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Title: Achieving zT > 1 in Inexpensive Zintl Phase Ca 9 Zn 4+ x Sb 9 by Phase Boundary Mapping

Authors:
 [1];  [2];  [2];  [3];  [4];  [5];  [3];  [4];  [2];  [1]
  1. Department of Applied Physics and Materials Science, California Institute of Technology, 1200 E. California Blvd Pasadena CA 91125 USA, Department of Materials Science and Engineering, Northwestern University, 2220 Campus Drive Evanston IL 60208 USA
  2. Department of Materials Science and Engineering, Northwestern University, 2220 Campus Drive Evanston IL 60208 USA
  3. Department of Physics and Atmospheric Science, Dalhousie University, 6274 Coburg Rd. Halifax Nova Scotia B3H 4R2 Canada
  4. Thermal Energy Conversion Technologies Group, NASA's Jet Propulsion Laboratory, 4800 Oak Grove Drive Pasadena CA 91109 USA
  5. Department of Chemical Engineering and Materials Science, Michigan State University, 428 S. Shaw Lane East Lansing MI 48824 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1401530
Grant/Contract Number:
FG02-07ER46433
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 27; Journal Issue: 20; Related Information: CHORUS Timestamp: 2017-10-20 17:21:23; Journal ID: ISSN 1616-301X
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Ohno, Saneyuki, Aydemir, Umut, Amsler, Maximilian, Pöhls, Jan-Hendrik, Chanakian, Sevan, Zevalkink, Alex, White, Mary Anne, Bux, Sabah K., Wolverton, Chris, and Snyder, G. Jeffrey. Achieving zT > 1 in Inexpensive Zintl Phase Ca 9 Zn 4+ x Sb 9 by Phase Boundary Mapping. Germany: N. p., 2017. Web. doi:10.1002/adfm.201606361.
Ohno, Saneyuki, Aydemir, Umut, Amsler, Maximilian, Pöhls, Jan-Hendrik, Chanakian, Sevan, Zevalkink, Alex, White, Mary Anne, Bux, Sabah K., Wolverton, Chris, & Snyder, G. Jeffrey. Achieving zT > 1 in Inexpensive Zintl Phase Ca 9 Zn 4+ x Sb 9 by Phase Boundary Mapping. Germany. doi:10.1002/adfm.201606361.
Ohno, Saneyuki, Aydemir, Umut, Amsler, Maximilian, Pöhls, Jan-Hendrik, Chanakian, Sevan, Zevalkink, Alex, White, Mary Anne, Bux, Sabah K., Wolverton, Chris, and Snyder, G. Jeffrey. Wed . "Achieving zT > 1 in Inexpensive Zintl Phase Ca 9 Zn 4+ x Sb 9 by Phase Boundary Mapping". Germany. doi:10.1002/adfm.201606361.
@article{osti_1401530,
title = {Achieving zT > 1 in Inexpensive Zintl Phase Ca 9 Zn 4+ x Sb 9 by Phase Boundary Mapping},
author = {Ohno, Saneyuki and Aydemir, Umut and Amsler, Maximilian and Pöhls, Jan-Hendrik and Chanakian, Sevan and Zevalkink, Alex and White, Mary Anne and Bux, Sabah K. and Wolverton, Chris and Snyder, G. Jeffrey},
abstractNote = {},
doi = {10.1002/adfm.201606361},
journal = {Advanced Functional Materials},
number = 20,
volume = 27,
place = {Germany},
year = {Wed Mar 29 00:00:00 EDT 2017},
month = {Wed Mar 29 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/adfm.201606361

Citation Metrics:
Cited by: 6works
Citation information provided by
Web of Science

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  • In this paper, we report the discovery of two ternary Zintl phases Ba 3Sn 3Sb 4 and Ba 7-xSn 11Sb 15-y, (x = 0.4, y = 0.6). Ba 3Sn 3Sb 4 adopts the monoclinic space group P2 1/c with a = 14.669(3) Å, b = 6.9649(14) Å, c = 13.629(3) Å, and β = 104.98(3)°. It features a unique corrugated two-dimensional (2D) structure consisting of [Sn 3Sb 4] 6- layers extending along the ab plane with Ba 2+ atoms sandwiched between them. The non-stoichiometric Ba 6.6Sn 11Sb 14.4 has a complex one-dimensional (1D) structure adopting the orthorhombic space group Pnma,more » with unit cell parameters a = 37.964(8) Å, b = 4.4090(9) Å and c = 24.682(5) Å. It consists of large double Sn-Sb ribbons separated by Ba 2+ atoms. Ba3Sn3Sb4 is an n-type semiconductor which has a narrow energy gap of ~0.18 eV and a room temperature carrier concentration of ~4.2 × 10 18 cm -3. Lastly, Ba 6.6Sn 11Sb 14.4 is determined to be a metal with electrons being the dominant carriers.« less
  • Crystals of three new ternary pnictides—Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9} have been prepared by reactions of the respective elements in molten Al or Pb fluxes. Single-crystal X-ray diffraction studies reveal that the three phases are isotypic, crystallizing in the orthorhombic Ba{sub 7}Ga{sub 4}Sb{sub 9}-type structure (space group Pmmn, Pearson symbol oP40, Z=2), for which only the prototype is known. The structure is based on TrPn{sub 4} tetrahedra (Tr=Al, Ga; Pn=P, As, Sb), connected in an intricate scheme into 1D-ribbons. Long interchain Pn–Pn bonds (d{sub P–P}>3.0 Å; d{sub As–As}>3.1 Å; d{sub Sb–Sb}>3.3 Å)more » account for the realization of 2D-layers, separated by Ba{sup 2+} cations. Applying the classic valance rules to rationalize the bonding apparently fails, and Ba{sub 7}Ga{sub 4}Sb{sub 9} has long been known as a metallic Zintl phase. Earlier theoretical calculations, both empirical and ab-initio, suggest that the possible metallic properties originate from filled anti-bonding Pn–Pn states, and the special roles of the “cations” in this crystal structure. To experimentally probe this hypothesis, we sought to synthesize the ordered quaternary phases Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga). Single-crystal X-ray diffraction work confirms Ba{sub 6.145(3)}Ca{sub 0.855}Al{sub 4}Sb{sub 9} and Ba{sub 6.235(3)}Ca{sub 0.765}Ga{sub 4}Sb{sub 9}, with Ca atoms preferably substituting Ba on one of the three available sites. The nuances of the five crystal structures are discussed, and the chemical bonding in Ba{sub 7}Ga{sub 4}As{sub 9} is interrogated by tight-binding linear muffin-tin orbital calculations. - Graphical abstract: The new Zintl phases—Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9}, and their quaternary variants Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga)—crystallize in the Ba{sub 7}Ga{sub 4}Sb{sub 9} structure type. The structures are based on TrPn{sub 4} tetrahedra (a perspective of the crystal structure is shown, as viewed along the c axis). - Highlights: • Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9} are new compounds in the respective phase diagrams. • The quaternary phases Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga) show nearly ordered Ba/Ca distribution. • Very weak Pn–Pn bonds and pairing distortion are observed for Ba{sub 7}Ga{sub 4}Pn{sub 9} (Pn=P, As).« less
  • It has been shown previously that the thermoelectric properties of the Zintl phase compound YbCd{sub 2}Sb{sub 2} can be finely tuned via Zn substitution at the Cd-site in the anionic (Cd{sub 2}Sb{sub 2}){sup 2-} framework. Here we report the results of the investigation of isoelectronic substitution of Yb by Ca. The p-type Yb{sub 1-x}Ca{sub x}Cd{sub 2}Sb{sub 2} (0.2{<=}x{<=}0.8) samples have been synthesized via a solid-state reaction followed by suitable cooling, annealing, grinding, and spark plasma sintering densification processes. In samples with x=0.2, 0.4, 0.5, 0.6, 0.8, the electrical conductivity, Seebeck coefficient, and thermal conductivity measurements have been carried out inmore » the temperature range from 300 to 650 K. It is found that the Ca substitution effectively lowers the thermal conductivity for all samples at high temperature, while it significantly increases the Seebeck coefficient. As a result, the dimensionless figure of merit ZT of 0.96 has been attained at 650 K for samples with x=0.4, while the value is 0.78 for the unsubstituted YbCd{sub 2}Sb{sub 2}« less