A Rutile Chevron Modulation in Delafossite-Like Ga3-xIn3TixO9+x/2

Karl Rickert; Philippe Boullay; Sylvie Malo; Vincent Caignaert; Kenneth R. Poeppelmeier

doi:10.1021/acs.inorgchem.6b00147

A Rutile Chevron Modulation in Delafossite-Like Ga_3-xIn₃Ti_xO_9+x/2

Karl Rickert, Philippe Boullay, Sylvie Malo, Vincent Caignaert, Kenneth R. Poeppelmeier^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

The structure solution of the modulated, delafossite-related, orthorhombic Ga_3-xIn₃Ti_xO_9+x/2 for x = 1.5 is reported here in conjunction with a model describing the modulation as a function of x for the entire system. Previously reported structures in the related A_3-xIn₃Ti_xO_9+x/2 (A = Al, Cr, or Fe) systems use X-ray diffraction to determine that the anion lattice is the source of modulation. Neutron diffraction, with its enhanced sensitivity to light atoms, offers a route to solving the modulation and is used here, in combination with precession electron diffraction tomography (PEDT), to solve the structure of Ga_1.5In₃Ti_1.5O_9.75. We construct a model that describes the anion modulation through the formation of rutile chevrons as a function of x. This model accommodates the orthorhombic phase (1.5 ≤ x ≤ 2.1) in the Ga_3-xIn₃Ti_xO_9+x/2 system, which transitions to a biphasic mixture (2.2 ≤ x ≤ 2.3) with a monoclinic, delafossite-related phase (2.4 ≤ x ≤ 2.5). The optical band gaps of this system are determined, and are stable at ∼3.4 eV before a ∼0.4 eV decrease between x = 1.9 and 2.0. After this decrease, stability resumes at ∼3.0 eV. Resistance to oxidation and reduction is also presented.

Original language	English (US)
Pages (from-to)	4403-4409
Number of pages	7
Journal	Inorganic chemistry
Volume	55
Issue number	9
DOIs	https://doi.org/10.1021/acs.inorgchem.6b00147
State	Published - May 2 2016

Funding

K.R. acknowledges that this material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant no. DGE- 1324585. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. K.R. also recognizes that this material is based upon research supported by the Chateaubriand Fellowship of the Office for Science and Technology of the Embassy of France in the United States. K.R. and K.R.P. gratefully acknowledge additional support from the Department of Energy Basic Energy Sciences Award no. DE-FG02-08ER46536. A portion of this research was performed at POWGEN at Oak Ridge National Laboratorys Spallation Neutron Source and was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. Use of 11BM on the Advanced Photon Source at Argonne National Laboratory (ANL) was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract no. DE-AC02-06CH11357. This work made use of the J. B. Cohen X-ray Diffraction Facility, which is supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Materials Research Center of NU. A portion of this work was supported by the NU Keck Biophysics Facility and a Cancer Center Support Grant (NCI CA060553).

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/acs.inorgchem.6b00147

Cite this

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title = "A Rutile Chevron Modulation in Delafossite-Like Ga3-xIn3TixO9+x/2",

abstract = "The structure solution of the modulated, delafossite-related, orthorhombic Ga3-xIn3TixO9+x/2 for x = 1.5 is reported here in conjunction with a model describing the modulation as a function of x for the entire system. Previously reported structures in the related A3-xIn3TixO9+x/2 (A = Al, Cr, or Fe) systems use X-ray diffraction to determine that the anion lattice is the source of modulation. Neutron diffraction, with its enhanced sensitivity to light atoms, offers a route to solving the modulation and is used here, in combination with precession electron diffraction tomography (PEDT), to solve the structure of Ga1.5In3Ti1.5O9.75. We construct a model that describes the anion modulation through the formation of rutile chevrons as a function of x. This model accommodates the orthorhombic phase (1.5 ≤ x ≤ 2.1) in the Ga3-xIn3TixO9+x/2 system, which transitions to a biphasic mixture (2.2 ≤ x ≤ 2.3) with a monoclinic, delafossite-related phase (2.4 ≤ x ≤ 2.5). The optical band gaps of this system are determined, and are stable at ∼3.4 eV before a ∼0.4 eV decrease between x = 1.9 and 2.0. After this decrease, stability resumes at ∼3.0 eV. Resistance to oxidation and reduction is also presented.",

author = "Karl Rickert and Philippe Boullay and Sylvie Malo and Vincent Caignaert and Poeppelmeier, {Kenneth R.}",

note = "Funding Information: K.R. acknowledges that this material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant no. DGE- 1324585. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. K.R. also recognizes that this material is based upon research supported by the Chateaubriand Fellowship of the Office for Science and Technology of the Embassy of France in the United States. K.R. and K.R.P. gratefully acknowledge additional support from the Department of Energy Basic Energy Sciences Award no. DE-FG02-08ER46536. A portion of this research was performed at POWGEN at Oak Ridge National Laboratorys Spallation Neutron Source and was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. Use of 11BM on the Advanced Photon Source at Argonne National Laboratory (ANL) was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract no. DE-AC02-06CH11357. This work made use of the J. B. Cohen X-ray Diffraction Facility, which is supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Materials Research Center of NU. A portion of this work was supported by the NU Keck Biophysics Facility and a Cancer Center Support Grant (NCI CA060553). Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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AU - Caignaert, Vincent

AU - Poeppelmeier, Kenneth R.

N1 - Funding Information: K.R. acknowledges that this material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant no. DGE- 1324585. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. K.R. also recognizes that this material is based upon research supported by the Chateaubriand Fellowship of the Office for Science and Technology of the Embassy of France in the United States. K.R. and K.R.P. gratefully acknowledge additional support from the Department of Energy Basic Energy Sciences Award no. DE-FG02-08ER46536. A portion of this research was performed at POWGEN at Oak Ridge National Laboratorys Spallation Neutron Source and was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. Use of 11BM on the Advanced Photon Source at Argonne National Laboratory (ANL) was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract no. DE-AC02-06CH11357. This work made use of the J. B. Cohen X-ray Diffraction Facility, which is supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Materials Research Center of NU. A portion of this work was supported by the NU Keck Biophysics Facility and a Cancer Center Support Grant (NCI CA060553). Publisher Copyright: © 2016 American Chemical Society.

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N2 - The structure solution of the modulated, delafossite-related, orthorhombic Ga3-xIn3TixO9+x/2 for x = 1.5 is reported here in conjunction with a model describing the modulation as a function of x for the entire system. Previously reported structures in the related A3-xIn3TixO9+x/2 (A = Al, Cr, or Fe) systems use X-ray diffraction to determine that the anion lattice is the source of modulation. Neutron diffraction, with its enhanced sensitivity to light atoms, offers a route to solving the modulation and is used here, in combination with precession electron diffraction tomography (PEDT), to solve the structure of Ga1.5In3Ti1.5O9.75. We construct a model that describes the anion modulation through the formation of rutile chevrons as a function of x. This model accommodates the orthorhombic phase (1.5 ≤ x ≤ 2.1) in the Ga3-xIn3TixO9+x/2 system, which transitions to a biphasic mixture (2.2 ≤ x ≤ 2.3) with a monoclinic, delafossite-related phase (2.4 ≤ x ≤ 2.5). The optical band gaps of this system are determined, and are stable at ∼3.4 eV before a ∼0.4 eV decrease between x = 1.9 and 2.0. After this decrease, stability resumes at ∼3.0 eV. Resistance to oxidation and reduction is also presented.

AB - The structure solution of the modulated, delafossite-related, orthorhombic Ga3-xIn3TixO9+x/2 for x = 1.5 is reported here in conjunction with a model describing the modulation as a function of x for the entire system. Previously reported structures in the related A3-xIn3TixO9+x/2 (A = Al, Cr, or Fe) systems use X-ray diffraction to determine that the anion lattice is the source of modulation. Neutron diffraction, with its enhanced sensitivity to light atoms, offers a route to solving the modulation and is used here, in combination with precession electron diffraction tomography (PEDT), to solve the structure of Ga1.5In3Ti1.5O9.75. We construct a model that describes the anion modulation through the formation of rutile chevrons as a function of x. This model accommodates the orthorhombic phase (1.5 ≤ x ≤ 2.1) in the Ga3-xIn3TixO9+x/2 system, which transitions to a biphasic mixture (2.2 ≤ x ≤ 2.3) with a monoclinic, delafossite-related phase (2.4 ≤ x ≤ 2.5). The optical band gaps of this system are determined, and are stable at ∼3.4 eV before a ∼0.4 eV decrease between x = 1.9 and 2.0. After this decrease, stability resumes at ∼3.0 eV. Resistance to oxidation and reduction is also presented.

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