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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

Abstract

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. 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)more » and Sr13LaZnAs11, 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)
OSTI Identifier:
1595733
Alternate Identifier(s):
OSTI ID: 1573528; OSTI ID: 1698003
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:https://doi.org/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:https://doi.org/10.1016/j.jssc.2019.120990. https://www.osti.gov/servlets/purl/1595733.
@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. 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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