Temperature Dependent n-Type Self Doping in Nominally 19-Electron Half-Heusler Thermoelectric Materials

Anand, Shashwat; Xia, Kaiyang; Zhu, Tiejun; Wolverton, Chris; Snyder, Gerald Jeffrey

doi:10.1002/aenm.201801409

Title: Temperature Dependent n-Type Self Doping in Nominally 19-Electron Half-Heusler Thermoelectric Materials

Journal Article · Wed Sep 19 00:00:00 EDT 2018 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.201801409· OSTI ID:1775289

^[1]; Xia, Kaiyang ^[2]; Zhu, Tiejun ^[2]; Wolverton, Chris ^[1]; Snyder, Gerald Jeffrey ^[1]

Northwestern Univ., Evanston, IL (United States)
Zhejiang Univ., Hangzhou (China)

Abstract The discovery of a semiconducting ground state X _y YZ ( y = 0.8 or 0.75) in nominally 19‐electron half‐Heusler materials warrants a closer look at their apparently metallic properties that often make them good thermoelectric (TE) materials. By systematically investigating the temperature dependence of off‐stoichiometry ( x ) in V _0.8+ _x CoSb, Nb _0.8+ _x CoSb, and Ti _0.75+ _x NiSb it is found that x invariably increases with increasing temperature, leading to an n‐type self‐doping behavior. In addition, there is also a large phase width (range of x ) associated with each phase that is temperature dependent. Thus, unlike in typical 18‐electron half‐Heuslers (e,g, TiNiSn), the temperature dependence of vacancy and carrier concentration ( n ) in nominally 19‐electron half‐Heuslers links its transport properties to synthesis conditions. The temperature dependence of x and n are understood using density functional theory based defect energies ( E _d ) and phase diagrams. E _d are calculated for 21 systems which can be used in predicting solubility in this family of compounds. Using this simple strategy, suitable composition and temperature synthesis conditions are devised for obtaining an optimized n to engineer TE properties in phase‐pure V _0.8+ _x CoSb, and the previously unexplored Ta _0.8+ _x CoSb.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Fund for Distinguished Young Scholars; National Natural Science Fund

Grant/Contract Number:: SC0014520; SC0001299; 51725102; 51761135127; DE‐SC0001299; DE‐SC0014520

OSTI ID:: 1775289

Alternate ID(s):: OSTI ID: 1472175

Journal Information:: Advanced Energy Materials, Vol. 8, Issue 30; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 45 works

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