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Title: Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A8GaxSn46–x (A = Rb, Cs; 6.9 < x < 7.5)

Abstract

Exploratory studies in the systems Rb–Ga–Sn and Cs–Ga–Sn yielded the cubic type-I clathrates with refined compositions Rb8GaxSn46–x and Cs8GaxSn46–x (6.9 < x < 7.5). Nearly single-phase materials with good crystallinity were obtained from stoichiometric reactions of the elements. The structures were characterized by means of single-crystal X-ray diffraction methods. Both Rb8GaxSn46–x and Cs8GaxSn46–x represents cases, where a Group 13 element randomly substitutes a Group 14 element in the structure. The extent of Ga/Sn mixing is apparently governed by the drive of the system to achieve an optimal valence electron count, and hence, Rb8GaxSn46–x and Cs8GaxSn46–x (x ≈ 8) can be regarded as Zintl phases. This notion is supported by structure refinements on a multitude of single-crystal X-ray diffraction data, which also confirm that both types of cages in the cubic type-I structure are fully occupied by Rb and Cs atoms. The open-framework, comprised of 46 nodes per formula unit, adapts to the incorporation of nearly eight Ga atoms within the matrix of Sn, whereby small, short-range distortions result. The exact nature of these effects is still unclear, as so far, the structural variations could only be modeled as both positional and occupational disorder at one of three framework sites. Sincemore » vacancies in the structures of the binary type-I clathrates A8Sn46–x x (A = Rb, Cs; = missing Sn atom) are also known to cause local distortions, the latter were also synthesized with the same protocols used for the synthesis of A8GaxSn46–x and structurally re-analyzed. The results from the latter studies confirm that homogeneity issues abound, and that the final structures/compositions are an intricate function of the experimental conditions.« less

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of Delaware, Newark, DE (United States)
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1697974
Grant/Contract Number:  
SC0008885
Resource Type:
Accepted Manuscript
Journal Name:
Crystals
Additional Journal Information:
Journal Volume: 10; Journal Issue: 4; Journal ID: ISSN 2073-4352
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; clathrates; type-I structure; Zintl phases; crystal structures

Citation Formats

Baranets, Sviatoslav A., Childs, Amanda B., He, Hua, and Bobev, Svilen. Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A8GaxSn46–x (A = Rb, Cs; 6.9 < x < 7.5). United States: N. p., 2020. Web. https://doi.org/10.3390/cryst10040298.
Baranets, Sviatoslav A., Childs, Amanda B., He, Hua, & Bobev, Svilen. Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A8GaxSn46–x (A = Rb, Cs; 6.9 < x < 7.5). United States. https://doi.org/10.3390/cryst10040298
Baranets, Sviatoslav A., Childs, Amanda B., He, Hua, and Bobev, Svilen. Mon . "Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A8GaxSn46–x (A = Rb, Cs; 6.9 < x < 7.5)". United States. https://doi.org/10.3390/cryst10040298. https://www.osti.gov/servlets/purl/1697974.
@article{osti_1697974,
title = {Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of A8GaxSn46–x (A = Rb, Cs; 6.9 < x < 7.5)},
author = {Baranets, Sviatoslav A. and Childs, Amanda B. and He, Hua and Bobev, Svilen},
abstractNote = {Exploratory studies in the systems Rb–Ga–Sn and Cs–Ga–Sn yielded the cubic type-I clathrates with refined compositions Rb8GaxSn46–x and Cs8GaxSn46–x (6.9 < x < 7.5). Nearly single-phase materials with good crystallinity were obtained from stoichiometric reactions of the elements. The structures were characterized by means of single-crystal X-ray diffraction methods. Both Rb8GaxSn46–x and Cs8GaxSn46–x represents cases, where a Group 13 element randomly substitutes a Group 14 element in the structure. The extent of Ga/Sn mixing is apparently governed by the drive of the system to achieve an optimal valence electron count, and hence, Rb8GaxSn46–x and Cs8GaxSn46–x (x ≈ 8) can be regarded as Zintl phases. This notion is supported by structure refinements on a multitude of single-crystal X-ray diffraction data, which also confirm that both types of cages in the cubic type-I structure are fully occupied by Rb and Cs atoms. The open-framework, comprised of 46 nodes per formula unit, adapts to the incorporation of nearly eight Ga atoms within the matrix of Sn, whereby small, short-range distortions result. The exact nature of these effects is still unclear, as so far, the structural variations could only be modeled as both positional and occupational disorder at one of three framework sites. Since vacancies in the structures of the binary type-I clathrates A8Sn46–x x (A = Rb, Cs; = missing Sn atom) are also known to cause local distortions, the latter were also synthesized with the same protocols used for the synthesis of A8GaxSn46–x and structurally re-analyzed. The results from the latter studies confirm that homogeneity issues abound, and that the final structures/compositions are an intricate function of the experimental conditions.},
doi = {10.3390/cryst10040298},
journal = {Crystals},
number = 4,
volume = 10,
place = {United States},
year = {2020},
month = {4}
}

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Works referenced in this record:

Why are Clathrates Good Candidates for Thermoelectric Materials?
journal, February 2000

  • Iversen, Bo B.; Palmqvist, Anders E. C.; Cox, David E.
  • Journal of Solid State Chemistry, Vol. 149, Issue 2
  • DOI: 10.1006/jssc.1999.8534

Thermoelectric clathrates of type I
journal, January 2010

  • Christensen, Mogens; Johnsen, Simon; Iversen, Bo Brummerstedt
  • Dalton Trans., Vol. 39, Issue 4
  • DOI: 10.1039/B916400F

Clathrate Structure of Silicon Na8Si46 and NaxSi136 (x < 11)
journal, December 1965


Clathrates of Group 14 with Alkali Metals: An Exploration
journal, August 2000

  • Bobev, Svilen; Sevov, Slavi C.
  • Journal of Solid State Chemistry, Vol. 153, Issue 1
  • DOI: 10.1006/jssc.2000.8755

Mechanism of Rare Earth Incorporation and Crystal Growth of Rare Earth Containing Type-I Clathrates
journal, November 2015

  • Prokofiev, Andrey; Svagera, Robert; Waas, Monika
  • Crystal Growth & Design, Vol. 16, Issue 1
  • DOI: 10.1021/acs.cgd.5b00461

New type-I clathrates with ordered Eu distribution
journal, August 2006


III–V Clathrate Semiconductors with Outstanding Hole Mobility: Cs 8 In 27 Sb 19 and A 8 Ga 27 Sb 19 ( A = Cs, Rb)
journal, December 2019

  • Owens-Baird, Bryan; Wang, Jian; Wang, Suyin Grass
  • Journal of the American Chemical Society, Vol. 142, Issue 4
  • DOI: 10.1021/jacs.9b12351

A guest-free germanium clathrate
journal, September 2006

  • Guloy, Arnold M.; Ramlau, Reiner; Tang, Zhongjia
  • Nature, Vol. 443, Issue 7109
  • DOI: 10.1038/nature05145

Inorganic clathrate-II materials of group 14: synthetic routes and physical properties
journal, January 2008

  • Beekman, M.; Nolas, G. S.
  • J. Mater. Chem., Vol. 18, Issue 8
  • DOI: 10.1039/B706808E

Structural Principles of Semiconducting Group 14 Clathrate Frameworks
journal, March 2011

  • Karttunen, Antti J.; Fässler, Thomas F.; Linnolahti, Mikko
  • Inorganic Chemistry, Vol. 50, Issue 5
  • DOI: 10.1021/ic102178d

New Type-I and Type-II Clathrates in the Systems Cs–Na–Ga–Si, Rb–Na–Ga–Si, and Rb–Na–Zn–Si
journal, March 2014


Synthesis and Structural Characterization of the New Clathrates K8Cd4Ge42, Rb8Cd4Ge42, and Cs8Cd4Ge42
journal, March 2016


Synthesis and structural characterization of the type-I clathrates K 8 Al x Sn 46– x and Rb 8 Al x Sn 46– x ( x ≃ 6.4–9.7)
journal, October 2019

  • Baranets, Sviatoslav; Schäfer, Marion; Bobev, Svilen
  • Acta Crystallographica Section C Structural Chemistry, Vol. 75, Issue 11
  • DOI: 10.1107/S205322961901427X

Zintl Phases: Transitions between Metallic and Ionic Bonding
journal, September 1973

  • Schäfer, Herbert; Eisenmann, Brigitte; Müller, Wiking
  • Angewandte Chemie International Edition in English, Vol. 12, Issue 9
  • DOI: 10.1002/anie.197306941

Preparation, Transport Properties, and Structure Analysis by Resonant X-ray Scattering of the Type I Clathrate Cs 8 Cd 4 Sn 42
journal, March 2002

  • Wilkinson, A. P.; Lind, C.; Young, R. A.
  • Chemistry of Materials, Vol. 14, Issue 3
  • DOI: 10.1021/cm0107880

Synthesis of Large Single Crystals and Thermoelectrical Properties of the Type-I Clathrate K 8 Zn 4 Sn 42: The Type-I Clathrate K 8 Zn 4 Sn 42
journal, August 2013

  • Baran, Volodymyr; Fischer, Andreas; Scherer, Wolfgang
  • Zeitschrift für anorganische und allgemeine Chemie, Vol. 639, Issue 12-13
  • DOI: 10.1002/zaac.201300383

Transport properties of polycrystalline type-I Sn clathrates
journal, April 2002


K and Ba distribution in the structures of the clathrate compounds K x Ba 16− x (Ga,Sn) 136 ( x = 0.8, 4.4, and 12.9) and K x Ba 8− x (Ga,Sn) 46 ( x = 0.3)
journal, March 2013

  • Schäfer, Marion C.; Bobev, Svilen
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 69, Issue 4
  • DOI: 10.1107/S0108270113006203

Structural characterization and low-temperature physical properties of p-type single-crystal K8Ga8.5Sn37.5 grown by self-flux method
journal, August 2013


Interplay between thermoelectric and structural properties of type-I clathrate K 8 Ga 8 Sn 38 single crystals
journal, April 2010


Crystal structure of the clathrates K8Al8Ge38 and K8Al8Sn38
journal, April 1998

  • Kröner, R.; Peters, K.; Schnering, H. G. von
  • Zeitschrift für Kristallographie - New Crystal Structures, Vol. 213, Issue 1-4
  • DOI: 10.1524/ncrs.1998.213.14.715

Crystal structure of the clathrates Rb8Al8Ge38 and Rb8Al8Sn38
journal, April 1998

  • Kröner, R.; Peters, K.; Schnering, H. G. von
  • Zeitschrift für Kristallographie - New Crystal Structures, Vol. 213, Issue 1-4
  • DOI: 10.1524/ncrs.1998.213.14.709

Crystal structure of the clathrates Rb8Ga8Sn38, Rb8Ga8Ge38 and Rb8Ga8Si38
journal, April 1998

  • Schnering, H. G. von; Kröner, R.; Menke, H.
  • Zeitschrift für Kristallographie - New Crystal Structures, Vol. 213, Issue 1-4
  • DOI: 10.1524/ncrs.1998.213.14.717

On the possibility for Rb- and Eu-cation ordering in type-I clathrates: synthesis and homogeneity range of the novel compounds Rb 8– x Eu x (In,Ge) 46 (0.6 ≤ x ≤ 1.8)
journal, November 2013

  • Schäfer, Marion C.; Bobev, Svilen
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 69, Issue 12
  • DOI: 10.1107/S0108270113030011

Crystal structure and thermoelectric properties of K x Ba 8− x Zn y Ge 46− y clathrates
journal, May 2012

  • Kishimoto, Kengo; Sasaki, Yuta; Koyanagi, Tsuyoshi
  • Journal of Applied Physics, Vol. 111, Issue 9
  • DOI: 10.1063/1.4711100

Crystal structure of the defect clathrate Cs8Sn44□2
journal, February 2000

  • von Schnering, H. G.; Kröner, R.; Baitinger, M.
  • Zeitschrift für Kristallographie - New Crystal Structures, Vol. 215, Issue 2
  • DOI: 10.1515/ncrs-2000-0207

Effects of the order–disorder phase transition on the physical properties of A8Sn44□2 (A = Rb, Cs)
journal, January 2008

  • Kaltzoglou, Andreas; Fässler, Thomas; Christensen, Mogens
  • Journal of Materials Chemistry, Vol. 18, Issue 46
  • DOI: 10.1039/b810783a

SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053273314026370

Crystal structure refinement with SHELXL
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218

STRUCTURE TIDY – a computer program to standardize crystal structure data
journal, April 1987


Niobium-bearing arsenides and germanides from elemental mixtures not involving niobium: a new twist to an old problem in solid-state synthesis
journal, April 2018

  • Baranets, Sviatoslav; He, Hua; Bobev, Svilen
  • Acta Crystallographica Section C Structural Chemistry, Vol. 74, Issue 5
  • DOI: 10.1107/S2053229618005739

A Combined Metal-Halide/Metal Flux Synthetic Route towards Type-I Clathrates: Crystal Structures and Thermoelectric Properties of A 8 Al 8 Si 38 (A=K, Rb, and Cs)
journal, September 2014

  • Baran, Volodymyr; Senyshyn, Anatoliy; Karttunen, Antti J.
  • Chemistry - A European Journal, Vol. 20, Issue 46
  • DOI: 10.1002/chem.201403416

Tin Clathrates with the Type II Structure
journal, January 2013

  • Schäfer, Marion C.; Bobev, Svilen
  • Journal of the American Chemical Society, Vol. 135, Issue 5
  • DOI: 10.1021/ja3112934

Structural Characterization and Thermal Conductivity of Type-I Tin Clathrates
journal, July 2000

  • Nolas, G. S.; Chakoumakos, B. C.; Mahieu, B.
  • Chemistry of Materials, Vol. 12, Issue 7
  • DOI: 10.1021/cm990686y

Ordering of Vacancies in Type-I Tin Clathrate:  Superstructure of Rb 8 Sn 442
journal, March 2005

  • Dubois, Franck; Fässler, Thomas F.
  • Journal of the American Chemical Society, Vol. 127, Issue 10
  • DOI: 10.1021/ja043500r

Order-Disorder Phase Transition in Type-I Clathrate Cs8Sn44□2
journal, September 2007

  • Kaltzoglou, Andreas; Hoffmann, Stephan D.; Fässler, Thomas F.
  • European Journal of Inorganic Chemistry, Vol. 2007, Issue 26
  • DOI: 10.1002/ejic.200700644

Clathrates and semiclathrates of Type-I: crystal structure and superstructures
journal, May 2013

  • Kirsanova, Maria A.; Shevelkov, Andrei V.
  • Zeitschrift für Kristallographie - Crystalline Materials, Vol. 228, Issue 5
  • DOI: 10.1524/zkri.2013.1608