Site Dependency of the High Conductivity of Ga 2 In 6 Sn 2 O 16 : The Role of the 7-Coordinate Site

Rickert, Karl; Huq, Ashfia; Lapidus, Saul H.; Wustrow, Allison; Ellis, Donald E.; Poeppelmeier, Kenneth R.

doi:10.1021/acs.chemmater.5b03790

Title: Site Dependency of the High Conductivity of Ga ₂ In ₆ Sn ₂ O ₁₆ : The Role of the 7-Coordinate Site

Full Record
Other Related Research

Abstract

In 6-coordinated cation sites, we find that it is the fundamental building block of the most effective transparent conducting oxides. Ga₂In₆SnO₁₆, however, maintains 4-, 6-, 7-, and 8-coordinated cation sites and still exhibits desirable transparency and high conductivity. To investigate the potential impact of these alternative sites, we partially replace the Sn in Ga₂In₆Sn₂O₁₆ with Ti, Zr, or Hf and use a combined approach of density functional theory-based calculations, X-ray diffraction, and neutron diffraction to establish that the substitution occurs preferentially on the 7-coordinate site. Conversely to Sn, the empty d orbitals of Ti, Zr, and Hf promote spd covalency with the surrounding oxygen, which decreases the conductivity. Pairing the substitutional site preference with the magnitude of this decrease demonstrates that the 7-coordinate site is the V major contributor to conductivity. The optical band gaps, in contrast, are shown to be site-independent and composition-dependent. After all 7-coordinate Sn has been replaced, the continued substitution of Sn results in the formation of a 7-coordinate In antisite or replacement of 6-coordinate Sn, depending on the identity of the d(0) substitute.

Authors:

Rickert, Karl ^[1]; Huq, Ashfia ^[2]; Lapidus, Saul H. ^[3]; Wustrow, Allison ^[1]; Ellis, Donald E. ^[1]; Poeppelmeier, Kenneth R. ^[1]

Northwestern Univ., Evanston, IL (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Publication Date:: Wed Nov 11 00:00:00 EST 2015

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1261489

Grant/Contract Number:: AC05-00OR22725; DGE-1324585; FG02-08ER46536

Resource Type:: Accepted Manuscript

Journal Name:: Chemistry of Materials

Additional Journal Information:: Journal Volume: 27; Journal Issue: 23; Journal ID: ISSN 0897-4756

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats


                    Rickert, Karl, Huq, Ashfia, Lapidus, Saul H., Wustrow, Allison, Ellis, Donald E., and Poeppelmeier, Kenneth R. Site Dependency of the High Conductivity of Ga 2 In 6 Sn 2 O 16 : The Role of the 7-Coordinate Site.  United States: N. p., 2015. 
Web.  doi:10.1021/acs.chemmater.5b03790.

Copy to clipboard


                    Rickert, Karl, Huq, Ashfia, Lapidus, Saul H., Wustrow, Allison, Ellis, Donald E., & Poeppelmeier, Kenneth R. Site Dependency of the High Conductivity of Ga 2 In 6 Sn 2 O 16 : The Role of the 7-Coordinate Site.  United States.  https://doi.org/10.1021/acs.chemmater.5b03790

Copy to clipboard


                    Rickert, Karl, Huq, Ashfia, Lapidus, Saul H., Wustrow, Allison, Ellis, Donald E., and Poeppelmeier, Kenneth R. Wed .  
"Site Dependency of the High Conductivity of Ga 2 In 6 Sn 2 O 16 : The Role of the 7-Coordinate Site".  United States.  https://doi.org/10.1021/acs.chemmater.5b03790.  https://www.osti.gov/servlets/purl/1261489.

Copy to clipboard


                    
@article{osti_1261489,

  title        = {Site Dependency of the High Conductivity of Ga 2 In 6 Sn 2 O 16 : The Role of the 7-Coordinate Site},

  author       = {Rickert, Karl and Huq, Ashfia and Lapidus, Saul H. and Wustrow, Allison and Ellis, Donald E. and Poeppelmeier, Kenneth R.},

  abstractNote = {In 6-coordinated cation sites, we find that it is the fundamental building block of the most effective transparent conducting oxides. Ga2In6SnO16, however, maintains 4-, 6-, 7-, and 8-coordinated cation sites and still exhibits desirable transparency and high conductivity. To investigate the potential impact of these alternative sites, we partially replace the Sn in Ga2In6Sn2O16 with Ti, Zr, or Hf and use a combined approach of density functional theory-based calculations, X-ray diffraction, and neutron diffraction to establish that the substitution occurs preferentially on the 7-coordinate site. Conversely to Sn, the empty d orbitals of Ti, Zr, and Hf promote spd covalency with the surrounding oxygen, which decreases the conductivity. Pairing the substitutional site preference with the magnitude of this decrease demonstrates that the 7-coordinate site is the V major contributor to conductivity. The optical band gaps, in contrast, are shown to be site-independent and composition-dependent. After all 7-coordinate Sn has been replaced, the continued substitution of Sn results in the formation of a 7-coordinate In antisite or replacement of 6-coordinate Sn, depending on the identity of the d(0) substitute.},

  doi          = {10.1021/acs.chemmater.5b03790},

  journal      = {Chemistry of Materials},

  number       = 23,

  volume       = 27,

  place        = {United States},

  year         = {Wed Nov 11 00:00:00 EST 2015},

  month        = {Wed Nov 11 00:00:00 EST 2015}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.chemmater.5b03790

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 3 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Site Dependency of the High Conductivity of Ga ₂ In ₆ Sn ₂ O ₁₆ : The Role of the 7-Coordinate Site

Journal Article Rickert, Karl ; Huq, Ashfia ; Lapidus, Saul H. ; ... - Chemistry of Materials

The 6-coordinated cation site is the fundamental building block of the most effective transparent conducting oxides. Ga2In6Sn2O16, however, maintains 4-, 6-, 7-, and 8-coordinated cation sites and still exhibits desirable transparency and high conductivity. To investigate the potential impact of these alternative sites, we partially replace the Sn in Ga2In6Sn2O16 with Ti, Zr, or Hf and use a combined approach of DFT-based calculations, X-ray diffraction, and neutron diffraction to establish that the substitution occurs preferentially on the 7-coordinate site. In contrast to Sn, the empty d orbitals of Ti, Zr, and Hf promote spd covalency with the surrounding oxygen whichmore »« less
https://doi.org/10.1021/acs.chemmater.5b03790
Site identity and importance in cosubstituted bixbyite In₂O₃

Journal Article Rickert, Karl ; Harris, Jeremy ; Sedefoglu, Nazmi ; ... - Crystals

The bixbyite structure of In₂O₃ has two nonequivalent, 6-coordinate cation sites and, when Sn is doped into In₂O₃, the Sn prefers the “b-site” and produces a highly conductive material. When divalent/tetravalent cation pairs are cosubstituted into In₂O₃, however, the conductivity increases to a lesser extent and the site occupancy is less understood. We examine the site occupancy in the Mg_xIn_2–2xSn_xO₃ and Zn_xIn_2–2xSn_xO₃ systems with high resolution X-ray and neutron diffraction and density functional theory computations, respectively. In these sample cases and those that are previously reported in the M_xIn_2–2xSn_xO₃ (M = Cu, Ni, or Zn) systems, the solubility limit ismore »« less
Cited by 1
https://doi.org/10.3390/cryst7020047

Full Text Available
Report on phase 2 of task 1.1: single phase synthesis to Lawrence Livermore National Laboratory for contract B345772

Technical Report Stewart, M W A ; Vance, E R ; Day, R A

Near single phase pyrochlores and zirconolites (with Hf substituted for Zr) of the following compositions have been prepared. The results obtained are summarized in Table 1. Details of the fabrication method and the results are given: (1) Mg-doped zirconolite (Ca{sub 0.4}Gd{sub 0.6}HfMg{sub 0.3}Ti{sub 1.7}O{sub 7}), Al-doped zirconolite (Ca{sub 0.5}Gd{sub 0.5}HfAl{sub 0.5}Ti{sub 1.5}O{sub 7}), Ta-doped pyrochlore (CaGdTaTiO{sub 7}), Pu-pyrochlore (CaPuTi{sub 2}O{sub 7}), and 4M zirconolite from the Ca-Gd-Hf-Ti-0 system (Ca{sub 0.6}Gd{sub 0.8}Hf{sub 0.6}Ti{sub 2}O{sub 7} and Ca{sub 0.7}Gd{sub 0.6}Hf{sub 0.7}Ti{sub 2}O{sub 7}). All but the Ta-doped pyrochlore were prepared via the alkoxide-route. The Ta-pyrochlore was prepared via the oxide-route. Mo-doped pyrochloremore »« less
https://doi.org/10.2172/15007521

Full Text Available
Connection between oxygen-ion conductivity of pyrochlore fuel-cell materials and structural with composition and temperature.

Journal Article Wuensch, B J ; Eberman, K W ; Heremans, C ; ... - Solid State Ionics

Oxides are believed to assume the A{sub 2}B{sub 2}O{sub 7} pyrochlore structure type for a specific range of ratios of the cation radii, R{sub A}/R{sub B}. Substitution of a larger B' ion in solid solution for B can progressively drive the system to complete disorder as in Y{sub 2}(Zr{sub y}Ti{sub 1-y}){sub 2}O{sub 7}, producing an oxygen-ion conductivity, {sigma}, greater than 10{sup -2} S/cm at 1000{sup o}C, comparable to the values of 10{sup -1} S/cm found for M{sup 3+}-stabilized cubic zirconias. Rietveld analyses of neutron and X-ray powder diffraction data have been employed to obtain structural data for the related systemsmore »« less
https://doi.org/10.1016/S0167-2738(99)00320-3
Probing the Local Site Disorder and Distortion in Pyrochlore High-Entropy Oxides

Journal Article Jiang, Bo ; Bridges, Craig A. ; Unocic, Raymond R. ; ... - Journal of the American Chemical Society

High-entropy oxides (HEOs) have attracted great interest in diverse fields because of their inherent opportunities to tailor and combine materials functionalities. The control of local order/disorder in the class is by extension a grand challenge toward realizing their vast potential. In this paper, we report the first examples of pyrochlore HEOs with five M-site cations, for Nd₂M₂O₇, in which the local structure has been investigated by neutron diffraction and pair distribution function (PDF) analysis. The average structure of the pyrochlores is found to be orthorhombic Imma, in agreement with radius-ratio rules governing the structural archetype. The computed PDFs from densitymore »« less
https://doi.org/10.1021/jacs.0c10739

Full Text Available

Similar Records

Title: Site Dependency of the High Conductivity of Ga 2 In 6 Sn 2 O 16 : The Role of the 7-Coordinate Site

Abstract

Citation Formats

Title: Site Dependency of the High Conductivity of Ga ₂ In ₆ Sn ₂ O ₁₆ : The Role of the 7-Coordinate Site