler MgAgAs-type LiZnSb polytype. Interestingly, this new cubic phase was calculated to be the most thermodynamically stable, despite prior literature reporting only two other ternary phases (the hexagonal half-Heusler LiGaGe-type LiZnSb, and the full-Heusler Li2ZnSb). This surprising discovery, coupled with the intriguing optoelectronic and transport properties of many antimony containing Zintl phases, required a thorough exploration of synthetic parameters. Here, we systematically study the effects that different precursor concentrations, injection order, nucleation and growth temperatures, and reaction time have on the solution-phase synthesis of these materials. By doing so, we identify conditions that selectively yield several unique ternary (c-LiZnSb vs. h*-LiZnSb), binary (ZnSb vs. Zn8Sb7), and metallic (Zn, Sb) products. Furt...

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Section: Resultsmentioning

confidence: 99%

“…[29][30][31][32][33][34][35] A computationally derived convex hull of formation enthalpies for various binary zinc antimonides predicts ZnSb to have the most negative formation enthalpy. 36 Low-temperature, soft chemistry techniques may provide a reproducible means to observe and isolate many of these compounds.…”

Section: Introductionmentioning

confidence: 99%

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

et al. 2018

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“…19,45,65,66 However, there are also experimental reports of a ZnSb band gap around 0.3 eV. 67 We chose to enlarge the calculated band gap by 0.5 eV in order to be consistent with recent ab initio studies employing the more reliable Heyd-Scuseria-Ernzerhof (HSE) hybrid functional, where the band gap was predicted to be 0.56 eV. 30,47 The adjustment was implemented by a simple scissor operator widening the gap in RðÞ and q i ðÞ by 0.5 eV, keeping their shapes otherwise fixed.…”

Section: B Boltzmann Transport Equationmentioning

confidence: 99%

Enhancement of thermoelectric properties by energy filtering: Theoretical potential and experimental reality in nanostructured ZnSb

Berland

Song

Carvalho

et al. 2016

Journal of Applied Physics

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Energy filtering has been suggested by many authors as a means to improve thermoelectric properties. The idea is to filter away low-energy charge carriers in order to increase Seebeck coefficient without compromising electronic conductivity. This concept was investigated in the present paper for a specific material (ZnSb) by a combination of first-principles atomic-scale calculations, Boltzmann transport theory, and experimental studies of the same system. The potential of filtering in this material was first quantified, and it was as an example found that the power factor could be enhanced by an order of magnitude when the filter barrier height was 0.5 eV. Measured values of the Hall carrier concentration in bulk ZnSb were then used to calibrate the transport calculations, and nanostructured ZnSb with average grain size around 70 nm was processed to achieve filtering as suggested previously in the literature. Various scattering mechanisms were employed in the transport calculations and compared with the measured transport properties in nanostructured ZnSb as a function of temperature. Reasonable correspondence between theory and experiment could be achieved when a combination of constant lifetime scattering and energy filtering with a 0.25 eV barrier was employed. However, the difference between bulk and nanostructured samples was not sufficient to justify the introduction of an energy filtering mechanism. The reasons for this and possibilities to achieve filtering were discussed in the paper.

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“…For polycrystalline ZnSb, the band gap is often reported to be around 0.31-0.35eV [13,48], which is smaller than that of single crystal material. It is justified to discuss whether the band gap really is different, or if it is due to that the idealizations of the measurement methods do not hold for polycrystalline material.…”

Section: Experimental Band Gapmentioning

confidence: 99%

Review of Research on the Thermoelectric Material ZnSb

Song¹,

Finstad²

2016

Thermoelectrics for Power Generation - A Look at Trends in the Technology

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The thermoelectric material ZnSb has been studied intensively in recent years and has shown promising features. The other zinc-antimonide compound, Zn 4 Sb 3 has remarkable low thermal conductivity, but it is accompanied with phase transitions at moderate temperature and has inherent stability problems. Compared to that, ZnSb is relatively phase stable and has a relative high charge carrier mobility and Seebeck coefficient, thus yielding a decent power factor. Meanwhile, its thermal conductivity can be reduced by means of nanostructuring, thus giving a good figure of merit at moderate temperatures, 400-600K. Many researchers have dedicated their efforts to study and improve ZnSb properties, and the figure of merit has been reported to be above one. Still, ZnSb as a thermoelectric material has features and behaviours that are not well-understood. The behaviour and properties of its intrinsic defects are not understood, but have interested researchers in recent years. This chapter intends to offer a comprehensive review on ZnSb to the readers. By combining own experiences from research on thermoelectric materials, the authors address the prospect for improving the thermoelectric properties of ZnSb and the concerns of transferring lab results to manufacturing.

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Effects of ZnSb and Zn inclusions on the thermoelectric properties of β-Zn4Sb3

Cited by 120 publications

References 10 publications

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

Enhancement of thermoelectric properties by energy filtering: Theoretical potential and experimental reality in nanostructured ZnSb

Review of Research on the Thermoelectric Material ZnSb

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