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

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 ^[3]; Snyder, Gerald Jeffrey ^[3]

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

The discovery of a semiconducting ground state X_yYZ (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. Here, by systematically investigating the temperature dependence of off-stoichiometry (x) in V_0.8+xCoSb, Nb_0.8+xCoSb, and Ti_0.75+xNiSb 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+xCoSb, and the previously unexplored Ta_0.8+xCoSb.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: SC0001299; SC0014520

OSTI ID:: 1775289

Alternate ID(s):: OSTI ID: 1566395
OSTI ID: 1472175

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

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Evaluation of Half-Heusler Compounds as Thermoelectric Materials Based on the Calculated Electrical Transport Properties Yang, Jiong; Li, Huanming; Wu, Ting Advanced Functional Materials, Vol. 18, Issue 19, p. 2880-2888 https://doi.org/10.1002/adfm.200701369	journal	October 2008
Beneficial Contribution of Alloy Disorder to Electron and Phonon Transport in Half-Heusler Thermoelectric Materials Xie, Hanhui; Wang, Heng; Pei, Yanzhong Advanced Functional Materials, Vol. 23, Issue 41 https://doi.org/10.1002/adfm.201300663	journal	April 2013
Applying Quantitative Microstructure Control in Advanced Functional Composites Heinz, Nicholas A.; Ikeda, Teruyuki; Pei, Yanzhong Advanced Functional Materials, Vol. 24, Issue 15 https://doi.org/10.1002/adfm.201302899	journal	December 2013
Enhanced Thermoelectric Performance in 18-Electron Nb _0.8 CoSb Half-Heusler Compound with Intrinsic Nb Vacancies Xia, Kaiyang; Liu, Yintu; Anand, Shashwat Advanced Functional Materials, Vol. 28, Issue 9 https://doi.org/10.1002/adfm.201705845	journal	January 2018
Compromise and Synergy in High-Efficiency Thermoelectric Materials Zhu, Tiejun; Liu, Yintu; Fu, Chenguang Advanced Materials, Vol. 29, Issue 14 https://doi.org/10.1002/adma.201605884	journal	March 2017
High Band Degeneracy Contributes to High Thermoelectric Performance in p-Type Half-Heusler Compounds Fu, Chenguang; Zhu, Tiejun; Pei, Yanzhong Advanced Energy Materials, Vol. 4, Issue 18 https://doi.org/10.1002/aenm.201400600	journal	August 2014
Defect-Controlled Electronic Properties in A Zn ₂ Sb ₂ Zintl Phases Pomrehn, Gregory S.; Zevalkink, Alex; Zeier, Wolfgang G. Angewandte Chemie, Vol. 126, Issue 13 https://doi.org/10.1002/ange.201311125	journal	February 2014
High Thermoelectric Performance of New Rhombohedral Phase of GeSe stabilized through Alloying with AgSbSe ₂ Huang, Zhiwei; Miller, Samuel A.; Ge, Binghui Angewandte Chemie, Vol. 129, Issue 45 https://doi.org/10.1002/ange.201708134	journal	October 2017
High Thermoelectric Performance of New Rhombohedral Phase of GeSe stabilized through Alloying with AgSbSe ₂ Huang, Zhiwei; Miller, Samuel A.; Ge, Binghui Angewandte Chemie International Edition, Vol. 56, Issue 45 https://doi.org/10.1002/anie.201708134	journal	October 2017
Materials Design and Discovery with High-Throughput Density Functional Theory: The Open Quantum Materials Database (OQMD) Saal, James E.; Kirklin, Scott; Aykol, Muratahan JOM, Vol. 65, Issue 11 https://doi.org/10.1007/s11837-013-0755-4	journal	September 2013
Physical properties of the weak itinerant ferromagnet CoVSb and related semi-Heusler compounds Kaczmarska, K.; Pierre, J.; Beille, J. Journal of Magnetism and Magnetic Materials, Vol. 187, Issue 2 https://doi.org/10.1016/S0304-8853(98)00125-5	journal	August 1998
Thermoelectric high ZT half-Heusler alloys Ti1−x−yZrxHfyNiSn (0 ≤ x ≤ 1; 0 ≤ y ≤ 1) Gürth, M.; Rogl, G.; Romaka, V. V. Acta Materialia, Vol. 104 https://doi.org/10.1016/j.actamat.2015.11.022	journal	February 2016
Mechanical properties of half-Heusler alloys Rogl, G.; Grytsiv, A.; Gürth, M. Acta Materialia, Vol. 107 https://doi.org/10.1016/j.actamat.2016.01.031	journal	April 2016
(V,Nb)-doped half Heusler alloys based on {Ti,Zr,Hf}NiSn with high ZT Rogl, G.; Sauerschnig, P.; Rykavets, Z. Acta Materialia, Vol. 131 https://doi.org/10.1016/j.actamat.2017.03.071	journal	June 2017
Synthesis and thermoelectric properties of n-type half-Heusler compound VCoSb with valence electron count of 19 Zhang, Hao; Wang, Yumei; Huang, Lihong Journal of Alloys and Compounds, Vol. 654 https://doi.org/10.1016/j.jallcom.2015.09.082	journal	January 2016
Phase Boundary Mapping to Obtain n-type Mg3Sb2-Based Thermoelectrics Ohno, Saneyuki; Imasato, Kazuki; Anand, Shashwat Joule, Vol. 2, Issue 1 https://doi.org/10.1016/j.joule.2017.11.005	journal	January 2018
Phase equilibria, formation, crystal and electronic structure of ternary compounds in Ti–Ni–Sn and Ti–Ni–Sb ternary systems Romaka, V. V.; Rogl, P.; Romaka, L. Journal of Solid State Chemistry, Vol. 197 https://doi.org/10.1016/j.jssc.2012.08.023	journal	January 2013
A new n-type half-Heusler thermoelectric material NbCoSb Huang, Lihong; He, Ran; Chen, Shuo Materials Research Bulletin, Vol. 70 https://doi.org/10.1016/j.materresbull.2015.06.022	journal	October 2015
Simple rules for the understanding of Heusler compounds Graf, Tanja; Felser, Claudia; Parkin, Stuart S. P. Progress in Solid State Chemistry, Vol. 39, Issue 1 https://doi.org/10.1016/j.progsolidstchem.2011.02.001	journal	May 2011
Using the 18-Electron Rule To Understand the Nominal 19-Electron Half-Heusler NbCoSb with Nb Vacancies Zeier, Wolfgang G.; Anand, Shashwat; Huang, Lihong Chemistry of Materials, Vol. 29, Issue 3 https://doi.org/10.1021/acs.chemmater.6b04583	journal	January 2017
Designing High-Efficiency Nanostructured Two-Phase Heusler Thermoelectrics Kocevski, Vancho; Wolverton, Chris Chemistry of Materials, Vol. 29, Issue 21 https://doi.org/10.1021/acs.chemmater.7b03379	journal	October 2017
High Thermoelectric Performance in SnTe–AgSbTe ₂ Alloys from Lattice Softening, Giant Phonon–Vacancy Scattering, and Valence Band Convergence Tan, Gangjian; Hao, Shiqiang; Hanus, Riley C. ACS Energy Letters, Vol. 3, Issue 3 https://doi.org/10.1021/acsenergylett.8b00137	journal	February 2018
Engineering half-Heusler thermoelectric materials using Zintl chemistry Zeier, Wolfgang G.; Schmitt, Jennifer; Hautier, Geoffroy Nature Reviews Materials, Vol. 1, Issue 6 https://doi.org/10.1038/natrevmats.2016.32	journal	May 2016
Design and discovery of a novel half-Heusler transparent hole conductor made of all-metallic heavy elements Yan, Feng; Zhang, Xiuwen; Yu, Yonggang G. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8308	journal	June 2015
Realizing high figure of merit in heavy-band p-type half-Heusler thermoelectric materials Fu, Chenguang; Bai, Shengqiang; Liu, Yintu Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9144	journal	September 2015
The Open Quantum Materials Database (OQMD): assessing the accuracy of DFT formation energies Kirklin, Scott; Saal, James E.; Meredig, Bryce npj Computational Materials, Vol. 1, Issue 1 https://doi.org/10.1038/npjcompumats.2015.10	journal	December 2015
The intrinsic disorder related alloy scattering in ZrNiSn half-Heusler thermoelectric materials Xie, Hanhui; Wang, Heng; Fu, Chenguang Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep06888	journal	November 2014
Determining dilute-limit solvus boundaries in multi-component systems using defect energetics: Na in PbTe and PbS Doak, Jeff W.; Michel, Kyle Jay; Wolverton, C. Journal of Materials Chemistry C, Vol. 3, Issue 40 https://doi.org/10.1039/C5TC02252E	journal	January 2015
Enhanced ideal strength of thermoelectric half-Heusler TiNiSn by sub-structure engineering Li, Guodong; An, Qi; Aydemir, Umut Journal of Materials Chemistry A, Vol. 4, Issue 38 https://doi.org/10.1039/C6TA04123J	journal	January 2016
The effect of Sn doping on thermoelectric performance of n-type half-Heusler NbCoSb Huang, Lihong; Zhang, Qinyong; Wang, Yumei Physical Chemistry Chemical Physics, Vol. 19, Issue 37 https://doi.org/10.1039/C7CP04801G	journal	January 2017
Impact of Ni content on the thermoelectric properties of half-Heusler TiNiSn Tang, Yinglu; Li, Xiaoshuang; Martin, Lukas H. J. Energy & Environmental Science, Vol. 11, Issue 2 https://doi.org/10.1039/C7EE03062B	journal	January 2018
A valence balanced rule for discovery of 18-electron half-Heuslers with defects Anand, Shashwat; Xia, Kaiyang; I. Hegde, Vinay Energy & Environmental Science, Vol. 11, Issue 6 https://doi.org/10.1039/C8EE00306H	journal	January 2018
Effect of Ti substitution on the thermoelectric properties of (Zr,Hf)NiSn half-Heusler compounds Sakurada, S.; Shutoh, N. Applied Physics Letters, Vol. 86, Issue 8 https://doi.org/10.1063/1.1868063	journal	February 2005
Atomic and magnetic order in the weak ferromagnet CoVSb: is it a half-metallic ferromagnet? Heyne, L.; Igarashi, T.; Kanomata, T. Journal of Physics: Condensed Matter, Vol. 17, Issue 33 https://doi.org/10.1088/0953-8984/17/33/004	journal	August 2005
False-positive and false-negative assignments of topological insulators in density functional theory and hybrids Vidal, J.; Zhang, X.; Yu, L. Physical Review B, Vol. 84, Issue 4 https://doi.org/10.1103/PhysRevB.84.041109	journal	July 2011
Coherent and incoherent phase stabilities of thermoelectric rocksalt IV-VI semiconductor alloys Doak, Jeff W.; Wolverton, C. Physical Review B, Vol. 86, Issue 14 https://doi.org/10.1103/PhysRevB.86.144202	journal	October 2012
First-Principles Theory of Competing Order Types, Phase Separation, and Phonon Spectra in Thermoelectric AgPb m SbTe m + 2 Alloys Barabash, S. V.; Ozolins, V.; Wolverton, C. Physical Review Letters, Vol. 101, Issue 15 https://doi.org/10.1103/PhysRevLett.101.155704	journal	October 2008
Half-Heusler Semiconductors as Piezoelectrics Roy, Anindya; Bennett, Joseph W.; Rabe, Karin M. Physical Review Letters, Vol. 109, Issue 3 https://doi.org/10.1103/PhysRevLett.109.037602	journal	July 2012
The Open Quantum Materials Database (OQMD): assessing the accuracy of DFT formation energies Kirklin, Scott; Saal, James E.; Meredig, Bryce London : Nature Publ. Group https://doi.org/10.34657/7521	text	January 2015
Half-Heusler semiconductors as piezoelectrics Roy, Anindya; Bennett, Joseph W.; Rabe, Karin M. arXiv https://doi.org/10.48550/arxiv.1107.5078	text	January 2011

Cited By (7)

Design of High‐Performance Disordered Half‐Heusler Thermoelectric Materials Using 18‐Electron Rule Liu, Zihang; Guo, Shuping; Wu, Yixuan Advanced Functional Materials, Vol. 29, Issue 44 https://doi.org/10.1002/adfm.201905044	journal	August 2019
Fiber‐Based Energy Conversion Devices for Human‐Body Energy Harvesting Huang, Liang; Lin, Shizhe; Xu, Zisheng Advanced Materials, Vol. 32, Issue 5 https://doi.org/10.1002/adma.201902034	journal	June 2019
Short-range order in defective half-Heusler thermoelectric crystals Xia, Kaiyang; Nan, Pengfei; Tan, Shihua Energy & Environmental Science, Vol. 12, Issue 5 https://doi.org/10.1039/c8ee03654c	journal	January 2019
The importance of phase equilibrium for doping efficiency: iodine doped PbTe Male, James; Agne, Matthias T.; Goyal, Anuj Materials Horizons, Vol. 6, Issue 7 https://doi.org/10.1039/c9mh00294d	journal	January 2019
Low thermal conductivity and promising thermoelectric performance in A _x CoSb (A = V, Nb or Ta) half-Heuslers with inherent vacancies Ferluccio, Daniella A.; Halpin, John E.; MacIntosh, Kathryn L. Journal of Materials Chemistry C, Vol. 7, Issue 22 https://doi.org/10.1039/c9tc00743a	journal	January 2019
Tuning of Mg content to enhance the thermoelectric properties in binary Mg _{2+ δ} Si ( δ = 0, 0.1, 0.15, 0.2) Balasubramanian, Priyadarshini; Battabyal, Manjusha; Das, Dhruba Materials Research Express, Vol. 6, Issue 12 https://doi.org/10.1088/2053-1591/ab58fb	journal	November 2019
Competition between cubic and tetragonal phases in all- d -metal Heusler alloys, X _{2− x} Mn _{1+ x} V ( X = Pd, Ni, Pt, Ag, Au, Ir, Co; x = 1, 0): a new potential direction of the Heusler family Han, Yilin; Wu, Mengxin; Feng, Yu IUCrJ, Vol. 6, Issue 3 https://doi.org/10.1107/s2052252519004007	journal	April 2019

Similar Records

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 · OSTI ID:1566395

A valence balanced rule for discovery of 18-electron half-Heuslers with defects

Journal Article · Mon Mar 19 20:00:00 EDT 2018 · Energy & Environmental Science · OSTI ID:1775288

Related Subjects

19-electron half-Heuslers
36 MATERIALS SCIENCE
NbCoSb
VCoSb
defects
vacancy

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

Citation Formats

References (40)

Cited By (7)

Similar Records

Related Subjects