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Title: Atomic-Scale Mechanism of Unidirectional Oxide Growth

Abstract

A basic knowledge of the unidirectional growth mechanisms is required for precise control on size, shape, and thereby functionalities of nanostructures. The oxidation of many metals results in oxide nanowire growth with a bicrystal grain boundary along the axial direction. Using transmission electron microscopy that spatially and temporally resolves CuO nanowire growth during the oxidation of copper, here we provide direct evidence of the correlation between unidirectional crystal growth and bicrystal grain boundary diffusion. Based on atomic scale observations of the upward growth at the nanowire tip, oscillatory downward growth of atomic layers on the nanowire sidewall and the parabolic kinetics of lengthening, bicrystal grain boundary diffusion is the mechanism by which Cu ions are delivered from the nanowire root to the tip. Together with density-functional theory calculations, we further show that the asymmetry in the corner-crossing barriers promotes the unidirectional oxide growth by hindering the transport of Cu ions from the nanowire tip to the sidewall facets. We anticipate the broader applicability of these results in manipulating the growth of nanostructured oxides by controlling the bicrystal grain boundary structure that favors anisotropic diffusion for unidirectional, one-dimensional crystal growth for nanowires or isotropic diffusion for two-dimensional platelet growth.

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [1];  [1];  [2];  [3]; ORCiD logo [1]
  1. State Univ. of New York (SUNY), Binghamton, NY (United States)
  2. Univ. of Pittsburgh, PA (United States)
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Publication Date:
Research Org.:
State Univ. of New York (SUNY), Binghamton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1593976
Alternate Identifier(s):
OSTI ID: 1591953
Grant/Contract Number:  
SC0001135; SC0012704; OCI‐1053575; DE‐SC0001135; DE‐SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 4; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; copper; CuO nanowires; environmental transmission electron microscopy; grain boundary diffusion; oxidation

Citation Formats

Sun, Xianhu, Zhu, Wenhui, Wu, Dongxiang, Liu, Zhenyu, Chen, Xiaobo, Yuan, Lu, Wang, Guofeng, Sharma, Renu, and Zhou, Guangwen. Atomic-Scale Mechanism of Unidirectional Oxide Growth. United States: N. p., 2019. Web. doi:10.1002/adfm.201906504.
Sun, Xianhu, Zhu, Wenhui, Wu, Dongxiang, Liu, Zhenyu, Chen, Xiaobo, Yuan, Lu, Wang, Guofeng, Sharma, Renu, & Zhou, Guangwen. Atomic-Scale Mechanism of Unidirectional Oxide Growth. United States. doi:10.1002/adfm.201906504.
Sun, Xianhu, Zhu, Wenhui, Wu, Dongxiang, Liu, Zhenyu, Chen, Xiaobo, Yuan, Lu, Wang, Guofeng, Sharma, Renu, and Zhou, Guangwen. Thu . "Atomic-Scale Mechanism of Unidirectional Oxide Growth". United States. doi:10.1002/adfm.201906504.
@article{osti_1593976,
title = {Atomic-Scale Mechanism of Unidirectional Oxide Growth},
author = {Sun, Xianhu and Zhu, Wenhui and Wu, Dongxiang and Liu, Zhenyu and Chen, Xiaobo and Yuan, Lu and Wang, Guofeng and Sharma, Renu and Zhou, Guangwen},
abstractNote = {A basic knowledge of the unidirectional growth mechanisms is required for precise control on size, shape, and thereby functionalities of nanostructures. The oxidation of many metals results in oxide nanowire growth with a bicrystal grain boundary along the axial direction. Using transmission electron microscopy that spatially and temporally resolves CuO nanowire growth during the oxidation of copper, here we provide direct evidence of the correlation between unidirectional crystal growth and bicrystal grain boundary diffusion. Based on atomic scale observations of the upward growth at the nanowire tip, oscillatory downward growth of atomic layers on the nanowire sidewall and the parabolic kinetics of lengthening, bicrystal grain boundary diffusion is the mechanism by which Cu ions are delivered from the nanowire root to the tip. Together with density-functional theory calculations, we further show that the asymmetry in the corner-crossing barriers promotes the unidirectional oxide growth by hindering the transport of Cu ions from the nanowire tip to the sidewall facets. We anticipate the broader applicability of these results in manipulating the growth of nanostructured oxides by controlling the bicrystal grain boundary structure that favors anisotropic diffusion for unidirectional, one-dimensional crystal growth for nanowires or isotropic diffusion for two-dimensional platelet growth.},
doi = {10.1002/adfm.201906504},
journal = {Advanced Functional Materials},
number = 4,
volume = 30,
place = {United States},
year = {2019},
month = {11}
}

Journal Article:
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