The Library
Characterization of structural disorder in γ-Ga2O3
Tools
Playford, Helen Y., Hannon, Alex C., Tucker, Matthew G., Dawson, Daniel M., Ashbrook, Sharon E., Kastiban, Reza J., Sloan, Jeremy and Walton, Richard I. (2014) Characterization of structural disorder in γ-Ga2O3. The Journal of Physical Chemistry C, Volume 118 (Number 29). pp. 16188-16198. doi:10.1021/jp5033806 ISSN 1932-7447.
Research output not available from this repository.
Request-a-Copy directly from author or use local Library Get it For Me service.
Official URL: http://dx.doi.org/10.1021/jp5033806
Abstract
Solvothermal oxidation of metallic gallium in monoethanolamine for 72 h at 240 °C yields a crystalline sample of γ-Ga2O3 (∼30 nm crystallites). While Rietveld refinement (cubic spinel structure, Fd3̅m; a = 8.23760(9) Å) reveals that Ga occupies two pairs of octahedral and tetrahedral sites (ideal spinel and nonspinel), it provides no information about their local distribution, which cannot be statistical owing to the short Ga–Ga contacts produced if neighboring ideal spinel and nonspinel sites are simultaneously occupied. To create an atomistic model to reconcile this situation, a 6 × 6 × 6 supercell of the crystal structure is constructed and refined against neutron total scattering data using a reverse Monte Carlo (RMC) approach. This accounts well for the local as well as long-range structure and reveals significant local distortion in the octahedral sites that resembles the structure of thermodynamically stable β-Ga2O3. 71Ga solid-state NMR results reveal a octahedral:tetrahedral Ga ratio that is consistent with the model obtained from RMC. Nanocrystalline samples of γ-Ga2O3 are produced by either a short solvothermal reaction (240 °C for 11 h in diethanolamine; ∼15 nm crystallites) or by precipitation from an ethanolic solution of gallium nitrate (∼5 nm crystallites). For these samples, the Bragg scattering profile is broadened by their smaller crystallite size, consistent with transmission electron microscopy results, and analysis of the relative Bragg peak intensities provides evidence that a greater proportion of tetrahedral versus octahedral sites are filled. In contrast, neutron total scattering shows the same average Ga–O distance with decreasing particle size, consistent with 71Ga solid-state NMR results that indicate that all samples contain the same overall proportion of octahedral:tetrahedral Ga. It is postulated that increased occupation of tetrahedral sites within the smaller crystallites is balanced by an increased proportion of octahedral surface Ga sites, owing to termination by bound solvent or hydroxide.
Item Type: | Journal Article | ||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Science > Physics |
||||||||||
Journal or Publication Title: | The Journal of Physical Chemistry C | ||||||||||
Publisher: | American Chemical Society | ||||||||||
ISSN: | 1932-7447 | ||||||||||
Official Date: | 24 June 2014 | ||||||||||
Dates: |
|
||||||||||
Volume: | Volume 118 | ||||||||||
Number: | Number 29 | ||||||||||
Page Range: | pp. 16188-16198 | ||||||||||
DOI: | 10.1021/jp5033806 | ||||||||||
Status: | Peer Reviewed | ||||||||||
Publication Status: | Published | ||||||||||
Access rights to Published version: | Restricted or Subscription Access |
Request changes or add full text files to a record
Repository staff actions (login required)
View Item |