Soft Chemistry, Coloring and Polytypism in Filled Tetrahedral Semiconductors: Toward Enhanced Thermoelectric and Battery Materials

White, Miles A.; Medina‐Gonzalez, Alan M.; Vela, Javier

doi:10.1002/chem.201704630

Cited by 14 publications

(13 citation statements)

References 113 publications

(237 reference statements)

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“…6,7 As would be expected due to their similar 8 electron network, a similar stabilization occurs in hexagonal LiGaGe-type structures, where the I + charge balances the wurtzite (II-V) -sublattice. 8 Zintl compounds enable precise tuning of transport properties by manipulating stoichiometry. [9][10][11] Their strong correlation between structural and electronic properties has garnered substantial interest for thermoelectric applications.…”

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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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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“…Moreover, the structural polytypism could be helpful in nanostructuring of such material by creating local site disorder. Such polytypism has been observed to contribute to enhanced thermoelectric performance in filled tetrahedral semiconductors . As, polytypism has already been reported for quaternary chalcogenides,, it would be interesting to study the effect of such aspect on their thermoelectric performance.…”

Section: Thermoelectric Applicationsmentioning

confidence: 82%

“…According to Wiedemann Franz law, for bulk thermoelectric materials the quantities S, σ and κ are interrelated in such a way that obtaining optimum ZT by controlling only single quantity is difficult. The nanostructuring approach to derive thermoelectric nanomaterials with suitable electrical and thermal properties has given a new way to detangled the interrelated electrical and thermal properties ,,. At nanoscale regime, the quantities S, σ and κ can be varied quasi‐independently as a new length variable is added .…”

Section: Thermoelectric Applicationsmentioning

confidence: 99%

Multifunctional Copper‐Based Quaternary Chalcogenide Semiconductors Toward State‐of‐the‐Art Energy Applications

Kush

Deka

2018

ChemNanoMat

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Cu-based quaternary chalcogenide semiconductors have been attractive materials in many aspects since the last decade. Most of the scientific literature about quaternary chalcogenides is dedicated to photovoltaic (PV) research with no astonishment as the material initially emerged as a costeffective replacement of expensive Si for PV applications. These materials possess all the important properties such as, abundant and non-toxic constituent elements, efficient charge transport, optimum band gap, and high absorption coefficient for being an efficient PV material in either thin film or nanoparticle form. However, in the recent few years, a new range of quaternary materials Cu 2 M I M II X 4 (where, M I =Zn, Ni, Co, Fe, Mn, Cd and Hg; M II =Si, Sn and Ge and X=S and/or Se) have evolved and found applications in thermoelectrics, photocatalysis and photoelectrocatalysis, sensors and bat-teries etc. The combination of properties exhibited by these quaternary chalcogenides such as optical and electric, optical and magnetic, electric and thermal makes them potential materials, which could be utilized in multiple applications. Although the PV properties of these quaternary chalcogenides has been discussed earlier in many reports, the other versatile applications of the material have not been reviewed yet. The present article sheds light on the multifunctional aspects of various new Cu-based quaternary chalcogenides, their synthesis, effect of doping on their properties, and then elaborating the discussion on their chemical and physical properties that are helpful in different applications along with photovoltaics. Here, we discuss synthetic methods bestowing enhanced features and also summarize their achieved efficiency in recent years. Scheme 1. Schematic representation for the derivation of quaternary chalcogenides. 2 3 4 5 6 7 8

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“…Of course, the rule of electronegativity differences can be extended by including other factors, such as size or electron configurations, which certainly influence crystal structures. More rigorous quantum calculations have been made to evaluate the relative importance of ionic vs covalent bonding character in dictating the site preferences, but these studies are necessarily restricted to limited sets of compounds. − It is also inevitable that ambiguous cases will arise when electronegativities or sizes are similar.…”

Section: Introductionmentioning

confidence: 99%

Solving the Coloring Problem in Half-Heusler Structures: Machine-Learning Predictions and Experimental Validation

et al. 2019

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The site preferences within the structures of half-Heusler compounds have been evaluated through a machinelearning approach. A support-vector machine algorithm was applied to develop a model which was trained on 179 experimentally reported structures and 23 descriptors based solely on the chemical composition. The model gave excellent performance, with sensitivity of 93%, selectivity of 96%, and accuracy of 95%. As an illustration of data sanitization, two compounds (GdPtSb, HoPdBi) flagged by the model to have potentially incorrect site assignments were resynthesized and structurally characterized. The predictions of the correct site assignments from the machine-learning model were confirmed by single-crystal and powder X-ray diffraction analysis. These site assignments also corresponded to the lowest total energy configurations as revealed from first-principles calculations.

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Soft Chemistry, Coloring and Polytypism in Filled Tetrahedral Semiconductors: Toward Enhanced Thermoelectric and Battery Materials

Cited by 14 publications

References 113 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

Multifunctional Copper‐Based Quaternary Chalcogenide Semiconductors Toward State‐of‐the‐Art Energy Applications

Solving the Coloring Problem in Half-Heusler Structures: Machine-Learning Predictions and Experimental Validation

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