From Three-Dimensional Clathrates to Two-Dimensional Zintl Phases AMSb2 (A = Rb, Cs; M = Ga, In) Composed of Pentagonal M–Sb Rings

Wang, Jian; Owens-Baird, Bryan; Kovnir, Kirill

doi:10.1021/acs.inorgchem.1c03217

Title: From Three-Dimensional Clathrates to Two-Dimensional Zintl Phases AMSb₂ (A = Rb, Cs; M = Ga, In) Composed of Pentagonal M–Sb Rings

Journal Article · 13 December 2021 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.1c03217 · OSTI ID:2341311

^[1];

^[2];

^[2]

Wichita State Univ., Wichita, KS (United States); University of California Davis
Ames Lab., and Iowa State Univ., Ames, IA (United States)

Three new antimonide Zintl phases, RbGaSb₂, CsGaSb₂, and CsInSb₂, were discovered during exploration of corresponding A–M–Sb (A = Rb, Cs; M = Ga, In) ternary systems while searching for new clathrates. The AGaSb₂ phases crystallize in the tetragonal space group P4₂/nmc (No. 137) in the LiBS₂ structure type, while CsInSb₂ crystallizes in lower symmetry in the orthorhombic space group Cmce (No. 64) in the KGaSb₂ structure type with additional disorder of one of the Cs sites. The crystal structures of all three reported AMSb₂ compounds are composed of two-dimensional [MSb₂]^– tetrahedral layers separated by Rb⁺ or Cs⁺ cations. [MSb₂]^– layers are built from fused M–Sb pentagons and hexagons, which are also the main structural units for A₈M₂₇Sb₁₉ clathrate cages. The semiconductor nature of AMSb₂ was suggested by band structure calculations and confirmed by transport property characterization. CsGaSb₂ is a rare example of an n-type pnictide Zintl phase. Finally, all reported compounds exhibit low thermal conductivity typical for complex antimonides of heavy elements.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Univ. of California, Davis, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: SC0022288

OSTI ID:: 2341311

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 1 Vol. 61; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (64)

Zintl Phases as Thermoelectric Materials: Tuned Transport Properties of the Compounds CaxYb1-xZn2Sb2 Gascoin, F.; Ottensmann, S.; Stark, D. Advanced Functional Materials, Vol. 15, Issue 11 https://doi.org/10.1002/adfm.200500043	journal	November 2005
The Zintl Compound Ca5Al2Sb6 for Low-Cost Thermoelectric Power Generation Toberer, Eric S.; Zevalkink, Alexandra; Crisosto, Nicole Advanced Functional Materials, Vol. 20, Issue 24 https://doi.org/10.1002/adfm.201000970	journal	September 2010
Achieving zT > 1 in Inexpensive Zintl Phase Ca ₉ Zn ₄₊ _x Sb ₉ by Phase Boundary Mapping Ohno, Saneyuki; Aydemir, Umut; Amsler, Maximilian Advanced Functional Materials, Vol. 27, Issue 20 https://doi.org/10.1002/adfm.201606361	journal	March 2017
Perspectives on Thermoelectricity in Layered and 2D Materials Wu, Jing; Chen, Yabin; Wu, Junqiao Advanced Electronic Materials, Vol. 4, Issue 12 https://doi.org/10.1002/aelm.201800248	journal	September 2018
LiBSi ₂ : A Tetrahedral Semiconductor Framework from Boron and Silicon Atoms Bearing Lithium Atoms in the Channels Zeilinger, Michael; van Wüllen, Leo; Benson, Daryn Angewandte Chemie International Edition, Vol. 52, Issue 23 https://doi.org/10.1002/anie.201301540	journal	April 2013
Clathrate XI K ₅₈ Zn ₁₂₂ Sb ₂₀₇ : A New Branch on the Clathrate Family Tree Cox, Tori; Gvozdetskyi, Volodymyr; Bertolami, Mark Angewandte Chemie International Edition, Vol. 60, Issue 1 https://doi.org/10.1002/anie.202011120	journal	October 2020
Growth of GaSb Crystal and Evaluation of Its Thermoelectric Properties Along (111) Plane Jin, Min; Tang, Ziqi; Zhang, Rulin Crystal Research and Technology, Vol. 55, Issue 1 https://doi.org/10.1002/crat.201900156	journal	October 2019
Dipotassium Sodium Diantimonidoindate, K2Na[InSb2], a compound with the polyanion?2[In2Sb2Sb4/2]6? Carrillo-Cabrera, Wilder; Caroca-Canales, Nubia; Von Schnering, Hans Georg Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 619, Issue 10 https://doi.org/10.1002/zaac.19936191015	journal	October 1993
Quantitative Advances in the Zintl–Klemm Formalism Miller, Gordon J.; Schmidt, Michael W.; Wang, Fei Zintl Phases https://doi.org/10.1007/430_2010_24	book	October 2010
The crystal structure and some properties of Eu2Sb3 Chapuis, G.; Hulliger, F.; Schmelczer, R. Journal of Solid State Chemistry, Vol. 31, Issue 1 https://doi.org/10.1016/0022-4596(80)90008-0	journal	January 1980
Thermopower and magneto-thermopower of CeRu2Si2 single crystals Amato, A.; Jaccard, D.; Sierro, J. Journal of Magnetism and Magnetic Materials, Vol. 76-77 https://doi.org/10.1016/0304-8853(88)90389-7	journal	December 1988
Preparation and thermoelectric properties of semiconducting Zn4Sb3 Caillat, T.; Fleurial, J. -P.; Borshchevsky, A. Journal of Physics and Chemistry of Solids, Vol. 58, Issue 7 https://doi.org/10.1016/S0022-3697(96)00228-4	journal	July 1997
Structural diversity of the Zintl pnictides with rare-earth metals Baranets, Sviatoslav; Ovchinnikov, Alexander; Bobev, Svilen Including Actinides https://doi.org/10.1016/bs.hpcre.2021.07.001	book	January 2021
Eu7Ga6Sb8: A Zintl phase with Ga–Ga bonds and polymeric gallium antimonide chains Park, Seon-Mi; Kim, Sung-Jin; Kanatzidis, Mercouri G. Journal of Solid State Chemistry, Vol. 177, Issue 8 https://doi.org/10.1016/j.jssc.2004.04.025	journal	August 2004
Synthesis, structure and properties of the new rare-earth Zintl phase Yb11GaSb9 Bobev, Svilen; Fritsch, Veronika; Thompson, Joe D. Journal of Solid State Chemistry, Vol. 178, Issue 4 https://doi.org/10.1016/j.jssc.2005.01.008	journal	April 2005
High-temperature thermoelectric studies of A11Sb10 (A=Yb, Ca) Brown, Shawna R.; Kauzlarich, Susan M.; Gascoin, Franck Journal of Solid State Chemistry, Vol. 180, Issue 4 https://doi.org/10.1016/j.jssc.2007.02.007	journal	April 2007
Clathrate thermoelectrics Dolyniuk, Juli-Anna; Owens-Baird, Bryan; Wang, Jian Materials Science and Engineering: R: Reports, Vol. 108 https://doi.org/10.1016/j.mser.2016.08.001	journal	October 2016
Unconventional Clathrates with Transition Metal–Phosphorus Frameworks Wang, Jian; Dolyniuk, Juli-Anna; Kovnir, Kirill Accounts of Chemical Research, Vol. 51, Issue 1 https://doi.org/10.1021/acs.accounts.7b00469	journal	December 2017
Observation of an Unexpected n -Type Semiconducting Behavior in the New Ternary Zintl Phase Eu ₃ InAs ₃ Rajput, Kalpna; Baranets, Sviatoslav; Bobev, Svilen Chemistry of Materials, Vol. 32, Issue 22 https://doi.org/10.1021/acs.chemmater.0c03168	journal	September 2020
p-Type to n-Type Conversion through the “Bypass” Phase Transition in the Zintl-Phase Thermoelectric Materials Yeon, Seongbeom; Shin, Seungeun; Jo, Hongil Chemistry of Materials, Vol. 33, Issue 17 https://doi.org/10.1021/acs.chemmater.1c01318	journal	August 2021
Thermoelectric Performance and Defect Chemistry in n-Type Zintl KGaSb ₄ Ortiz, Brenden R.; Gorai, Prashun; Stevanović, Vladan Chemistry of Materials, Vol. 29, Issue 10 https://doi.org/10.1021/acs.chemmater.7b01217	journal	May 2017
Chemical Flexibility of Mg in Pnictide Materials: Structure and Properties Diversity Wang, Jian; Mark, Justin; Woo, Katherine E. Chemistry of Materials, Vol. 31, Issue 20 https://doi.org/10.1021/acs.chemmater.9b03740	journal	September 2019
Discovery of n-Type Zintl Phases RbAlSb ₄ , RbGaSb ₄ , CsAlSb ₄ , and CsGaSb ₄ Ortiz, Brenden R.; Gorai, Prashun; Braden, Tara ACS Applied Energy Materials, Vol. 3, Issue 3 https://doi.org/10.1021/acsaem.0c00048	journal	February 2020
Yb ₁₄ MnSb ₁₁ : New High Efficiency Thermoelectric Material for Power Generation Brown, Shawna R.; Kauzlarich, Susan M.; Gascoin, Franck Chemistry of Materials, Vol. 18, Issue 7 https://doi.org/10.1021/cm060261t	journal	April 2006
Thermoelectric Enhancement in BaGa ₂ Sb ₂ by Zn Doping Aydemir, Umut; Zevalkink, Alex; Ormeci, Alim Chemistry of Materials, Vol. 27, Issue 5 https://doi.org/10.1021/cm5042937	journal	February 2015
New bulk Materials for Thermoelectric Power Generation: Clathrates and Complex Antimonides ^† Kleinke, Holger Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm901591d	journal	February 2010
Zintl Chemistry for Designing High Efficiency Thermoelectric Materials ^† ^‡ Toberer, Eric S.; May, Andrew F.; Snyder, G. Jeffrey Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm901956r	journal	February 2010
A Unique Framework in BaGa ₂ Sb ₂ : A New Zintl Phase with Large Tunnels Kim, Sung-Jin; Kanatzidis, Mercouri G. Inorganic Chemistry, Vol. 40, Issue 15 https://doi.org/10.1021/ic010069n	journal	July 2001
Diverse Polyanions Based on MnBi ₄ and MnSb ₄ Tetrahedra: Polymorphism, Structure, and Bonding in Ca ₂₁ Mn ₄ Bi ₁₈ and Ca ₂₁ Mn ₄ Sb ₁₈ Xia, Sheng-qing; Bobev, Svilen Inorganic Chemistry, Vol. 46, Issue 3 https://doi.org/10.1021/ic061958j	journal	February 2007
A ₅ Sn ₂ As ₆ (A = Sr, Eu). Synthesis, Crystal and Electronic Structure, and Thermoelectric Properties Wang, Jian; Xia, Sheng-Qing; Tao, Xu-Tang Inorganic Chemistry, Vol. 51, Issue 10 https://doi.org/10.1021/ic300308w	journal	May 2012
High Thermoelectric and Reversible p-n-p Conduction Type Switching Integrated in Dimetal Chalcogenide Xiao, Chong; Qin, Xinming; Zhang, Jie Journal of the American Chemical Society, Vol. 134, Issue 44 https://doi.org/10.1021/ja308936b	journal	October 2012
Elusive β-Zn ₈ Sb ₇ : A New Zinc Antimonide Thermoelectric Wang, Jian; Kovnir, Kirill Journal of the American Chemical Society, Vol. 137, Issue 39 https://doi.org/10.1021/jacs.5b08214	journal	September 2015
III–V Clathrate Semiconductors with Outstanding Hole Mobility: Cs ₈ In ₂₇ Sb ₁₉ and A ₈ Ga ₂₇ Sb ₁₉ ( A = Cs, Rb) Owens-Baird, Bryan; Wang, Jian; Wang, Suyin Grass Journal of the American Chemical Society, Vol. 142, Issue 4 https://doi.org/10.1021/jacs.9b12351	journal	December 2019
Reversible switching between p- and n-type conduction in the semiconductor Ag10Te4Br3 Nilges, Tom; Lange, Stefan; Bawohl, Melanie Nature Materials, Vol. 8, Issue 2 https://doi.org/10.1038/nmat2358	journal	January 2009
Ca ₃ AlSb ₃ : an inexpensive, non-toxic thermoelectric material for waste heat recovery Zevalkink, Alex; Toberer, Eric S.; Zeier, Wolfgang G. Energy Environ. Sci., Vol. 4, Issue 2 https://doi.org/10.1039/C0EE00517G	journal	January 2011
Glass-like lattice thermal conductivity and high thermoelectric efficiency in Yb ₉ Mn _4.2 Sb ₉ Bux, Sabah K.; Zevalkink, Alexandra; Janka, Oliver J. Mater. Chem. A, Vol. 2, Issue 1 https://doi.org/10.1039/C3TA14021K	journal	January 2014
Thermoelectric properties of the Zintl phases Yb ₅ M ₂ Sb ₆ (M = Al, Ga, In) Aydemir, Umut; Zevalkink, Alex; Ormeci, Alim Dalton Transactions, Vol. 44, Issue 15 https://doi.org/10.1039/C4DT03773A	journal	January 2015
Synthesis, crystal structure, and thermoelectric properties of two new barium antimony selenides: Ba ₂ Sb ₂ Se ₅ and Ba ₆ Sb ₇ Se _16.11 Wang, Jian; Lee, Kathleen; Kovnir, Kirill Journal of Materials Chemistry C, Vol. 3, Issue 38 https://doi.org/10.1039/C5TC01721A	journal	January 2015
Potential for high thermoelectric performance in n-type Zintl compounds: a case study of Ba doped KAlSb ₄ Ortiz, Brenden R.; Gorai, Prashun; Krishna, Lakshmi Journal of Materials Chemistry A, Vol. 5, Issue 8 https://doi.org/10.1039/C6TA09532A	journal	January 2017
Grain boundary dominated charge transport in Mg ₃ Sb ₂ -based compounds Kuo, Jimmy Jiahong; Kang, Stephen Dongmin; Imasato, Kazuki Energy & Environmental Science, Vol. 11, Issue 2 https://doi.org/10.1039/C7EE03326E	journal	January 2018
Phonon glass behavior beyond traditional cage structures: synthesis, crystal and electronic structure, and properties of KMg ₄ Sb ₃ Wang, Jian; Wang, Lin-Lin; Kovnir, Kirill Journal of Materials Chemistry A, Vol. 6, Issue 11 https://doi.org/10.1039/C8TA00553B	journal	January 2018
Chemically driven superstructural ordering leading to giant unit cells in unconventional clathrates Cs ₈ Zn ₁₈ Sb ₂₈ and Cs ₈ Cd ₁₈ Sb ₂₈ Owens-Baird, Bryan; Yox, Philip; Lee, Shannon Chemical Science, Vol. 11, Issue 37 https://doi.org/10.1039/D0SC03846F	journal	January 2020
The Zintl phases A In ₂ As ₂ (A = Ca, Sr, Ba): new topological insulators and thermoelectric material candidates Ogunbunmi, Michael O.; Baranets, Sviatoslav; Childs, Amanda B. Dalton Transactions, Vol. 50, Issue 26 https://doi.org/10.1039/D1DT01521D	journal	January 2021
Zintl phases for thermoelectric devices Kauzlarich, Susan M.; Brown, Shawna R.; Jeffrey Snyder, G. Dalton Transactions, Issue 21 https://doi.org/10.1039/b702266b	journal	January 2007
Crystal structure, electronic structure, and thermoelectric properties of Ca5Al2Sb6 Yan, Yu Li; Wang, Yuan Xu Journal of Materials Chemistry, Vol. 21, Issue 33 https://doi.org/10.1039/c1jm11463h	journal	January 2011
Phonon engineering through crystal chemistry Toberer, Eric S.; Zevalkink, Alex; Snyder, G. Jeffrey Journal of Materials Chemistry, Vol. 21, Issue 40 https://doi.org/10.1039/c1jm11754h	journal	January 2011
Thermoelectric properties of Sr3GaSb3 – a chain-forming Zintl compound Zevalkink, Alex; Zeier, Wolfgang G.; Pomrehn, Gregory Energy & Environmental Science, Vol. 5, Issue 10 https://doi.org/10.1039/c2ee22378c	journal	January 2012
Thermoelectric properties of Zn-doped Ca3AlSb3 Zeier, Wolfgang G.; Zevalkink, Alex; Schechtel, Eugen Journal of Materials Chemistry, Vol. 22, Issue 19 https://doi.org/10.1039/c2jm31324c	journal	January 2012
Improved thermoelectric properties in Zn-doped Ca5Ga2Sb6 Johnson, Samantha I.; Zevalkink, Alex; Snyder, G. Jeffrey Journal of Materials Chemistry A, Vol. 1, Issue 13 https://doi.org/10.1039/c3ta00844d	journal	January 2013
Enhancing hole mobility in III-V semiconductors Nainani, Aneesh; Bennett, Brian R.; Brad Boos, J. Journal of Applied Physics, Vol. 111, Issue 10 https://doi.org/10.1063/1.4718381	journal	May 2012
A practical field guide to thermoelectrics: Fundamentals, synthesis, and characterization Zevalkink, Alex; Smiadak, David M.; Blackburn, Jeff L. Applied Physics Reviews, Vol. 5, Issue 2 https://doi.org/10.1063/1.5021094	journal	June 2018
A local exchange-correlation potential for the spin polarized case. i Barth, U. von; Hedin, L. Journal of Physics C: Solid State Physics, Vol. 5, Issue 13 https://doi.org/10.1088/0022-3719/5/13/012	journal	July 1972
Thermopower of Ce _{1− x} La _x TiGe with highly degenerate orbital ground state Oeschler, N.; Deppe, M.; Hartmann, S. Journal of Physics: Conference Series, Vol. 200, Issue 1 https://doi.org/10.1088/1742-6596/200/1/012148	journal	January 2010
Layered La Cu O Se : A Promising Anisotropic Thermoelectric Material Wang, Ning; Li, Menglu; Xiao, Haiyan Physical Review Applied, Vol. 13, Issue 2 https://doi.org/10.1103/PhysRevApplied.13.024038	journal	February 2020
Structure of GaSb to 35 GPa McMahon, M. I.; Nelmes, R. J.; Wright, N. G. Physical Review B, Vol. 50, Issue 17 https://doi.org/10.1103/PhysRevB.50.13047	journal	November 1994
Rubidium Indium Antimonide, Rb2In2Sb3 Gourdon, O.; Boucher, F.; Gareh, J. Acta Crystallographica Section C Crystal Structure Communications, Vol. 52, Issue 12 https://doi.org/10.1107/S0108270196010104	journal	December 1996
A short history of SHELX Sheldrick, George M. Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122 https://doi.org/10.1107/S0108767307043930	journal	December 2007
Perantimonidogallate und -indate: Zur Kenntnis von Ca5Ga2Sb6 , Ca5In2Sb6 und Sr5In2Sb6 / Ca5Ga2Sb6, Ca5In2Sb6 and Sr5In2Sb6 : the First Perantimonidogallate and -indates Cordier, Gerhard; Schäfer, Herbert; Stelter, Michael Zeitschrift für Naturforschung B, Vol. 40, Issue 1 https://doi.org/10.1515/znb-1985-0103	journal	January 1985
Crystal structure of dirubidium catenadiantimonidogallate, Rb ₂ GaSb ₂ Cordier, G.; Ochmann, H. Zeitschrift für Kristallographie, Vol. 195, Issue 1-2 https://doi.org/10.1524/zkri.1991.195.1-2.125	journal	January 1991
Crystal structure of dicaesium catena-diantimonidogallate, Cs ₂ GaSb ₂ Cordier, G.; Ochmann, H. Zeitschrift für Kristallographie, Vol. 195, Issue 3-4 https://doi.org/10.1524/zkri.1991.195.3-4.310	journal	January 1991
Crystal structure of dipotassium phyllo-triantimonidodiindate, K ₂ In ₂ Sb ₃ Zeitschrift für Kristallographie - Crystalline Materials, Vol. 197, Issue 3-4 https://doi.org/10.1524/zkri.1991.197.3-4.291	journal	February 1991
Crystal structure of potassium phyllo-diantimonidogallate, KGaSb ₂ Zeitschrift für Kristallographie - Crystalline Materials, Vol. 197, Issue 3-4 https://doi.org/10.1524/zkri.1991.197.3-4.297	journal	February 1991
Crystal structure of hexacaesium triantimonidogallate, Cs ₆ InSb ₃ Blase, W.; Cordier, G.; Somer, M. Zeitschrift für Kristallographie, Vol. 199, Issue 3-4 https://doi.org/10.1524/zkri.1992.199.3-4.277	journal	January 1992
Crystal structure of dicaesium phyllo-triantimonidodiindate, Cs ₂ In ₂ Sb ₃ Zeitschrift für Kristallographie - Crystalline Materials, Vol. 210, Issue 1 https://doi.org/10.1524/zkri.1995.210.1.60	journal	January 1995

Linked Research (3)

Similar Records

Discovery of Ternary Antimonides A–Al–Sb (A = Rb or Cs) with Desired Structural Motifs Guided by Machine Learning

Journal Article · 2024 · Chemistry of Materials · OSTI ID:2382781

Owens-Baird, Bryan; Gvozdetskyi, Volodymyr; Sarkar, Arka; +3 more

From Three-Dimensional Clathrates to Two-Dimensional Zintl Phases AMSb ₂ (A = Rb, Cs; M = Ga, In) Composed of Pentagonal M–Sb Rings

Journal Article · 2021 · Inorganic Chemistry · OSTI ID:1977875

Wang, Jian; Owens-Baird, Bryan; Kovnir, Kirill

Synthesis, Crystal and Electronic Structure of Layered AMSb Compounds (A = Rb, Cs; M = Zn, Cd): Synthesis, Crystal and Electronic Structure of Layered AM Sb Compounds (A = Rb, Cs; M = Zn, Cd)

Journal Article · 2020 · Zeitschrift fuer Anorganische und Allgemeine Chemie · OSTI ID:1597465

Owens-Baird, Bryan; Wang, Lin-Lin; Lee, Shannon; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
cations
crystal structure
elements
solvates
thermal conductivity

CSD 2092907: Experimental Crystal Structure Determination Jian, Wang,; Bryan, Owens-Baird,; Kirill, Kovnir, https://doi.org/10.25505/fiz.icsd.cc287v4j The current record is supplemented by this dataset	dataset	January 2022
CSD 2092908: Experimental Crystal Structure Determination Jian, Wang,; Bryan, Owens-Baird,; Kirill, Kovnir, https://doi.org/10.25505/fiz.icsd.cc287v5k The current record is supplemented by this dataset	dataset	January 2022
CSD 2110517: Experimental Crystal Structure Determination Jian, Wang,; Bryan, Owens-Baird,; Kirill, Kovnir, https://doi.org/10.25505/fiz.icsd.cc28v56j The current record is supplemented by this dataset	dataset	January 2022

Title: From Three-Dimensional Clathrates to Two-Dimensional Zintl Phases AMSb2 (A = Rb, Cs; M = Ga, In) Composed of Pentagonal M–Sb Rings

Citation Formats

References (64)

Linked Research (3)

Similar Records

Related Subjects

Title: From Three-Dimensional Clathrates to Two-Dimensional Zintl Phases AMSb₂ (A = Rb, Cs; M = Ga, In) Composed of Pentagonal M–Sb Rings