Site identity and importance in cosubstituted bixbyite In2O3

Rickert, Karl; Harris, Jeremy; Sedefoglu, Nazmi; Kavak, Hamide; Ellis, Donald E.; Poeppelmeier, Kenneth R.

doi:10.3390/cryst7020047

Title: Site identity and importance in cosubstituted bixbyite In₂O₃

Full Record
Other Related Research

Abstract

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 is greater than 25%, ensuring that the b-site cannot be the exclusively preferred site as it is in Sn:In₂O₃. Prior to this saturation point, we report that the M²⁺ cation always has at least a partial occupancy on the d-site and the Sn⁴⁺ cation has at least a partial occupancy on the b-site. The energies of formation for these configurations are highly favored, and prefer that the divalent and tetravalent substitutes are adjacent in the crystal lattice, which suggests short range ordering. Diffuse reflectance and 4-point probe measurements of Mg_xIn_2–xSn_xO₃ demonstrate that it can maintain an optical band gap >2.8 eVmore »« less

Authors:

^[1]; Harris, Jeremy ^[1]; Sedefoglu, Nazmi ^[2]; Kavak, Hamide ^[3]; Ellis, Donald E. ^[1]; Poeppelmeier, Kenneth R. ^[1]

Northwestern Univ., Evanston, IL (United States)
Osmaniye Korkut Ata Univ., Osmaniye (Turkey)
Cukurova Univ., Adana (Turkey)

Publication Date:: Thu Feb 09 00:00:00 EST 2017

Research Org.:: Northwestern Univ., Evanston, IL (United States)

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

OSTI Identifier:: 1356105

Grant/Contract Number:: FG02-08ER46536

Resource Type:: Accepted Manuscript

Journal Name:: Crystals

Additional Journal Information:: Journal Volume: 7; Journal Issue: 2; Journal ID: ISSN 2073-4352

Publisher:: MDPI

Country of Publication:: United States

Language:: English

Subject:: 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; bixbyite; indium oxide; transparent conducting oxide

Citation Formats


                    Rickert, Karl, Harris, Jeremy, Sedefoglu, Nazmi, Kavak, Hamide, Ellis, Donald E., and Poeppelmeier, Kenneth R. Site identity and importance in cosubstituted bixbyite In2O3.  United States: N. p., 2017. 
Web.  doi:10.3390/cryst7020047.

Copy to clipboard


                    Rickert, Karl, Harris, Jeremy, Sedefoglu, Nazmi, Kavak, Hamide, Ellis, Donald E., & Poeppelmeier, Kenneth R. Site identity and importance in cosubstituted bixbyite In2O3.  United States.  https://doi.org/10.3390/cryst7020047

Copy to clipboard


                    Rickert, Karl, Harris, Jeremy, Sedefoglu, Nazmi, Kavak, Hamide, Ellis, Donald E., and Poeppelmeier, Kenneth R. Thu .  
"Site identity and importance in cosubstituted bixbyite In2O3".  United States.  https://doi.org/10.3390/cryst7020047.  https://www.osti.gov/servlets/purl/1356105.

Copy to clipboard


                    
@article{osti_1356105,

  title        = {Site identity and importance in cosubstituted bixbyite In2O3},

  author       = {Rickert, Karl and Harris, Jeremy and Sedefoglu, Nazmi and Kavak, Hamide and Ellis, Donald E. and Poeppelmeier, Kenneth R.},

  abstractNote = {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 MgxIn2–2xSnxO3 and ZnxIn2–2xSnxO3 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 MxIn2–2xSnxO3 (M = Cu, Ni, or Zn) systems, the solubility limit is greater than 25%, ensuring that the b-site cannot be the exclusively preferred site as it is in Sn:In2O3. Prior to this saturation point, we report that the M2+ cation always has at least a partial occupancy on the d-site and the Sn4+ cation has at least a partial occupancy on the b-site. The energies of formation for these configurations are highly favored, and prefer that the divalent and tetravalent substitutes are adjacent in the crystal lattice, which suggests short range ordering. Diffuse reflectance and 4-point probe measurements of MgxIn2–xSnxO3 demonstrate that it can maintain an optical band gap >2.8 eV while surpassing 1000 S/cm in conductivity. Furthermore, understanding how multiple constituents occupy the two nonequivalent cation sites can provide information on how to optimize cosubstituted systems to increase Sn solubility while maintaining its dopant nature, achieving maximum conductivity.},

  doi          = {10.3390/cryst7020047},

  journal      = {Crystals},

  number       = 2,

  volume       = 7,

  place        = {United States},

  year         = {Thu Feb 09 00:00:00 EST 2017},

  month        = {Thu Feb 09 00:00:00 EST 2017}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.3390/cryst7020047

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 1 work

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Probing the local structure of crystalline ZITO: In{sub 2-2x}Sn{sub x}Zn{sub x}O{sub 3} (x<=0.4)

Journal Article Hoel, Cathleen A ; Gaillard, Jean-Francois ; Poeppelmeier, Kenneth R., E-mail: krp@northwestern.ed - Journal of Solid State Chemistry

The local structure of In{sub 2}O{sub 3} cosubstituted with Zn and Sn (In{sub 2-2x}Sn{sub x}Zn{sub x}O{sub 3}, x<=0.4 or ZITO) was determined by extended X-ray absorption fine structure (EXAFS) for x=0.1, 0.2, 0.3 and 0.4. The host bixbyite In{sub 2}O{sub 3} structure is maintained up to the enhanced substitution limit (x=0.4). The EXAFS spectra are consistent with random substitution of In by the smaller Zn and Sn cations, a result that is consistent with the 'good-to-excellent' conductivities reported for ZITO. - Graphical abstract Text3: The local structure of Zn and Sn cosubstituted In{sub 2}O{sub 3} was determined by X-ray absorptionmore »« less
https://doi.org/10.1016/j.jssc.2010.01.014
Probing the local structure of crystalline ZITO: In[subscript 2-2x]Sn[subscript x]Zn[subscript x]O[subscript 3] (x=<0.4)

Journal Article Hoel, Cathleen A ; Gaillard, Jean-Francois ; Poeppelmeier, Kenneth R - J. Solid State Chem.

The local structure of In{sub 2}O{sub 3} cosubstituted with Zn and Sn (In{sub 2-2x}Sn{sub x}Zn{sub x}O{sub 3}, x {le} 0.4 or ZITO) was determined by extended X-ray absorption fine structure (EXAFS) for x = 0.1, 0.2, 0.3 and 0.4. The host bixbyite In{sub 2}O{sub 3} structure is maintained up to the enhanced substitution limit (x = 0.4). The EXAFS spectra are consistent with random substitution of In by the smaller Zn and Sn cations, a result that is consistent with the 'good-to-excellent' conductivities reported for ZITO.
https://doi.org/10.1016/j.jssc.2010.01.014
High-Pressure Synthesis and Local Structure of Corundum-Type In[subscript 2−2x]Zn[subscript x]Sn[subscript x]O[subscript 3] (x ≤ 0.7)

Journal Article Hoel, Cathleen A ; Amores, Jos Manuel Gallardo ; Morn, Emilio ; ... - J. Am. Chem. Soc.

The corundum-type In{sub 2-2x}Zn{sub x}Sn{sub x}O{sub 3} solid solution (cor-ZITO, x {le} 0.7) was synthesized at 1000 C under a high pressure of 70 kbar. cor-ZITO is a high-pressure polymorph of the transparent conducting oxide bixbyite-In{sub 2-2x}Zn{sub x}Sn{sub x}O{sub 3} (x {le} 0.4). Analysis of the extended X-ray absorption fine structure suggests that significant face-sharing of Zn and Sn octahedra occurs, as expected for the corundum structure type. In contrast to the ideal corundum structure, however, Zn and Sn are displaced and form oxygen bonds with lengths that are similar to those observed in high-pressure ZnSnO{sub 3}. Powder X-ray diffractionmore »« less
https://doi.org/10.1021/ja106048x
High-Pressure Synthesis and Local Structure of Corundum-Type In[subscript 2;#8722;2x]Zn[subscript x]Sn[subscript x]O[subscript 3] (x ;#8804; 0.7)

Journal Article Hoel, Cathleen A ; Amores, Jose Manuel Gallardo ; Moran, Emilio ; ... - J. Am. Chem. Soc.

The corundum-type In{sub 2-2x}Zn{sub x}Sn{sub x}O{sub 3} solid solution (cor-ZITO, x {<=} 0.7) was synthesized at 1000 C under a high pressure of 70 kbar. cor-ZITO is a high-pressure polymorph of the transparent conducting oxide bixbyite-In{sub 2-2x}Zn{sub x}Sn{sub x}O{sub 3} (x {<=} 0.4). Analysis of the extended X-ray absorption fine structure suggests that significant face-sharing of Zn and Sn octahedra occurs, as expected for the corundum structure type. In contrast to the ideal corundum structure, however, Zn and Sn are displaced and form oxygen bonds with lengths that are similar to those observed in high-pressure ZnSnO{sub 3}. Powder X-ray diffractionmore »« less
https://doi.org/10.1021/ja106048x
Phase Stability and Optoelectronic Properties of the Bixbyite Phase in the Gallium–Indium–Tin–Oxide System

Journal Article Dolgonos, Alex ; Wells, Spencer A. ; Poeppelmeier, Kenneth R. ; ... - Journal of the American Ceramic Society

X‐ray diffraction techniques were used to determine the phase boundaries of the In ₂ O ₃ solid solution phase in the Ga ₂ O ₃ – In ₂ O ₃ – SnO ₂ ternary system. The effects of Ga and Sn content on the unit cell dimensions of the bixbyite phase were calculated by a linear regression fit, the results of which indicate the two substitutive cations have opposite and independent effects on the lattice parameter. These results suggest that the cations do not strongly interact with each other in the crystal. Measurements of optoelectronic properties were also taken onmore »« less
Cited by 2
https://doi.org/10.1111/jace.13334

Similar Records

Title: Site identity and importance in cosubstituted bixbyite In2O3

Abstract

Citation Formats

Title: Site identity and importance in cosubstituted bixbyite In₂O₃