Zn<sub>13</sub>Sb<sub>10</sub>:  A Structural and Landau Theoretical Analysis of Its Phase Transitions

Mozharivskyj, Yurij; Janssen, Y.; Harringa, J. L.; Kracher, A.; Tsokol, and Alexandra O.; Miller, Gordon J.

doi:10.1021/cm0515505

Cited by 99 publications

(104 citation statements)

References 20 publications

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“…17, 18 The plateau in resistivity, observed between 230 K and 140 K, may be due to the effect of an impurity scattering process, arising from a phase impurity caused by a ''premature effect'' of the order-disorder phase transition at 250 K. A second phase transition at T Ϸ 234 K has been reported by another group. 19 The slope in resistivity changes below 140 K, decreasing with decrease in temperature in a semimetallic manner. The room temperature resistivity is somewhat higher than that reported in Ref.…”

Section: Resultsmentioning

confidence: 99%

Effect of disorder on the thermal transport and elastic properties in thermoelectricZn4Sb3

et al. 2006

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Zn 4 Sb 3 undergoes a phase transition from ␣ to ␤ phase at T 1 Ϸ 250 K. The high temperature ␤-Zn 4 Sb 3 phase has been widely investigated as a potential state-of-the-art thermoelectric ͑TE͒ material, due to its remarkably low thermal conductivity. We have performed electronic and thermal transport measurements exploring the structural phase transition at 250 K. The ␣ to ␤ phase transition manifests itself by anomalies in the resistivity, thermopower, and specific heat at 250 K as well as by a reduction in the thermal conductivity as Zn 4 Sb 3 changes phase from the ordered ␣ to the disordered ␤-phase. Moreover, measurements of the elastic constants using resonant ultrasound spectroscopy ͑RUS͒ reveal a dramatic softening at the order-disorder transition upon warming. These measurements provide further evidence that the remarkable thermoelectric properties of ␤-Zn 4 Sb 3 are tied to the disorder in the crystal structure.

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Section: Resultsmentioning

confidence: 99%

Effect of disorder on the thermal transport and elastic properties in thermoelectricZn4Sb3

et al. 2006

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“…[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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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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“…Besides increasing the zT, many studies have also been conducted to investigate the thermal stability of this material [11,[21][22][23][24][25][26] . Caillat et al have shown that TE properties of Zn4Sb3 are stable up to 670 K under argon and static vacuum, but unstable in the dynamic vacuum due to the evaporation of Sb at temperatures higher than 543 K resulting in an increased electrical resistivity [11] .…”

Section: Introductionmentioning

confidence: 99%

In Operando Study of High‐Performance Thermoelectric Materials for Power Generation: A Case Study of β‐Zn₄sb₃

Hưng

Ngo

Han

et al. 2017

Adv Elect Materials

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To date, many high-performance thermoelectric (TE) materials for power generation have been studied and reported. However, so far they have not been implemented in reliable commercial devices. To bring current achievements into a device for power generation, a full understanding the dynamic behavior of thermoelectric materials under operating conditions is needed. In this work, an in operando study is conducted on the high-performance TE material β-Zn4Sb3 under large temperature gradient and thermal cycling by a new approach using in-situ transmission electron microscopy combined with characterization of the TE properties. We found that after 30 thermal cycles in a low-pressure helium atmosphere the TE performance of β-Zn4Sb3 is maintained with the zT value of 1.4 at 718 K. Nevertheless, under a temperature gradient of 380 K (Thot = 673 K and Tcold = 293 K) operating for only 30 hours, zinc whiskers gradually precipitate on the cold side of the β-Zn4Sb3 leg. The dynamical evolution of Zn in the matrix of β-Zn4Sb3 was found to be the source that leads to a high zT value by lowering of the thermal conductivity and electrical resistivity, but it is also the failure mechanism for the leg under these conditions. The in operando study brings deep insight into the dynamic behavior of Advanced Electronic Materials 2 nanostructured TE materials for tailoring future TE materials and devices with higher efficiency and longer durability.

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Zn₁₃Sb₁₀: A Structural and Landau Theoretical Analysis of Its Phase Transitions

Cited by 99 publications

References 20 publications

Effect of disorder on the thermal transport and elastic properties in thermoelectricZn4Sb3

Effect of disorder on the thermal transport and elastic properties in thermoelectricZn4Sb3

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

In Operando Study of High‐Performance Thermoelectric Materials for Power Generation: A Case Study of β‐Zn₄sb₃

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Zn13Sb10: A Structural and Landau Theoretical Analysis of Its Phase Transitions

Cited by 99 publications

References 20 publications

Effect of disorder on the thermal transport and elastic properties in thermoelectricZn4Sb3

Effect of disorder on the thermal transport and elastic properties in thermoelectricZn4Sb3

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

In Operando Study of High‐Performance Thermoelectric Materials for Power Generation: A Case Study of β‐Zn4sb3

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Zn₁₃Sb₁₀: A Structural and Landau Theoretical Analysis of Its Phase Transitions

In Operando Study of High‐Performance Thermoelectric Materials for Power Generation: A Case Study of β‐Zn₄sb₃