TU Darmstadt / ULB / TUbiblio

Indium hydroxide to oxide decomposition observed in one nanocrystal during in situ transmission electron microscopy studies

Miehe, Gerhard and Lauterbach, Stefan and Kleebe, Hans-Joachim and Gurlo, Aleksander (2013):
Indium hydroxide to oxide decomposition observed in one nanocrystal during in situ transmission electron microscopy studies.
In: Journal of Solid State Chemistry, 198Elsevier Science Publishing, pp. 364-370, ISSN 00224596,
[Online-Edition: http://dx.doi.org/10.1016/j.jssc.2012.09.022],
[Article]

Abstract

The high-resolution transmission electron microscopy (HR-TEM) is used to study, in situ, spatially resolved decomposition in individual nanocrystals of metal hydroxides and oxyhydroxides. This case study reports on the decomposition of indium hydroxide (c-In(OH)3) to bixbyite-type indium oxide (c-In2O3). The electron beam is focused onto a single cube-shaped In(OH)3 crystal of {100} morphology with ca. 35 nm edge length and a sequence of HR-TEM images was recorded during electron beam irradiation. The frame-by-frame analysis of video sequences allows for the in situ, time-resolved observation of the shape and orientation of the transformed crystals, which in turn enables the evaluation of the kinetics of c-In2O3 crystallization. Supplementary material (video of the transformation) related to this article can be found online at 10.1016/j.jssc.2012.09.022. After irradiation the shape of the parent cube-shaped crystal is preserved, however, its linear dimension (edge) is reduced by the factor 1.20. The corresponding spotted selected area electron diffraction (SAED) pattern representing zone [001] of c-In(OH)3 is transformed to a diffuse strongly textured ring-like pattern of c-In2O3 that indicates the transformed cube is no longer a single crystal but is disintegrated into individual c-In2O3 domains with the size of about 5–10 nm. The induction time of approximately 15 s is estimated from the time-resolved Fourier transforms. The volume fraction of the transformed phase (c-In2O3), calculated from the shrinkage of the parent c-In(OH)3 crystal in the recorded HR-TEM images, is used as a measure of the kinetics of c-In2O3 crystallization within the framework of Avrami–Erofeev formalism. The Avrami exponent of ∼3 is characteristic for a reaction mechanism with fast nucleation at the beginning of the reaction and subsequent three-dimensional growth of nuclei with a constant growth rate. The structural transformation path in reconstructive decomposition of c-In(OH)3 to c-In2O3 is discussed in terms of (i) the displacement of hydrogen atoms that lead to breaking the hydrogen bond between OH groups of [In(OH)6] octahedra and finally to their destabilization and (ii) transformation of the vertices-shared indium–oxygen octahedra in c-In(OH)3 to vertices- and edge-shared octahedra in c-In2O3.

Item Type: Article
Erschienen: 2013
Creators: Miehe, Gerhard and Lauterbach, Stefan and Kleebe, Hans-Joachim and Gurlo, Aleksander
Title: Indium hydroxide to oxide decomposition observed in one nanocrystal during in situ transmission electron microscopy studies
Language: English
Abstract:

The high-resolution transmission electron microscopy (HR-TEM) is used to study, in situ, spatially resolved decomposition in individual nanocrystals of metal hydroxides and oxyhydroxides. This case study reports on the decomposition of indium hydroxide (c-In(OH)3) to bixbyite-type indium oxide (c-In2O3). The electron beam is focused onto a single cube-shaped In(OH)3 crystal of {100} morphology with ca. 35 nm edge length and a sequence of HR-TEM images was recorded during electron beam irradiation. The frame-by-frame analysis of video sequences allows for the in situ, time-resolved observation of the shape and orientation of the transformed crystals, which in turn enables the evaluation of the kinetics of c-In2O3 crystallization. Supplementary material (video of the transformation) related to this article can be found online at 10.1016/j.jssc.2012.09.022. After irradiation the shape of the parent cube-shaped crystal is preserved, however, its linear dimension (edge) is reduced by the factor 1.20. The corresponding spotted selected area electron diffraction (SAED) pattern representing zone [001] of c-In(OH)3 is transformed to a diffuse strongly textured ring-like pattern of c-In2O3 that indicates the transformed cube is no longer a single crystal but is disintegrated into individual c-In2O3 domains with the size of about 5–10 nm. The induction time of approximately 15 s is estimated from the time-resolved Fourier transforms. The volume fraction of the transformed phase (c-In2O3), calculated from the shrinkage of the parent c-In(OH)3 crystal in the recorded HR-TEM images, is used as a measure of the kinetics of c-In2O3 crystallization within the framework of Avrami–Erofeev formalism. The Avrami exponent of ∼3 is characteristic for a reaction mechanism with fast nucleation at the beginning of the reaction and subsequent three-dimensional growth of nuclei with a constant growth rate. The structural transformation path in reconstructive decomposition of c-In(OH)3 to c-In2O3 is discussed in terms of (i) the displacement of hydrogen atoms that lead to breaking the hydrogen bond between OH groups of [In(OH)6] octahedra and finally to their destabilization and (ii) transformation of the vertices-shared indium–oxygen octahedra in c-In(OH)3 to vertices- and edge-shared octahedra in c-In2O3.

Journal or Publication Title: Journal of Solid State Chemistry
Volume: 198
Publisher: Elsevier Science Publishing
Uncontrolled Keywords: Indium oxide, In situ, Transmission electron microscopy, Kinetics, Crystallographic transformation, Decomposition reaction
Divisions: 11 Department of Materials and Earth Sciences > Earth Science > Geo-Material-Science
11 Department of Materials and Earth Sciences > Material Science > Dispersive Solids
11 Department of Materials and Earth Sciences > Material Science > Structure Research
11 Department of Materials and Earth Sciences > Earth Science
11 Department of Materials and Earth Sciences > Material Science
11 Department of Materials and Earth Sciences
Date Deposited: 04 Feb 2014 08:53
Official URL: http://dx.doi.org/10.1016/j.jssc.2012.09.022
Identification Number: doi:10.1016/j.jssc.2012.09.022
Funders: The financial support by the priority program SPP 1236 of the German Research Foundation (DFG) is greatly acknowledged.
Export:
Suche nach Titel in: TUfind oder in Google
Send an inquiry Send an inquiry

Options (only for editors)

View Item View Item