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Temperature Dependent n‐Type Self Doping in Nominally 19‐Electron Half‐Heusler Thermoelectric Materials
Author(s) -
Anand Shashwat,
Xia Kaiyang,
Zhu Tiejun,
Wolverton Chris,
Snyder Gerald Jeffrey
Publication year - 2018
Publication title -
advanced energy materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.08
H-Index - 220
eISSN - 1614-6840
pISSN - 1614-6832
DOI - 10.1002/aenm.201801409
Subject(s) - materials science , thermoelectric effect , doping , condensed matter physics , thermoelectric materials , phase (matter) , electron , vacancy defect , stoichiometry , atmospheric temperature range , seebeck coefficient , density functional theory , thermodynamics , chemistry , computational chemistry , optoelectronics , physics , quantum mechanics
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.