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

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)4403-4409
Number of pages7
JournalInorganic chemistry
Volume55
Issue number9
DOIs
StatePublished - 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

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