(CuxZn1- x)0.456In1.084Ge0.46O3 (0 ≤ x ≤ 1): A Complex, Ordered, Anion-Deficient Fluorite with Unusual Site-Specific Cation Mixing

Steven Flynn, A. J. Adekoya, Saeed Saeed, Chi Zhang, Vinayak P. Dravid, Gabriela B. Gonzalez, Kenneth R. Poeppelmeier*

*Corresponding author for this work

Research output: Contribution to journalArticle

Abstract

The anion-deficient fluorite-related family of materials exhibits a number of commercially useful properties arising from the specific arrangement of anion vacancies in each structure. One recently reported member, Zn0.456In1.084Ge0.46O3, is the only known example with its particular complex structure in which cation coordinations span one 4-coordinate (4b), two 6-coordinate (8e and 16f), and one 8-coordinate (4a) site. A new, complete, solid solution (CuxZn1-x)0.456In1.084Ge0.46O3, (0 ≤ x ≤ 1) has been discovered via the isovalent substitution of Cu2+ for Zn2+, significantly expanding the known phase space of this structure. Synchrotron X-ray data confirm the ZIGO structure over the entire composition range. Inclusion of Cu in the structure is found to occur exclusively at the 16f site, increasing the number of cations mixed on that site from three to four, while all others remain singly occupied, including the other 6-coordinate (8e) position. Furthermore, transmission electron microscopy investigations show no evidence of long-range cation ordering. Thus, disorder on the 16f site appears remarkably favorable in this otherwise highly ordered structure. Nonideal trends in the lattice parameters and diffuse reflectance spectra as a function of Cu content are examined. Further implications of the mixed order and disorder in the solid solution for materials discovery and possible properties of interest are briefly discussed.

Original languageEnglish (US)
Pages (from-to)15610-15617
Number of pages8
JournalInorganic chemistry
Volume58
Issue number22
DOIs
StatePublished - Nov 18 2019

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Fluorspar
fluorite
Anions
Cations
anions
cations
Solid solutions
solid solutions
disorders
Synchrotrons
Lattice constants
Vacancies
Substitution reactions
Transmission electron microscopy
X rays
lattice parameters
synchrotrons
inclusions
substitutes
Chemical analysis

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

@article{db5b60fd83ca469a90b798fd806baf01,
title = "(CuxZn1- x)0.456In1.084Ge0.46O3 (0 ≤ x ≤ 1): A Complex, Ordered, Anion-Deficient Fluorite with Unusual Site-Specific Cation Mixing",
abstract = "The anion-deficient fluorite-related family of materials exhibits a number of commercially useful properties arising from the specific arrangement of anion vacancies in each structure. One recently reported member, Zn0.456In1.084Ge0.46O3, is the only known example with its particular complex structure in which cation coordinations span one 4-coordinate (4b), two 6-coordinate (8e and 16f), and one 8-coordinate (4a) site. A new, complete, solid solution (CuxZn1-x)0.456In1.084Ge0.46O3, (0 ≤ x ≤ 1) has been discovered via the isovalent substitution of Cu2+ for Zn2+, significantly expanding the known phase space of this structure. Synchrotron X-ray data confirm the ZIGO structure over the entire composition range. Inclusion of Cu in the structure is found to occur exclusively at the 16f site, increasing the number of cations mixed on that site from three to four, while all others remain singly occupied, including the other 6-coordinate (8e) position. Furthermore, transmission electron microscopy investigations show no evidence of long-range cation ordering. Thus, disorder on the 16f site appears remarkably favorable in this otherwise highly ordered structure. Nonideal trends in the lattice parameters and diffuse reflectance spectra as a function of Cu content are examined. Further implications of the mixed order and disorder in the solid solution for materials discovery and possible properties of interest are briefly discussed.",
author = "Steven Flynn and Adekoya, {A. J.} and Saeed Saeed and Chi Zhang and Dravid, {Vinayak P.} and Gonzalez, {Gabriela B.} and Poeppelmeier, {Kenneth R.}",
year = "2019",
month = "11",
day = "18",
doi = "10.1021/acs.inorgchem.9b02692",
language = "English (US)",
volume = "58",
pages = "15610--15617",
journal = "Inorganic Chemistry",
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publisher = "American Chemical Society",
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(CuxZn1- x)0.456In1.084Ge0.46O3 (0 ≤ x ≤ 1) : A Complex, Ordered, Anion-Deficient Fluorite with Unusual Site-Specific Cation Mixing. / Flynn, Steven; Adekoya, A. J.; Saeed, Saeed; Zhang, Chi; Dravid, Vinayak P.; Gonzalez, Gabriela B.; Poeppelmeier, Kenneth R.

In: Inorganic chemistry, Vol. 58, No. 22, 18.11.2019, p. 15610-15617.

Research output: Contribution to journalArticle

TY - JOUR

T1 - (CuxZn1- x)0.456In1.084Ge0.46O3 (0 ≤ x ≤ 1)

T2 - A Complex, Ordered, Anion-Deficient Fluorite with Unusual Site-Specific Cation Mixing

AU - Flynn, Steven

AU - Adekoya, A. J.

AU - Saeed, Saeed

AU - Zhang, Chi

AU - Dravid, Vinayak P.

AU - Gonzalez, Gabriela B.

AU - Poeppelmeier, Kenneth R.

PY - 2019/11/18

Y1 - 2019/11/18

N2 - The anion-deficient fluorite-related family of materials exhibits a number of commercially useful properties arising from the specific arrangement of anion vacancies in each structure. One recently reported member, Zn0.456In1.084Ge0.46O3, is the only known example with its particular complex structure in which cation coordinations span one 4-coordinate (4b), two 6-coordinate (8e and 16f), and one 8-coordinate (4a) site. A new, complete, solid solution (CuxZn1-x)0.456In1.084Ge0.46O3, (0 ≤ x ≤ 1) has been discovered via the isovalent substitution of Cu2+ for Zn2+, significantly expanding the known phase space of this structure. Synchrotron X-ray data confirm the ZIGO structure over the entire composition range. Inclusion of Cu in the structure is found to occur exclusively at the 16f site, increasing the number of cations mixed on that site from three to four, while all others remain singly occupied, including the other 6-coordinate (8e) position. Furthermore, transmission electron microscopy investigations show no evidence of long-range cation ordering. Thus, disorder on the 16f site appears remarkably favorable in this otherwise highly ordered structure. Nonideal trends in the lattice parameters and diffuse reflectance spectra as a function of Cu content are examined. Further implications of the mixed order and disorder in the solid solution for materials discovery and possible properties of interest are briefly discussed.

AB - The anion-deficient fluorite-related family of materials exhibits a number of commercially useful properties arising from the specific arrangement of anion vacancies in each structure. One recently reported member, Zn0.456In1.084Ge0.46O3, is the only known example with its particular complex structure in which cation coordinations span one 4-coordinate (4b), two 6-coordinate (8e and 16f), and one 8-coordinate (4a) site. A new, complete, solid solution (CuxZn1-x)0.456In1.084Ge0.46O3, (0 ≤ x ≤ 1) has been discovered via the isovalent substitution of Cu2+ for Zn2+, significantly expanding the known phase space of this structure. Synchrotron X-ray data confirm the ZIGO structure over the entire composition range. Inclusion of Cu in the structure is found to occur exclusively at the 16f site, increasing the number of cations mixed on that site from three to four, while all others remain singly occupied, including the other 6-coordinate (8e) position. Furthermore, transmission electron microscopy investigations show no evidence of long-range cation ordering. Thus, disorder on the 16f site appears remarkably favorable in this otherwise highly ordered structure. Nonideal trends in the lattice parameters and diffuse reflectance spectra as a function of Cu content are examined. Further implications of the mixed order and disorder in the solid solution for materials discovery and possible properties of interest are briefly discussed.

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AN - SCOPUS:85074733574

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