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.
N1 - Funding Information:
We thank Brian Toby and Roberto dos Reis for helpful discussions. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Northwestern MRSEC is supported by NSF DMR-1720139. This work made use of the Jerome B. Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205). Elemental analysis was performed at the Northwestern University Quantitative Bioelement Imaging Center and diffuse reflectance was collected at the NU Keck Biophysics Facility. This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN.
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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U2 - 10.1021/acs.inorgchem.9b02692
DO - 10.1021/acs.inorgchem.9b02692
M3 - Article
C2 - 31687823
AN - SCOPUS:85074733574
VL - 58
SP - 15610
EP - 15617
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 22
ER -