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Title: Synthesis and structure of Sr 14Zn 1+xAs 11 and Eu 14Zn 1+xAs 11 (x ≤ 0.5). New members of the family of pnictides isotypic with Ca 14AlSb 11, exhibiting a new type of structural disorder

Abstract

Systematic investigation of the ternary systems A–Zn–As (A = Sr, Eu) led to the discovery of two new ternary phases, Sr 14Zn 1+xAs 11 and Eu 14Zn 1+xAs 11 (x ≤ 0.5). Both title compounds were structurally characterized by single-crystal X-ray diffraction. The basic structure of these new arsenides is akin to that of the numerous other pnictides adopting the tetragonal Ca 14AlSb 11 structure type (space group I4 1/ acd (No. 142); Z = 8). The main difference is the presence of an interstitial Zn atom, located in a nearly trigonal-planar coordination environment of three As atoms. Four such fragments share common edges with the regular ZnAs 4 tetrahedron, to form an unusual new structural unit with the formula [Zn 1+xSb 8]. The small uptake of additional zinc is needed to augment the overall valence electron count, thereby driving the system to an electronically charge-balanced state. Upon partial substitution of the nominally divalent Sr with a trivalent La, the equivalent of electron doping, the structure rids itself of the interstitial zinc, as demonstrated on the example of Sr 13.30(2)La 0.70ZnAs 11, which was also structurally characterized by single-crystal X-ray diffraction as part of this study. In conclusion, electronic structuremore » calculations for the idealized composition Sr 14ZnAs 11 confirm the speculated electron-deficient assignment, and suggest intrinsic semiconducting behavior for the one-electron richer Sr 14Zn 1+xAs 11 (x = 0.5) and Sr 13LaZnAs 11, respectively.« less

Authors:
 [1];  [2]; ORCiD logo [1]
  1. Univ. of Delaware, Newark, DE (United States)
  2. Univ. of Delaware, Newark, DE (United States); Charter School of Wilmington, Wilmington, 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) (SC-22)
OSTI Identifier:
1595733
Alternate Identifier(s):
OSTI ID: 1573528
Grant/Contract Number:  
SC0008885
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 280; Journal Issue: C; Journal ID: ISSN 0022-4596
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Arsenides; Crystal structure; Electronic structure; Single-crystal X-ray diffraction; Zintl phases

Citation Formats

Baranets, Sviatoslav, Darone, Gregory M., and Bobev, Svilen. Synthesis and structure of Sr14Zn1+xAs11 and Eu14Zn1+xAs11 (x ≤ 0.5). New members of the family of pnictides isotypic with Ca14AlSb11, exhibiting a new type of structural disorder. United States: N. p., 2019. Web. doi:10.1016/j.jssc.2019.120990.
Baranets, Sviatoslav, Darone, Gregory M., & Bobev, Svilen. Synthesis and structure of Sr14Zn1+xAs11 and Eu14Zn1+xAs11 (x ≤ 0.5). New members of the family of pnictides isotypic with Ca14AlSb11, exhibiting a new type of structural disorder. United States. doi:10.1016/j.jssc.2019.120990.
Baranets, Sviatoslav, Darone, Gregory M., and Bobev, Svilen. Tue . "Synthesis and structure of Sr14Zn1+xAs11 and Eu14Zn1+xAs11 (x ≤ 0.5). New members of the family of pnictides isotypic with Ca14AlSb11, exhibiting a new type of structural disorder". United States. doi:10.1016/j.jssc.2019.120990.
@article{osti_1595733,
title = {Synthesis and structure of Sr14Zn1+xAs11 and Eu14Zn1+xAs11 (x ≤ 0.5). New members of the family of pnictides isotypic with Ca14AlSb11, exhibiting a new type of structural disorder},
author = {Baranets, Sviatoslav and Darone, Gregory M. and Bobev, Svilen},
abstractNote = {Systematic investigation of the ternary systems A–Zn–As (A = Sr, Eu) led to the discovery of two new ternary phases, Sr14Zn1+xAs11 and Eu14Zn1+xAs11 (x ≤ 0.5). Both title compounds were structurally characterized by single-crystal X-ray diffraction. The basic structure of these new arsenides is akin to that of the numerous other pnictides adopting the tetragonal Ca14AlSb11 structure type (space group I41/acd (No. 142); Z = 8). The main difference is the presence of an interstitial Zn atom, located in a nearly trigonal-planar coordination environment of three As atoms. Four such fragments share common edges with the regular ZnAs4 tetrahedron, to form an unusual new structural unit with the formula [Zn1+xSb8]. The small uptake of additional zinc is needed to augment the overall valence electron count, thereby driving the system to an electronically charge-balanced state. Upon partial substitution of the nominally divalent Sr with a trivalent La, the equivalent of electron doping, the structure rids itself of the interstitial zinc, as demonstrated on the example of Sr13.30(2)La0.70ZnAs11, which was also structurally characterized by single-crystal X-ray diffraction as part of this study. In conclusion, electronic structure calculations for the idealized composition Sr14ZnAs11 confirm the speculated electron-deficient assignment, and suggest intrinsic semiconducting behavior for the one-electron richer Sr14Zn1+xAs11 (x = 0.5) and Sr13LaZnAs11, respectively.},
doi = {10.1016/j.jssc.2019.120990},
journal = {Journal of Solid State Chemistry},
number = C,
volume = 280,
place = {United States},
year = {2019},
month = {10}
}

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