Synthesis and structural characterization of the new Zintl phases Ba3Cd2P4 and Ba2Cd2P3. Rare example of small gap semiconducting behavior with negative thermopower within the range 300 K-700 K
Abstract
The new Zintl phases Ba3Cd2P4 and Ba2Cd2P3 have been synthesized using Pb flux, which allowed for the growth of 4-5 mm large crystals. The structures were determined utilizing single-crystal X-ray diffraction methods. Both compounds crystalize in the monoclinic crystal system (space group C2/m (No. 12)) and their structures are closely related. The structure of Ba3Cd2P4 can be seen as being comprised of divalent Ba atoms and conjoined CdP4 tetrahedra in the form of [Cd2P4]6- layers. Within the layers, homoatomic P–P bonds are present, which if cleaved, leave two infinite [CdP3]7- chains running along the crystallographic b-axis. The other structure, that of Ba2Cd2P3, can be rationalized as also having divalent Ba atoms and conjoined CdP4 tetrahedra in the form of [Cd2P3]6- layers. These layers, again, can be visualized as chains that run down the crystallographic b-axis, which are further connected by P-P dimers. Electronic band structure calculations show that each structure has an optimal number of valence electrons, and therefore conform to the Zintl-Klemm concept. Accordingly, the two compounds can be considered small band gap semiconductors, with band gaps of ca. 0.1 eV and 0.6 eV for Ba3Cd2P4 and Ba2Cd2P3, respectively. Electrical resistivity measurements show that Ba3Cd2P4 displays a large resistivitymore »
- Publication Date:
- Research Org.:
- Univ. of Delaware, Newark, DE (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1696968
- Alternate Identifier(s):
- OSTI ID: 1776100
- Grant/Contract Number:
- SC0008885
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Solid State Chemistry
- Additional Journal Information:
- Journal Volume: 289; Journal ID: ISSN 0022-4596
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Crystal structure; Single-crystal X-ray diffraction; Thermoelectrics; Zintl phases
Citation Formats
Balvanz, Adam, Baranets, Sviatoslav, and Bobev, Svilen. Synthesis and structural characterization of the new Zintl phases Ba3Cd2P4 and Ba2Cd2P3. Rare example of small gap semiconducting behavior with negative thermopower within the range 300 K-700 K. United States: N. p., 2020.
Web. doi:10.1016/j.jssc.2020.121476.
Balvanz, Adam, Baranets, Sviatoslav, & Bobev, Svilen. Synthesis and structural characterization of the new Zintl phases Ba3Cd2P4 and Ba2Cd2P3. Rare example of small gap semiconducting behavior with negative thermopower within the range 300 K-700 K. United States. https://doi.org/10.1016/j.jssc.2020.121476
Balvanz, Adam, Baranets, Sviatoslav, and Bobev, Svilen. Thu .
"Synthesis and structural characterization of the new Zintl phases Ba3Cd2P4 and Ba2Cd2P3. Rare example of small gap semiconducting behavior with negative thermopower within the range 300 K-700 K". United States. https://doi.org/10.1016/j.jssc.2020.121476. https://www.osti.gov/servlets/purl/1696968.
@article{osti_1696968,
title = {Synthesis and structural characterization of the new Zintl phases Ba3Cd2P4 and Ba2Cd2P3. Rare example of small gap semiconducting behavior with negative thermopower within the range 300 K-700 K},
author = {Balvanz, Adam and Baranets, Sviatoslav and Bobev, Svilen},
abstractNote = {The new Zintl phases Ba3Cd2P4 and Ba2Cd2P3 have been synthesized using Pb flux, which allowed for the growth of 4-5 mm large crystals. The structures were determined utilizing single-crystal X-ray diffraction methods. Both compounds crystalize in the monoclinic crystal system (space group C2/m (No. 12)) and their structures are closely related. The structure of Ba3Cd2P4 can be seen as being comprised of divalent Ba atoms and conjoined CdP4 tetrahedra in the form of [Cd2P4]6- layers. Within the layers, homoatomic P–P bonds are present, which if cleaved, leave two infinite [CdP3]7- chains running along the crystallographic b-axis. The other structure, that of Ba2Cd2P3, can be rationalized as also having divalent Ba atoms and conjoined CdP4 tetrahedra in the form of [Cd2P3]6- layers. These layers, again, can be visualized as chains that run down the crystallographic b-axis, which are further connected by P-P dimers. Electronic band structure calculations show that each structure has an optimal number of valence electrons, and therefore conform to the Zintl-Klemm concept. Accordingly, the two compounds can be considered small band gap semiconductors, with band gaps of ca. 0.1 eV and 0.6 eV for Ba3Cd2P4 and Ba2Cd2P3, respectively. Electrical resistivity measurements show that Ba3Cd2P4 displays a large resistivity value at room temperature and an experimental band gap of ca. 0.05 eV, which fits reasonably well with the theoretical predictions. Thermopower measurements show that throughout the temperature range 300 K-700 K, Ba3Cd2P4 displays a negative Seebeck coefficient. Here, the extremum value of -84 μV is reached at 630 K, suggestive of an n-type semiconductor, a rarity among Zintl phases.},
doi = {10.1016/j.jssc.2020.121476},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 289,
place = {United States},
year = {Thu May 28 00:00:00 EDT 2020},
month = {Thu May 28 00:00:00 EDT 2020}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Einige Probleme aus der Physik und der Chemie der Halbmetalle und der Metametalle
journal, March 1950
- Klemm, W.
- Angewandte Chemie, Vol. 62, Issue 6
Zintl phases with group 15 elements and the transition metals: A brief overview of pnictides with diverse and complex structures
journal, February 2019
- Ovchinnikov, Alexander; Bobev, Svilen
- Journal of Solid State Chemistry, Vol. 270
Structure and chemical bonding in zintl-phases containing lithium
journal, January 1990
- Nesper, Reinhard
- Progress in Solid State Chemistry, Vol. 20, Issue 1
Zintl phases for thermoelectric devices
journal, January 2007
- Kauzlarich, Susan M.; Brown, Shawna R.; Jeffrey Snyder, G.
- Dalton Transactions, Issue 21
Recent progress and future challenges on thermoelectric Zintl materials
journal, June 2017
- Shuai, Jing; Mao, Jun; Song, Shaowei
- Materials Today Physics, Vol. 1
New Manganese-Bearing Antimonides and Bismuthides with Complex Structures. Synthesis, Structural Characterization, and Electronic Properties of Yb 9 Mn 4+ x Pn 9 ( Pn = Sb or Bi) †
journal, February 2010
- Xia, Sheng-Qing; Bobev, Svilen
- Chemistry of Materials, Vol. 22, Issue 3
Interplay between Size and Electronic Effects in Determining the Homogeneity Range of the A 9 Zn 4+ x Pn 9 and A 9 Cd 4+ x Pn 9 Phases (0 ≤ x ≤ 0.5), A = Ca, Sr, Yb, Eu; Pn = Sb, Bi
journal, August 2007
- Xia, Sheng-qing; Bobev, Svilen
- Journal of the American Chemical Society, Vol. 129, Issue 32
Zintl Phase Variations Through Cation Selection. Synthesis and Structure of A 21 Cd 4 Pn 18 (A = Eu, Sr, Ba; Pn = Sb, Bi)
journal, March 2008
- Xia, Sheng-Qing; Bobev, Svilen
- Inorganic Chemistry, Vol. 47, Issue 6
Ba 11 Cd 8 Bi 14 : Bismuth Zigzag Chains in a Ternary Alkaline-Earth Transition-Metal Zintl Phase
journal, September 2006
- Xia, Sheng-qing; Bobev, Svilen
- Inorganic Chemistry, Vol. 45, Issue 18
Synthesis, Structural Characterization, Electronic Structure, and Magnetic Properties of the Zintl Phase Eu10Cd6Bi12
journal, May 2007
- Xia, Sheng-qing; Bobev, Svilen
- Chemistry – An Asian Journal, Vol. 2, Issue 5
Synthesis, structure and physical properties of the new Zintl phases Eu11Zn6Sb12 and Eu11Cd6Sb12
journal, October 2008
- Saparov, Bayrammurad; Bobev, Svilen; Ozbay, Arif
- Journal of Solid State Chemistry, Vol. 181, Issue 10
New ternary phosphides and arsenides. Syntheses, crystal structures, physical properties of Eu2ZnP2, Eu2Zn2P3 and Eu2Cd2As3
journal, September 2013
- Wang, Jian; Xia, Sheng-Qing; Tao, Xu-Tang
- Journal of Solid State Chemistry, Vol. 205
Synthesis, crystal structures, and physical properties of the new Zintl phases A21Zn4Pn18 (A=Ca, Eu; Pn=As, Sb)—Versatile arrangements of [ZnPn4] tetrahedra
journal, July 2015
- Suen, Nian-Tzu; Wang, Yi; Bobev, Svilen
- Journal of Solid State Chemistry, Vol. 227
Cation−Anion Interactions as Structure Directing Factors: Structure and Bonding of Ca 2 CdSb 2 and Yb 2 CdSb 2
journal, April 2007
- Xia, Sheng-qing; Bobev, Svilen
- Journal of the American Chemical Society, Vol. 129, Issue 13
Synthesis, Crystal and Electronic Structures, and Properties of the New Pnictide Semiconductors A 2 Cd Pn 2 ( A = Ca, Sr, Ba, Eu; Pn = P, As)
journal, September 2011
- Wang, Jian; Yang, Min; Pan, Ming-Yan
- Inorganic Chemistry, Vol. 50, Issue 17
Isolated ∞ 1 [ZnPn 2 ] 4− Chains in the Zintl Phases Ba 2 ZnPn 2 (Pn = As, Sb, Bi)—Synthesis, Structure, and Bonding
journal, June 2010
- Saparov, Bayrammurad; Bobev, Svilen
- Inorganic Chemistry, Vol. 49, Issue 11
Synthesis, Crystal Structures and Properties of the Zintl Phases Sr2ZnP2, Sr2ZnAs2, A2ZnSb2 and A2ZnBi2 (A = Sr and Eu)
journal, August 2011
- Wilson, Dereck K.; Saparov, Bayrammurad; Bobev, Svilen
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 637, Issue 13
Synthesis, crystallographic and theoretical studies of the new Zintl phases Ba2Cd2Pn3 (Pn = As, Sb), and the solid solutions (Ba 1–x Sr x ) 2 Cd 2 Sb 3 and Ba 2 Cd 2 (Sb 1–x As x ) 3
journal, January 2010
- Saparov, Bayrammurad; He, Hua; Zhang, Xiaohang
- Dalton Trans., Vol. 39, Issue 4
Electronic structure and transport properties of Ba2Cd2Pn3 (Pn = As and Sb): An efficient materials for energy conversion
journal, June 2016
- Reshak, A. H.
- Journal of Alloys and Compounds, Vol. 670
Synthesis, Structure, and Bonding of the Zintl Phase Ba 3 Cd 2 Sb 4
journal, December 2008
- Saparov, Bayrammurad; Xia, Sheng-qing; Bobev, Svilen
- Inorganic Chemistry, Vol. 47, Issue 23
Syntheses, crystal structure and physical properties of new Zintl phases Ba3T2As4 (T=Zn, Cd)
journal, February 2013
- Wang, Jian; Xia, Sheng-Qing; Tao, Xu-Tang
- Journal of Solid State Chemistry, Vol. 198
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
OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009
- Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
- Journal of Applied Crystallography, Vol. 42, Issue 2
Crystal structure refinement with SHELXL
journal, January 2015
- Sheldrick, George M.
- Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
A local exchange-correlation potential for the spin polarized case. i
journal, July 1972
- Barth, U. von; Hedin, L.
- Journal of Physics C: Solid State Physics, Vol. 5, Issue 13
Improved tetrahedron method for Brillouin-zone integrations
journal, June 1994
- Blöchl, Peter E.; Jepsen, O.; Andersen, O. K.
- Physical Review B, Vol. 49, Issue 23
Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations
journal, August 1993
- Dronskowski, Richard; Bloechl, Peter E.
- The Journal of Physical Chemistry, Vol. 97, Issue 33
Ternary Arsenides A 2 Zn 2 As 3 (A = Sr, Eu) and Their Stuffed Derivatives A 2 Ag 2 ZnAs 3
journal, January 2012
- Stoyko, Stanislav S.; Khatun, Mansura; Mar, Arthur
- Inorganic Chemistry, Vol. 51, Issue 4
Some Revisions of the Covalent Radii and the Additivity Rule for the Lengths of Partially Ionic Single Covalent Bonds *
journal, January 1941
- Schomaker, Verner; Stevenson, D. P.
- Journal of the American Chemical Society, Vol. 63, Issue 1
Darstellung und Kristallstruktur von BaMn2Sb2, BaZn2Sb2 und BaCd2Sb2 / Preparation and Crystal Structure of BaMn2Sb2 , BaZn2Sb2 and BaCd2Sb2
journal, July 1979
- Brechtel, Erwin; Cordier, Gerhard; Schäfer, Herbert
- Zeitschrift für Naturforschung B, Vol. 34, Issue 7
Two polymorphs of Ba3Sn2P4: Single crystal and electronic structures
journal, March 2007
- Dong, Yongkwan; Ranjan, Chinmoy; DiSalvo, Francis J.
- Journal of Alloys and Compounds, Vol. 430, Issue 1-2
Flux Growth and Electronic Properties of Ba 2 In 5 Pn 5 (Pn = P, As): Zintl Phases Exhibiting Metallic Behavior
journal, September 2008
- Mathieu, Josiah; Achey, Randall; Park, Ju-Hyun
- Chemistry of Materials, Vol. 20, Issue 17
BaGa 2 Pn 2 ( Pn = P, As): New Semiconducting Phosphides and Arsenides with Layered Structures
journal, September 2010
- He, Hua; Stearrett, Ryan; Nowak, Edmund R.
- Inorganic Chemistry, Vol. 49, Issue 17
Synthesis, Crystal and Electronic Structures of the New Zintl phases Ba 3 Al 3 Pn 5 ( Pn = P, As) and Ba 3 Ga 3 P 5
journal, December 2012
- He, Hua; Tyson, Chauntae; Saito, Maia
- Inorganic Chemistry, Vol. 52, Issue 1
Five new ternary indium-arsenides discovered. Synthesis and structural characterization of the Zintl phases Sr3In2As4, Ba3In2As4, Eu3In2As4, Sr5In2As6 and Eu5In2As6
journal, October 2019
- Childs, Amanda B.; Baranets, Sviatoslav; Bobev, Svilen
- Journal of Solid State Chemistry, Vol. 278
Synthesis and structure of Sr14Zn1+As11 and Eu14Zn1+As11 (x ≤ 0.5). New members of the family of pnictides isotypic with Ca14AlSb11, exhibiting a new type of structural disorder
journal, December 2019
- Baranets, Sviatoslav; Darone, Gregory M.; Bobev, Svilen
- Journal of Solid State Chemistry, Vol. 280
From the Ternary Phase Ca 14 Zn 1+δ Sb 11 (δ ≈ 0.4) to the Quaternary Solid Solutions Ca 14– x RE x ZnSb 11 (RE = La–Nd, Sm, Gd, x ≈ 0.9). A Tale of Electron Doping via Rare-Earth Metal Substitutions and the Concomitant Structural Transformations
journal, June 2019
- Baranets, Sviatoslav; Bobev, Svilen
- Inorganic Chemistry, Vol. 58, Issue 13
Synthesis, crystal structure and physical properties of the solid solutions Ca 14– x RE x CdSb 11 ( RE = La–Nd, Sm, Gd–Yb, x ≈ 0.85 ± 0.15)
journal, June 2019
- Baranets, Sviatoslav; Voss, Leonard; Stoyko, Stanislav
- Journal of Applied Physics, Vol. 125, Issue 24
Are Ba 11 Cd 6 Sb 12 and Sr 11 Cd 6 Sb 12 Zintl phases or not? A density-functional theory study
journal, October 2008
- Xia, Sheng-Qing; Bobev, Svilen
- Journal of Computational Chemistry, Vol. 29, Issue 13
Crystal chemistry and magnetic properties of the solid solutions Ca 14−x RE x MnBi 11 (RE = La–Nd, Sm, and Gd–Ho; x ≈ 0.6–0.8)
journal, January 2017
- Ovchinnikov, Alexander; Prakash, Jai; Bobev, Svilen
- Dalton Transactions, Vol. 46, Issue 46
Unusual Sb-Sb bonding in high temperature thermoelectric materials
journal, October 2008
- Xu, Jianxiao; Kleinke, Holger
- Journal of Computational Chemistry, Vol. 29, Issue 13
Pentaeuropium dicadmium pentaantimonide oxide, Eu 5 Cd 2 Sb 5 O
journal, January 2011
- Saparov, Bayrammurad; Bobev, Svilen
- Acta Crystallographica Section E Structure Reports Online, Vol. 67, Issue 2
Synthesis, crystal and electronic structures of the new quaternary phases A5Cd2Sb5F (A = Sr, Ba, Eu), and Ba5Cd2Sb5Ox (0.5
journal, January 2010
- Saparov, Bayrammurad; Bobev, Svilen
- Dalton Transactions, Vol. 39, Issue 47
Ba5Cd2Sb4O2—A New Antimonide Oxide with a Complex Structure
journal, September 2011
- Darone, Gregory M.; Bobev, Svilen
- Crystals, Vol. 1, Issue 3
Band gap estimation from temperature dependent Seebeck measurement—Deviations from the 2e|S|maxTmax relation
journal, January 2015
- Gibbs, Zachary M.; Kim, Hyun-Sik; Wang, Heng
- Applied Physics Letters, Vol. 106, Issue 2
Yb 14 MnSb 11 : New High Efficiency Thermoelectric Material for Power Generation
journal, April 2006
- Brown, Shawna R.; Kauzlarich, Susan M.; Gascoin, Franck
- Chemistry of Materials, Vol. 18, Issue 7
A simple chemical guide for finding novel n-type dopable Zintl pnictide thermoelectric materials
journal, January 2019
- Gorai, Prashun; Goyal, Anuj; Toberer, Eric S.
- Journal of Materials Chemistry A, Vol. 7, Issue 33
Thermoelectric Performance and Defect Chemistry in n-Type Zintl KGaSb 4
journal, May 2017
- Ortiz, Brenden R.; Gorai, Prashun; Stevanović, Vladan
- Chemistry of Materials, Vol. 29, Issue 10