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Natural off-stoichiometry causes carrier doping in half-Heusler filled tetrahedral structures

Journal Article · · Physical Review. B
 [1];  [2];  [2]
  1. Univ. of Colorado, Boulder, CO (United States); DOE/OSTI
  2. Univ. of Colorado, Boulder, CO (United States)
+ Show Author Affiliations
The half-Heusler filled tetrahedral structures (FTSs) are zinc-blende-like compounds, where an additional atom is filling its previously empty interstitial site. The FTSs having 18 valence electrons per formula unit are an emerging family of functional materials, whose intrinsic doping trends underlying a wide range of electronic functionalities are yet to be understood. Interestingly, even pristine compounds without any attempt at impurity/chemical doping exhibit intriguing trends in the free carriers they exhibit. Applying the first principles theory of doping to a few prototype compounds in the AIV BXCIV and AIVBIXCV groups, we describe the key ingredients controlling the materials’ propensity for both intrinsic and extrinsic doping: (a) The spontaneous deviations from 1:1:1 stoichiometry reflect predictable thermodynamic stability of specific competing phases. (b) Bulk ABC compounds containing 3d elements in the B position (ZrNiSn and ZrCoSb) are predicted to be naturally 3 d rich. The B = 3d interstitials are the prevailing shallow donors, whereas the potential acceptors (e.g., Zr vacancy and Sn-on-Zr antisite) are ineffective electron killers, resulting in an overall uncompensated n-type character, even without any chemical doping. In these materials, the band edges are “natural impurity bands” due to non-Daltonian off-stoichiometry, such as B interstitials, not intrinsic bulk controlled states as in a perfect crystal. (c) Bulk ABC compounds containing 5d elements in the B position (ZrPtSn, ZrIrSb, and TaIrGe) are predicted to be naturally C rich and A poor. This promotes the hole-producing C-on- A antisite defects rather than B-interstitial donors. The resultant p-type character (without chemical doping) therein is “latent” for C = Sn and Sb; however, as the C-on-A hole-producing acceptors are rather deep and p typeness is manifest only at high temperature or via impurity doping. In contrast, in TaIrGe (B = Ir, 5d), the prevailing hole-producing Ge-on-Ta antisite (C-on- A) is shallow, making it a real p-type compound. This general physical picture establishes the basic trends of carriers in this group of materials.
Research Organization:
Univ. of California, Oakland, CA (United States); Univ. of Colorado, Boulder, CO (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
Grant/Contract Number:
AC02-05CH11231; SC0010467
OSTI ID:
1535862
Alternate ID(s):
OSTI ID: 1342611
Journal Information:
Physical Review. B, Journal Name: Physical Review. B Journal Issue: 8 Vol. 95; ISSN 2469-9950; ISSN PRBMDO
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

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Hf/Sb co-doping induced a high thermoelectric performance of ZrNiSn: First-principles calculation journal November 2017
Prediction of Novel p -Type Transparent Conductors in Layered Double Perovskites: A First-Principles Study journal April 2018
Design of n-Type Transparent Conducting Oxides: The Case of Transition Metal Doping in In 2 O 3 journal February 2018
Manipulation of Ni Interstitials for Realizing Large Power Factor in TiNiSn‐Based Materials journal May 2019
Design of Mixed‐Cation Tri‐Layered Pb‐Free Halide Perovskites for Optoelectronic Applications journal May 2019
Instilling defect tolerance in new compounds journal September 2017
Native defects and impurity band behavior in half-Heusler thermoelectric NbFeSb journal January 2018
Self-propagation high-temperature synthesis of half-Heusler thermoelectric materials: reaction mechanism and applicability journal January 2018
Valence-band offsets of CoTiSb/In 0.53 Ga 0.47 As and CoTiSb/In 0.52 Al 0.48 As heterojunctions journal August 2017
Electronic structure of epitaxial half-Heusler Co 1-x Ni x TiSb across the semiconductor to metal transition journal August 2018
Heusler interfaces—Opportunities beyond spintronics? journal August 2019
Physical, electronic and thermoelectric properties of [001] surfaces of TiCoSb half-Heusler compound journal May 2019
Native defects in the Co 2 Ti Z ( Z = Si , Ge , Sn ) full Heusler alloys: Formation and influence on the thermoelectric properties journal August 2017
Band structure and thermoelectric properties of half-Heusler semiconductors from many-body perturbation theory journal January 2018
Band Structures and Transport Properties of High-Performance Half-Heusler Thermoelectric Materials by First Principles journal May 2018

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