Campus Units

Chemical and Biological Engineering, Chemistry, Materials Science and Engineering, Ames Laboratory

Document Type

Article

Publication Version

Submitted Manuscript

Publication Date

2017

Journal or Book Title

Chemistry of Materials

Volume

29

Issue

18

First Page

7888

Last Page

7900

DOI

10.1021/acs.chemmater.7b02769

Abstract

We here describe a bottom-up approach to control the composition of solid/solid interfaces in nanostructured materials, and we test its effectiveness on tetragonal ZrO2, an inorganic phase of great technological significance. Colloidal nanocrystals capped with trioctylphosphine oxide (TOPO) or oleic acid (OA) are deposited, and the organic fraction of the ligands is selectively etched with O2 plasma. The interfaces in the resulting all-inorganic colloidal nanocrystal assemblies are either nearly bare (for OA-capped nanocrystals) or terminated with phosphate groups (for TOPO-capped nanocrystals) resulting from the reaction of phosphine oxide groups with plasma species. The chemical modification of the interfaces has extensive effects on the thermodynamics and kinetics of the material. Different growth kinetics indicate different rate limiting processes of growth (surface diffusion for the phosphate-terminated surfaces and dissolution for the “bare” surfaces). Phosphate termination led to a higher activation energy of growth, and a 3-fold reduction in interfacial energy, and facilitated significantly the conversion of the tetragonal phase into the monoclinic phase. Films devoid of residual ligands persisted in the tetragonal phase at temperatures as high as 900 °C for 24 h.

Comments

This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Chemistry of Materials, copyright © American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/acs.chemmater.7b02769. Posted with permission.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Published Version

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