Mechanisms for Enhancing Interface Bonding Strength between High-aspect-ratio TiO2 Nanotube Arrays and Substrate

LAN Jianfeng; ZHANG Xianhui; CHANG Jiangfan; WU Bo; CHEN Baiyi; WU Jianhua

doi:10.16490/j.cnki.issn.1001-3660.2025.18.014

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Surface Technology ›› 2025, Vol. 54 ›› Issue (18) : 142-155. DOI: 10.16490/j.cnki.issn.1001-3660.2025.18.014

Surface Functionalization

Mechanisms for Enhancing Interface Bonding Strength between High-aspect-ratio TiO₂ Nanotube Arrays and Substrate

LAN Jianfeng, ZHANG Xianhui, CHANG Jiangfan, WU Bo, CHEN Baiyi, WU Jianhua^*

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Abstract

This study aims to explore the factors that influence the interface bonding strength between the high-aspect-ratio TiO₂ nanotube arrays and the substrate, so as to provide a comprehensive understanding of the mechanisms responsible for enhancing this interface bonding strength. TiO₂ nanotube arrays with an aspect ratio of 130 were subjected to a two-step post-anodization treatment followed by a heat treatment. The interface bonding strength between the high-aspect-ratio TiO₂ nanotube arrays and the substrate was measured by column pulling tests and micro-scratch tests, which allowed for the evaluation of the effects of different treatment processes on the interface bonding strength.
The results showed that the interface bonding strength between the TiO₂ nanotube arrays and the substrate was significantly influenced by two main factors: the presence of a soluble F^--containing layer and the residual stress layer at the TiO₂ nanotube arrays bottom. Among these influencing factors, the soluble F^--containing layer had a more pronounced effect on the interface bonding strength than the residual stress layer. The interaction between these layers and the substrate was found to play a crucial role in determining the overall interface bonding strength. One important finding of the study was that the heat treatment at 400 ℃ for 1 h was highly effective in eliminating the soluble F^--containing layer at the bottom of the TiO₂ nanotube arrays. This step significantly improved the interface bonding strength, as the F^- ions, which could potentially weaken the interface bonding strength between the TiO₂ nanotube arrays and the substrate, were removed. In parallel, a post-anodization treatment at 10 V for 5 min in an electrolyte consisting of 99vol% C₂H₆O₂, 1vol% H₂O, and 0.5wt.% NH₄F was applied. This treatment reduced the residual stress layer at the bottom of the TiO₂ nanotube arrays. Additionally, a post-anodization treatment at 60 V for 5 min in an electrolyte consisting of 95wt.% C₂H₆O₂ and 5wt.% H₃PO₄ resulted in the formation of a connecting layer with a thickness of 140 nm at the bottom of the TiO₂ nanotube arrays. This connecting layer was found to further enhance the interface bonding strength by providing a more stable and robust attachment to the substrate. Both the heat treatment and post-anodization treatments slightly enhanced the interface bonding strength between the TiO₂ nanotube arrays and the substrate, with the heat treatment providing a more substantial improvement.
The underlying mechanism for enhancing interface bonding strength was found to involve the elimination of the soluble F^--containing layer and the reduction of the residual stress layer at the bottom of the TiO₂ nanotube arrays. Furthermore, the combined approach of the two-step post-anodization treatment followed by heat treatment was found to have a significant synergistic effect on the interface bonding strength. Specifically, this combined processes led to a dramatic increase in the tensile bonding strength, which was enhanced by 5.87 times, and the critical load, which showed an improvement of 7.06 times. These results highlight the effectiveness of combining post-treatment techniques to achieve a significant enhancement in the interface bonding strength between the TiO₂ nanotube arrays and the substrate, which is crucial for the performance and stability of devices incorporating high-aspect-ratio TiO₂ nanotube arrays.

Key words

TiO₂ nanotube arrays / high-aspect-ratio / interface bonding strength / post-anodization treatment / heat treatment

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LAN Jianfeng, ZHANG Xianhui, CHANG Jiangfan, WU Bo, CHEN Baiyi, WU Jianhua. Mechanisms for Enhancing Interface Bonding Strength between High-aspect-ratio TiO₂ Nanotube Arrays and Substrate[J]. Surface Technology. 2025, 54(18): 142-155 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.18.014

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Funding

National Natural Science Foundation of China (42276216, 52301087, U20A20233); Fujian Province University-Industry Collaborative Innovation Project (2023H6028); Education and Scientific Research Project for Middle-aged and Young Teachers of Fujian Province, China (Science and Technology Category) (JAT231049); Natural Science Foundation of Fujian Province, China (2023J01783)